Dithizone-functionalized solid phase extraction-displacement elution-high performance liquid chromatography-inductively coupled plasma mass spectrometry for mercury speciation in water samples.

PubMed

Yin, Yong-guang; Chen, Ming; Peng, Jin-feng; Liu, Jing-fu; Jiang, Gui-bin

2010-06-15

A novel and simple solid phase extraction (SPE)-high performance liquid chromatography (HPLC)-inductively coupled plasma mass spectrometry (ICP-MS) method was developed for determination of inorganic mercury (IHg), methylmercury MeHg and ethylmercury (EtHg) in water samples in the present work. The procedure involves pre-functionalization of the commercially available C18 SPE column with dithizone, loading water sample, displacement elution of mercury species by Na(2)S(2)O(3) solution, followed by HPLC-ICP-MS determination. Characterization and optimization of operation parameters of this new SPE procedure were discussed, including eluting reagent selection, concentration of eluting reagent, volume of eluting reagent, effect of NaCl and humic acid in sample matrix. At optimized conditions, the detection limits of mercury species for 100mL water sample were about 3ngL(-1) and the average recoveries were 93.7, 83.4, and 71.7% for MeHg, IHg and EtHg, respectively, by spiking 0.2microgL(-1) mercury species into de-ion water. Stability experiment reveals that both the dithizone-functionalized SPE cartridge and the mercury species incorporated were stable in the storage procedure. These results obtained demonstrate that SPE-HPLC-ICP-MS is a simple and sensitive technique for the determination of mercury species at trace level in water samples with high reproducibility and accuracy.

Electrokinetic coupling in unsaturated porous media.

PubMed

Revil, A; Linde, N; Cerepi, A; Jougnot, D; Matthäi, S; Finsterle, S

2007-09-01

We consider a charged porous material that is saturated by two fluid phases that are immiscible and continuous on the scale of a representative elementary volume. The wetting phase for the grains is water and the nonwetting phase is assumed to be an electrically insulating viscous fluid. We use a volume-averaging approach to derive the linear constitutive equations for the electrical current density as well as the seepage velocities of the wetting and nonwetting phases on the scale of a representative elementary volume. These macroscopic constitutive equations are obtained by volume-averaging Ampère's law together with the Nernst-Planck equation and the Stokes equations. The material properties entering the macroscopic constitutive equations are explicitly described as functions of the saturation of the water phase, the electrical formation factor, and parameters that describe the capillary pressure function, the relative permeability functions, and the variation of electrical conductivity with saturation. New equations are derived for the streaming potential and electro-osmosis coupling coefficients. A primary drainage and imbibition experiment is simulated numerically to demonstrate that the relative streaming potential coupling coefficient depends not only on the water saturation, but also on the material properties of the sample, as well as the saturation history. We also compare the predicted streaming potential coupling coefficients with experimental data from four dolomite core samples. Measurements on these samples include electrical conductivity, capillary pressure, the streaming potential coupling coefficient at various levels of saturation, and the permeability at saturation of the rock samples. We found very good agreement between these experimental data and the model predictions.

Analysis of iodinated X-ray contrast agents in water samples by ion chromatography and inductively-coupled plasma mass spectrometry.

PubMed

Sacher, Frank; Raue, Brigitte; Brauch, Heinz-Jürgen

2005-08-26

In this paper, an analytical method for the determination of six iodinated X-ray contrast agents (amidotrizoic acid, iohexol, iomeprol, iopamidol, iopromide, and ioxitalamic acid), iodide, and iodate in water samples is presented. The method is based on a separation of the analytes by ion chromatography (IC) and a subsequent detection by inductively-coupled plasma mass spectrometry (ICP-MS). The method was optimised with respect to separation conditions (column type and eluent composition) and extensively validated. Without pre-concentration of the samples, limits of detection below 0.2 microg/l could be achieved whereby reproducibility was below 6% for all compounds under investigation.

Constraining Unsaturated Hydraulic Parameters Using the Latin Hypercube Sampling Method and Coupled Hydrogeophysical Approach

NASA Astrophysics Data System (ADS)

Farzamian, Mohammad; Monteiro Santos, Fernando A.; Khalil, Mohamed A.

2017-12-01

The coupled hydrogeophysical approach has proved to be a valuable tool for improving the use of geoelectrical data for hydrological model parameterization. In the coupled approach, hydrological parameters are directly inferred from geoelectrical measurements in a forward manner to eliminate the uncertainty connected to the independent inversion of electrical resistivity data. Several numerical studies have been conducted to demonstrate the advantages of a coupled approach; however, only a few attempts have been made to apply the coupled approach to actual field data. In this study, we developed a 1D coupled hydrogeophysical code to estimate the van Genuchten-Mualem model parameters, K s, n, θ r and α, from time-lapse vertical electrical sounding data collected during a constant inflow infiltration experiment. van Genuchten-Mualem parameters were sampled using the Latin hypercube sampling method to provide a full coverage of the range of each parameter from their distributions. By applying the coupled approach, vertical electrical sounding data were coupled to hydrological models inferred from van Genuchten-Mualem parameter samples to investigate the feasibility of constraining the hydrological model. The key approaches taken in the study are to (1) integrate electrical resistivity and hydrological data and avoiding data inversion, (2) estimate the total water mass recovery of electrical resistivity data and consider it in van Genuchten-Mualem parameters evaluation and (3) correct the influence of subsurface temperature fluctuations during the infiltration experiment on electrical resistivity data. The results of the study revealed that the coupled hydrogeophysical approach can improve the value of geophysical measurements in hydrological model parameterization. However, the approach cannot overcome the technical limitations of the geoelectrical method associated with resolution and of water mass recovery.

Comparison of four-hour and twenty-four-hour refrigerated storage of nonpotable water for fecal coliform analysis.

PubMed Central

Standridge, J H; Lesar, D J

1977-01-01

The problem of extending the storage time of water samples for fecal coliform analysis was addressed. Included in this report is a literature review of the storage problem. Twenty-eight samples were analyzed in replicate to determine the effect of 24-h storage of water samples at 4 degrees C. A new statistical approach to data analysis, coupled with the concept of practical acceptability, is presented. According to our results, many samples can successfully be stored at 4 degrees C for 24 h. PMID:335972

Investigating the presence of omeprazole in waters by liquid chromatography coupled to low and high resolution mass spectrometry: degradation experiments.

PubMed

Boix, C; Ibáñez, M; Sancho, J V; Niessen, W M A; Hernández, F

2013-10-01

Omeprazole is one of the most consumed pharmaceuticals around the world. However, this compound is scarcely detected in urban wastewater and surface water. The absence of this pharmaceutical in the aquatic ecosystem might be due to its degradation in wastewater treatment plants, as well as in receiving water. In this work, different laboratory-controlled degradation experiments have been carried out on surface water in order to elucidate generated omeprazole transformation products (TPs). Surface water spiked with omeprazole was subjected to hydrolysis, photo-degradation under both sunlight and ultraviolet radiation and chlorination. Analyses by liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (LC-QTOF MS) permitted identification of up to 17 omeprazole TPs. In a subsequent step, the TPs identified were sought in surface water and urban wastewater by LC-QTOF MS and by LC coupled to tandem mass spectrometry with triple quadrupole. The parent omeprazole was not detected in any of the samples, but four TPs were found in several water samples. The most frequently detected compound was OTP 5 (omeprazole sulfide), which might be a reasonable candidate to be included in monitoring programs rather than the parent omeprazole. Copyright © 2013 John Wiley & Sons, Ltd.

Using High Frequency Focused Water-Coupled Ultrasound for 3-D Surface Depression Profiling

NASA Technical Reports Server (NTRS)

Roth, Don J.; Whalen, Mike F.; Hendricks, J. Lynne; Bodis, James R.

1999-01-01

Surface topography is an important variable in the performance of many industrial components and is normally measured with diamond-tip profilometry over a small area or using optical scattering methods for larger area measurement. A prior study was performed demonstrating that focused air-coupled ultrasound at 1 MHz was capable of profiling surfaces with 25 micron depth resolution and 400 micron lateral resolution over a 1.4 mm depth range. In this article, the question of whether higher-frequency focused water-coupled ultrasound can improve on these specifications is addressed. 10 and 25 MHz focused ultrasonic transducers were employed in the water-coupled mode. Time-of-flight images of the sample surface were acquired and converted to depth / surface profile images using the simple relation (d = V*t/2) between distance (d), time-of-flight (t), and the velocity of sound in water (V). Results are compared for the two frequencies used and with those from the 1 MHz air-coupled configuration.

[Determination of nitroaromatics and cyclo ketones in sea water' by gas chromatography coupled with activated carbon fiber solid-phase micro-extraction].

PubMed

Ma, Hanna; Zhu, Mengya; Wang, Yalin; Sun, Tonghua; Jia, Jinping

2009-05-01

A gas chromatography (GC) coupled with solid-phase micro-extraction using a special activated carbon fiber (ACF) was developed for the analysis of 6 nitroaromatics and cyclic ketones, nitrobenzene (NB), 1,3-dinitrobenzene (1,3-DNB), 2,4-dinitrotoluene (2,4-DNT), 2,6-dinitrotoluene (2,6-DNT), isophorone, 1,4-naphthaquinone (1,4-NPQ), in sea water samples. The sample was extracted for 30 min under saturation of NaCl at 1,500 r/min and 60 degrees C in head space. The desorption was performance at 280 degrees C for 2 min. The linear ranges were from 0.01 to 400 microg/L. The limits of detection (LODs) were 1.4 - 3.2 ng/L. This method has been successfully applied to the determination of nitroaromatics and cyclic ketones in the sea water samples obtained from East China Sea. The concentrations of nitrobenzene, 1,3-dinitrobenzene and 2,6-dinitrotoluene in the sea water sample were 0.756, 0.944, 0.890 microg/L, respectively. The recoveries were 86.3% - 101.8% with the relative standard deviations (RSDs) of 3.7% -7.8%. The method is suitable for analyzing nitroaromatics and cyclic ketones at low concentration levels in sea water samples.

A novel HS-SBSE system coupled with gas chromatography and mass spectrometry for the analysis of organochlorine pesticides in water samples.

PubMed

Grossi, Paula; Olivares, Igor R B; de Freitas, Diego R; Lancas, Fernando M

2008-10-01

A methodology to analyze organochlorine pesticides (OCPs) in water samples has been accomplished by using headspace stir bar sorptive extraction (HS-SBSE). The bars were in house coated with a thick film of PDMS in order to properly work in the headspace mode. Sampling was done by a novel HS-SBSE system whereas the analysis was performed by capillary GC coupled mass spectrometric detection (HS-SBSE-GC-MS). The extraction optimization, using different experimental parameters has been established by a standard equilibrium time of 120 min at 85 degrees C. A mixture of ACN/toluene as back extraction solvent promoted a good performance to remove the OCPs sorbed in the bar. Reproducibility between 2.1 and 14.8% and linearity between 0.96 and 1.0 were obtained for pesticides spiked in a linear range between 5 and 17 ng/g in water samples during the bar evaluation.

Determination of pyrazole and pyrrole pesticides in environmental water samples by solid-phase extraction using multi-walled carbon nanotubes as adsorbent coupled with high-performance liquid chromatography.

PubMed

Ma, Jiping; Lu, Xi; Xia, Yan; Yan, Fengli

2015-02-01

A solid-phase extraction (SPE) method using multi-walled carbon nanotubes as adsorbent coupled with high-performance liquid chromatography was developed for the determination of four pyrazole and pyrrole pesticides (fenpyroximate, chlorfenapyr, fipronil and flusilazole) in environmental water samples. Several parameters, such as extraction adsorbent, elution solvent and volume and sample loading flow rate were optimized to obtain high SPE recoveries and extraction efficiency. The calibration curves for the pesticides extracted were linear in the range of 0.05-10 μg L(-1) for chlorfenapyr and fenpyroximate and 0.05-20 μg L(-1) for fipronil and flusilazole, with the correlation coefficients (r(2)) between 0.9966 and 0.9990. The method gave good precisions (relative standard deviation %) from 2.9 to 10.1% for real spiked samples from reservoir water and seawater; method recoveries ranged 92.2-105.9 and 98.5-103.9% for real spiked samples from reservoir water and seawater, respectively. Limits of detection (S/N = 3) for the method were determined to be 8-19 ng L(-1). The optimized method was successfully applied to the determination of four pesticides of pyrazoles and pyrroles in real environmental water samples. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Determination of total arsenic and arsenic species in drinking water, surface water, wastewater, and snow from Wielkopolska, Kujawy-Pomerania, and Lower Silesia provinces, Poland.

PubMed

Komorowicz, Izabela; Barałkiewicz, Danuta

2016-09-01

Arsenic is a ubiquitous element which may be found in surface water, groundwater, and drinking water. In higher concentrations, this element is considered genotoxic and carcinogenic; thus, its level must be strictly controlled. We investigated the concentration of total arsenic and arsenic species: As(III), As(V), MMA, DMA, and AsB in drinking water, surface water, wastewater, and snow collected from the provinces of Wielkopolska, Kujawy-Pomerania, and Lower Silesia (Poland). The total arsenic was analyzed by inductively coupled plasma mass spectrometry (ICP-MS), and arsenic species were analyzed with use of high-performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC/ICP-MS). Obtained results revealed that maximum total arsenic concentration determined in drinking water samples was equal to 1.01 μg L(-1). The highest concentration of total arsenic in surface water, equal to 3778 μg L(-1) was determined in Trująca Stream situated in the area affected by geogenic arsenic contamination. Total arsenic concentration in wastewater samples was comparable to those determined in drinking water samples. However, significantly higher arsenic concentration, equal to 83.1 ± 5.9 μg L(-1), was found in a snow sample collected in Legnica. As(V) was present in all of the investigated samples, and in most of them, it was the sole species observed. However, in snow sample collected in Legnica, more than 97 % of the determined concentration, amounting to 81 ± 11 μg L(-1), was in the form of As(III), the most toxic arsenic species.

Miscellaneous geochemical data from waters in the Upper Animas River Watershed, Colorado

USGS Publications Warehouse

Johnson, Raymond H.; Yager, Douglas B.

2013-01-01

This report releases geochemistry data in waters from the upper Animas River watershed that have been analyzed by inductively coupled plasma–mass spectrometry. These samples were collected at various sites and at various dates (41 sites and 86 samples from 2008 to 2010). A main data table is provided and the text discusses the sampling methods and locations in relation to other published reports.

Fast screening and quantitation of microcystins in microalgae dietary supplement products and water by liquid chromatography coupled to time of flight mass spectrometry.

PubMed

Ortelli, Didier; Edder, Patrick; Cognard, Emmanuelle; Jan, Philippe

2008-06-09

Cyanobacteria, commonly called "blue-green algae", may accumulate in surface water supplies as "blooms" and may concentrate on the surface as blue-green "scums". Some species of cyanobacteria produce toxins and are of relevance to water supplies and to microalgae dietary supplements. To ensure the safety of drinking water and blue-green algae products, analyses are the only way to determine the presence or absence of toxins. This paper shows the use of ultra performance liquid chromatography (UPLC) coupled to orthogonal acceleration time of flight (TOF) mass spectrometry for the detection and quantitation of microcystins. The method presented is very sensitive, simple, fast, robust and did not require fastidious clean-up step. Limits of detection of 0.1 microg L(-1) in water and 0.1-0.2 microg g(-1) in microalgae samples were achieved. Method performances were satisfactory and appropriate for monitoring of water and dietary supplements. The method was applied in routine to samples taken from Swiss market or buy on internet website. Among 19 samples, six showed the presence of microcystins LR and LA at harmful levels.

Evaluating data worth for ground-water management under uncertainty

USGS Publications Warehouse

Wagner, B.J.

1999-01-01

A decision framework is presented for assessing the value of ground-water sampling within the context of ground-water management under uncertainty. The framework couples two optimization models-a chance-constrained ground-water management model and an integer-programing sampling network design model-to identify optimal pumping and sampling strategies. The methodology consists of four steps: (1) The optimal ground-water management strategy for the present level of model uncertainty is determined using the chance-constrained management model; (2) for a specified data collection budget, the monitoring network design model identifies, prior to data collection, the sampling strategy that will minimize model uncertainty; (3) the optimal ground-water management strategy is recalculated on the basis of the projected model uncertainty after sampling; and (4) the worth of the monitoring strategy is assessed by comparing the value of the sample information-i.e., the projected reduction in management costs-with the cost of data collection. Steps 2-4 are repeated for a series of data collection budgets, producing a suite of management/monitoring alternatives, from which the best alternative can be selected. A hypothetical example demonstrates the methodology's ability to identify the ground-water sampling strategy with greatest net economic benefit for ground-water management.A decision framework is presented for assessing the value of ground-water sampling within the context of ground-water management under uncertainty. The framework couples two optimization models - a chance-constrained ground-water management model and an integer-programming sampling network design model - to identify optimal pumping and sampling strategies. The methodology consists of four steps: (1) The optimal ground-water management strategy for the present level of model uncertainty is determined using the chance-constrained management model; (2) for a specified data collection budget, the monitoring network design model identifies, prior to data collection, the sampling strategy that will minimize model uncertainty; (3) the optimal ground-water management strategy is recalculated on the basis of the projected model uncertainty after sampling; and (4) the worth of the monitoring strategy is assessed by comparing the value of the sample information - i.e., the projected reduction in management costs - with the cost of data collection. Steps 2-4 are repeated for a series of data collection budgets, producing a suite of management/monitoring alternatives, from which the best alternative can be selected. A hypothetical example demonstrates the methodology's ability to identify the ground-water sampling strategy with greatest net economic benefit for ground-water management.

Membrane solid phase microextraction with alumina hollow fiber on line coupled with ICP-OES for the determination of trace copper, manganese and nickel in environmental water samples.

PubMed

Cui, Chao; He, Man; Hu, Bin

2011-03-15

A novel alumina hollow fiber was synthesized by sol-gel template method and was characterized by scanning electron microscopy, N(2) adsorption technique and X-ray diffraction. With the use of prepared alumina hollow fiber as extraction membrane, a new method of flow injection (FI)-membrane solid phase microextraction (MSPME) on-line coupled to inductively coupled plasma-optical emission spectrometry (ICP-OES) was developed for simultaneous determination of trace metals (Cu, Mn and Ni) in environmental water samples. The adsorption capacities of the alumina hollow fiber for Cu, Mn and Ni were found to be 6.6, 8.7 and 13.3 mg g(-1), respectively. With a preconcentration factor of 10, the limits of detection (LODs) for Cu, Mn and Ni were found to be 0.88, 0.61 and 0.38 ng mL(-1), respectively, and the relative standard deviations (RSDs) were ranging from 6.2 to 7.9% (n = 7, c = 10 ng mL(-1)). To validate the accuracy, the proposed method was applied to the analysis of certified reference material GSBZ50009-88 environmental water and the determined values are in good agreement with the certified values. The developed method was also employed for the analysis of Yangtze River water and East Lake water, and the recoveries for the spiked samples were in the range of 87.4-110.2%. Copyright © 2011 Elsevier B.V. All rights reserved.

Rapid sequential determination of arsenic and selenium in waters and plant digests by hydride generation inductively coupled plasma-mass spectrometry

NASA Astrophysics Data System (ADS)

Menegário, Amauri A.; Giné, Maria Fernanda

2000-04-01

A synchronised flow system with hydride generation coupled to ICP-MS is proposed for the sequential determination of As and Se in natural waters and plant digests. The alternated mixing of the sample solution with thiourea or HCl for the determination of As or Se under optimized conditions was achieved using a flow commutator before the reaction with NaBH 4. The on-line addition of thiourea promoted the quantitative reduction of As(V) to As(III), thus enhancing sensitivity and precision. The selenium pre-reduction from Se(VI) to Se(IV) was produced by heating the sample with HCl, and the hydride generation was performed in 4 mol l -1 HCl, thus avoiding interference from thiourea. The system allowed the analysis of 20 samples h -1 with LOD values of 0.02 μg l -1 As and 0.03 μg l -1 Se. Results were in agreement with the certified values at the 95% confidence level for reference waters from the Canadian National Water Research Institute and plant samples from the National Institute of Standards and Technology (NIST).

Fast trace determination of nine odorant and estrogenic chloro- and bromo-phenolic compounds in real water samples through automated solid-phase extraction coupled with liquid chromatography tandem mass spectrometry.

PubMed

Yuan, Su-Fen; Liu, Ze-Hua; Lian, Hai-Xian; Yang, Chuang-Tao; Lin, Qing; Yin, Hua; Lin, Zhang; Dang, Zhi

2018-02-01

A fast and reliable method was developed for simultaneous trace determination of nine odorous and estrogenic chloro- and bromo-phenolic compounds (CPs and BPs) in water samples using solid-phase extraction (SPE) coupled with liquid chromatography tandem mass spectrometry (LC-MS/MS). For sample preparation, the extraction efficiencies of two widely applied cartridges Oasis HLB and Sep-Pak C18 were compared, and the Oasis HLB cartridge showed much better extraction performance; pH of water sample also plays important role on extraction, and pH = 2-3 was found to be most appropriate. For separation of the target compounds, small addition of ammonium hydroxide can obviously improve the detection sensitivity, and the optimized addition concentration was determined as 0.2%. The developed efficient method was validated and showed excellent linearity (R 2  > 0.995), low limit of detection (LOD, 1.9-6.2 ng/L), and good recovery efficiencies of 57-95% in surface and tap water with low relative standard deviation (RSD, 1.3-17.4%). The developed method was finally applied to one tap and one surface water samples and most of these nine targets were detected, but all of them were below their odor thresholds, and their estrogen equivalent (EEQ) were also very low.

DC thermal microscopy: study of the thermal exchange between a probe and a sample

NASA Astrophysics Data System (ADS)

Gomès, Séverine; Trannoy, Nathalie; Grossel, Philippe

1999-09-01

The Scanning Thermal Microscopic (SThM) probe, a thin Pt resistance wire, is used in the constant force mode of an Atomic Force Microscope (AFM). Thermal signal-distance curves for differing degrees of relative humidity and different surrounding gases demonstrate how heat is transferred from the heated probe to the sample. It is known that water affects atomic force microscopy and thermal measurements; we report here on the variation of the water interaction on the thermal coupling versus the probe temperature. Measurements were taken for several solid materials and show that the predominant heat transfer mechanisms taking part in thermal coupling are dependent on the thermal conductivity of the sample. The results have important implications for any quantitative interpretation of thermal images made in air.

Solid-Phase Extraction Coupled to a Paper-Based Technique for Trace Copper Detection in Drinking Water.

PubMed

Quinn, Casey W; Cate, David M; Miller-Lionberg, Daniel D; Reilly, Thomas; Volckens, John; Henry, Charles S

2018-03-20

Metal contamination of natural and drinking water systems poses hazards to public and environmental health. Quantifying metal concentrations in water typically requires sample collection in the field followed by expensive laboratory analysis that can take days to weeks to obtain results. The objective of this work was to develop a low-cost, field-deployable method to quantify trace levels of copper in drinking water by coupling solid-phase extraction/preconcentration with a microfluidic paper-based analytical device. This method has the advantages of being hand-powered (instrument-free) and using a simple "read by eye" quantification motif (based on color distance). Tap water samples collected across Fort Collins, CO, were tested with this method and validated against ICP-MS. We demonstrate the ability to quantify the copper content of tap water within 30% of a reference technique at levels ranging from 20 to 500 000 ppb. The application of this technology, which should be sufficient as a rapid screening tool, can lead to faster, more cost-effective detection of soluble metals in water systems.

Scanning electron microscopy coupled with energy-dispersive X-ray spectrometry for quick detection of sulfur-oxidizing bacteria in environmental water samples

NASA Astrophysics Data System (ADS)

Sun, Chengjun; Jiang, Fenghua; Gao, Wei; Li, Xiaoyun; Yu, Yanzhen; Yin, Xiaofei; Wang, Yong; Ding, Haibing

2017-01-01

Detection of sulfur-oxidizing bacteria has largely been dependent on targeted gene sequencing technology or traditional cell cultivation, which usually takes from days to months to carry out. This clearly does not meet the requirements of analysis for time-sensitive samples and/or complicated environmental samples. Since energy-dispersive X-ray spectrometry (EDS) can be used to simultaneously detect multiple elements in a sample, including sulfur, with minimal sample treatment, this technology was applied to detect sulfur-oxidizing bacteria using their high sulfur content within the cell. This article describes the application of scanning electron microscopy imaging coupled with EDS mapping for quick detection of sulfur oxidizers in contaminated environmental water samples, with minimal sample handling. Scanning electron microscopy imaging revealed the existence of dense granules within the bacterial cells, while EDS identified large amounts of sulfur within them. EDS mapping localized the sulfur to these granules. Subsequent 16S rRNA gene sequencing showed that the bacteria detected in our samples belonged to the genus Chromatium, which are sulfur oxidizers. Thus, EDS mapping made it possible to identify sulfur oxidizers in environmental samples based on localized sulfur within their cells, within a short time (within 24 h of sampling). This technique has wide ranging applications for detection of sulfur bacteria in environmental water samples.

Investigating Uranium Concentrations in Groundwaters in the State of Idaho Using Kinetic Phosphorescence Analysis and Inductively Coupled Plasma Mass Spectrometry.

PubMed

Tkavadze, Levan; Dunker, Roy E; Brey, Richard R; Dudgeon, John

2016-11-01

The determination of uranium concentrations in natural water samples is of great interest due to the environmental consequences of this radionuclide. In this study, 380 groundwater samples from various locations within the state of Idaho were analyzed using two different techniques. The first method was Kinetic Phosphorescence Analysis (KPA), which gives the total uranium concentrations in water samples. The second analysis method was inductively coupled plasma mass spectrometry (ICP- MS). This method determines the total uranium concentration as well as the separate isotope concentrations of uranium. The U/U isotopic ratio was also measured for each sample to confirm that there was no depleted or enriched uranium present. The results were compared and mapped separately from each other. The study also found that in some areas of the state, natural uranium concentrations are relatively high.

Magnetic sporopollenin-cyanopropyltriethoxysilane-dispersive micro-solid phase extraction coupled with high performance liquid chromatography for the determination of selected non-steroidal anti-inflammatory drugs in water samples.

PubMed

Abd Wahib, Siti Munirah; Wan Ibrahim, Wan Aini; Sanagi, Mohd Marsin; Kamboh, Muhammad Afzal; Abdul Keyon, Aemi S

2018-01-12

A facile dispersive-micro-solid phase extraction (D-μ-SPE) method coupled with HPLC for the analysis of selected non-steroidal anti-inflammatory drugs (NSAIDs) in water samples was developed using a newly prepared magnetic sporopollenin-cyanopropyltriethoxysilane (MS-CNPrTEOS) sorbent. Sporopollenin homogenous microparticles of Lycopodium clavatum spores possessed accessible functional groups that facilitated surface modification. Simple modification was performed by functionalization with 3-cyanopropyltriethoxysilane (CNPrTEOS) and magnetite was introduced onto the biopolymer to simplify the extraction process. MS-CNPrTEOS was identified by infrared spectrometrywhile the morphology and the magnetic property were confirmed by scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM), respectively. To maximize the extraction performance of ketoprofen, ibuprofen, diclofenac and mefenamic acid using the proposed MS-CNPrTEOS, important D-μ-SPE parameters were comprehensively optimized. The optimum extraction conditions were sorbent amount, 40 mg; extraction time, 5 min; desorption time; 5 min; sample volume, 15 mL; sample pH 2.0; and salt addition, 2.5% (w/v). The feasibility of the developed method was evaluated using spiked tap water, lake water, river water and waste water samples. Results showed that ketoprofen and ibuprofen were linear in the range of 1.0-1000 μg L -1 whilst diclofenac and mefenamic acid were linear in the range 0.8-500 μg L -1 . The results also showed good detection limits for the studied NSAIDs in the range of 0.21-0.51 μg L -1 and good recoveries for spiked water samples in the range of 85.1-106.4%. The MS-CNPrTEOS proved a promising dispersive sorbent and applicable to facile and rapid assay of NSAIDs in water samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Coupling solid-phase extraction and enzyme-linked immunosorbent assay for ultratrace determination of herbicides in pristine water

USGS Publications Warehouse

Aga, D.S.; Thurman, E.M.

1993-01-01

Solid-phase extraction (SPE) and enzyme-linked immunosorbent assay (ELISA) were coupled for automated trace analysis of pristine water samples containing 2-chloro-4-ethylamino-6-isopropylamine-s-triazine (atrazine) and 2-chloro-2???,6???-diethyl-N-(methoxymethyl)acetanilide (alachlor). The isolation of the two herbicides on a C18-resin involved the selection of an elution solvent that both removes interfering substances and is compatible with ELISA. Ethyl acetate was selected as the elution solvent followed by a solvent exchange with methanol/water (20/80, % v/v). The SPE-ELISA method has a detection limit of 5.0 ng/L (5 ppt), >90% recovery, and a relative standard deviation of ??10%. The performance of a microtiter plate-based ELISA and a magnetic particle-based ELISA coupled to SPE was also evaluated. Although the sensitivity of the two ELISA methods was comparable, the precision using magnetic particles was improved considerably (??10% versus ??20%) because of the faster reaction kinetics provided by the magnetic particles. Finally, SPE-ELISA and isotope dilution gas chromatography/ mass spectrometry correlated well (correlation coefficient of 0.96) for lake-water samples. The SPE-ELISA method is simple and may have broader applications for the inexpensive automated analysis of other contaminants in water at trace levels.

Automated fluid analysis apparatus and techniques

DOEpatents

Szecsody, James E.

2004-03-16

An automated device that couples a pair of differently sized sample loops with a syringe pump and a source of degassed water. A fluid sample is mounted at an inlet port and delivered to the sample loops. A selected sample from the sample loops is diluted in the syringe pump with the degassed water and fed to a flow through detector for analysis. The sample inlet is also directly connected to the syringe pump to selectively perform analysis without dilution. The device is airtight and used to detect oxygen-sensitive species, such as dithionite in groundwater following a remedial injection to treat soil contamination.

Determination of the Presence of Three Antimicrobials in Surface Water Collected from Urban and Rural Areas

PubMed Central

Iglesias, Alejandra; Nebot, Carolina; Miranda, Jose M.; Vázquez, Beatriz I.; Abuín, Carlos M. Franco; Cepeda, Alberto

2013-01-01

Due to the continuous release of antimicrobials into the environment, the aim of this study was to compare the frequency of detection of sulfamethazine, sulfamethoxypyridazine and trimethoprim in surface water collected from urban and rural areas in Northwestern Spain. A monitoring study was conducted with 314 river water samples analyzed by high-performance liquid chromatography coupled to tandem mass spectrometry. The results indicated that 37% of the samples contained residues of at least one of the investigated antimicrobials, and every sampling site yielded positive samples. At sites located near the discharge points of wastewater treatment plants and near the collection point of a drinking-water treatment plant, more than 6% of the samples were positive for the presence of antimicrobial residues. PMID:27029291

PRESERVATION OF TRACE METALS IN WATER SAMPLES

EPA Science Inventory

Questions about trace metal preservation are resurfacing because the health effect risks associated with certain metals continue to drive the required reporting limits lower. Inductively coupled plasma-mass spectrometry was used in this study to analyze preservation of samples co...

An on-line coupling of nanofibrous extraction with column-switching high performance liquid chromatography - A case study on the determination of bisphenol A in environmental water samples.

PubMed

Háková, Martina; Chocholoušová Havlíková, Lucie; Chvojka, Jiří; Solich, Petr; Šatínský, Dalibor

2018-02-01

Polyamide 6 nanofiber polymers were used as modern sorbents for on-line solid phase extraction (SPE) coupled with liquid chromatography. The on-line SPE system was tested for the determination of bisphenol A in river water samples. Polyamide nanofibers were prepared using needleless electrospinning, inserted into a mini-column cartridge (5 × 4.6mm) and coupled with HPLC. The effect of column packing and the amount of polyamide 6 on extraction efficiency was tested and the packing process was optimized. The proposed method was performed using a 50-µL sample injection followed by an on-line nanofibrous extraction procedure. The influence of the washing mobile phase on the retention of bisphenol A during the extraction procedure was evaluated. Ascentis ® Express C18 (10cm × 4.6mm) core-shell column was used as an analytical column. Fluorescence detection wavelengths (λ ex = 225nm and λ em = 320nm) were used for identification and quantification of Bisphenol A in river waters. The linearity was tested in the range from 2 to 500µgL -1 (using nine calibration points). The limits of detection and quantification were 0.6 and 2µgL -1 , respectively. The developed method was successfully used for the determination of bisphenol A in various samples of river waters in the Czech Republic (The Ohře, Labe, Nisa, Úpa, and Opava Rivers). Copyright © 2017 Elsevier B.V. All rights reserved.

Identification of trace levels of selenomethionine and related organic selenium species in high-ionic-strength waters.

PubMed

LeBlanc, Kelly L; Ruzicka, Josef; Wallschläger, Dirk

2016-02-01

A new anion-exchange chromatographic separation method was used for the simultaneous speciation analysis of selenoamino acids and the more ubiquitous inorganic selenium oxyanions, selenite and selenate. For quantification, this separation was coupled to inductively coupled plasma-mass spectrometry to achieve an instrumental detection limit of 5 ng Se L(-1) for all species. This chromatographic method was also coupled to electrospray tandem mass spectrometry to observe the negative ion mode fragmentation of selenomethionine and one of its oxidation products. Low detection limits were achieved, which were similar to those obtained using inductively coupled plasma-mass spectrometry. An extensive preconcentration and cleanup procedure using cation-exchange solid-phase extraction was developed for the identification and quantification of trace levels of selenomethionine in environmental samples. Preconcentration factors of up to five were observed for selenomethionine, which in addition to the removal of high concentrations of sulphate and chloride from industrial process waters, allowed for an unambiguous analysis that would have been impossible otherwise. Following these methods, selenomethionine was identified at an original concentration of 3.2 ng Se L(-1) in samples of effluent collected at a coal-fired power plant's biological remediation site. It is the first time that this species has been identified in the environment, outside of a biological entity. Additionally, oxidation products of selenomethionine were identified in river water and laboratory algal culture samples. High-resolution mass spectrometry was employed to postulate the chemical structures of these species.

Lithotype characterizations by Nuclear Magnetic Resonance (NMR): A case study on limestone and associated rocks from the eastern Dahomey Basin, Nigeria

NASA Astrophysics Data System (ADS)

Olatinsu, O. B.; Olorode, D. O.; Clennell, B.; Esteban, L.; Josh, M.

2017-05-01

Three representative rock types (limestone, sandstone, and shale) and glauconite samples collected from Ewekoro Quarry, eastern Dahomey Basin in Nigeria were characterized using low field 2 MHz and 20 MHz Nuclear Magnetic Resonance (NMR) techniques. NMR T2 relaxation time decay measurement was conducted on disc samples under partial water-saturation and full water-saturation conditions using CPMG spin-echo routine. The T2 relaxation decay was converted into T2 distribution in the time domain to assess and evaluate the pore size distribution of the samples. Good agreement exists between water content from T2 NMR distributions and water imbibition porosity (WIP) technique. Results show that the most useful characteristics to discriminate the different facies come from full saturation NMR 2 MHz pore size distribution (PSD). Shale facies depict a quasi-unimodal distribution with greater than 90% contribution from clay bound water component (T2s) coupled to capillary bound water component (T2i) centred on 2 ms. The other facies with well connected pore structure show either bimodal or trimodal T2 distribution composed of the similar clay bound water component centred on 0.3 ms and quasi-capillary bound water component centred on 10 ms. But their difference depends on the movable water T2 component (T2l) that does not exist in the glauconite facies (bimodal distribution) while it exists in both the sandstone and limestone facies. The basic difference between the limestone and sandstone facies is related to the longer T2 coupling: T2i and T2l populations are coupled in sandstone generating a single population which convolves both populations (bimodal distribution). Limestone with a trimodal distribution attests to the fact that carbonate rocks have more complex pore system than siliclastic rocks. The degree of pore connectivity is highest in sandstone, followed by limestone and least in glauconite. Therefore a basic/quick NMR log run on samples along a geological formation can provide precise lithofacies characterization with quantitative information on pore size, structure and distributions.

Geophysical remote sensing of water reservoirs suitable for desalinization.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aldridge, David Franklin; Bartel, Lewis Clark; Bonal, Nedra

2009-12-01

In many parts of the United States, as well as other regions of the world, competing demands for fresh water or water suitable for desalination are outstripping sustainable supplies. In these areas, new water supplies are necessary to sustain economic development and agricultural uses, as well as support expanding populations, particularly in the Southwestern United States. Increasing the supply of water will more than likely come through desalinization of water reservoirs that are not suitable for present use. Surface-deployed seismic and electromagnetic (EM) methods have the potential for addressing these critical issues within large volumes of an aquifer at amore » lower cost than drilling and sampling. However, for detailed analysis of the water quality, some sampling utilizing boreholes would be required with geophysical methods being employed to extrapolate these sampled results to non-sampled regions of the aquifer. The research in this report addresses using seismic and EM methods in two complimentary ways to aid in the identification of water reservoirs that are suitable for desalinization. The first method uses the seismic data to constrain the earth structure so that detailed EM modeling can estimate the pore water conductivity, and hence the salinity. The second method utilizes the coupling of seismic and EM waves through the seismo-electric (conversion of seismic energy to electrical energy) and the electro-seismic (conversion of electrical energy to seismic energy) to estimate the salinity of the target aquifer. Analytic 1D solutions to coupled pressure and electric wave propagation demonstrate the types of waves one expects when using a seismic or electric source. A 2D seismo-electric/electro-seismic is developed to demonstrate the coupled seismic and EM system. For finite-difference modeling, the seismic and EM wave propagation algorithms are on different spatial and temporal scales. We present a method to solve multiple, finite-difference physics problems that has application beyond the present use. A limited field experiment was conducted to assess the seismo-electric effect. Due to a variety of problems, the observation of the electric field due to a seismic source is not definitive.« less

EPA Method 200.8: Determination of Trace Elements in Waters and Wastes by Inductively Coupled Plasma-Mass Spectrometry

EPA Pesticide Factsheets

\\tEPA’s Selected Analytical Methods for Environmental Remediation and Recovery (SAM) lists this method for preparation and analysis of drinking water samples to detect and measure compounds containing arsenic, thallium and vanadium.

Simple and quick determination of analgesics and other contaminants of emerging concern in environmental waters by on-line solid phase extraction coupled to liquid chromatography-tandem mass spectrometry.

PubMed

Ferrer-Aguirre, Alejandra; Romero-González, Roberto; Vidal, J L Martínez; Frenich, Antonia Garrido

2016-05-13

A simple and quick analytical method has been developed for the determination of pharmaceutical compounds in water. An on-line solid-phase extraction (SPE) coupled to liquid chromatography-tandem mass spectrometry (LC-MS/MS) method has been optimized to determine 7 contaminants of emerging concern in environmental waters at ngL(-1) levels. This procedure requires minimal sample handling and small sample volume (900μL) with a total running time of 18min. Several SPE parameters were evaluated and optimized in order to achieve a high sample throughput. Therefore sample volume, carryover and reusability of the cartridges were evaluated. Performance characteristics were evaluated and good linearity was obtained (R(2)>0.98). Recoveries were evaluated in spiked samples at three concentrations and the values ranged from 71 to 104%. Intra and inter-day precision was lower than 10 and 13% respectively. Limits of quantification were equal to or lower than 10ngL(-1), except for 1,7-dimethylxanthine (20ngL(-1)) and ibuprofen (50ngL(-1)). The method was applied to 20 environmental water samples, and ibuprofen was the compound most widely detected at concentrations up to 42.06μgL(-1), whereas the other compounds were detected in fewer samples at lower concentrations (up to 15.99μgL(-1)). Copyright © 2016 Elsevier B.V. All rights reserved.

Quality-assurance data for routine water analysis in the National Water-Quality Laboratory of the US Geological Survey for water year 1988

USGS Publications Warehouse

Lucey, K.J.

1989-01-01

The US Geological Survey maintains a quality assurance program based on the analysis of reference samples for its National Water Quality Laboratory located in Denver, Colorado. Reference samples containing selected inorganic, nutrient, and precipitation (low-level concentration) constituents are prepared at the Survey 's Water Quality Services Unit in Ocala, Florida, disguised as routine samples, and sent daily or weekly, as appropriate, to the laboratory through other Survey offices. The results are stored permanently in the National Water Data Storage and Retrieval System (WATSTORE), the Survey 's database for all water data. These data are analyzed statistically for precision and bias. An overall evaluation of the inorganic major ion and trace metal constituent data for water year 1988 indicated a lack of precision in the National Water Quality Laboratory for the determination of 8 out of 58 constituents: calcium (inductively coupled plasma emission spectrometry), fluoride, iron (atomic absorption spectrometry), iron (total recoverable), magnesium (atomic absorption spectrometry), manganese (total recoverable), potassium, and sodium (inductively coupled plasma emission spectrometry). The results for 31 constituents had positive or negative bias during water year 1988. A lack of precision was indicated in the determination of three of the six nutrient constituents: nitrate plus nitrite nitrogen as nitrogen, nitrite nitrogen as nitrogen, and orthophosphate as phosphorus. A biased condition was indicated in the determination of ammonia nitrogen as nitrogen, ammonia plus organic nitrogen as nitrogen, and nitrate plus nitrite nitrogen as nitrogen. There was acceptable precision in the determination of all 10 constituents contained in precipitation samples. Results for ammonia nitrogen as nitrogen, sodium, and fluoride indicated a biased condition. (Author 's abstract)

Ionic liquid foam floatation coupled with ionic liquid dispersive liquid-liquid microextraction for the separation and determination of estrogens in water samples by high-performance liquid chromatography with fluorescence detection.

PubMed

Zhang, Rui; Wang, Chuanliu; Yue, Qiaohong; Zhou, Tiecheng; Li, Na; Zhang, Hanqi; Hao, Xiaoke

2014-11-01

An ionic liquid foam floatation coupled with ionic liquid dispersive liquid-liquid microextraction method was proposed for the extraction and concentration of 17-α-estradiol, 17-β-estradiol-benzoate, and quinestrol in environmental water samples by high-performance liquid chromatography with fluorescence detection. 1-Hexyl-3-methylimidazolium tetrafluoroborate was applied as foaming agent in the foam flotation process and dispersive solvent in microextraction. The introduction of the ion-pairing and salting-out agent NH4 PF6 was beneficial to the improvement of recoveries for the hydrophobic ionic liquid phase and analytes. Parameters of the proposed method including concentration of 1-hexyl-3-methylimidazolium tetrafluoroborate, flow rate of carrier gas, floatation time, types and concentration of ionic liquids, salt concentration in samples, extraction time, and centrifugation time were evaluated. The recoveries were between 98 and 105% with relative standard deviations lower than 7% for lake water and well water samples. The isolation of the target compounds from the water was found to be efficient, and the enrichment factors ranged from 4445 to 4632. This developing method is free of volatile organic solvents compared with regular extraction. Based on the unique properties of ionic liquids, the application of foam floatation, and dispersive liquid-liquid microextraction was widened. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Determination of estrogen residues in drinking water by on-line solid phase extraction based on sol-gel technique coupled with high performance liquid chromatography].

PubMed

Li, Longfei; Su, Min; Shi, Xiaolei; Wang, Yana; Wang, Minmin; He, Jinxing

2014-02-01

A method for the determination of diethylstilbestrol (DES), hexestrol (HEX) and dienestrol (DS) residues in drinking water was established by on-line solid phase extraction (SPE) coupled with high performance liquid chromatography (HPLC). The material synthesized on the base of sol-gel technology was employed as adsorbent. This material was prepared using 3-aminopropyltriethoxysilane (APTES) as the functional monomer, tetraethoxysilane (TEOS) as the crosslinking agent, and acetic acid as the initiator. The synthesized adsorbent showed outstanding property for the estrogen extraction. The estrogen can be caught effectively from water samples and the extraction can be achieved rapidly. Some important parameters, such as pH of sample solution, eluent solvents, loading flow rate, which might influence extraction efficiency, were optimized. The results indicated that the limit of detection (S/N = 3) of the developed method could reach 0.07-0.13 microg/L under the conditions of pH 7.0 of sample solution, methanol and 1% (v/v) acetic acid aqueous solution as the eluent solvent and the loading flow rate of 2 mL/min. The recoveries of the three estrogens from the water samples at three spiked levels ranged from 82.31% to 99.43% with RSD of 1.61%-7.15%. The method was simple, rapid, and suitable to detect the trace residues of estrogens in drinking water.

Optimization and determination of Cd (II) in different environmental water samples with dispersive liquid-liquid microextraction preconcentration combined with inductively coupled plasma optical emission spectrometry.

PubMed

Salahinejad, Maryam; Aflaki, Fereydoon

2011-06-01

Dispersive liquid-liquid microextraction followed by inductively coupled plasma-optical emission spectrometry has been investigated for determination of Cd(II) ions in water samples. Ammonium pyrrolidine dithiocarbamate was used as chelating agent. Several factors influencing the microextraction efficiency of Cd (II) ions such as extracting and dispersing solvent type and their volumes, pH, sample volume, and salting effect were optimized. The optimization was performed both via one variable at a time, and central composite design methods and the optimum conditions were selected. Both optimization methods showed nearly the same results: sample size 5 mL; dispersive solvent ethanol; dispersive solvent volume 2 mL; extracting solvent chloroform; extracting solvent volume 200 [Formula: see text]L; pH and salt amount do not affect significantly the microextraction efficiency. The limits of detection and quantification were 0.8 and 2.5 ng L( - 1), respectively. The relative standard deviation for five replicate measurements of 0.50 mg L( - 1) of Cd (II) was 4.4%. The recoveries for the spiked real samples from tap, mineral, river, dam, and sea waters samples ranged from 92.2% to 104.5%.

Multi-elemental analysis of aqueous geological samples by inductively coupled plasma-optical emission spectrometry

USGS Publications Warehouse

Todorov, Todor I.; Wolf, Ruth E.; Adams, Monique

2014-01-01

Typically, 27 major, minor, and trace elements are determined in natural waters, acid mine drainage, extraction fluids, and leachates of geological and environmental samples by inductively coupled plasma-optical emission spectrometry (ICP-OES). At the discretion of the analyst, additional elements may be determined after suitable method modifications and performance data are established. Samples are preserved in 1–2 percent nitric acid (HNO3) at sample collection or as soon as possible after collection. The aqueous samples are aspirated into the ICP-OES discharge, where the elemental emission signals are measured simultaneously for 27 elements. Calibration is performed with a series of matrix-matched, multi-element solution standards.

Determination of trace metals in drinking water in Irbid City-Northern Jordan.

PubMed

Alomary, Ahmed

2013-02-01

Drinking water samples from Irbid, the second populated city in Jordan were analyzed for trace metals (As, Ba, Cd, Pb, Cr, Cu, Fe, Zn, Mn, Ni, and Se) content. The study was undertaken to determine if the metal concentrations were within the national and international guidelines. A total of 90 drinking water samples were collected from Al-Yarmouk University area. The samples were collected from three different water types: tap water (TW), home-purified water (HPW), and plant-purified water (PPW). All the samples were analyzed for trace metals using an inductively coupled plasma-optical emission spectrometry. All the samples analyzed were within the United States Environmental Protection Agency admissible pH limit (6.5-8.5). The results showed that concentrations of the trace metals vary significantly between the three drinking water types. The results showed that HPW samples have the lowest level of trace metals and the concentrations of some essential trace metals in these samples are less than the recommended amounts. Slight differences in the metal contents were found between HPW samples, little differences between PPW samples; however, significant differences were found between TW samples. Although some TW samples showed high levels of trace metals, however, the mean level of most elements determined in the samples were well within the Jordanian standards as well as the World Health Organization standards for drinking water.

Determination of toxic inorganic elements pollution in ground waters of Kahuta Industrial Triangle Islamabad, Pakistan using inductively coupled plasma mass spectrometry.

PubMed

Kausar, Rubina; Ahmad, Zulfiqar

2009-10-01

The present study deals with the ground water quality assessment in Kahuta Industrial Triangle Islamabad, Pakistan. The objective of the study was to assess ground water quality against the drinking water standards for various toxic inorganic elements. Representative groundwater samples were collected and analyzed in the Water Quality Laboratory of Pakistan Council of Research in Water Resources (PCRWR) at Islamabad, Pakistan. The samples were run on ICP-MS (Inductively coupled plasma mass spectrometry), which has the capability to separate and quantify 70 elements at a time. One of the finding of study is that ICP-MS is a very good tool to analyze broad range of toxic inorganic elements to the level of parts per billion (ppb). World Health Organization drinking water standards shows that these toxic inorganic elements such as heavy metals even at this concentration level (ppb) are injurious to human health. This analysis indicated pollution of various toxic elements including Selenium. Vertical leachate through industrial waste septic tanks is identified as major cause of groundwater pollution in the Industrial Triangle. Monitoring of the septic tanks and groundwater quality in study area is suggested along with remedial measures.

A lab in the field: high-frequency analysis of water quality and stable isotopes in stream water and precipitation

NASA Astrophysics Data System (ADS)

von Freyberg, Jana; Studer, Bjørn; Kirchner, James W.

2017-03-01

High-frequency measurements of solutes and isotopes (18O and 2H) in rainfall and streamflow can shed important light on catchment flow pathways and travel times, but the workload and sample storage artifacts involved in collecting, transporting, and analyzing thousands of bottled samples severely constrain catchment studies in which conventional sampling methods are employed. However, recent developments towards more compact and robust analyzers have now made it possible to measure chemistry and water isotopes in the field at sub-hourly frequencies over extended periods. Here, we present laboratory and field tests of a membrane-vaporization continuous water sampler coupled to a cavity ring-down spectrometer for real-time measurements of δ18O and δ2H combined with a dual-channel ion chromatograph (IC) for the synchronous analysis of major cations and anions. The precision of the isotope analyzer was typically better than 0.03 ‰ for δ18O and 0.17 ‰ for δ2H in 10 min average readings taken at intervals of 30 min. Carryover effects were less than 1.2 % between isotopically contrasting water samples for 30 min sampling intervals, and instrument drift could be corrected through periodic analysis of secondary reference standards. The precision of the ion chromatograph was typically ˜ 0.1-1 ppm or better, with relative standard deviations of ˜ 1 % or better for most major ions in stream water, which is sufficient to detect subtle biogeochemical signals in catchment runoff. We installed the coupled isotope analyzer/IC system in an uninsulated hut next to a stream of a small catchment and analyzed stream water and precipitation samples every 30 min over 28 days. These high-frequency measurements facilitated a detailed comparison of event-water fractions via endmember mixing analysis with both chemical and isotope tracers. For two events with relatively dry antecedent moisture conditions, the event-water fractions were < 21 % based on isotope tracers but were significantly overestimated (40 to 82 %) by the chemical tracers. These observations, coupled with the storm-to-storm patterns in precipitation isotope inputs and the associated stream water isotope response, led to a conceptual hypothesis for runoff generation in the catchment. Under this hypothesis, the pre-event water that is mobilized by precipitation events may, depending on antecedent moisture conditions, be significantly shallower, younger, and less mineralized than the deeper, older water that feeds baseflow and thus defines the pre-event endmember used in hydrograph separation. This proof-of-concept study illustrates the potential advantages of capturing isotopic and hydrochemical behavior at a high frequency over extended periods that span multiple hydrologic events.

Dual cloud point extraction coupled with hydrodynamic-electrokinetic two-step injection followed by micellar electrokinetic chromatography for simultaneous determination of trace phenolic estrogens in water samples.

PubMed

Wen, Yingying; Li, Jinhua; Liu, Junshen; Lu, Wenhui; Ma, Jiping; Chen, Lingxin

2013-07-01

A dual cloud point extraction (dCPE) off-line enrichment procedure coupled with a hydrodynamic-electrokinetic two-step injection online enrichment technique was successfully developed for simultaneous preconcentration of trace phenolic estrogens (hexestrol, dienestrol, and diethylstilbestrol) in water samples followed by micellar electrokinetic chromatography (MEKC) analysis. Several parameters affecting the extraction and online injection conditions were optimized. Under optimal dCPE-two-step injection-MEKC conditions, detection limits of 7.9-8.9 ng/mL and good linearity in the range from 0.05 to 5 μg/mL with correlation coefficients R(2) ≥ 0.9990 were achieved. Satisfactory recoveries ranging from 83 to 108% were obtained with lake and tap water spiked at 0.1 and 0.5 μg/mL, respectively, with relative standard deviations (n = 6) of 1.3-3.1%. This method was demonstrated to be convenient, rapid, cost-effective, and environmentally benign, and could be used as an alternative to existing methods for analyzing trace residues of phenolic estrogens in water samples.

A Very Much Faster and More Sensitive In Situ Stable Isotope Analysis Instrument

NASA Astrophysics Data System (ADS)

Coleman, M.; Christensen, L. E.; Kriesel, J. M.; Kelly, J. F.; Moran, J. J.; Vance, S.

2016-10-01

We are developing, Capillary Absorption Spectrometry (CAS) for H and O stable isotope analyses, giving > 4 orders of magnitude improved sensitivity, allowing analysis of 5 nano-moles of water and coupled to laser sampling to free water from hydrated minerals and ice.

Determination of chlorinated polycyclic aromatic hydrocarbons in water by solid-phase extraction coupled with gas chromatography and mass spectrometry.

PubMed

Wang, Xianli; Kang, Haiyan; Wu, Junfeng

2016-05-01

Given the potential risks of chlorinated polycyclic aromatic hydrocarbons, the analysis of their presence in water is very urgent. We have developed a novel procedure for determining chlorinated polycyclic aromatic hydrocarbons in water based on solid-phase extraction coupled with gas chromatography and mass spectrometry. The extraction parameters of solid-phase extraction were optimized in detail. Under the optimal conditions, the proposed method showed wide linear ranges (1.0-1000 ng/L) with correlation coefficients ranging from 0.9952 to 0.9998. The limits of detection and the limits of quantification were in the range of 0.015-0.591 and 0.045-1.502 ng/L, respectively. Recoveries ranged from 82.5 to 102.6% with relative standard deviations below 9.2%. The obtained method was applied successfully to the determination of chlorinated polycyclic aromatic hydrocarbons in real water samples. Most of the chlorinated polycyclic aromatic hydrocarbons were detected and 1-monochloropyrene was predominant in the studied water samples. This is the first report of chlorinated polycyclic aromatic hydrocarbons in water samples in China. The toxic equivalency quotients of chlorinated polycyclic aromatic hydrocarbons in the studied tap water were 9.95 ng the toxic equivalency quotient m(-3) . 9,10-Dichloroanthracene and 1-monochloropyrene accounted for the majority of the total toxic equivalency quotients of chlorinated polycyclic aromatic hydrocarbons in tap water. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

PALOMA : an isotope analyzer using static mass spectrometry, coupled with cryogenic and chemical trapping, for the MSL mission to Mars

NASA Astrophysics Data System (ADS)

Chassefiere, E.; Jambon, A.; Berthelier, J.-J.; Goulpeau, G.; Leblanc, F.; Montmessin, F.; Sarda, P.; Agrinier, P.; Fouchet, T.; Waite, H.

The technique of GCMS analysis has to be completed by static mass spectrometry for precise in-situ measurements of the isotopic composition of planetary atmospheres (noble gases, stable isotopes), and volatile outgassed products from solid sample pyrolysis. Static mass spectrometry, coupled with gas separation by cryo-separation and gettering, is commonly used in the laboratory to study volatiles extracted from terrestrial and meteoritic samples. Such an instrument (PALOMA) is presently developed in our laboratories, and it will be coupled with a Pyr-GCMS analyzer (MACE), built by a US consortium of science laboratories and industrials (University of Michigan, Southwest Research Institute, JPL, Ball Aerospace). The MACE/PALOMA experiment will be proposed on the NASA Mars Science Laboratory mission, planned to be launched in 2009. The scientific objectives of PALOMA, coupled with MACE, may be listed as follows : (i) search for isotopic signatures of past life in atmosphere, rock, dust and ice samples, with emphasis on carbon, nitrogen and hydrogen; (ii) accurately measure isotopic composition of atmospheric noble gases, and stable isotopes, in order to better constrain past escape, surface interaction, outgassing history and climate evolution; (iii) precisely measure diurnal/ seasonal variations of isotopic ratios of H2O, CO2, and N2, for improving our understanding of present and past climate, and of the role of water cycle. Main measurement objectives are : (i) C, H, O, N isotopic composition in both organic evolved samples (provided by MACE pyrolysis system) and atmosphere with high accuracy (a few per mil at 1-s level); (ii) noble gas (He, Ne, Ar, Kr, Xe) and stable (C, H, O, N) isotope composition in atmosphere with high accuracy (a few per mil at 1-s level); (iii) molecular and isotopic composition of inorganic evolved samples (salts, hydrates, nitrates, {ldots}), including ices; (iv) diurnal and seasonal monitoring of D/H in water vapor, and water ice.

Analytical method development for the determination of emerging contaminants in water using supercritical-fluid chromatography coupled with diode-array detection.

PubMed

Del Carmen Salvatierra-Stamp, Vilma; Ceballos-Magaña, Silvia G; Gonzalez, Jorge; Ibarra-Galván, Valentin; Muñiz-Valencia, Roberto

2015-05-01

An analytical method using supercritical-fluid chromatography coupled with diode-array detection for the determination of seven emerging contaminants-two pharmaceuticals (carbamazepine and glyburide), three endocrine disruptors (17α-ethinyl estradiol, bisphenol A, and 17β-estradiol), one bactericide (triclosan), and one pesticide (diuron)-was developed and validated. These contaminants were chosen because of their frequency of use and their toxic effects on both humans and the environment. The optimized chromatographic separation on a Viridis BEH 2-EP column achieved baseline resolution for all compounds in less than 10 min. This separation was applied to environmental water samples after sample preparation. The optimized sample treatment involved a preconcentration step by means of solid-phase extraction using C18-OH cartridges. The proposed method was validated, finding recoveries higher than 94 % and limits of detection and limits of quantification in the range of 0.10-1.59 μg L(-1) and 0.31-4.83 μg L(-1), respectively. Method validation established the proposed method to be selective, linear, accurate, and precise. Finally, the method was successfully applied to environmental water samples.

Uncertainty estimation in the determination of metals in superficial water by ICP-OES

NASA Astrophysics Data System (ADS)

Faustino, Mainara G.; Marques, Joyce R.; Monteiro, Lucilena R.; Stellato, Thamiris B.; Soares, Sabrina M. V.; Silva, Tatiane B. S. C.; da Silva, Douglas B.; Pires, Maria Aparecida F.; Cotrim, Marycel E. B.

2016-07-01

From validation studies, it was possible to estimate a measurement uncertainty of several elements such as Al, Ba, Ca, Cu, Cr, Cd, Fe, Mg, Mn, Ni and K in water samples from Guarapiranga Dam. These elements were analyzed by optical emission spectrometry with inductively coupled plasma (ICP-OES). The value of relative estimated uncertainties were between 3% and 15%. The greatest uncertainty contributions were analytical curve, and the recovery method, which were related with elements concentrations and the equipment response. Water samples analyzed were compared with CONAMA Resolution #357/2005.

A METHOD FOR AUTOMATED ANALYSIS OF 10 ML WATER SAMPLES CONTAINING ACIDIC, BASIC, AND NEUTRAL SEMIVOLATILE COMPOUNDS LISTED IN USEPA METHOD 8270 BY SOLID PHASE EXTRACTION COUPLED IN-LINE TO LARGE VOLUME INJECTION GAS CHROMATOGRAPHY/MASS SPECTROMETRY

EPA Science Inventory

Data is presented showing the progress made towards the development of a new automated system combining solid phase extraction (SPE) with gas chromatography/mass spectrometry for the single run analysis of water samples containing a broad range of acid, base and neutral compounds...

Environmental Levels Of 129I Present In Bovine Thyroid And Fresh Water In Argentina

DOE Office of Scientific and Technical Information (OSTI.GOV)

Negri, A. E.; Arazi, A.; Carnellia, P. F. F.

2010-08-04

Concentrations of {sup 129}I in bovine thyroid and fresh water samples coming from all over Argentina were analyzed by Accelerator Mass Spectrometry (AMS) and total iodine present in samples by Gas Chromatography (GC) and Inductive Coupled Plasma Mass Spectrometry (ICP-MS), respectively. Once we complete this study, it will be the first set of data of this kind from an extended region of the south American subcontinent.

Relationships between groundwater, surface water, and soil salinity in Polder 32, Southwest Bangladesh

NASA Astrophysics Data System (ADS)

Fry, D. C.; Ayers, J. C.

2014-12-01

In the coastal areas of Southwest Bangladesh polders are surrounded by tidal channels filled with brackish water. In the wet season, farmers create openings in the embankments to irrigate rice paddies. In the dry season, farmers do the same to create saline shrimp ponds. Residents on Polder 32, located within the Ganges-Brahmaputra-Meghna delta system, practice these seasonal farming techniques. Soils in the area are entisols, being sediment recently deposited, and contain mostly silt-sized particles. Brackish water in brine shrimp ponds may deposit salt in the soil, causing soil salinization. However, saline connate groundwater could also be contributing to soil salinization. Groundwater, surface water (fresh water pond, rice paddy and tidal channel water) and soil samples have been analyzed via inductively coupled plasma optical emission spectroscopy, inductively coupled plasma mass spectroscopy and ion chromatography in an attempt to correlate salinity measurements with each other in order to determine major sources of soil salinity. Multiple parameters, including distances of samples from tidal channels, inland streams, shrimp ponds and tube wells were measured to see if spatial correlations exist. Similarly, values from wet and dry seasons were compared to quantify temporal variations. Salt content in many soil samples were found to be high enough to significantly decrease rice yields. Continued soil salinization can decrease these yields even more, leading to farmers not producing enough food to sustain their families.

Determination of eight nitrosamines in water at the ng L(-1) levels by liquid chromatography coupled to atmospheric pressure chemical ionization tandem mass spectrometry.

PubMed

Ripollés, Cristina; Pitarch, Elena; Sancho, Juan V; López, Francisco J; Hernández, Félix

2011-09-19

In this work, we have developed a sensitive method for detection and quantification of eight N-nitrosamines, N-nitrosodimethylamine (NDMA), N-nitrosomorpholine (NMor), N-nitrosomethylethylamine (NMEA), N-nitrosopirrolidine (NPyr), N-nitrosodiethylamine (NDEA), N-nitrosopiperidine (NPip), N-nitroso-n-dipropylamine (NDPA) and N-nitrosodi-n-butylamine (NDBA) in drinking water. The method is based on liquid chromatography coupled to tandem mass spectrometry, using atmospheric pressure chemical ionization (APCI) in positive mode with a triple quadrupole analyzer (QqQ). The simultaneous acquisition of two MS/MS transitions in selected reaction monitoring mode (SRM) for each compound, together with the evaluation of their relative intensity, allowed the simultaneous quantification and reliable identification in water at ppt levels. Empirical formula of the product ions selected was confirmed by UHPLC-(Q)TOF MS accurate mass measurements from reference standards. Prior to LC-MS/MS QqQ analysis, a preconcentration step by off-line SPE using coconut charcoal EPA 521 cartridges (by passing 500 mL of water sample) was necessary to improve the sensitivity and to meet regulation requirements. For accurate quantification, two isotope labelled nitrosamines (NDMA-d(6) and NDPA-d(14)) were added as surrogate internal standards to the samples. The optimized method was validated at two concentration levels (10 and 100 ng L(-1)) in drinking water samples, obtaining satisfactory recoveries (between 90 and 120%) and precision (RSD<20%). Limits of detection were found to be in the range of 1-8 ng L(-1). The described methodology has been applied to different types of water samples: chlorinated from drinking water and wastewater treatment plants (DWTP and WWTP, respectively), wastewaters subjected to ozonation and tap waters. Copyright © 2011 Elsevier B.V. All rights reserved.

Selected problems with boron determination in water treatment processes. Part I: comparison of the reference methods for ICP-MS and ICP-OES determinations.

PubMed

Kmiecik, Ewa; Tomaszewska, Barbara; Wątor, Katarzyna; Bodzek, Michał

2016-06-01

The aim of the study was to compare the two reference methods for the determination of boron in water samples and further assess the impact of the method of preparation of samples for analysis on the results obtained. Samples were collected during different desalination processes, ultrafiltration and the double reverse osmosis system, connected in series. From each point, samples were prepared in four different ways: the first was filtered (through a membrane filter of 0.45 μm) and acidified (using 1 mL ultrapure nitric acid for each 100 mL of samples) (FA), the second was unfiltered and not acidified (UFNA), the third was filtered but not acidified (FNA), and finally, the fourth was unfiltered but acidified (UFA). All samples were analysed using two analytical methods: inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma optical emission spectrometry (ICP-OES). The results obtained were compared and correlated, and the differences between them were studied. The results show that there are statistically significant differences between the concentrations obtained using the ICP-MS and ICP-OES techniques regardless of the methods of sampling preparation (sample filtration and preservation). Finally, both the ICP-MS and ICP-OES methods can be used for determination of the boron concentration in water. The differences in the boron concentrations obtained using these two methods can be caused by several high-level concentrations in selected whole-water digestates and some matrix effects. Higher concentrations of iron (from 1 to 20 mg/L) than chromium (0.02-1 mg/L) in the samples analysed can influence boron determination. When iron concentrations are high, we can observe the emission spectrum as a double joined and overlapping peak.

Dispersive liquid-phase microextraction with solidification of floating organic droplet coupled with high-performance liquid chromatography for the determination of Sudan dyes in foodstuffs and water samples.

PubMed

Chen, Bo; Huang, Yuming

2014-06-25

Dispersive liquid-phase microextraction with solidification of floating organic drop (SFO-DLPME) is one of the most interesting sample preparation techniques developed in recent years. In this paper, a new, rapid, and efficient SFO-DLPME coupled with high-performance liquid chromatography (HPLC) was established for the extraction and sensitive detection of banned Sudan dyes, namely, Sudan I, Sudan II, Sudan III, and Sudan IV, in foodstuff and water samples. Various factors, such as the type and volume of extractants and dispersants, pH and volume of sample solution, extraction time and temperature, ion strength, and humic acid concentration, were investigated and optimized to achieve optimal extraction of Sudan dyes in one single step. After optimization of extraction conditions using 1-dodecanol as an extractant and ethanol as a dispersant, the developed procedure was applied for extraction of the target Sudan dyes from 2 g of food samples and 10 mL of the spiked water samples. Under the optimized conditions, all Sudan dyes could be easily extracted by the proposed SFO-DLPME method. Limits of detection of the four Sudan dyes obtained were 0.10-0.20 ng g(-1) and 0.03 μg L(-1) when 2 g of foodstuff samples and 10 mL of water samples were adopted, respectively. The inter- and intraday reproducibilities were below 4.8% for analysis of Sudan dyes in foodstuffs. The method was satisfactorily used for the detection of Sudan dyes, and the recoveries of the target for the spiked foodstuff and water samples ranged from 92.6 to 106.6% and from 91.1 to 108.6%, respectively. These results indicated that the proposed method is simple, rapid, sensitive, and suitable for the pre-concentration and detection of the target dyes in foodstuff samples.

Water analysis via portable X-ray fluorescence spectrometry

NASA Astrophysics Data System (ADS)

Pearson, Delaina; Chakraborty, Somsubhra; Duda, Bogdan; Li, Bin; Weindorf, David C.; Deb, Shovik; Brevik, Eric; Ray, D. P.

2017-01-01

Rapid, in-situ elemental water analysis would be an invaluable tool in studying polluted and/or salt-impacted waters. Analysis of water salinity has commonly used electrical conductance (EC); however, the identity of the elements responsible for the salinity are not revealed using EC. Several studies have established the viability of using portable X-ray fluorescence (PXRF) spectrometry for elemental data analysis of soil, sediment, and other matrices. However, the accuracy of PXRF is known to be affected while scanning moisture-laden soil samples. This study used PXRF elemental data in water samples to predict water EC. A total of 256 water samples, from 10 different countries were collected and analyzed via PXRF, inductively coupled plasma atomic emission spectroscopy (ICP-AES), and a digital salinity bridge. The PXRF detected some elements more effectively than others, but overall results indicated that PXRF can successfully predict water EC via quantifying Cl in water samples (validation R2 and RMSE of 0.77 and 0.95 log μS cm-1, respectively). The findings of this study elucidated the potential of PXRF for future analysis of pollutant and/or metal contaminated waters.

Determination of N-nitrosodimethylamine in drinking water by UPLC-MS/MS.

PubMed

Wang, Wanfeng; Hu, Jianying; Yu, Jianwei; Yang, Min

2010-01-01

The method for detecting N-nitrosodimethylamine (NDMA) in drinking water using ultra performance liquid chromatography (UPLC) coupled with tandem mass spectrometry (MS/MS) was improved by optimizing the clean-up procedure to remove the matrix interference in pretreatment process, and was then applied to a survey of NDMA in both raw and finished water samples from five water treatment plants in South China. The NDMA concentrations ranged from 4.7 to 15.1 ng/L in raw water samples, and from 4.68 to 46.9 ng/L in finished water. The NDMA concentration in raw water was found to be related with nitrite concentration, and during the treatment, the NDMA concentration increased following ozonation but decreased after subsequent activated carbon treatment.

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory; determination of dissolved arsenic, boron, lithium, selenium, strontium, thallium, and vanadium using inductively coupled plasma-mass spectrometry

USGS Publications Warehouse

Garbarino, John R.

1999-01-01

The inductively coupled plasma?mass spectrometric (ICP?MS) methods have been expanded to include the determination of dissolved arsenic, boron, lithium, selenium, strontium, thallium, and vanadium in filtered, acidified natural water. Method detection limits for these elements are now 10 to 200 times lower than by former U.S. Geological Survey (USGS) methods, thus providing lower variability at ambient concentrations. The bias and variability of the method was determined by using results from spike recoveries, standard reference materials, and validation samples. Spike recoveries at 5 to 10 times the method detection limit and 75 micrograms per liter in reagent-water, surface-water, and groundwater matrices averaged 93 percent for seven replicates, although selected elemental recoveries in a ground-water matrix with an extremely high iron sulfate concentration were negatively biased by 30 percent. Results for standard reference materials were within 1 standard deviation of the most probable value. Statistical analysis of the results from about 60 filtered, acidified natural-water samples indicated that there was no significant difference between ICP?MS and former USGS official methods of analysis.

Fabrication of visible light-triggered photocatalytic materials from the coupling of n-type zinc oxide and p-type copper oxide

NASA Astrophysics Data System (ADS)

Gorospe, A. B.; Herrera, M. U.

2017-04-01

Coupling of copper oxide (CuO) and zinc oxide (ZnO) was done by chemical precipitation method. In this method, copper sulfate pentahydrate and zinc sulfate heptahydrate salt precursors were separately dissolved in distilled water; then were mixed together. The copper sulfate-zinc sulfate solution was then combined with a sodium hydroxide solution. The precipitates were collected and washed in distilled water and ethanol several times, then filtered and dried. The dried sample was grounded, and then undergone heat treatment. After heating, the sample was grounded again. Zinc oxide powder and copper oxide powder were also fabricated using chemical precipitation method. X-Ray Diffraction measurements of the coupled CuO/ZnO powder showed the presence of CuO and ZnO in the fabricated sample. Furthermore, other peaks shown by XRD were also identified corresponding to copper, copper (II) oxide, copper sulfate and zinc sulfate. Results of the photocatalytic activity investigation show that the sample exhibited superior photocatalytic degradation of methyl orange under visible light illumination compared to copper oxide powder and zinc oxide powder. This may be attributed to the lower energy gap at the copper oxide-zinc oxide interface, compared to zinc oxide, allowing visible light to trigger its photocatalytic activity.

Application of cotton as a solid phase extraction sorbent for on-line preconcentration of copper in water samples prior to inductively coupled plasma optical emission spectrometry determination.

PubMed

Faraji, Mohammad; Yamini, Yadollah; Shariati, Shahab

2009-07-30

Copper, as a heavy metal, is toxic for many biological systems. Thus, the determination of trace amounts of copper in environmental samples is of great importance. In the present work, a new method was developed for the determination of trace amounts of copper in water samples. The method is based on the formation of ternary Cu(II)-CAS-CTAB ion-pair and adsorption of it into a mini-column packed with cotton prior applying inductively coupled plasma optical emission spectrometry (ICP-OES). The experimental parameters that affected the extraction efficiency of the method such as pH, flow rate and volume of the sample solution, concentration of chromazurol S (CAS) and cethyltrimethylammonium bromide (CTAB) as well as type and concentration of eluent were investigated and optimized. The ion-pair (Cu(II)-CAS-CTAB) was quantitatively retained on the cotton under the optimum conditions, then eluted completely using a solution of 25% (v/v) 1-propanol in 0.5 mol L(-1) HNO(3) and directly introduced into the nebulizer of the ICP-OES. The detection limit (DL) of the method for copper was 40 ng L(-1) (V(sample)=100mL) and the relative standard deviation (R.S.D.) for the determination of copper at 10 microg L(-1) level was found to be 1.3%. The method was successfully applied to determine the trace amounts of copper in tap water, deep well water, seawater and two different mineral waters, and suitable recoveries were obtained (92-106%).

Semi-permeable surface analytical reversed-phase column for the improved trace analysis of acidic pesticides in water with coupled-column reversed-phase liquid chromatography with UV detection. Determination of bromoxynil and bentazone in surface water.

PubMed

Hogendoorn, E A; Westhuis, K; Dijkman, E; Heusinkveld, H A; den Boer, A C; Evers, E A; Baumann, R A

1999-10-08

The coupled-column (LC-LC) configuration consisting of a 3 microm C18 column (50 x 4.6 mm I.D.) as the first column and a 5 microm C18 semi-permeable-surface (SPS) column (150 x 4.6 mm I.D.) as the second column appeared to be successful for the screening of acidic pesticides in surface water samples. In comparison to LC-LC employing two C18 columns, the combination of C18/SPS-C18 significantly decreased the baseline deviation caused by the hump of the co-extracted humic substances when using UV detection (217 nm). The developed LC-LC procedure allowed the simultaneous determination of the target analytes bentazone and bromoxynil in uncleaned extracts of surface water samples to a level of 0.05 microg/l in less than 15 min. In combination with a simple solid-phase extraction step (200 ml of water on a 500 mg C18-bonded silica) the analytical procedure provides a high sample throughput. During a period of about five months more than 200 ditch-water samples originating from agricultural locations were analyzed with the developed procedure. Validation of the method was performed by randomly analyzing recoveries of water samples spiked at levels of 0.1 microg/l (n=10), 0.5 microg/l (n=7) and 2.5 microg/l (n=4). Weighted regression of the recovery data showed that the method provides overall recoveries of 95 and 100% for bentazone and bromoxynil, respectively, with corresponding intra-laboratory reproducibilities of 10 and 11%, respectively. Confirmation of the analytes in part of the samples extracts was carried out with GC-negative ion chemical ionization MS involving a derivatization step with bis(trifluoromethyl)benzyl bromide. No false negatives or positives were observed.

Online in-tube microextractor coupled with UV-Vis spectrophotometer for bisphenol A detection.

PubMed

Poorahong, Sujittra; Thammakhet, Chongdee; Thavarungkul, Panote; Kanatharana, Proespichaya

2013-01-01

A simple and high extraction efficiency online in-tube microextractor (ITME) was developed for bisphenol A (BPA) detection in water samples. The ITME was fabricated by a stepwise electrodeposition of polyaniline, polyethylene glycol and polydimethylsiloxane composite (CPANI) inside a silico-steel tube. The obtained ITME coupled with UV-Vis detection at 278 nm was investigated. By this method, the extraction and pre-concentration of BPA in water were carried out in a single step. Under optimum conditions, the system provided a linear dynamic range of 0.1 to 100 μM with a limit of detection of 20 nM (S/N ≥3). A single in-tube microextractor had a good stability of more than 60 consecutive injections for 10.0 μM BPA with a relative standard deviation of less than 4%. Moreover, a good tube-to-tube reproducibility and precision were obtained. The system was applied to detect BPA in water samples from six brands of baby bottles and the results showed good agreement with those obtained from the conventional GC-MS method. Acceptable percentage recoveries from the spiked water samples were obtained, ranging from 83-102% for this new method compared with 73-107% for the GC-MS standard method. This new in-tube CPANI microextractor provided an excellent extraction efficiency and a good reproducibility. In addition, it can also be easily applied for the analysis of other polar organic compounds contaminated in water sample.

Assessment of nonpoint source chemical loading potential to watersheds containing uranium waste dumps associated with uranium exploration and mining, San Rafael Swell, Utah

USGS Publications Warehouse

Freeman, Michael L.; Naftz, David L.; Snyder, Terry; Johnson, Greg

2008-01-01

During July and August of 2006, 117 solid-phase samples were collected from abandoned uranium waste dumps, geologic background sites, and adjacent streambeds in the San Rafael Swell, in southeastern Utah. The objective of this sampling program was to assess the nonpoint source chemical loading potential to ephemeral and perennial watersheds from uranium waste dumps on Bureau of Land Management property. Uranium waste dump samples were collected using solid-phase sampling protocols. After collection, solid-phase samples were homogenized and extracted in the laboratory using a field leaching procedure. Filtered (0.45 micron) water samples were obtained from the field leaching procedure and were analyzed for Ag, As, Ba, Be, Cd, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Se, U, V, and Zn at the Inductively Coupled Plasma-Mass Spectrometry Metals Analysis Laboratory at the University of Utah, Salt Lake City, Utah and for Hg at the U.S. Geological Survey National Water Quality Laboratory, Denver, Colorado. For the initial ranking of chemical loading potential of suspect uranium waste dumps, leachate analyses were compared with existing aquatic life and drinking-water-quality standards and the ratio of samples that exceeded standards to the total number of samples was determined for each element having a water-quality standard for aquatic life and drinking-water. Approximately 56 percent (48/85) of the leachate samples extracted from uranium waste dumps had one or more chemical constituents that exceeded aquatic life and drinking-water-quality standards. Most of the uranium waste dump sites with elevated trace-element concentrations in leachates were along Reds Canyon Road between Tomsich Butte and Family Butte. Twelve of the uranium waste dump sites with elevated trace-element concentrations in leachates contained three or more constituents that exceeded drinking-water-quality standards. Eighteen of the uranium waste dump sites had three or more constituents that exceeded trace-element concentrations for aquatic life water-quality standards. The proximity of the uranium waste dumps in the Tomsich Butte area near Muddy Creek, coupled with the elevated concentration of trace elements, increases the offsite impact potential to water resources. Future assessment and remediation priority of these areas may be done by using GIS-based risk-mapping techniques, such as Sensitive Catchment Integrated Mapping and Analysis Project.

Assessment of the analytical capabilities of inductively coupled plasma-mass spectrometry

USGS Publications Warehouse

Taylor, Howard E.; Garbarino, John R.

1988-01-01

A thorough assessment of the analytical capabilities of inductively coupled plasma-mass spectrometry was conducted for selected analytes of importance in water quality applications and hydrologic research. A multielement calibration curve technique was designed to produce accurate and precise results in analysis times of approximately one minute. The suite of elements included Al, As, B, Ba, Be, Cd, Co, Cr, Cu, Hg, Li, Mn, Mo, Ni, Pb, Se, Sr, V, and Zn. The effects of sample matrix composition on the accuracy of the determinations showed that matrix elements (such as Na, Ca, Mg, and K) that may be present in natural water samples at concentration levels greater than 50 mg/L resulted in as much as a 10% suppression in ion current for analyte elements. Operational detection limits are presented.

Determination of hydroxyaromatic compounds in water by solid-phase microextraction coupled to high-performance liquid chromatography.

PubMed

Wu, Y C; Huang, S D

1999-03-12

Solid-phase microextraction (SPME) coupled with high-performance liquid chromatography (HPLC) for the analysis of hydroxyaromatic compounds is described. Three kinds of fibers [50 microns carbowax-templated resin (CW-TPR), 60 microns polydimethylsiloxane-divinylbenzene (PDMS-DVB) and 85 microns polyacrylate (PA) fibers] were evaluated. CW-TPR and PDMS-DVB were selected for further study. The parameters of the desorption procedure (such as desorption mode, the composition of the solvent for desorption and the duration of fiber soaking) were studied and optimized. The effect of the structure and physical properties of analytes, carryover, duration of absorption, temperature of absorption, pH and ionic strength of samples were also investigated. The method was applied to environmental samples (lake water) using a simple calibration curve.

Radon Concentrations in Drinking Water in Beijing City, China and Contribution to Radiation Dose

PubMed Central

Wu, Yun-Yun; Ma, Yong-Zhong; Cui, Hong-Xing; Liu, Jian-Xiang; Sun, Ya-Ru; Shang, Bing; Su, Xu

2014-01-01

222Rn concentrations in drinking water samples from Beijing City, China, were determined based on a simple method for the continuous monitoring of radon using a radon-in-air monitor coupled to an air-water exchanger. A total of 89 water samples were sampled and analyzed for their 222Rn content. The observed radon levels ranged from detection limit up to 49 Bq/L. The calculated arithmetic and geometric means of radon concentrations in all measured samples were equal to 5.87 and 4.63 Bq/L, respectively. The average annual effective dose from ingestion of radon in drinking water was 2.78 μSv, and that of inhalation of water-borne radon was 28.5 μSv. It is concluded that it is not the ingestion of waterborne radon, but inhalation of the radon escaping from water that is a substantial part of the radiological hazard. Radon in water is a big concern for public health, especially for consumers who directly use well water with very high radon concentration. PMID:25350007

Determination of aluminium in groundwater samples by GF-AAS, ICP-AES, ICP-MS and modelling of inorganic aluminium complexes.

PubMed

Frankowski, Marcin; Zioła-Frankowska, Anetta; Kurzyca, Iwona; Novotný, Karel; Vaculovič, Tomas; Kanický, Viktor; Siepak, Marcin; Siepak, Jerzy

2011-11-01

The paper presents the results of aluminium determinations in ground water samples of the Miocene aquifer from the area of the city of Poznań (Poland). The determined aluminium content amounted from <0.0001 to 752.7 μg L(-1). The aluminium determinations were performed using three analytical techniques: graphite furnace atomic absorption spectrometry (GF-AAS), inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The results of aluminium determinations in groundwater samples for particular analytical techniques were compared. The results were used to identify the ascent of ground water from the Mesozoic aquifer to the Miocene aquifer in the area of the fault graben. Using the Mineql+ program, the modelling of the occurrence of aluminium and the following aluminium complexes: hydroxy, with fluorides and sulphates was performed. The paper presents the results of aluminium determinations in ground water using different analytical techniques as well as the chemical modelling in the Mineql+ program, which was performed for the first time and which enabled the identification of aluminium complexes in the investigated samples. The study confirms the occurrence of aluminium hydroxy complexes and aluminium fluoride complexes in the analysed groundwater samples. Despite the dominance of sulphates and organic matter in the sample, major participation of the complexes with these ligands was not stated based on the modelling.

Radio Frequency Detection and Characterization of Water-Ethanol Solution through Spiral-Coupled Passive Micro-Resonator Sensor.

PubMed

Koirala, Gyan Raj; Dhakal, Rajendra; Kim, Eun-Seong; Yao, Zhao; Kim, Nam-Young

2018-04-03

We present a microfabricated spiral-coupled passive resonator sensor realized through integrated passive device (IPD) technology for the sensitive detection and characterization of water-ethanol solutions. In order to validate the performance of the proposed device, we explicitly measured and analyzed the radio frequency (RF) characteristics of various water-ethanol solution compositions. The measured results showed a drift in the resonance frequency from 1.16 GHz for deionized (DI) water to 1.68 GHz for the solution containing 50% ethanol, whereas the rejection level given by the reflection coefficient decreased from -29.74 dB to -14.81 dB. The obtained limit of detection was 3.82% volume composition of ethanol in solution. The derived loaded capacitance was 21.76 pF for DI water, which gradually decreased to 8.70 pF for the 50% ethanol solution, and the corresponding relative permittivity of the solution decreased from 80.14 to 47.79. The dissipation factor increased with the concentration of ethanol in the solution. We demonstrated the reproducibility of the proposed sensor through iterative measures of the samples and the study of surface morphology. Successive measurement of different samples had no overlapping and had very minimum bias between RF characteristics for each measured sample. The surface profile for bare sensors was retained after the sample test, resulting a root mean square (RMS) value of 11.416 nm as compared to 10.902 nm for the bare test. The proposed sensor was shown to be a viable alternative to existing sensors for highly sensitive water-ethanol concentration detection.

Fast, sensitive and reliable multi-residue method for routine determination of 34 pesticides from various chemical groups in water samples by using dispersive liquid-liquid microextraction coupled with gas chromatography-mass spectrometry.

PubMed

Tankiewicz, Maciej; Biziuk, Marek

2018-02-01

A simple and efficient dispersive liquid-liquid microextraction technique (DLLME) was developed by using a mixture of two solvents: 40 μL of tetrachlorethylene (extraction solvent) and 1.0 mL of methanol (disperser solvent), which was rapidly injected with a syringe into 10 mL of water sample. Some important parameters affecting the extraction efficiency, such as type and volume of solvents, water sample volume, extraction time, temperature, pH adjustment and salt addition effect were investigated. Simultaneous determination of 34 commonly used pesticides was performed by using gas chromatography coupled with mass spectrometry (GC-MS). The procedure has been validated in order to obtain the highest efficiency at the lowest concentration levels of analytes to fulfill the requirements of regulations on maximum residue limits. Under the optimum conditions, the linearity range was within 0.0096-100 μg L -1 . The limits of detection (LODs) of the developed DLLME-GC-MS methodology for all investigated pesticides were in the range of 0.0032 (endrin)-0.0174 (diazinon) μg L -1 and limits of quantification (LOQs) from 0.0096 to 0.052 μg L -1 . At lower concentration of 1 μg L -1 for each pesticide, recoveries ranged between 84% (tebufenpyrad) and 108% (deltamethrin) with relative standard deviations (RSDs) (n = 7) from 1.1% (metconazole) to 11% (parathion-mehtyl). This methodology was successfully applied to check contamination of environmental samples. The procedure has proved to be selective, sensitive and precise for the simultaneous determination of various pesticides. The optimized analytical method is very simple and rapid (less than 5 min). Graphical abstract Analytical procedure for testing water samples consists of dispersive liquid-liquid microextraction (DLLME) and gas chromatography coupled with mass spectrometry (GC-MS).

Coupling of multi-walled carbon nanotubes/polydimethylsiloxane coated stir bar sorptive extraction with pulse glow discharge-ion mobility spectrometry for analysis of triazine herbicides in water and soil samples.

PubMed

Zou, Nan; Yuan, Chunhao; Liu, Shaowen; Han, Yongtao; Li, Yanjie; Zhang, Jialei; Xu, Xiang; Li, Xuesheng; Pan, Canping

2016-07-29

An analytical method based on stir bar sorptive extraction (SBSE) coupled with pulse glow discharge-ion mobility spectrometry (PGD-IMS) was developed for analysis of three triazine pesticide residues in water and soil samples. An injection port with sealing device and stir bars hold device were designed and constructed to directly position the SBSE fiber including the extracted samples into the heating device, making desorption and detection of analytes proceeded simultaneously. The extraction conditions such as SBSE solid phase material, extraction time, extraction temperature, pH value and salt concentration were optimized. Mixture of MWCNTs-COOH and PDMS were shown to be effective in enriching the triazines. The LODs and LOQs of three triazines were found to be 0.006-0.015μgkg(-1) and 0.02-0.05μgkg(-1), and the linear range was 0.05-10μgL(-1) with determination coefficients from 0.9987 to 0.9993. The SBSE-PGD-IMS method was environmentally friendly without organic solvent consumption in the entire experimental procedures, and it was demonstrated to be a commendable rapid analysis technique for analysis of triazine pesticide residues in environmental samples on site. The proposed method was applied for the analysis of real ground water, surface water and soil samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Determination of six sulfonylurea herbicides in environmental water samples by magnetic solid-phase extraction using multi-walled carbon nanotubes as adsorbents coupled with high-performance liquid chromatography.

PubMed

Ma, Jiping; Jiang, Lianhua; Wu, Gege; Xia, Yan; Lu, Wenhui; Li, Jinhua; Chen, Lingxin

2016-09-30

Magnetic solid-phase extraction (MSPE) using magnetic multi-walled carbon nanotubes (mag-MWCNTs) as adsorbents, coupled with high-performance liquid chromatography-diode-array detector (HPLC-DAD), was developed for the simultaneous separation and determination of six types of sulfonylurea herbicides (SUs) in environmental water samples. Several variables affecting MSPE efficiency were systematically investigated, including the type and volume of desorption solvent, sample solution pH, salt concentration, amount of mag-MWCNTs, and extraction and desorption time. Response surface was employed to assist in the MSPE optimization. Under optimized conditions, excellent linearity was achieved in the range of 0.05-5.0μg/L for all six SUs, with coefficients of correlation r>0.9994, and preconcentration factors ranging from 178 to 210. Limits of detection and quantification were 0.01-0.04μg/L and 0.03-0.13μg/L, respectively. The intra-day and inter-day precision (relative standard deviations, n=6, %) at three spiked levels were 2.0-11.0% and 2.1-12.9% in terms of peak area, respectively. The method recoveries at three fortified concentrations were obtained within 76.7-106.9% for reservoir water samples and 78.2-105.4% for tap water samples. The developed MSPE-HPLC method demonstrated high sensitivity, repeatability, simplicity, rapidity, and excellent practical applicability. Copyright © 2016 Elsevier B.V. All rights reserved.

Evaluation of Air Coupled Ultrasound for Composite Aerospace Structure

NASA Astrophysics Data System (ADS)

Tat, H.; Georgeson, G.; Bossi, R.

2009-03-01

Non-contact air coupled ultrasound suffers from the high acoustic impedance mismatch characteristics of air to solid interfaces. Advances in transducer technology, particularly MEMS, have improved the acoustic impedance match at the transmission stage and the signal to noise at the reception stage. Comparisons of through transmission (TTU) scanning of laminate and honeycomb test samples using conventional piezoelectric air coupled transducers, new MEMS air coupled transducers, and standard water coupled inspections have been performed to assess the capability. An additional issue for air coupled UT inspection is the need for a lean implementation for both manufacturing and in-service operations. Concepts and applications utilizing magnetic coupling of transducers have been developed that allows air coupled inspection operations in compact low cost configurations.

Coprecipitation-assisted coacervative extraction coupled to high-performance liquid chromatography: An approach for determining organophosphorus pesticides in water samples.

PubMed

Mammana, Sabrina B; Berton, Paula; Camargo, Alejandra B; Lascalea, Gustavo E; Altamirano, Jorgelina C

2017-05-01

An analytical methodology based on coprecipitation-assisted coacervative extraction coupled to HPLC-UV was developed for determination of five organophosphorus pesticides (OPPs), including fenitrothion, guthion, parathion, methidathion, and chlorpyrifos, in water samples. It involves a green technique leading to an efficient and simple analytical methodology suitable for high-throughput analysis. Relevant physicochemical variables were studied and optimized on the analytical response of each OPP. Under optimized conditions, the resulting methodology was as follows: an aliquot of 9 mL of water sample was placed into a centrifuge tube and 0.5 mL sodium citrate 0.1 M, pH 4; 0.08 mL Al 2 (SO 4 ) 3 0.1 M; and 0.7 mL SDS 0.1 M were added and homogenized. After centrifugation the supernatant was discarded. A 700 μL aliquot of the coacervate-rich phase obtained was dissolved with 300 μL of methanol and 20 μL of the resulting solution was analyzed by HPLC-UV. The resulting LODs ranged within 0.7-2.5 ng/mL and the achieved RSD and recovery values were <8% (n = 3) and >81%, respectively. The proposed analytical methodology was successfully applied for the analysis of five OPPs in water samples for human consumption of different locations of Mendoza. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of metal-laden water via portable X-ray fluorescence spectrometry

NASA Astrophysics Data System (ADS)

Pearson, Delaina; Weindorf, David C.; Chakraborty, Somsubhra; Li, Bin; Koch, Jaco; Van Deventer, Piet; de Wet, Jandre; Kusi, Nana Yaw

2018-06-01

A rapid method for in-situ elemental composition analysis of metal-laden water would be indispensable for studying polluted water. Current analytical lab methods to determine water quality include flame atomic absorption spectrometry (FAAS), atomic absorption spectrophotometry (AAS), electrothermal atomic absorption spectrometry (EAAS), and inductively coupled plasma (ICP) spectroscopy. However only two field methods, colorimetry and absorptiometry, exist for elemental analysis of water. Portable X-ray fluorescence (PXRF) spectrometry is an effective method for elemental analysis of soil, sediment, and other matrices. However, the accuracy of PXRF is known to be affected while scanning moisture-laden soil samples. This study sought to statistically establish PXRF's predictive ability for various elements in water at different concentrations relative to inductively coupled plasma atomic emission spectroscopy (ICP-AES). A total of 390 metal-laden water samples collected from leaching columns of mine tailings in South Africa were analyzed via PXRF and ICP-AES. The PXRF showed differential effectiveness in elemental quantification. For the collected water samples, the best relationships between ICP and PXRF elemental data were obtained for K and Cu (R2 = 0.92). However, when scanning ICP calibration solutions with elements in isolation, PXRF results indicated near perfect agreement; Ca, K, Fe, Cu and Pb produced an R2 of 0.99 while Zn and Mn produced an R2 of 1.00. The utilization of multiple PXRF (stacked) beams produced stronger correlation to ICP relative to the use of a single beam in isolation. The results of this study demonstrated the PXRF's ability to satisfactorily predict the composition of metal-laden water as reported by ICP for several elements. Additionally this study indicated the need for a "Water Mode" calibration for the PXRF and demonstrates the potential of PXRF for future study of polluted or contaminated waters.

Natural fluoride levels in some springs and streams from the late Maastrichtian Ajali formation in Ohafia-Arochukwu area of south eastern Nigeria.

PubMed

Ibe, K K; Adlegbembo, A O; Mafeni, J O; Danfillo, I S

1999-09-01

The aim of this study was to provide baseline data on the fluoride levels in waters associated with the late Maastrichtian Ajali formation in Ohafia-Arochukwu area of South Eastern Nigeria. Water samples from 14 artesian, perched springs and eight streams from the formation were collected with plastic containers. Fluoride analysis was carried out with inductively coupled plasma Atomic Emission Spectrometry (ICP-AES) equipment at the laboratories of the Department of Earth Science, University of Leeds, United Kingdom. The results showed that fluoride occurred in only one of the 14 spring water samples. Fluoride level in the sample was 0.03 ppm. The spring water, which contained some fluoride, was possibly associated with another rock formation: namely, the limestone bearing Nsukka formation, which overlies the Ajali formation. No fluoride was observed in all the stream water samples. This study reported the absence of fluoride in spring and stream waters associated with the late Maastrichtian formations in Nigeria.

[Determination of four phenolic endocrine disruptors in environmental water samples by high performance liquid chromatography-fluorescence detection using dispersive liquid-liquid microextraction coupled with derivatization].

PubMed

Wang, Xiaoyan; Qi, Weimei; Zhao, Xian'en; Lü, Tao; Wang, Xiya; Zheng, Longfang; Yan, Yehao; You, Jinmao

2014-06-01

To achieve accurate, fast and sensitive detection of phenolic endocrine disruptors in small volume of environmental water samples, a method of dispersive liquid-liquid microextraction (DLLME) coupled with fluorescent derivatization was developed for the determination of bisphenol A, nonylphenol, octylphenol and 4-tert-octylphenol in environmental water samples by high performance liquid chromatography-fluorescence detection (HPLC-FLD). The DLLME and derivatization conditions were investigated, and the optimized DLLME conditions for small volume of environmental water samples (pH 4.0) at room temperature were as follows: 70 microL chloroform as extraction solvent, 400 microL acetonitrile as dispersing solvent, vortex mixing for 3 min, and then high-speed centrifugation for 2 min. Using 2-[2-(7H-dibenzo [a, g] carbazol-7-yl)-ethoxy] ethyl chloroformate (DBCEC-Cl) as precolumn derivatization reagent, the stable derivatives of the four phenolic endocrine disruptors were obtained in pH 10.5 Na2CO3-NaHCO3 buffer/acetonitrile at 50 degrees C for 3 min, and then separated within 10 min by HPLC-FLD. The limits of detection (LODs) were in the range of 0.9-1.6 ng/L, and the limits of quantification (LOQs) were in the range of 3.8-7.1 ng/L. This method had perfect linearity, precision and recovery results, and showed obvious advantages and practicality comparing to the previously reported methods. It is a convenient and validated method for the routine analysis of phenolic endocrine disruptors in waste water of paper mill, lake water, domestic wastewater, tap water, etc.

Determination of phenylurea herbicides in water samples using online sorptive preconcentration and high-performance liquid chromatography with UV or electrospray mass spectrometric detection.

PubMed

Baltussen, E; Snijders, H; Janssen, H G; Sandra, P; Cramers, C A

1998-04-10

A recently developed method for the extraction of organic micropollutants from aqueous samples based on sorptive enrichment in columns packed with 100% polydimethylsiloxane (PDMS) particles was coupled on-line with HPLC analysis. The sorptive enrichment procedure originally developed for relatively nonpolar analytes was used to preconcentrate polar phenylurea herbicides from aqueous samples. PDMS extraction columns of 5, 10 and 25 cm were used to extract the herbicides from distilled, tap and river water samples. A model that allows prediction of retention and breakthrough volumes is presented. Despite the essentially apolar nature of the PDMS material, it is possible to concentrate sample volumes up to 10 ml on PDMS cartridges without losses of the most polar analyte under investigation, fenuron. For less polar analytes significantly larger sample volumes can be applied. Since standard UV detection does not provide adequate selectivity for river water samples, an electrospray (ES)-MS instrument was used to determine phenylurea herbicides in a water sample from the river Dommel. Methoxuron was present at a level of 80 ng/l. The detection limit of the current set-up, using 10 ml water samples and ES-MS detection is 10 ng/l in river water samples. Strategies for further improvement of the detection limits are identified.

Antibiotics in Drinking Water in Shanghai and Their Contribution to Antibiotic Exposure of School Children.

PubMed

Wang, Hexing; Wang, Na; Wang, Bin; Zhao, Qi; Fang, Hong; Fu, Chaowei; Tang, Chuanxi; Jiang, Feng; Zhou, Ying; Chen, Yue; Jiang, Qingwu

2016-03-01

A variety of antibiotics have been found in aquatic environments, but antibiotics in drinking water and their contribution to antibiotic exposure in human are not well-explored. For this, representative drinking water samples and 530 urine samples from schoolchildren were selected in Shanghai, and 21 common antibiotics (five macrolides, two β-lactams, three tetracyclines, four fluoquinolones, four sulfonamides, and three phenicols) were measured in water samples and urines by isotope dilution two-dimensional ultraperformance liquid chromatography coupled with high-resolution quadrupole time-of-flight mass spectrometry. Drinking water included 46 terminal tap water samples from different spots in the distribution system of the city, 45 bottled water samples from 14 common brands, and eight barreled water samples of different brands. Of 21 antibiotics, only florfenicol and thiamphenicol were found in tap water, with the median concentrations of 0.0089 ng/mL and 0.0064 ng/mL, respectively; only florfenicol was found in three bottled water samples from a same brand, with the concentrations ranging from 0.00060 to 0.0010 ng/mL; no antibiotics were found in barreled water. In contrast, besides florfenicol and thiamphenicol, an additional 17 antibiotics were detected in urine samples, and the total daily exposure doses and detection frequencies of florfenicol and thiamphenicol based on urine samples were significantly and substantially higher than their predicted daily exposure doses and detection frequencies from drinking water by Monte Carlo Simulation. These data indicated that drinking water was contaminated by some antibiotics in Shanghai, but played a limited role in antibiotic exposure of children.

Determination of tetrabromobisphenol-A/S and their main derivatives in water samples by high performance liquid chromatography coupled with inductively coupled plasma tandem mass spectrometry.

PubMed

Liu, Lihong; Liu, Aifeng; Zhang, Qinghua; Shi, Jianbo; He, Bin; Yun, Zhaojun; Jiang, Guibin

2017-05-12

As the most widely used brominated flame retardants (BFRs), Tetrabromobisphenol-A (TBBPA) as well as its alternative Tetrabromobisphenol-S (TBBPS) and their derivatives have raised wide concerns due to their adverse effects on human health and hence the sensitive detection of those BFRs was urgently needed. Herein, a novel analytical method based on high-performance liquid chromatography (HPLC) coupled with inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) has been developed for the determination of TBBPA/S and their derivatives, including TBBPA-bis(2-hydroxyethyl ether) (TBBPA-BHEE), TBBPA-bis(allylether) (TBBPA-BAE), TBBPA-bis(glycidyl ether) (TBBPA-BGE), TBBPA-bis(2,3-dibromopropyl ether) (TBBPA-BDBPE) and TBBPS-bis(2,3-dibromopropyl ether) (TBBPS-BDBPE) in water samples. After optimization, the TBBPA/S and their derivatives, especially the TBBPA-BAE and TBBPA-BDBPE were simultaneously and sensitively quantified by determination of bromine (m/z=79) by using the ICP-MS. The instrument limits of detection (LODs) for the TBBPA, TBBPA-BHEE, TBBPA-BGE, TBBPA-BAE, TBBPA-BDBPE, TBBPS and TBBPS-BDBPE were determined to be 0.12, 0.14, 0.19, 0.14, 0.12, 0.17 and 0.13μgL -1 , respectively, which was close to or much better than the reported methods. The relative standard deviations (RSDs, n=5) of peak area and retention time were better than 2.2% and 0.2% for intra-day analysis, indicating good repeatability and high precision. The proposed method had been successfully applied for the analysis of TBBPA/S and their derivatives in water samples with satisfactory recoveries (67.7%-113%). Copyright © 2017 Elsevier B.V. All rights reserved.

Determination of microcystin-LR in drinking water using UPLC tandem mass spectrometry-matrix effects and measurement.

PubMed

Li, Wei; Duan, Jinming; Niu, Chaoying; Qiang, Naichen; Mulcahy, Dennis

2011-10-01

A simple detection method using ultra-performance liquid chromatography electrospray ionisation tandem mass spectrometry (UPLC-ESI-MS-MS) coupled with the sample dilution method for determining trace microcystin-LR (MC-LR) in drinking water is presented. The limit of detection (LOD) was 0.04 µg/L and the limit of quantitation (LOQ) was 0.1 µg/L. Water matrix effects of ionic strength, dissolved organic carbon (DOC) and pH were examined. The results indicate that signal detection intensity for MC-LR was significantly suppressed as the ionic strength increased from ultrapure water condition, whereas it increased slightly with solution pH and DOC at low concentrations. However, addition of methanol (MeOH) into the sample was able to counter the signal suppression effects. In this study, dilution of the tap water sample by adding 4% MeOH (v/v) was observed to be adequate to compensate for the signal suppression. The recoveries of the samples fortified with MC-LR (0.2, 1, and 10 µg/L) for three different tap water samples ranged from 84.4% to 112.9%.

Efficiency of a closed-coupled solar pasteurization system in treating roof harvested rainwater.

PubMed

Dobrowsky, P H; Carstens, M; De Villiers, J; Cloete, T E; Khan, W

2015-12-01

Many studies have concluded that roof harvested rainwater is susceptible to chemical and microbial contamination. The aim of the study was thus to conduct a preliminary investigation into the efficiency of a closed-coupled solar pasteurization system in reducing the microbiological load in harvested rainwater and to determine the change in chemical components after pasteurization. The temperature of the pasteurized tank water samples collected ranged from 55 to 57°C, 64 to 66°C, 72 to 74°C, 78 to 81°C and 90 to 91°C. Cations analyzed were within drinking water guidelines, with the exception of iron [195.59 μg/L (55°C)-170.1 μg/L (91°C)], aluminum [130.98 μg/L (78°C)], lead [12.81 μg/L (55°C)-13.2 μg/L (91°C)] and nickel [46.43 μg/L (55°C)-32.82 μg/L (78°C)], which were detected at levels above the respective guidelines in the pasteurized tank water samples. Indicator bacteria including, heterotrophic bacteria, Escherichia coli and total coliforms were reduced to below the detection limit at pasteurization temperatures of 72°C and above. However, with the use of molecular techniques Yersinia spp., Legionella spp. and Pseudomonas spp. were detected in tank water samples pasteurized at temperatures greater than 72°C. The viability of the bacteria detected in this study at the higher temperature ranges should thus be assessed before pasteurized harvested rainwater is used as a potable water source. In addition, it is recommended that the storage tank of the pasteurization system be constructed from an alternative material, other than stainless steel, in order for a closed-coupled pasteurization system to be implemented and produce large quantities of potable water from roof harvested rainwater. Copyright © 2015 Elsevier B.V. All rights reserved.

Analysis of 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) and its brominated analogues in chlorine-treated water by gas chromatography coupled to triple quadrupole tandem mass spectrometry (GC-QqQ-MS/MS).

PubMed

Planas, Carles; Ventura, Francesc; Caixach, Josep; Martín, Jordi; Boleda, M Rosa; Paraira, Miquel

2015-11-01

A simple, selective and sensitive method for the analysis of the strong mutagen 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) and its brominated analogues (BMXs) in chlorine-treated water has been developed. The method is based on gas chromatography coupled to triple quadrupole tandem mass spectrometry (GC-QqQ-MS/MS), previous liquid-liquid extraction (LLE) of a smaller sample volume compared to other methods and on-line derivatization with a silylation reactive. GC-QqQ-MS/MS has been raised as an alternative easier to perform than gas chromatography coupled to high resolution mass spectrometry (GC-HRMS) for the analysis of MX and BMXs, and it allows to achieve low LODs (0.3 ng/L for MX and 0.4-0.9 ng/L for BMXs). This technique had not been previously described for the analysis of MX and BMXs. Quality parameters were calculated and real samples related to 3 drinking water treatment plants (DWTPs), tap water and both untreated and chlorinated groundwater were analyzed. Concentrations of 0.3-6.6 ng/L for MX and 1.0-7.3 ng/L for BMXs were detected. Results were discussed according to five of the main factors affecting MX and BMXs formation in chlorine-treated water (organic precursors, influence of bromide ions, evolution of MX and BMXs in the drinking water distribution system, groundwater chlorination and infiltration of water coming from chlorination processes in groundwater). Copyright © 2015 Elsevier B.V. All rights reserved.

Post-acquisition data processing for the screening of transformation products of different organic contaminants. Two-year monitoring of river water using LC-ESI-QTOF-MS and GCxGC-EI-TOF-MS.

PubMed

López, S Herrera; Ulaszewska, M M; Hernando, M D; Martínez Bueno, M J; Gómez, M J; Fernández-Alba, A R

2014-11-01

This study describes a comprehensive strategy for detecting and elucidating the chemical structures of expected and unexpected transformation products (TPs) from chemicals found in river water and effluent wastewater samples, using liquid chromatography coupled to electrospray ionization quadrupole-time-of-flight mass spectrometer (LC-ESI-QTOF-MS), with post-acquisition data processing and an automated search using an in-house database. The efficacy of the mass defect filtering (MDF) approach to screen metabolites from common biotransformation pathways was tested, and it was shown to be sufficiently sensitive and applicable for detecting metabolites in environmental samples. Four omeprazole metabolites and two venlafaxine metabolites were identified in river water samples. This paper reports the analytical results obtained during 2 years of monitoring, carried out at eight sampling points along the Henares River (Spain). Multiresidue monitoring, for targeted analysis, includes a group of 122 chemicals, amongst which are pharmaceuticals, personal care products, pesticides and PAHs. For this purpose, two analytical methods were used based on direct injection with a LC-ESI-QTOF-MS system and stir bar sorptive extraction (SBSE) with bi-dimensional gas chromatography coupled with a time-of-flight spectrometer (GCxGC-EI-TOF-MS).

In-situ pre-concentration through repeated sampling and pyrolysis for ultrasensitive determination of thallium in drinking water by electrothermal atomic absorption spectrometry.

PubMed

Liu, Liwei; Zheng, Huaili; Xu, Bincheng; Xiao, Lang; Chigan, Yong; Zhangluo, Yilan

2018-03-01

In this paper, a procedure for in-situ pre-concentration in graphite furnace by repeated sampling and pyrolysis is proposed for the determination of ultra-trace thallium in drinking water by graphite furnace atomic absorption spectrometry (GF-AAS). Without any other laborious enrichment processes that routinely result in analyte loss and contamination, thallium was directly concentrated in the graphite furnace automatically and subsequently subject to analysis. The effects of several key factors, such as the temperature for pyrolysis and atomization, the chemical modifier, and the repeated sampling times were investigated. Under the optimized conditions, a limit of detection of 0.01µgL -1 was obtained, which fulfilled thallium determination in drinking water by GB 5749-2006 regulated by China. Successful analysis of thallium in certified water samples and drinking water samples was demonstrated, with analytical results in good agreement with the certified values and those by inductively coupled plasma mass spectrometry (ICP-MS), respectively. Routine spike-recovery tests with randomly selected drinking water samples showed satisfactory results of 80-96%. The proposed method is simple and sensitive for screening of ultra-trace thallium in drinking water samples. Copyright © 2017. Published by Elsevier B.V.

“Nanofiltration” Enabled by Super-Absorbent Polymer Beads for Concentrating Microorganisms in Water Samples

NASA Astrophysics Data System (ADS)

Xie, Xing; Bahnemann, Janina; Wang, Siwen; Yang, Yang; Hoffmann, Michael R.

2016-02-01

Detection and quantification of pathogens in water is critical for the protection of human health and for drinking water safety and security. When the pathogen concentrations are low, large sample volumes (several liters) are needed to achieve reliable quantitative results. However, most microbial identification methods utilize relatively small sample volumes. As a consequence, a concentration step is often required to detect pathogens in natural waters. Herein, we introduce a novel water sample concentration method based on superabsorbent polymer (SAP) beads. When SAP beads swell with water, small molecules can be sorbed within the beads, but larger particles are excluded and, thus, concentrated in the residual non-sorbed water. To illustrate this approach, millimeter-sized poly(acrylamide-co-itaconic acid) (P(AM-co-IA)) beads are synthesized and successfully applied to concentrate water samples containing two model microorganisms: Escherichia coli and bacteriophage MS2. Experimental results indicate that the size of the water channel within water swollen P(AM-co-IA) hydrogel beads is on the order of several nanometers. The millimeter size coupled with a negative surface charge of the beads are shown to be critical in order to achieve high levels of concentration. This new concentration procedure is very fast, effective, scalable, and low-cost with no need for complex instrumentation.

"Nanofiltration" Enabled by Super-Absorbent Polymer Beads for Concentrating Microorganisms in Water Samples.

PubMed

Xie, Xing; Bahnemann, Janina; Wang, Siwen; Yang, Yang; Hoffmann, Michael R

2016-02-15

Detection and quantification of pathogens in water is critical for the protection of human health and for drinking water safety and security. When the pathogen concentrations are low, large sample volumes (several liters) are needed to achieve reliable quantitative results. However, most microbial identification methods utilize relatively small sample volumes. As a consequence, a concentration step is often required to detect pathogens in natural waters. Herein, we introduce a novel water sample concentration method based on superabsorbent polymer (SAP) beads. When SAP beads swell with water, small molecules can be sorbed within the beads, but larger particles are excluded and, thus, concentrated in the residual non-sorbed water. To illustrate this approach, millimeter-sized poly(acrylamide-co-itaconic acid) (P(AM-co-IA)) beads are synthesized and successfully applied to concentrate water samples containing two model microorganisms: Escherichia coli and bacteriophage MS2. Experimental results indicate that the size of the water channel within water swollen P(AM-co-IA) hydrogel beads is on the order of several nanometers. The millimeter size coupled with a negative surface charge of the beads are shown to be critical in order to achieve high levels of concentration. This new concentration procedure is very fast, effective, scalable, and low-cost with no need for complex instrumentation.

“Nanofiltration” Enabled by Super-Absorbent Polymer Beads for Concentrating Microorganisms in Water Samples

PubMed Central

Xie, Xing; Bahnemann, Janina; Wang, Siwen; Yang, Yang; Hoffmann, Michael R.

2016-01-01

Detection and quantification of pathogens in water is critical for the protection of human health and for drinking water safety and security. When the pathogen concentrations are low, large sample volumes (several liters) are needed to achieve reliable quantitative results. However, most microbial identification methods utilize relatively small sample volumes. As a consequence, a concentration step is often required to detect pathogens in natural waters. Herein, we introduce a novel water sample concentration method based on superabsorbent polymer (SAP) beads. When SAP beads swell with water, small molecules can be sorbed within the beads, but larger particles are excluded and, thus, concentrated in the residual non-sorbed water. To illustrate this approach, millimeter-sized poly(acrylamide-co-itaconic acid) (P(AM-co-IA)) beads are synthesized and successfully applied to concentrate water samples containing two model microorganisms: Escherichia coli and bacteriophage MS2. Experimental results indicate that the size of the water channel within water swollen P(AM-co-IA) hydrogel beads is on the order of several nanometers. The millimeter size coupled with a negative surface charge of the beads are shown to be critical in order to achieve high levels of concentration. This new concentration procedure is very fast, effective, scalable, and low-cost with no need for complex instrumentation. PMID:26876979

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory; use of a modified ultrasonic nebulizer for the analysis of low ionic-strength water by inductively coupled optical emission spectrometry

USGS Publications Warehouse

Harris, Carl M.; Litteral, Charles J.; Damrau, Donna L.

1997-01-01

The U.S. Geological Survey National Water Quality Laboratory has developed a method for the determination of dissolved calcium, iron, magnesium, manganese, silica, and sodium using a modified ultrasonic nebulizer sample-introduction system to an inductively coupled plasma-optical emission spectrometer. The nebulizer's spray chamber has been modified to avoid carryover and memory effects common in some conventional ultrasonic designs. The modified ultrasonic nebulizer is equipped with a high-speed rinse cycle to remove previously analyzed samples from the spray chamber without excessive flush times. This new rinse cycle decreases sample washout times by reducing carryover and memory effects from salt or analytes in previously analyzed samples by as much as 45 percent. Plasma instability has been reduced by repositioning the argon carrier gas inlet on the spray chamber and by directly pumping waste from the chamber, instead of from open drain traps, thereby maintaining constant pressure to the plasma. The ultrasonic nebulizer improves signal intensities, which are 8 to 16 times greater than for a conventional cross-flow pneumatic nebulizer, without being sensitive to clogging from salt buildup as in cross-flow nebulizers. Detection limits for the ultrasonic nebulizer are 4 to 18 times less than detection limits achievable using a cross-flow pneumatic nebulizer, with equivalent sample analysis time.

Determination of biomass burning tracers in air samples by GC/MS

NASA Astrophysics Data System (ADS)

Janoszka, Katarzyna

2018-01-01

Levoglucosan (LG) as a main cellulose burning product at 300°C is a biomass burning tracer. LG characterize by relatively high molar mass and it is sorbed by particulate matter. In the study of air pollution monitoring LG is mainly analyzed in particulate matter, PM1 and PM2,5. The tracer create relatively high O-H…O bond and weaker C-H…O bond. Due to the hydrogen bond, LG dissolves very well in water. Analytical procedure of LG determination include: extraction, derivatization and analysis by gas chromatography coupled with mass spectrometry detector. In water samples levoglucosan is determined by liquid chromatography. The paper presents a methodology for particulate matter samples determination their analysis by gas chromatography coupled with a mass spectrometry detector. Determination of LG content in particulate matter was performed according to an analytical method based on simultaneous pyridine extraction and derivatization using N,O-bis (trimethylsilyl) trifluoroacetamide and trimethylchlorosilane mixture (BSTFA: TMCS, 99: 1).

Prediction of mechanical property loss in polyamide during immersion in sea water

NASA Astrophysics Data System (ADS)

Le Gac, Pierre Yves; Arhant, Mael; Le Gall, Maelenn; Burtin, Christian; Davies, Peter

2016-05-01

It is well known that the water absorption in polyamide leads to a large reduction in the mechanical properties of the polymer, which is induced by the plasticization of the amorphous phase. However, predicting such a loss in a marine environment is not straightforward, especially when thick samples are considered. This study presents a modeling study of the water absorption in polyamide 6 based on the free volume theory. Using this modeling coupled with a description of the stress yield changes with Tg, it is possible to predict the long term behavior of thick samples when immersed in sea water. Reliability of the prediction is checked by a comparison with experimental results.

Preconcentration determination of arsenic species by sorption of As(V) on Amberlite IRA-410 coupled with fluorescence quenching of L-cysteine capped CdS nanoparticles.

PubMed

Hosseini, Mohammad Saeid; Nazemi, Sahar

2013-10-07

A simple and accurate method for arsenic speciation analysis in natural and drinking water samples is described in which preconcentration of arsenic as As(V) was coupled with spectrofluorometric determination. The extracted As(V) species with a column containing Amberlite IRA-410 were subjected to L-cysteine capped CdS quantum dots (QDs) and the fluorescence quenching of the QDs due to reduction of As(V) by L-cysteine was considered as a signal relevant to As(V) concentration. The As(III) species were also determined after oxidation of As(III) ions to As(V) with H2O2 and measurement of the total arsenic content. In treatment with 400 mL portions of water samples containing 30 μg L(-1) As(V), the relative standard deviation was 2.8%. The detection limit of arsenic was also found to be 0.75 μg L(-1) (1 × 10(-8) M). The reliability of proposed method was confirmed using certified reference materials. The trace amounts of arsenic species were then determined in different water samples, satisfactorily.

Thallium release from acid mine drainages: Speciation in river and tap water from Valdicastello mining district (northwest Tuscany).

PubMed

Campanella, Beatrice; Casiot, Corinne; Onor, Massimo; Perotti, Martina; Petrini, Riccardo; Bramanti, Emilia

2017-08-15

In this work we present an advantageous method for the simultaneous separation and detection of Tl(I) and Tl(III) species through ion chromatography coupled with on-line inductively coupled plasma - mass spectrometry. Chromatographic separation between Tl(III) and Tl(I) was achieved in less than two minutes. The method was validated by recovery experiments on real samples, and by comparing the sum of the concentrations of individual Tl species with total thallium values obtained from continuous flow ICP-MS. The experimental procedure offers an accurate, sensitive and interference-free method for Tl speciation at trace levels in environmental samples. This allowed us to investigate the Tl speciation in acid mine drainages (AMD), surface waters and springs in a mining catchment in Valdicastello Carducci (Tuscany, Italy), where severe Tl contamination ad been evidenced previously. This study shows for the first time that Tl(III), in addition to Tl(I), is present in considerable amounts in water samples affected by acid mining outflow, raising the question of the origin of this thermodynamically unstable species. Copyright © 2017 Elsevier B.V. All rights reserved.

Fate and transport of plutonium-239 + 240 and Americium-241 in the soil of Rocky Flats, Colorado

DOE Office of Scientific and Technical Information (OSTI.GOV)

Litaor, M.I.; Barth, G.R.; Zika, E.M.

1996-07-01

Actinides contamination of soils around Rocky Flats, CO, resulted from leaking drums of Pu-contaminated oil stored at an outdoor site. The transport of these actinides through the soil to groundwater was studied using an advanced monitoring system (MS). The fully automated, remotely controlled MS gathered real-time data on soil water content, groundwater level, and timing of gravitationally flowing water. Controlled rain simulations coupled with measurements of volume flux and actinide activities provided essential information about the fate and transport of Pu-239 + 240 and Am-241. Volume fluxes at most sampling locations were similar, regardless of the antecedent moisture or themore » duration, frequency, and intensity of the simulated rain. Actinide activities were not correlated with the measured volume flux, or the duration, frequency, and intensity of the simulated rain. Flow was facilitated primarily via macropore channeling. The relatively short residence time precluded a continuous interaction between the soil and the flowing water, which minimized the movement of actinides in the soil. Actinide activities in the interstitial water collected from the upper 20 cm of the soil were significantly higher (P>0.001) than water collected at deeper sampling depths (20-70 cm). Actinide activity in water samples from the deepest sampling depth (40-70 cm) did not exceed 0.4 Bq/L. These results suggest that, under the experimental conditions, the movement of actinides was restricted to the top 20 cm. A transport mechanism involving discrete Pu oxide particles, coupled with macropore channeling is proposed to explain the observed actinide activities in the soil. 31 refs., 6 figs., 7 tabs.« less

Contaminant screening of wastewater with HPLC-IM-qTOF-MS and LC+LC-IM-qTOF-MS using a CCS database.

PubMed

Stephan, Susanne; Hippler, Joerg; Köhler, Timo; Deeb, Ahmad A; Schmidt, Torsten C; Schmitz, Oliver J

2016-09-01

Non-target analysis has become an important tool in the field of water analysis since a broad variety of pollutants from different sources are released to the water cycle. For identification of compounds in such complex samples, liquid chromatography coupled to high resolution mass spectrometry are often used. The introduction of ion mobility spectrometry provides an additional separation dimension and allows determining collision cross sections (CCS) of the analytes as a further physicochemical constant supporting the identification. A CCS database with more than 500 standard substances including drug-like compounds and pesticides was used for CCS data base search in this work. A non-target analysis of a wastewater sample was initially performed with high performance liquid chromatography (HPLC) coupled to an ion mobility-quadrupole-time of flight mass spectrometer (IM-qTOF-MS). A database search including exact mass (±5 ppm) and CCS (±1 %) delivered 22 different compounds. Furthermore, the same sample was analyzed with a two-dimensional LC method, called LC+LC, developed in our group for the coupling to IM-qTOF-MS. This four dimensional separation platform revealed 53 different compounds, identified over exact mass and CCS, in the examined wastewater sample. It is demonstrated that the CCS database can also help to distinguish between isobaric structures exemplified for cyclophosphamide and ifosfamide. Graphical Abstract Scheme of sample analysis and database screening.

Considerations in As analysis and speciation

USGS Publications Warehouse

Edwards, M.; Patel, S.; McNeil, L.; Chen, H.W.; Frey, M.; Eaton, A.D.; Antweiler, Ronald C.; Taylor, Howard E.

1998-01-01

This article summarizes recent experiences in arsenic (As) quantification, preservation, and speciation developed during AWWA Research Foundation (AWWARF) and Water Industry Technical Action Fund (WITAF) projects. The goal of this article is to alert analysts and decision-makers to potential problems in As analysis and speciation, because there appear to be several unresolved problems with routine analytical approaches. In true split drinking water samples As was quantified by three accepted analytical methods in three laboratories. The techniques used were graphite furnace atomic absorption spectrometry (GFAAS), inductively coupled plasma mass spectrometry (ICP-MS), and hydride generation inductively coupled plasma-emission spectrometry (HG-ICP-AES). Experimental findings are organized into sections on As analysis, particulate As in water supplies, and examination of As speciation methods.

Magnetic solid-phase extraction of heterocyclic pesticides in environmental water samples using metal-organic frameworks coupled to high performance liquid chromatography determination.

PubMed

Ma, Jiping; Wu, Gege; Li, Shuang; Tan, Weiqiang; Wang, Xiaoyan; Li, Jinhua; Chen, Lingxin

2018-06-08

A simple method of magnetic solid-phase extraction (MSPE) coupled to high performance liquid chromatography (HPLC) was developed for the simultaneous extraction and determination of four kinds of heterocyclic pesticides (carbendazim, triadimefon, chlorfenapyr and fenpyroximate) in environmental water samples. Magnetic metal-organic frameworks (MOFs) of type MOF-5 were prepared and used as adsorbents of MSPE. Several main parameters influencing MSPE efficiency were investigated, including amount of magnetic MOF-5, sample solution pH, extraction time, salt concentration, type and volume of desorption solvents and desorption time. Under optimal conditions, the MSPE-HPLC method presented fast simple separation and analysis, and excellent linearity in the range of 0.3-500.0 μg/L for carbendazim and triadimefon, and 0.1-500.0 μg/L for chlorfenapyr and fenpyroximate, with correlation coefficients (r) higher than 0.9992. High sensitivity with limits of detection and quantification ranging from 0.04-0.11 μg/L and 0.13-0.35 μg/L, respectively, were achieved, as well as good precision with relative standard deviations of 2.98-7.11% (intra-day) and 3.31-7.12% (inter-day). Furthermore, the method was successfully applied to reservoir and Yellow River water samples, and satisfactory recoveries at three spiked concentration levels were between 80.20% and 108.33%.The magnetic MOF-5 composites based MSPE followed by HPLC proved promising for convenient and efficient determination of heterocyclic pesticides in environmental water samples. Copyright © 2018 Elsevier B.V. All rights reserved.

Spatial and Temporal Patterns In Ecohydrological Separation

NASA Astrophysics Data System (ADS)

Jarvis, S. K.; Barnard, H. R.; Singha, K.; Harmon, R. E.; Szutu, D.

2017-12-01

The model of ecohydrological separation suggests that trees source water from a different subsurface pool than what is contributing to stream flow during dry periods, however diel fluctuations in stream flow and transpiration are tightly coupled. To better understand the mechanism of this coupling, this study examines spatiotemporal patterns in water isotopic relationships between tree, soil, and stream water. Preliminary analysis of data collected in 2015 show a trend in δ18O enrichment in xylem water, suggesting an increased reliance on enriched soil water not flowing to the stream as the growing season progresses, while xylem samples from 2016, a particularly wet year, do not have this trend. Variations in these temporal trends are explored with regard to distance from stream, aspect of hillslope, position in the watershed, size of the tree, and soil depth. Additionally, a near-stream site is examined at high resolution using water isotope data, sap flow, and electrical resistivity surveying to examine soil moisture and water use patterns across the riparian-hillslope transition.

Automated dispersive liquid-liquid microextraction coupled to high performance liquid chromatography - cold vapour atomic fluorescence spectroscopy for the determination of mercury species in natural water samples.

PubMed

Liu, Yao-Min; Zhang, Feng-Ping; Jiao, Bao-Yu; Rao, Jin-Yu; Leng, Geng

2017-04-14

An automated, home-constructed, and low cost dispersive liquid-liquid microextraction (DLLME) device that directly coupled to a high performance liquid chromatography (HPLC) - cold vapour atomic fluorescence spectroscopy (CVAFS) system was designed and developed for the determination of trace concentrations of methylmercury (MeHg + ), ethylmercury (EtHg + ) and inorganic mercury (Hg 2+ ) in natural waters. With a simple, miniaturized and efficient automated DLLME system, nanogram amounts of these mercury species were extracted from natural water samples and injected into a hyphenated HPLC-CVAFS for quantification. The complete analytical procedure, including chelation, extraction, phase separation, collection and injection of the extracts, as well as HPLC-CVAFS quantification, was automated. Key parameters, such as the type and volume of the chelation, extraction and dispersive solvent, aspiration speed, sample pH, salt effect and matrix effect, were thoroughly investigated. Under the optimum conditions, linear range was 10-1200ngL -1 for EtHg + and 5-450ngL -1 for MeHg + and Hg 2+ . Limits of detection were 3.0ngL -1 for EtHg + and 1.5ngL -1 for MeHg + and Hg 2+ . Reproducibility and recoveries were assessed by spiking three natural water samples with different Hg concentrations, giving recoveries from 88.4-96.1%, and relative standard deviations <5.1%. Copyright © 2017 Elsevier B.V. All rights reserved.

Speciation analysis of Mn(II)/Mn(VII) using Fe3O4@ionic liquids-β-cyclodextrin polymer magnetic solid phase extraction coupled with ICP-OES.

PubMed

Chen, Songqing; Qin, Xingxiu; Gu, Weixi; Zhu, Xiashi

2016-12-01

Ionic liquids-β-cyclodextrin polymer (ILs-β-CDCP) was attached on Fe 3 O 4 nanoparticles to prepare magnetic solid phase extraction agent (Fe 3 O 4 @ILs-β-CDCP). The properties and morphology of Fe 3 O 4 @ILs-β-CDCP were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction(XRD), size distribution and magnetic analysis. A new method of magnetic solid phase extraction (MSPE) coupled to ICP-OES for the speciation of Mn(II)/Mn(VII) in water samples was established. The results showed that Mn(VII) and total manganese [Mn(II)+Mn(VII)] were quantitatively extracted after adjusting aqueous sample solution to pH 6.0 and 10.0, respectively. Mn(II) was calculated by subtraction of Mn(VII) from total manganese. Fe 3 O 4 @ILs-β-CDCP showed a higher adsorption capacity toward Mn(II) and Mn(VII). Several factors, such as the pH value, extraction temperature and sample volume, were optimized to achieve the best extraction efficiency. Moreover, the adsorption ability of Fe 3 O 4 @ILs-β-CDCP would not be significantly lower after reusing of 10 times. The accuracy of the developed method was confirmed by analyzing certified reference materials (GSB 07-1189-2000), and by spiking spring water, city water and lake water samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Drop-to-drop solvent microextraction coupled with gas chromatography/mass spectrometry for rapid determination of trimeprazine in urine and blood of rats: application to pharmacokinetic studies.

PubMed

Agrawal, Kavita; Wu, Hui-Fen

2007-01-01

A simple and rapid method based on drop-to-drop solvent microextraction (DDSME) coupled with gas chromatography/mass spectrometry (GC/MS) has been successfully applied for the pharmacokinetic studies of trimeprazine in 8 microL of urine and blood samples of rats. Several factors that influenced the extraction efficiency of DDSME, such as selection of organic solvent, extraction time, exposure volume of organic phase, addition of salt and pH, were optimized. Linearity was obtained over the concentration ranges of 0.2-10, 0.25-7.0 and 0.5-6.0 microg/mL with correlation coefficients of 0.998, 0.996 and 0.993 in deionized water, urine and blood samples of rats, respectively. The limits of detection (LODs) of trimeprazine were 0.05, 0.06 and 0.1 microg/mL in deionized water, urine and blood samples. The concentrations of trimeprazine obtained in urine and blood samples of rats were 0.21-1.25 and 2.72-0.22 microg/mL, respectively, after a single intravenous administration of this drug. The enrichment factors and LOD values obtained by DDSME coupled to GC/MS were compared with those of hollow fiber liquid-phase microextraction (HF-LPME) combined with GC/MS. We believe that this novel approach can be very useful in clinical application since only one microdrop of biological samples was required to perform the pharmacokinetic studies from rats, so the sample pretreatments for animal experiments can be very easy too. Copyright (c) 2007 John Wiley & Sons, Ltd.

Arsenic exposure in drinking water: an unrecognized health threat in Peru.

PubMed

George, Christine Marie; Sima, Laura; Arias, M Helena Jahuira; Mihalic, Jana; Cabrera, Lilia Z; Danz, David; Checkley, William; Gilman, Robert H

2014-08-01

To assess the extent of arsenic contamination of groundwater and surface water in Peru and, to evaluate the accuracy of the Arsenic Econo-Quick(™) (EQ) kit for measuring water arsenic concentrations in the field. Water samples were collected from 151 water sources in 12 districts of Peru, and arsenic concentrations were measured in the laboratory using inductively-coupled plasma mass spectrometry. The EQ field kit was validated by comparing a subset of 139 water samples analysed by laboratory measurements and the EQ kit. In 86% (96/111) of the groundwater samples, arsenic exceeded the 10 µg/l arsenic concentration guideline given by the World Health Organization (WHO) for drinking water. In 56% (62/111) of the samples, it exceeded the Bangladeshi threshold of 50 µg/l; the mean concentration being 54.5 µg/l (range: 0.1-93.1). In the Juliaca and Caracoto districts, in 96% (27/28) of groundwater samples arsenic was above the WHO guideline; and in water samples collected from the section of the Rímac river running through Lima, all had arsenic concentrations exceeding the WHO limit. When validated against laboratory values, the EQ kit correctly identified arsenic contamination relative to the guideline in 95% (106/111) of groundwater and in 68% (19/28) of surface water samples. In several districts of Peru, drinking water shows widespread arsenic contamination, exceeding the WHO arsenic guideline. This poses a public health threat requiring further investigation and action. For groundwater samples, the EQ kit performed well relative to the WHO arsenic limit and therefore could provide a vital tool for water arsenic surveillance.

A nationwide survey of NDMA in raw and drinking water in Japan.

PubMed

Asami, Mari; Oya, Masami; Kosaka, Koji

2009-05-15

A nationwide survey of N-nitrosodimethylamine (NDMA) in both raw and finished water samples from drinking water treatment plants (DWTPs) in Japan was conducted. NDMA was analyzed by solid-phase extraction (SPE) followed by ultra performance liquid chromatography (UPLC) coupled with tandem mass spectrometry (MS/MS). NDMA was detected in 15 of 31 raw water samples collected in the summer at concentrations up to 2.6 ng/L, and in 9 of 28 raw water samples collected in winter at concentrations up to 4.3 ng/L. The NDMA concentrations were higher in raw water samples collected from treatment plants with catchment areas that have high population densities. The NDMA concentrations were higher in river water samples collected from the east and west of Japan than in those collected from other areas. NDMA was detected in 10 of 31 finished samples collected in summer at reduced concentrations of up to 2.2 ng/L, while 5 of 28 finished samples collected in winter showed NDMA concentrations up to 10 ng/L. The highest NDMA levels were detected in finished water samples collected from the Yodo River basin DWTP, which uses ozonation. Furthermore, evaluation of the process water produced at six advanced water treatment plants was conducted. Influent from the Yodo River indicated that the NDMA concentration increased during ozonation to as high as 20 ng/L, and then decreased with subsequent biological activated carbon treatment. To our knowledge, this is the first nationwide evaluation of NDMA concentrations in water conducted in Japan to date.

Standard reference water samples for rare earth element determinations

USGS Publications Warehouse

Verplanck, P.L.; Antweiler, Ronald C.; Nordstrom, D. Kirk; Taylor, Howard E.

2001-01-01

Standard reference water samples (SRWS) were collected from two mine sites, one near Ophir, CO, USA and the other near Redding, CA, USA. The samples were filtered, preserved, and analyzed for rare earth element (REE) concentrations (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) by inductively coupled plasma-mass spectrometry (ICP-MS). These two samples were acid mine waters with elevated concentrations of REEs (0.45-161 ??g/1). Seventeen international laboratories participated in a 'round-robin' chemical analysis program, which made it possible to evaluate the data by robust statistical procedures that are insensitive to outliers. The resulting most probable values are reported. Ten to 15 of the participants also reported values for Ba, Y, and Sc. Field parameters, major ion, and other trace element concentrations, not subject to statistical evaluation, are provided.

Orthogonal Design Study on Factors Affecting the Determination of Common Odors in Water Samples by Headspace Solid-Phase Microextraction Coupled to GC/MS

PubMed Central

Ding, Zhen; Xia, Weiwen; Zheng, Hao; Xia, Yuting; Chen, Xiaodong

2013-01-01

Geosmin and 2-MIB are responsible for the majority of earthy and musty events related to the drinking water. These two odorants have extremely low odor threshold concentrations at ng L−1 level in the water, so a simple and sensitive method for the analysis of such trace levels was developed by headspace solid-phase microextraction coupled to gas chromatography/mass spectrometry. In this study, the orthogonal experiment design L32 (49) was applied to arrange and optimize experimental conditions. The optimum was the following: temperatures of extraction and desorption, 65°C and 260°C, respectively; times of extraction and desorption, 30 min and 5 min, respectively; ionic strength, 25% (w/v); rotate-speed, 600 rpm; solution pH, 5.0. Under the optimized conditions, limits of detection (S/N = 3) were 0.04 and 0.13 ng L−1 for geosmin and 2-MIB, respectively. Calculated calibration curves gave high levels of linearity with a correlation coefficient value of 0.9999 for them. Finally, the proposed method was applied to water samples, which were previously analyzed and confirmed to be free of target analytes. Besides, the proposal method was applied to test environmental water samples. The RSDs were 2.75%~3.80% and 4.35%~7.6% for geosmin and 2-MIB, respectively, and the recoveries were 91%~107% and 91%~104% for geosmin and 2-MIB, respectively. PMID:24000317

Determination of glyphosate and phosphate in water by ion chromatography--inductively coupled plasma mass spectrometry detection.

PubMed

Guo, Zhong-Xian; Cai, Qiantao; Yang, Zhaoguang

2005-12-30

Quantitative determination of trace glyphosate and phosphate in waters was achieved by coupling ion chromatography (IC) separation with inductively coupled plasma mass spectrometry (ICP-MS) detection. The separation of glyphosate and phosphate on a polymer anion-exchange column (Dionex IonPac AS16, 4.0 mm x 250 mm) was obtained by eluting them with 20 mM citric acid at 0.50 mL min(-1), and the analytes were detected directly and selectively by ICP-MS at m/z = 31. Parameters affecting their chromatographic behaviors and ICP-MS characteristics were systematically examined. Based on a 500-microL sample injection volume, the detection limits were 0.7 microgL(-1) for both glyphosate and phosphate, and the calibrations were linear up to 400 microgL(-1). Polyphosphates, aminomethylphosphonic acid (the major metabolite of glyphosate), non-polar and other polar phosphorus-containing pesticides showed different chromatographic behaviors from the analytes of interest and therefore did not interference. The determination was also interference free from the matrix anions (nitrate, nitrite, sulphate, chloride, etc.) and metallic ions. The analysis of certified reference material, drinking water, reservoir water and Newater yielded satisfactory results with spiked recoveries of 97.1-107.0% and relative standard deviations of < or = 7.4% (n = 3). Compared to other reported methods for glyphosate and phosphate, the developed IC-ICP-MS method is sensitive and simple, and does not require any chemical derivatization, sample preconcentration and mobile phase conductivity suppression.

Relationship between arsenic content of food and water applied for food processing.

PubMed

Sugár, Eva; Tatár, Enikő; Záray, Gyula; Mihucz, Victor G

2013-12-01

As part of a survey conducted by the Central Agricultural Office of Hungary, 67 food samples including beverages were taken from 57 food industrial and catering companies, 75% of them being small and medium-sized enterprises (SMEs). Moreover, 40% of the SMEs were micro entities. Water used for food processing was simultaneously sampled. The arsenic (As) content of solid food stuff was determined by hydride generation atomic absorption spectrometry after dry ashing. Food stuff with high water content and water samples were analyzed by inductively coupled plasma mass spectrometry. The As concentration exceeded 10 μg/L in 74% of the water samples taken from SMEs. The As concentrations of samples with high water content and water used were linearly correlated. Estimated As intake from combined exposure to drinking water and food of the population was on average 40% of the daily lower limit of WHO on the benchmark dose for a 0.5% increased incidence of lung cancer (BMDL0.5) for As. Five settlements had higher As intake than the BMDL0.5. Three of these settlements are situated in Csongrád county and the distance between them is less than 55 km. The maximum As intake might be 3.8 μg/kg body weight. Copyright © 2013 Elsevier Ltd. All rights reserved.

Effects of sterilization treatments on the analysis of TOC in water samples.

PubMed

Shi, Yiming; Xu, Lingfeng; Gong, Dongqin; Lu, Jun

2010-01-01

Decomposition experiments conducted with and without microbial processes are commonly used to study the effects of environmental microorganisms on the degradation of organic pollutants. However, the effects of biological pretreatment (sterilization) on organic matter often have a negative impact on such experiments. Based on the principle of water total organic carbon (TOC) analysis, the effects of physical sterilization treatments on determination of TOC and other water quality parameters were investigated. The results revealed that two conventional physical sterilization treatments, autoclaving and 60Co gamma-radiation sterilization, led to the direct decomposition of some organic pollutants, resulting in remarkable errors in the analysis of TOC in water samples. Furthermore, the extent of the errors varied with the intensity and the duration of sterilization treatments. Accordingly, a novel sterilization method for water samples, 0.45 microm micro-filtration coupled with ultraviolet radiation (MCUR), was developed in the present study. The results indicated that the MCUR method was capable of exerting a high bactericidal effect on the water sample while significantly decreasing the negative impact on the analysis of TOC and other water quality parameters. Before and after sterilization treatments, the relative errors of TOC determination could be controlled to lower than 3% for water samples with different categories and concentrations of organic pollutants by using MCUR.

Set Up of an Automatic Water Quality Sampling System in Irrigation Agriculture

PubMed Central

Heinz, Emanuel; Kraft, Philipp; Buchen, Caroline; Frede, Hans-Georg; Aquino, Eugenio; Breuer, Lutz

2014-01-01

We have developed a high-resolution automatic sampling system for continuous in situ measurements of stable water isotopic composition and nitrogen solutes along with hydrological information. The system facilitates concurrent monitoring of a large number of water and nutrient fluxes (ground, surface, irrigation and rain water) in irrigated agriculture. For this purpose we couple an automatic sampling system with a Wavelength-Scanned Cavity Ring Down Spectrometry System (WS-CRDS) for stable water isotope analysis (δ2H and δ18O), a reagentless hyperspectral UV photometer (ProPS) for monitoring nitrate content and various water level sensors for hydrometric information. The automatic sampling system consists of different sampling stations equipped with pumps, a switch cabinet for valve and pump control and a computer operating the system. The complete system is operated via internet-based control software, allowing supervision from nearly anywhere. The system is currently set up at the International Rice Research Institute (Los Baños, The Philippines) in a diversified rice growing system to continuously monitor water and nutrient fluxes. Here we present the system's technical set-up and provide initial proof-of-concept with results for the isotopic composition of different water sources and nitrate values from the 2012 dry season. PMID:24366178

Monitoring pharmaceuticals and personal care products in reservoir water used for drinking water supply.

PubMed

Aristizabal-Ciro, Carolina; Botero-Coy, Ana María; López, Francisco J; Peñuela, Gustavo A

2017-03-01

In this work, the presence of selected emerging contaminants has been investigated in two reservoirs, La Fe (LF) and Rio Grande (RG), which supply water to two drinking water treatment plants (DWTPs) of Medellin, one of the most populated cities of Colombia. An analytical method based on solid-phase extraction (SPE) of the sample followed by measurement by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was developed and validated for this purpose. Five monitoring campaigns were performed in each reservoir, collecting samples from 7 sites (LF) and 10 sites (RG) at 3 different depths of the water column. In addition, water samples entering in the DWTPs and treated water samples from these plans were also analysed for the selected compounds. Data from this work showed that parabens, UV filters and the pharmaceutical ibuprofen were commonly present in most of the reservoir samples. Thus, methyl paraben was detected in around 90% of the samples collected, while ibuprofen was found in around 60% of the samples. Water samples feeding the DWTPs also contained these two compounds, as well as benzophenone at low concentrations, which was in general agreement with the results from the reservoir samples. After treatment in the DWTPs, these three compounds were still present in the samples although at low concentrations (<40 ng/L), which evidenced that they were not completely removed after the conventional treatment applied. The potential effects of the presence of these compounds at the ppt levels in drinking water are still unknown. Further research is needed to evaluate the effect of chronic exposure to these compounds via consumption of drinking water.

Investigation of Adhesive Bond Cure Conditions using Nonlinear Ultrasonic Methods

NASA Technical Reports Server (NTRS)

Berndt, Tobias P.; Green, Robert E., Jr.

1999-01-01

The objective of this presentation is to investigate various cure conditions of adhesive bonds using nonlinear ultrasonic methods with water coupling. Several samples were used to obtain normal incidence, oblique incidence, and wave mixing.

Chromatographic background drift correction coupled with parallel factor analysis to resolve coelution problems in three-dimensional chromatographic data: quantification of eleven antibiotics in tap water samples by high-performance liquid chromatography coupled with a diode array detector.

PubMed

Yu, Yong-Jie; Wu, Hai-Long; Fu, Hai-Yan; Zhao, Juan; Li, Yuan-Na; Li, Shu-Fang; Kang, Chao; Yu, Ru-Qin

2013-08-09

Chromatographic background drift correction has been an important field of research in chromatographic analysis. In the present work, orthogonal spectral space projection for background drift correction of three-dimensional chromatographic data was described in detail and combined with parallel factor analysis (PARAFAC) to resolve overlapped chromatographic peaks and obtain the second-order advantage. This strategy was verified by simulated chromatographic data and afforded significant improvement in quantitative results. Finally, this strategy was successfully utilized to quantify eleven antibiotics in tap water samples. Compared with the traditional methodology of introducing excessive factors for the PARAFAC model to eliminate the effect of background drift, clear improvement in the quantitative performance of PARAFAC was observed after background drift correction by orthogonal spectral space projection. Copyright © 2013 Elsevier B.V. All rights reserved.

A rapid and high-precision method for sulfur isotope δ(34)S determination with a multiple-collector inductively coupled plasma mass spectrometer: matrix effect correction and applications for water samples without chemical purification.

PubMed

Lin, An-Jun; Yang, Tao; Jiang, Shao-Yong

2014-04-15

Previous studies have indicated that prior chemical purification of samples, although complex and time-consuming, is essential in obtaining precise and accurate results for sulfur isotope ratios using multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). In this study, we introduce a new, rapid and precise MC-ICP-MS method for sulfur isotope determination from water samples without chemical purification. The analytical work was performed on an MC-ICP-MS instrument with medium mass resolution (m/Δm ~ 3000). Standard-sample bracketing (SSB) was used to correct samples throughout the analytical sessions. Reference materials included an Alfa-S (ammonium sulfate) standard solution, ammonium sulfate provided by the lab of the authors and fresh seawater from the South China Sea. A range of matrix-matched Alfa-S standard solutions and ammonium sulfate solutions was used to investigate the matrix (salinity) effect (matrix was added in the form of NaCl). A seawater sample was used to confirm the reliability of the method. Using matrix-matched (salinity-matched) Alfa-S as the working standard, the measured δ(34)S value of AS (-6.73 ± 0.09‰) was consistent with the reference value (-6.78 ± 0.07‰) within the uncertainty, suggesting that this method could be recommended for the measurement of water samples without prior chemical purification. The δ(34)S value determination for the unpurified seawater also yielded excellent results (21.03 ± 0.18‰) that are consistent with the reference value (20.99‰), thus confirming the feasibility of the technique. The data and the results indicate that it is feasible to use MC-ICP-MS and matrix-matched working standards to measure the sulfur isotopic compositions of water samples directly without chemical purification. In comparison with the existing MC-ICP-MS techniques, the new method is better for directly measuring δ(34)S values in water samples with complex matrices; therefore, it can significantly accelerate analytical turnover. Copyright © 2014 John Wiley & Sons, Ltd.

Determination of nitroaromatic explosives and their degradation products in unsaturated-zone water samples by high-performance liquid chromatography with photodiode-array, mass spectrometric, and tandem mass spectrometric detection

USGS Publications Warehouse

Gates, Paul M.; Furlong, E.T.; Dorsey, T.F.; Burkhardt, M.R.

1996-01-01

Mass spectrometry and tandem mass spectrometry, coupled by a thermospray interface to a high-performance liguid chromatography system and equipped with a photodiode array detector, were used to determine the presence of nitroaromatic explosives and their degradation products in USA unsaturated-zone water samples. Using this approach, the lower limits of quantitation for explosives determined by mass spectrometry in this study typically ranged from 10 to 100 ng/l.

Assessment of bacteriological quality of drinking water from various sources in Amritsar district of northern India.

PubMed

Malhotra, Sita; Sidhu, Shailpreet K; Devi, Pushpa

2015-08-29

Safe water is a precondition for health and development and is a basic human right, yet it is still denied to hundreds of millions of people throughout the developing world. Water-related diseases caused by insufficient safe water supplies, coupled with poor sanitation and hygiene, cause 3.4 million deaths a year, mostly in children. The present study was conducted on 1,317 drinking water samples from various water sources in Amritsar district in northern India. All the samples were analyzed to assess bacteriological quality of water for presumptive coliform count by the multiple tube test. A total of 42.9% (565/1,317) samples from various sources were found to be unfit for human consumption. Of the total 565 unsatisfactory samples, 253 were from submersible pumps, 197 were from taps of piped supply (domestic/public), 79 were from hand pumps, and 36 were from various other sources A significantly high level of contamination was observed in samples collected from submersible pumps (47.6%) and water tanks (47.3%), as these sources of water are more exposed and liable to contamination. Despite continuous efforts by the government, civil society, and the international community, over a billion people still do not have access to improved water resources. Bacteriological assessment of all sources of drinking should be planned and conducted on regular basis to prevent waterborne dissemination of diseases.

Ionic liquid-salt aqueous two-phase extraction based on salting-out coupled with high-performance liquid chromatography for the determination of sulfonamides in water and food.

PubMed

Han, Juan; Wang, Yun; Liu, Yan; Li, Yanfang; Lu, Yang; Yan, Yongsheng; Ni, Liang

2013-02-01

Ionic liquid-salt aqueous two-phase extraction coupled with high-performance liquid chromatography with ultraviolet detection was developed for the determination of sulfonamides in water and food samples. In the procedure, the analytes were extracted from the aqueous samples into the ionic liquid top phase in one step. Three sulfonamides, sulfamerazine, sulfamethoxazole, and sulfamethizole were selected here as model compounds for developing and evaluating the method. The effects of various experimental parameters in extraction step were studied using two optimization methods, one variable at a time and Box-Behnken design. The results showed that the amount of sulfonamides did not have effect on the extraction efficiency. Therefore, a three-level Box-Behnken experimental design with three factors, which combined the response surface modeling, was used to optimize sulfonamides extraction. Under the most favorable extraction parameters, the detection limits (S/N = 3) and quantification limits (S/N = 10) of the proposed method for the target compounds were achieved within the range of 0.15-0.3 ng/mL and 0.5-1.0 ng/mL from spiked samples, respectively, which are lower than or comparable with other reported approaches applied to the determination of the same compounds. Finally, the proposed method was successfully applied to the determination of sulfonamide compounds in different water and food samples and satisfactory recoveries of spiked target compounds in real samples were obtained.

Development of a New Microextraction Fiber Combined to On-Line Sample Stacking Capillary Electrophoresis UV Detection for Acidic Drugs Determination in Real Water Samples.

PubMed

Espina-Benitez, Maria; Araujo, Lilia; Prieto, Avismelsi; Navalón, Alberto; Vílchez, José Luis; Valera, Paola; Zambrano, Ana; Dugas, Vincent

2017-07-07

A new analytical method coupling a (off-line) solid-phase microextraction with an on-line capillary electrophoresis (CE) sample enrichment technique was developed for the analysis of ketoprofen, naproxen and clofibric acid from water samples, which are known as contaminants of emerging concern in aquatic environments. New solid-phase microextraction fibers based on physical coupling of chromatographic supports onto epoxy glue coated needle were studied for the off-line preconcentration of these micropollutants. Identification and quantification of such acidic drugs were done by capillary zone electrophoresis (CZE) using ultraviolet diode array detection (DAD). Further enhancement of concentration sensitivity detection was achieved by on-line CE "acetonitrile stacking" preconcentration technique. Among the eight chromatographic supports investigated, Porapak Q sorbent showed higher extraction and preconcentration capacities. The screening of parameters that influence the microextraction process was carried out using a two-level fractional factorial. Optimization of the most relevant parameters was then done through a surface response three-factor Box-Behnken design. The limits of detection and limits of quantification for the three drugs ranged between 0.96 and 1.27 µg∙L -1 and 2.91 and 3.86 µg∙L -1 , respectively. Recovery yields of approximately 95 to 104% were measured. The developed method is simple, precise, accurate, and allows quantification of residues of these micropollutants in Genil River water samples using inexpensive fibers.

Development of a New Microextraction Fiber Combined to On-Line Sample Stacking Capillary Electrophoresis UV Detection for Acidic Drugs Determination in Real Water Samples

PubMed Central

Araujo, Lilia; Prieto, Avismelsi; Navalón, Alberto; Vílchez, José Luis; Valera, Paola; Zambrano, Ana; Dugas, Vincent

2017-01-01

A new analytical method coupling a (off-line) solid-phase microextraction with an on-line capillary electrophoresis (CE) sample enrichment technique was developed for the analysis of ketoprofen, naproxen and clofibric acid from water samples, which are known as contaminants of emerging concern in aquatic environments. New solid-phase microextraction fibers based on physical coupling of chromatographic supports onto epoxy glue coated needle were studied for the off-line preconcentration of these micropollutants. Identification and quantification of such acidic drugs were done by capillary zone electrophoresis (CZE) using ultraviolet diode array detection (DAD). Further enhancement of concentration sensitivity detection was achieved by on-line CE “acetonitrile stacking” preconcentration technique. Among the eight chromatographic supports investigated, Porapak Q sorbent showed higher extraction and preconcentration capacities. The screening of parameters that influence the microextraction process was carried out using a two-level fractional factorial. Optimization of the most relevant parameters was then done through a surface response three-factor Box-Behnken design. The limits of detection and limits of quantification for the three drugs ranged between 0.96 and 1.27 µg∙L−1 and 2.91 and 3.86 µg∙L−1, respectively. Recovery yields of approximately 95 to 104% were measured. The developed method is simple, precise, accurate, and allows quantification of residues of these micropollutants in Genil River water samples using inexpensive fibers. PMID:28686186

Metal-organic framework MIL-101 as sorbent based on double-pumps controlled on-line solid-phase extraction coupled with high-performance liquid chromatography for the determination of flavonoids in environmental water samples.

PubMed

Liu, Yue; Hu, Jia; Li, Yan; Li, Xiao-Shuang; Wang, Zhong-Liang

2016-10-01

A novel method with high sensitivity for the rapid determination of chrysin, apigenin and luteolin in environment water samples was developed by double-pumps controlled on-line solid-phase extraction (SPE) coupled with high-performance liquid chromatography (HPLC). In the developed technique, metal organic framework MIL-101 was synthesized and applied as a sorbent for SPE. The as-synthesized MIL-101 was characterized by scanning electron microscope, X-ray diffraction spectrometry, thermal gravimetric analysis and micropore physisorption analysis. The MIL-101 behaved as a fast kinetics in the adsorption of chrysin, apigenin and luteolin. On-line SPE of chrysin, apigenin and luteolin was processed by loading a sample solution at a flow rate of 1.0 mL/min for 10 min. The extracted analytes were subsequently eluted into a ZORBAX Bonus-RP analytical column (25 cm long × 4.6 mm i.d.) for HPLC separation under isocratic condition with a mobile phase (MeOH: ACN: 0.02 M H 3 PO 4 = 35:35:30) at a flow rate of 1.0 mL/min. Experimental conditions, including ionic strength, sample pH, sample loading rates, sample loading time and desorption analytes time, were further optimized to obtain efficient preconcentration and high-precision determination of the analytes mentioned above. The method achieved the merits of simplicity, rapidity, sensitivity, wide linear range and high sample throughput. The possible mechanism for the adsorption of flavonoids on MIL-101 was proposed. The developed method has been applied to determine trace chrysin, apigenin and luteolin in a variety of environmental water samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stable isotope dilution analysis of hydrologic samples by inductively coupled plasma mass spectrometry

USGS Publications Warehouse

Garbarino, John R.; Taylor, Howard E.

1987-01-01

Inductively coupled plasma mass spectrometry is employed in the determination of Ni, Cu, Sr, Cd, Ba, Ti, and Pb in nonsaline, natural water samples by stable isotope dilution analysis. Hydrologic samples were directly analyzed without any unusual pretreatment. Interference effects related to overlapping isobars, formation of metal oxide and multiply charged ions, and matrix composition were identified and suitable methods of correction evaluated. A comparability study snowed that single-element isotope dilution analysis was only marginally better than sequential multielement isotope dilution analysis. Accuracy and precision of the single-element method were determined on the basis of results obtained for standard reference materials. The instrumental technique was shown to be ideally suited for programs associated with certification of standard reference materials.

Seasonal and high-resolution variability in hydrochemistry of the Andes-Amazon

NASA Astrophysics Data System (ADS)

Burt, E.; West, A. J.

2017-12-01

Stream hydrochemistry acts as a record of integrated catchment processes such as the amount of time it takes precipitation to flow through the subsurface and become streamflow (water transit times), water-rock interaction and biogeochemical cycling. Although it is understood that sampling interval affects observed patterns in hydrochemistry, most studies collect samples on a weekly, bi-weekly or monthly schedule due to lack of resources or the difficulty of maintaining automated sampling devices. Here, we attempt to combine information from two sampling time scales, comparing a year-long hydrochemical time series to data from a recent sub-daily sampling campaign. Starting in April 2016, river, soil and rain waters have been collected every two weeks at five small catchments spanning the tropical Andes and Amazon - a natural laboratory for its gradients in topography, erosion rates, precipitation, temperature and flora. Between January and March, 2017, we conducted high frequency sampling for approximately one week at each catchment, sampling at least every four hours including overnight. We will constrain young water fractions (Kirchner, 2016) and storm water fluxes for the experimental catchments using stable isotopes of water as conservative tracers. Major element data will provide the opportunity to make initial constraints on geochemical and hydrologic coupling. Preliminary results suggest that in the Amazon, hydrochemistry patterns are dependent on sampling frequency: the seasonal cycle in stable isotopes of water is highly damped, while the high resolution sampling displays large variability. This suggests that a two-week sampling interval is not frequent enough to capture rapid transport of water, perhaps through preferential flow networks. In the Andes, stable isotopes of water are highly damped in both the seasonal and high resolution cycle, suggesting that the catchment behaves as a "well-mixed" system.

Nonequilibrium Phase Transitions in Supercooled Water

NASA Astrophysics Data System (ADS)

Limmer, David; Chandler, David

2012-02-01

We present results of a simulation study of water driven out of equilibrium. Using transition path sampling, we can probe stationary path distributions parameterize by order parameters that are extensive in space and time. We find that by coupling external fields to these parameters, we can drive water through a first order dynamical phase transition into amorphous ice. By varying the initial equilibrium distributions we can probe pathways for the creation of amorphous ices of low and high densities.

Arsenic exposure in drinking water: an unrecognized health threat in Peru

PubMed Central

Sima, Laura; Arias, M Helena Jahuira; Mihalic, Jana; Cabrera, Lilia Z; Danz, David; Checkley, William; Gilman, Robert H

2014-01-01

Abstract Objective To assess the extent of arsenic contamination of groundwater and surface water in Peru and, to evaluate the accuracy of the Arsenic Econo-Quick™ (EQ) kit for measuring water arsenic concentrations in the field. Methods Water samples were collected from 151 water sources in 12 districts of Peru, and arsenic concentrations were measured in the laboratory using inductively-coupled plasma mass spectrometry. The EQ field kit was validated by comparing a subset of 139 water samples analysed by laboratory measurements and the EQ kit. Findings In 86% (96/111) of the groundwater samples, arsenic exceeded the 10 µg/l arsenic concentration guideline given by the World Health Organization (WHO) for drinking water. In 56% (62/111) of the samples, it exceeded the Bangladeshi threshold of 50 µg/l; the mean concentration being 54.5 µg/l (range: 0.1–93.1). In the Juliaca and Caracoto districts, in 96% (27/28) of groundwater samples arsenic was above the WHO guideline; and in water samples collected from the section of the Rímac river running through Lima, all had arsenic concentrations exceeding the WHO limit. When validated against laboratory values, the EQ kit correctly identified arsenic contamination relative to the guideline in 95% (106/111) of groundwater and in 68% (19/28) of surface water samples. Conclusion In several districts of Peru, drinking water shows widespread arsenic contamination, exceeding the WHO arsenic guideline. This poses a public health threat requiring further investigation and action. For groundwater samples, the EQ kit performed well relative to the WHO arsenic limit and therefore could provide a vital tool for water arsenic surveillance. PMID:25177071

Hydrogeochemistry of the drinking water sources of Derebogazi Village (Kahramanmaras) and their effects on human health.

PubMed

Uras, Yusuf; Uysal, Yagmur; Arikan, Tugba Atilan; Kop, Alican; Caliskan, Mustafa

2015-06-01

The aim of this study was to investigate the sources of drinking water for Derebogazi Village, Kahramanmaras Province, Turkey, in terms of hydrogeochemistry, isotope geochemistry, and medical geology. Water samples were obtained from seven different water sources in the area, all of which are located within quartzite units of Paleozoic age, and isotopic analyses of (18)O and (2)H (deuterium) were conducted on the samples. Samples were collected from the region for 1 year. Water quality of the samples was assessed in terms of various water quality parameters, such as temperature, pH, conductivity, alkalinity, trace element concentrations, anion-cation measurements, and metal concentrations, using ion chromatography, inductively coupled plasma (ICP) mass spectrometry, ICP-optical emission spectrometry techniques. Regional health surveys had revealed that the heights of local people are significantly below the average for the country. In terms of medical geology, the sampled drinking water from the seven sources was deficient in calcium and magnesium ions, which promote bone development. Bone mineral density screening tests were conducted on ten females using dual energy X-ray absorptiometry to investigate possible developmental disorder(s) and potential for mineral loss in the region. Of these ten women, three had T-scores close to the osteoporosis range (T-score < -2.5).

Evaluation of on-line concentration coupled to liquid chromatography tandem mass spectrometry for the quantification of neonicotinoids and fipronil in surface water and tap water.

PubMed

Montiel-León, Juan Manuel; Duy, Sung Vo; Munoz, Gabriel; Amyot, Marc; Sauvé, Sébastien

2018-04-01

A study was initiated to investigate a fast and reliable method for the determination of selected systemic insecticides in water matrixes and to evaluate potential sources of bias in their analysis. Acetamiprid, clothianidin, desnitro-imidacloprid, dinotefuran, fipronil, imidacloprid, nitenpyram, thiacloprid, and thiamethoxam were amenable to analysis via on-line sample enrichment hyphenated to ultra-high-performance liquid chromatography tandem mass spectrometry. The selection of on-line solid-phase extraction parameters was dictated by a multicriterion desirability approach. A 2-mL on-line injection volume with a 1500 μL min -1 loading flow rate met the objectives sought in terms of chromatographic requirements, extraction efficiency, sensitivity, and precision. A total analysis time of 8 min per sample was obtained with method limits of detection in the range of 0.1-5 ng L -1 for the scope of targeted analytes. Automation at the sample concentration step yielded intraday and interday precisions in the range of 1-23 and 2-26%, respectively. Factors that could affect the whole method accuracy were further evaluated in matrix-specific experiments. The impact of the initial filtration step on analyte recovery was evaluated in ultra-pure water, tap water, and surface water. Out of the nine membranes tested, glass fiber filters and polyester filters appeared as the most appropriate materials. Sample storage stability was also investigated across the three matrix types; the targeted analytes displayed suitable stability during 28 days at either 4 °C or - 20 °C, with little deviations (± 10%) with respect to the initial T 0 concentration. Method applicability was demonstrated in a range of tap water and surface water samples from the province of Québec, Canada. Results from the present survey indicated a predominance of thiamethoxam (< 0.5-10 and 3-61 ng L -1 in tap water and river water, respectively), clothianidin (< 0.5-6 and 2-88 ng L -1 in tap water and river water, respectively), and imidacloprid (< 0.1-1 and 0.8-38 ng L -1 in tap water and river water, respectively) among the targeted analytes. Graphical abstract ᅟ Development of solid-phase extraction coupled on-line to UHPLC-MS/MS for the rapid screening of systemic insecticides in water.

Ternary and coupled binary zinc tin oxide nanopowders: Synthesis, characterization, and potential application in photocatalytic processes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ivetić, T.B., E-mail: tamara.ivetic@df.uns.ac.rs; Finčur, N.L.; Đačanin, Lj. R.

2015-02-15

Highlights: • Mechanochemically synthesized nanocrystalline zinc tin oxide (ZTO) powders. • Photocatalytic degradation of alprazolam in the presence of ZTO water suspensions. • Coupled binary ZTO exhibits enhanced photocatalytic activity compared to ternary ZTO. - Abstract: In this paper, ternary and coupled binary zinc tin oxide nanocrystalline powders were prepared via simple solid-state mechanochemical method. X-ray diffraction, scanning electron microscopy, Raman and reflectance spectroscopy were used to study the structure and optical properties of the obtained powder samples. The thermal behavior of zinc tin oxide system was examined through simultaneous thermogravimetric-differential scanning calorimetric analysis. The efficiencies of ternary (Zn{sub 2}SnO{submore » 4} and ZnSnO{sub 3}) and coupled binary (ZnO/SnO{sub 2}) zinc tin oxide water suspensions in the photocatalytic degradation of alprazolam, short-acting anxiolytic of the benzodiazepine class of psychoactive drugs, under UV irradiation were determined and compared with the efficiency of pure ZnO and SnO{sub 2}.« less

Re-evaluation and extension of the scope of elements in US Geological Survey Standard Reference Water Samples

USGS Publications Warehouse

Peart, D.B.; Antweiler, Ronald C.; Taylor, Howard E.; Roth, D.A.; Brinton, T.I.

1998-01-01

More than 100 US Geological Survey (USGS) Standard Reference Water Samples (SRWSs) were analyzed for numerous trace constituents, including Al, As, B, Ba, Be, Bi, Br, Cd, Cr, Co, Cu, I, Fe, Pb, Li, Mn, Mo, Ni, Rb, Sb, Se, Sr, Te, Tl, U, V, Zn and major elements (Ca, Mg, Na, SiO2, SO4, Cl) by inductively coupled plasma mass spectrometry and inductively coupled plasma atomic emission spectrometry. In addition, 15 USGS SRWSs and National Institute of Standards and Technology (NIST) standard reference material (SRM) 1641b were analyzed for mercury using cold vapor atomic fluorescence spectrometry. Also USGS SRWS Hg-7 was analyzed using isotope dilution-inductively coupled plasma mass spectrometry. The results were compared with the reported certified values of the following standard reference materials: NIST SRM 1643a, 1643b, 1643c and 1643d and National Research Council of Canada Riverine Water Reference Materials for Trace Metals SLRS-1, SLRS-2 and SLRS-3. New concentration values for trace and major elements in the SRWSs, traceable to the certified standards, are reported. Additional concentration values are reported for elements that were neither previously published for the SRWSs nor traceable to the certified reference materials. Robust statistical procedures were used that were insensitive to outliers. These data can be used for quality assurance/quality control purposes in analytical laboratories.

Microvolume trace environmental analysis using peak-focusing online solid-phase extraction-nano-liquid chromatography-high-resolution mass spectrometry.

PubMed

Stravs, Michael A; Mechelke, Jonas; Ferguson, P Lee; Singer, Heinz; Hollender, Juliane

2016-03-01

Online solid-phase extraction was combined with nano-liquid chromatography coupled to high-resolution mass spectrometry (HRMS) for the analysis of micropollutants in environmental samples from small volumes. The method was validated in surface water, Microcystis aeruginosa cell lysate, and spent Microcystis growth medium. For 41 analytes, quantification limits of 0.1-28 ng/L (surface water) and 0.1-32 ng/L (growth medium) were obtained from only 88 μL of sample. In cell lysate, quantification limits ranged from 0.1-143 ng/L or 0.33-476 ng/g dry weight from a sample of 88 μL, or 26 μg dry weight, respectively. The method matches the sensitivity of established online and offline solid-phase extraction-liquid chromatography-mass spectrometry methods but requires only a fraction of the sample used by those techniques, and is among the first applications of nano-LC-MS for environmental analysis. The method was applied to the determination of bioconcentration in Microcystis aeruginosa in a laboratory experiment, and the benefit of coupling to HRMS was demonstrated in a transformation product screening.

Resolution of rare earth element interferences in fossil energy by-product samples using sector-field ICP-MS

DOE PAGES

Thompson, Robert L.; Bank, Tracy; Roth, Elliot; ...

2016-07-30

Here, the supply and price of rare earth elements (REEs) have become a concern to many countries in the world, which has led to renewed interest in exploration and recovery of REEs from secondary or waste sources. Potential high REE waste sources that are of particular interest are coal mining, preparation, combustion, and other fossil energy by-products, including those from natural gas production. In this work, we have examined a set of five solid samples from the treatment of produced and flowback water containing elevated concentrations of barium. In order to confirm the correct concentrations of Eu, we studied thesemore » materials using sector field inductively coupled plasma mass spectrometry (SF-ICP-MS), which is capable of resolving species of nearly identical masses, including Eu and BaO. While the use of quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS) for the REE analysis of most geological sample matrices should pose no problem, the presence of large amounts of Ba, as encountered in water treatment solids from natural gas produced and flowback samples may require SF-ICP-MS for accurate determination of all REEs.« less

Rapid and direct determination of glyphosate, glufosinate, and aminophosphonic acid by online preconcentration CE with contactless conductivity detection.

PubMed

See, Hong Heng; Hauser, Peter C; Ibrahim, Wan Aini Wan; Sanagi, Mohd Marsin

2010-01-01

Rapid and direct online preconcentration followed by CE with capacitively coupled contactless conductivity detection (CE-C(4)D) is evaluated as a new approach for the determination of glyphosate, glufosinate (GLUF), and aminophosphonic acid (AMPA) in drinking water. Two online preconcentration techniques, namely large volume sample stacking without polarity switching and field-enhanced sample injection, coupled with CE-C(4)D were successfully developed and optimized. Under optimized conditions, LODs in the range of 0.01-0.1 microM (1.7-11.1 microg/L) and sensitivity enhancements of 48- to 53-fold were achieved with the large volume sample stacking-CE-C(4)D method. By performing the field-enhanced sample injection-CE-C(4)D procedure, excellent LODs down to 0.0005-0.02 microM (0.1-2.2 microg/L) as well as sensitivity enhancements of up to 245- to 1002-fold were obtained. Both techniques showed satisfactory reproducibility with RSDs of peak height of better than 10%. The newly established approaches were successfully applied to the analysis of glyphosate, glufosinate, and aminophosphonic acid in spiked tap drinking water.

De-coupling seasonal changes in water content and dry matter to predict live conifer foliar moisture content

Treesearch

W. Matt Jolly; Ann M. Hadlow; Kathleen Huguet

2014-01-01

Live foliar moisture content (LFMC) significantly influences wildland fire behaviour. However, characterising variations in LFMC is difficult because both foliar mass and dry mass can change throughout the season. Here we quantify the seasonal changes in both plant water status and dry matter partitioning. We collected new and old foliar samples from Pinus contorta for...

Coupling pervaporation to AAS for inorganic and organic mercury determination. A new approach to speciation of Hg in environmental samples.

PubMed

Fernandez-Rivas, C; Muñoz-Olivas, R; Camara, C

2001-12-01

The design and development of a new approach for Hg speciation in environmental samples is described in detail. This method, consisting of the coupling of pervaporation and atomic absorption spectrometry, is based on a membrane phenomenon that combines the evaporation of volatile analytes and their diffusion through a polymeric membrane. It is proposed here as an alternative to gas chromatography for speciation of inorganic and organic Hg compounds, as the latter compounds are volatile and can be separated by applying the principles mentioned above. The interest of this method lies in its easy handling, low cost, and rapidity for the analysis of liquid and solid samples. This method has been applied to Hg speciation in a compost sample provided by a waste water treatment plant.

Fast preconcentration of trace rare earth elements from environmental samples by di(2-ethylhexyl)phosphoric acid grafted magnetic nanoparticles followed by inductively coupled plasma mass spectrometry detection

NASA Astrophysics Data System (ADS)

Yan, Ping; He, Man; Chen, Beibei; Hu, Bin

2017-10-01

In this work, di(2-ethylhexyl)phosphoric acid (P204) grafted magnetic nanoparticles were synthesized by fabricating P204 onto Fe3O4@TiO2 nanoparticles based on Lewis acid-base interaction between Ti and phosphate group under weakly acidic condition. The prepared Fe3O4@TiO2@P204 nanoparticles exhibited excellent selectivity for rare earth elements, and good anti-interference ability. Based on it, a method of magnetic solid phase extraction (MSPE) combined with inductively coupled plasma mass spectrometry (ICP-MS) was developed for fast preconcentration and determination of trace rare earth elements in environmental samples. Under the optimal conditions, the detection limits of rare earth elements were in the range of 0.01 (Tm)-0.12 (Nd) ng L- 1 with an enrichment factor of 100-fold, and the relative standard deviations ranged from 4.9 (Pr) to 10.7% (Er). The proposed method was successfully applied to the determination of rare earth elements in environmental samples, including river water, lake water, seawater and sediment.

Method development and optimization for the determination of benzene, toluene, ethylbenzene and xylenes in water at trace levels by static headspace extraction coupled to gas chromatography-barrier ionization discharge detection.

PubMed

Pascale, Raffaella; Bianco, Giuliana; Calace, Stefania; Masi, Salvatore; Mancini, Ignazio M; Mazzone, Giuseppina; Caniani, Donatella

2018-05-04

Benzene, toluene, ethylbenzene, and xylenes, more commonly named BTEX, represent one of the most ubiquitous and hazardous groups of atmospheric pollutants. The goal of our research was the trace quantification of BTEX in water by using a new simple, low-cost, and accurate method, based on headspace (HS) extraction and gas chromatography (GC) coupled to barrier ionization discharge detector (BID). This water application dealt with simple matrices without protein, fat, or humic material that adsorb target analytes, thus the external standard calibration was suitable to quantify each compound. The validation steps included the study of linearity, detection and quantification limits, and accuracy. LODs and LOQs varied from 0.159 to 1.845 μg/L and from 0.202 to 2.452 μg/L, respectively. The recovery was between 0.74 ± 0.13 and 1.15 ± 0.09; relative standard deviations (% RDSs) were less than 12.81% (n = 5) and 14.84% (n = 10). Also, GC performance was evaluated in term of efficiency, peak tailing and resolution. Preliminary results from practical applications to analyses of real samples are presented. The results indicate that static HS coupled to GC-BID is a successful method for BTEX analysis in water samples at the μg/L levels, provided that hydrocarbons interference occur at similar concentration levels. GC-BID may become a routine reference method alongside the official analytical techniques for quality control purposes of contaminated waters. Moreover, the new method is amenable to automation by using commercial HS units. Copyright © 2018. Published by Elsevier B.V.

HPLC-PFD determination of priority pollutant PAHs in water, sediment, and semipermeable membrane devices

USGS Publications Warehouse

Williamson, K.S.; Petty, J.D.; Huckins, J.N.; Lebo, J.A.; Kaiser, E.M.

2002-01-01

High performance liquid chromatography coupled with programmable fluorescence detection was employed for the determination of 15 priority pollutant polycyclic aromatic hydrocarbons (PPPAHs) in water, sediment, and semipermeable membrane devices (SPMDs). Chromatographic separation using this analytical method facilitates selectivity, sensitivity (ppt levels), and can serve as a non-destructive technique for subsequent analysis by other chromatographic and spectroscopic techniques. Extraction and sample cleanup procedures were also developed for water, sediment, and SPMDs using various chromatographic and wet chemical methods. The focus of this publication is to examine the enrichment techniques and the analytical methodologies used in the isolation, characterization, and quantitation of 15 PPPAHs in different sample matrices.

Membrane inlet laser spectroscopy to measure H and O stable isotope compositions of soil and sediment pore water with high sample throughput

DOE PAGES

Oerter, Erik J.; Perelet, Alexei; Pardyjak, Eric; ...

2016-10-20

Here, the fast and accurate measurement of H and O stable isotope compositions (δ 2H and δ 18O values) of soil and sediment pore water remains an impediment to scaling-up the application of these isotopes in soil and vadose hydrology. Here we describe a method and its calibration to measuring soil and sediment pore water δ 2H and δ 18O values using a water vapor-permeable probe coupled to an isotope ratio infrared spectroscopy analyzer.

Hyperspectral Remote Sensing of the Coastal Ocean: Adaptive Sampling and Forecasting of In situ Optical Properties

DTIC Science & Technology

2002-09-30

integrated observation system that is being coupled to a data assimilative hydrodynamic bio-optical ecosystem model. The system was used adaptively to develop hyperspectral remote sensing techniques in optically complex nearshore coastal waters.

Inductively coupled plasma optical emission spectrometry for trace multi-element determination in vegetable oils, margarine and butter after stabilization with propan-1-ol and water

NASA Astrophysics Data System (ADS)

de Souza, Roseli M.; Mathias, Bárbara M.; da Silveira, Carmem Lúcia P.; Aucélio, Ricardo Q.

2005-06-01

The quantitative evaluation of trace elements in foodstuffs is of considerable interest due to the potential toxicity of many elements, and because the presence of some metallic species might affect the overall quality (flavor and stability) of these products. In the present work, an inductively coupled plasma optical emission spectrometric method has been developed for the determination of six elements (Cd, Co, Cr, Cu, Ni and Mn) in olive oil, soy oil, margarine and butter. Organic samples (oils and fats) were stabilized using propan-1-ol and water, which enabled long-time sample dispersion in the solution. This simple sample preparation procedure, together with an efficient sample introduction strategy (using a Meinhard K3 nebulizer and a twister cyclonic spray chamber), facilitated the overall analytical procedure, allowing quantification using calibration curves prepared with inorganic standards. Internal standardization (Sc) was used for correction of matrix effects and signal fluctuations. Good sensitivities with limits of detection in the ng g -1 range were achieved for all six elements. These sensitivities were appropriate for the intended application. The method was tested through the analysis of laboratory-fortified samples with good recoveries (between 91.3% and 105.5%).

Ionic liquid foam floatation coupled with solid phase extraction for separation and determination of hormones by high-performance liquid chromatography.

PubMed

Zhang, Rui; Li, Na; Wang, Chuanliu; Bai, Yuping; Ren, Ruibing; Gao, Shiqian; Yu, Wenzhi; Zhao, Tianqi; Zhang, Hanqi

2011-10-17

The foaming property of ionic liquids (ILs) was found and the factors that can influence foamability of the ILs were investigated. Based on the property of the ILs, the foam floatation-solid phase extraction (FF-SPE) was developed. The IL-based FF-SPE was applied to the extraction and concentration of steroid hormones, including corticosterone, 17-β-estadiol, 17-α-estradiol, 19-nortestosterone, estrone, testosterone, 17-α-hydroxyprogesterone, medroxyprogesterone, chloromadinon 17-acetate, norethisterone acetate, medroxyprogesterone-17-acetate, progesterone, 17-β-estradiol 3-benzoate and testosteron 17-propionate in water samples and then the steroid hormones were determined by high-performance liquid chromatography. The extraction and concentration were performed synchronously in 10 min. Some experimental conditions were examined and optimized. The recoveries ranged from 50.6% to 95.2% for lake water sample and from 53.4% to 98.7% for rain water sample. The precision ranged from 2.43% to 7.43% for the lake water sample and 2.07-7.01% for rain water sample. Based on the foaming property of ILs, the application of foam floatation should be widened. Copyright © 2011 Elsevier B.V. All rights reserved.

Influences of coal mining water irrigation on the maize losses in the Xingdong Mine area, China.

PubMed

Sun, Yuzhuang; Ling, Pei; Li, Yanheng; Li, Qingxue; Sun, Quande; Wang, Jinxi

2014-02-01

In 2008, a maize underproduction disaster occurred in the Xianyu village after irrigation using the coal mining water from the Xingdong Mine, China. This disaster resulted in about 40 hectare maize underproduction and 20 hectare total loss of the maize yields. In order to study the reason, a total of 25 soil, water and plant samples were taken from the study area. These samples were analysed by inductively coupled plasma mass spectrometry and ion chromatography. The results indicate that the contents of both water-soluble fluorine and total fluorine are very high and resulting of maize underproduction and total loss of production. The possible pollution sources of fluorine in the study area could be from the coal mine water used for irrigation and glass chemical factory near the study area.

Statistical evaluation of an inductively coupled plasma atomic emission spectrometric method for routine water quality testing

USGS Publications Warehouse

Garbarino, J.R.; Jones, B.E.; Stein, G.P.

1985-01-01

In an interlaboratory test, inductively coupled plasma atomic emission spectrometry (ICP-AES) was compared with flame atomic absorption spectrometry and molecular absorption spectrophotometry for the determination of 17 major and trace elements in 100 filtered natural water samples. No unacceptable biases were detected. The analysis precision of ICP-AES was found to be equal to or better than alternative methods. Known-addition recovery experiments demonstrated that the ICP-AES determinations are accurate to between plus or minus 2 and plus or minus 10 percent; four-fifths of the tests yielded average recoveries of 95-105 percent, with an average relative standard deviation of about 5 percent.

Behavior of quizalofop-p and its commercial products in water by liquid chromatography coupled to high resolution mass spectrometry.

PubMed

López-Ruiz, Rosalía; Romero-González, Roberto; Martínez Vidal, José Luis; Garrido Frenich, Antonia

2018-08-15

A degradation study of quizalofop-p and its commercial products (quizalofop-p-ethyl, quizalofop-p-tefuryl and propaquizafop) in water samples has been performed using ultra high-performance liquid chromatography coupled to Orbitrap mass spectrometry (UHPLC-Orbitrap-MS). CHHQ (dihydroxychloroquinoxalin), CHQ (6-chloroquinoxalin-2-ol) and PPA ((R)-2-(4-hydroxyphenoxy)propionicacid) were the main metabolites of this active substance (quizalofop-p) in water. The degradation of the parent compound has been monitored in distilled water. Several commercial products (Panarex®, Master-D® and Dixon®) were used to evaluate the degradation of the target compounds into their metabolites. The concentration of the main active substances (quizalofop-p-tefuryl, quizalofop-p-ethyl and propaquizafop) decreased during the degradation studies, whereas the concentration of quizalofop-p increased. DT 50 of the main active substances ranged from 10 days to 70 days for most of the analytes, so it can be concluded that compounds are medium-high persistent in this matrix. Metabolites, such as PPA, CHHQ and CHQ, were detected in water samples after 7 days of the application of the commercial products at concentrations higher than their limits of quantification (> 0.1 µg/L). CHQ was detected at 1400 µg/L after 75 days of the application of quizalofop-p-ethyl commercial product. CHHQ and CHQ were found at the highest concentrations at 7-45 days after the application of quizalofop-p-tefuryl, whereas PPA was detected at higher concentrations (up to 5.37 µg/L) in propaquizafop samples. Copyright © 2018 Elsevier Inc. All rights reserved.

Determination of glyphosate and AMPA in surface and waste water using high-performance ion chromatography coupled to inductively coupled plasma dynamic reaction cell mass spectrometry (HPIC-ICP-DRC-MS).

PubMed

Popp, Maximilian; Hann, Stephan; Mentler, Axel; Fuerhacker, Maria; Stingeder, Gerhard; Koellensperger, Gunda

2008-05-01

A novel method employing high-performance cation chromatography in combination with inductively coupled plasma dynamic reaction cell mass spectrometry (ICP-DRC-MS) for the simultaneous determination of the herbicide glyphosate (N-phosphonomethylglycine) and its main metabolite aminomethyl phosphonic acid (AMPA) is presented. P was measured as (31)P(16)O(+) using oxygen as reaction gas. For monitoring the stringent target value of 0.1 μg L(-1) for glyphosate, applicable for drinking and surface water within the EU, a two-step enrichment procedure employing Chelex 100 and AG1-X8 resins was applied prior to HPIC-ICP-MS analysis. The presented approach was validated for surface water, revealing concentrations of 0.67 μg L(-1) glyphosate and 2.8 μg L(-1) AMPA in selected Austrian river water samples. Moreover, investigations at three waste water-treatment plants showed that elimination of the compounds at the present concentration levels was not straightforward. On the contrary, all investigated plant effluents showed significant amounts of both compounds. Concentration levels ranged from 0.5-2 μg L(-1) and 4-14 μg L(-1) for glyphosate and AMPA, respectively.

Total and Viable Legionella pneumophila Cells in Hot and Natural Waters as Measured by Immunofluorescence-Based Assays and Solid-Phase Cytometry ▿†

PubMed Central

Parthuisot, N.; Binet, M.; Touron-Bodilis, A.; Pougnard, C.; Lebaron, P.; Baudart, J.

2011-01-01

A new method was developed for the rapid and sensitive detection of viable Legionella pneumophila. The method combines specific immunofluorescence (IF) staining using monoclonal antibodies with a bacterial viability marker (ChemChrome V6 cellular esterase activity marker) by means of solid-phase cytometry (SPC). IF methods were applied to the detection and enumeration of both the total and viable L. pneumophila cells in water samples. The sensitivity of the IF methods coupled to SPC was 34 cells liter−1, and the reproducibility was good, with the coefficient of variation generally falling below 30%. IF methods were applied to the enumeration of total and viable L. pneumophila cells in 46 domestic hot water samples as well as in cooling tower water and natural water samples, such as thermal spring water and freshwater samples. Comparison with standard plate counts showed that (i) the total direct counts were always higher than the plate counts and (ii) the viable counts were higher than or close to the plate counts. With domestic hot waters, when the IF assay was combined with the viability test, SPC detected up to 3.4 × 103 viable but nonculturable L. pneumophila cells per liter. These direct IF methods could be a powerful tool for high-frequency monitoring of domestic hot waters or for investigating the occurrence of viable L. pneumophila in both man-made water systems and environmental water samples. PMID:21742913

Quantification of soil water retention parameters using multi-section TDR-waveform analysis

NASA Astrophysics Data System (ADS)

Baviskar, S. M.; Heimovaara, T. J.

2017-06-01

Soil water retention parameters are important for describing flow in variably saturated soils. TDR is one of the standard methods used for determining water content in soil samples. In this study, we present an approach to estimate water retention parameters of a sample which is initially saturated and subjected to an incremental decrease in boundary head causing it to drain in a multi-step fashion. TDR waveforms are measured along the height of the sample at assumed different hydrostatic conditions at daily interval. The cumulative discharge outflow drained from the sample is also recorded. The saturated water content is obtained using volumetric analysis after the final step involved in multi-step drainage. The equation obtained by coupling the unsaturated parametric function and the apparent dielectric permittivity is fitted to a TDR wave propagation forward model. The unsaturated parametric function is used to spatially interpolate the water contents along TDR probe. The cumulative discharge outflow data is fitted with cumulative discharge estimated using the unsaturated parametric function. The weight of water inside the sample estimated at the first and final boundary head in multi-step drainage is fitted with the corresponding weights calculated using unsaturated parametric function. A Bayesian optimization scheme is used to obtain optimized water retention parameters for these different objective functions. This approach can be used for samples with long heights and is especially suitable for characterizing sands with a uniform particle size distribution at low capillary heads.

Estimation of Heavy Metal Contamination in Groundwater and Development of a Heavy Metal Pollution Index by Using GIS Technique.

PubMed

Tiwari, Ashwani Kumar; Singh, Prasoon Kumar; Singh, Abhay Kumar; De Maio, Marina

2016-04-01

Heavy metal (Al, As, Ba, Cr, Cu, Fe, Mn, Ni, Se and Zn) concentration in sixty-six groundwater samples of the West Bokaro coalfield were analyzed using inductively coupled plasma-mass spectroscopy for determination of seasonal fluctuation, source apportionment and heavy metal pollution index (HPI). Metal concentrations were found higher in the pre-monsoon season as compared to the post-monsoon season. Geographic information system (GIS) tool was attributed to study the metals risk in groundwater of the West Bokaro coalfield. The results show that 94 % of water samples were found as low class and 6 % of water samples were in medium class in the post-monsoon season. However, 79 % of water samples were found in low class, 18 % in medium class and 3 % in high class in the pre-monsoon season. The HPI values were below the critical pollution index value of 100. The concentrations of Al, Fe, Mn, and Ni are exceeding the desirable limits in many groundwater samples in both seasons.

Direct quantification of test bacteria in synthetic water-polluted samples by square wave voltammetry and chemometric methods.

PubMed

Carpani, Irene; Conti, Paolo; Lanteri, Silvia; Legnani, Pier Paolo; Leoni, Erica; Tonelli, Domenica

2008-02-28

A home-made microelectrode array, based on reticulated vitreous carbon, was used as working electrode in square wave voltammetry experiments to quantify the bacterial load of Escherichia coli ATCC 13706 and Pseudomonas aeruginosa ATCC 27853, chosen as test microorganisms, in synthetic samples similar to drinking water (phosphate buffer). Raw electrochemical signals were analysed with partial least squares regression coupled to variable selection in order to correlate these values with the bacterial load estimated by aerobic plate counting. The results demonstrated the ability of the method to detect even low loads of microorganisms in synthetic water samples. In particular, the model detects the bacterial load in the range 3-2,020 CFU ml(-1) for E. coli and in the range 76-155,556 CFU ml(-1) for P. aeruginosa.

Simultaneous determination of estrogenic odorant alkylphenols, chlorophenols, and their derivatives in water using online headspace solid phase microextraction coupled with gas chromatography-mass spectrometry.

PubMed

Yuan, Su-Fen; Liu, Ze-Hua; Lian, Hai-Xian; Yang, Chuangtao; Lin, Qing; Yin, Hua; Dang, Zhi

2016-10-01

A simple online headspace solid-phase microextraction (HS-SPME) coupled with the gas chromatography-mass spectrometry (GC-MS) method was developed for simultaneous determination of trace amounts of nine estrogenic odorant alkylphenols and chlorophenols and their derivatives in water samples. The extraction conditions of HS-SPME were optimized including fiber selection, extraction temperature, extraction time, and salt concentration. Results showed that divinylbenzene/Carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber was the most appropriate one among the three selected commercial fibers, and the optimal extraction temperature, time, and salt concentration were 70 °C, 30 min, and 0.25 g/mL, respectively. The developed method was validated and showed good linearity (R (2) > 0.989), low limit of detection (LOD, 0.002-0.5 μg/L), and excellent recoveries (76-126 %) with low relative standard deviation (RSD, 0.7-12.9 %). The developed method was finally applied to two surface water samples and some of these target compounds were detected. All these detected compounds were below their odor thresholds, except for 2,4,6-TCAS and 2,4,6-TBAS wherein their concentrations were near their odor thresholds. However, in the two surface water samples, these detected compounds contributed to a certain amount of estrogenicity, which seemed to suggest that more attention should be paid to the issue of estrogenicity rather than to the odor problem.

APPLICATION OF MULTISPECTRAL TECHNIQUES TO THE PRECISE IDENTIFICATION OF ALDEHYDES IN THE ENVIRONMENT

EPA Science Inventory

By using gas chromatography coupled with low- and high-resolution electron impact mass spectrometry, low- and high-resolution chemical ionization mass spectrometry, and Fourier transform infrared spectroscopy, eight straight-chain aldehydes were identified in a water sample taken...

AUTOMATED ANALYSIS OF AQUEOUS SAMPLES CONTAINING PESTICIDES, ACIDIC/BASIC/NEUTRAL SEMIVOLATILES AND VOLATILE ORGANIC COMPOUNDS BY SOLID PHASE EXTRACTION COUPLED IN-LINE TO LARGE VOLUME INJECTION GC/MS

EPA Science Inventory

Data is presented on the development of a new automated system combining solid phase extraction (SPE) with GC/MS spectrometry for the single-run analysis of water samples containing a broad range of organic compounds. The system uses commercially available automated in-line 10-m...

Multivariate curve resolution-assisted determination of pseudoephedrine and methamphetamine by HPLC-DAD in water samples.

PubMed

Vosough, Maryam; Mohamedian, Hadi; Salemi, Amir; Baheri, Tahmineh

2015-02-01

In the present study, a simple strategy based on solid-phase extraction (SPE) with a cation exchange sorbent (Finisterre SCX) followed by fast high-performance liquid chromatography (HPLC) with diode array detection coupled with chemometrics tools has been proposed for the determination of methamphetamine and pseudoephedrine in ground water and river water. At first, the HPLC and SPE conditions were optimized and the analytical performance of the method was determined. In the case of ground water, determination of analytes was successfully performed through univariate calibration curves. For river water sample, multivariate curve resolution and alternating least squares was implemented and the second-order advantage was achieved in samples containing uncalibrated interferences and uncorrected background signals. The calibration curves showed good linearity (r(2) > 0.994).The limits of detection for pseudoephedrine and methamphetamine were 0.06 and 0.08 μg/L and the average recovery values were 104.7 and 102.3% in river water, respectively. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Electron, proton and hydrogen-atom transfers in photosynthetic water oxidation.

PubMed Central

Tommos, Cecilia

2002-01-01

When photosynthetic organisms developed so that they could use water as an electron source to reduce carbon dioxide, the stage was set for efficient proliferation. Algae and plants spread globally and provided the foundation for our atmosphere and for O(2)-based chemistry in biological systems. Light-driven water oxidation is catalysed by photosystem II, the active site of which contains a redox-active tyrosine denoted Y(Z), a tetramanganese cluster, calcium and chloride. In 1995, Gerald Babcock and co-workers presented the hypothesis that photosynthetic water oxidation occurs as a metallo-radical catalysed process. In this model, the oxidized tyrosine radical is generated by coupled proton/electron transfer and re-reduced by abstracting hydrogen atoms from substrate water or hydroxide-ligated to the manganese cluster. The proposed function of Y(Z) requires proton transfer from the tyrosine site upon oxidation. The oxidation mechanism of Y(Z) in an inhibited and O(2)-evolving photosystem II is discussed. Domino-deprotonation from Y(Z) to the bulk solution is shown to be consistent with a variety of data obtained on metal-depleted samples. Experimental data that suggest that the oxidation of Y(Z) in O(2)-evolving samples is coupled to proton transfer in a hydrogen-bonding network are described. Finally, a dielectric-dependent model for the proton release that is associated with the catalytic cycle of photosystem II is discussed. PMID:12437877

Determination of organophosphorus pesticides in bovine tissue by an on-line coupled matrix solid-phase dispersion-solid phase extraction-high performance liquid chromatography with diode array detection method.

PubMed

Gutiérrez Valencia, Tania M; García de Llasera, Martha P

2011-09-28

A miniaturized method based on matrix solid-phase dispersion coupled to solid phase extraction and high performance liquid chromatography with diode array detection (MSPD-SPE-HPLC/DAD) was developed for the trace simultaneous determination of the following organophosphorus pesticides (OPPs) in bovine tissue: parathion-methyl, fenitrothion, parathion, chlorfenvinphos, diazinon, ethion, fenchlorphos, chlorpyrifos and carbophenothion. To perform the coupling between MSPD and SPE, 0.05 g of sample was dispersed with 0.2 g of C(18) silica sorbent and packed into a stainless steel cartridge containing 0.05 g of silica gel in the bottom. After a clean-up of high and medium polarity interferences with water and an acetonitrile:water mixture, the OPPs were desorbed from the MSPD cartridge with pure acetonitrile and directly transferred to a dynamic mixing chamber for dilution with water and preconcentration into an SPE 20 mm × 2.0 mm I.D. C(18) silica column. Subsequently, the OPPs were eluted on-line with the chromatographic mobile phase to the analytical column and the diode array detector for their separation and detection, respectively. The method was validated and yielded recovery values between 91% and 101% and precision values, expressed as relative standard deviations (RSD), which were less than or equal to 12%. Linearity was good and ranged from 0.5 to 10 μg g(-1), and the limits of detection of the OPPs were in the range of 0.04-0.25 μg g(-1). The method was satisfactorily applied to the analysis of real samples and is recommended for food control, research efforts when sample amounts are limited, and laboratories that have ordinary chromatographic instrumentation. Copyright © 2011 Elsevier B.V. All rights reserved.

Sensitive determination of polycyclic aromatic hydrocarbons in water samples by HPLC coupled with SPE based on graphene functionalized with triethoxysilane.

PubMed

Huang, Ke-Jing; Li, Jing; Liu, Yan-Ming; Wang, Lan

2013-02-01

The graphene functionalized with (3-aminopropyl) triethoxysilane was synthesized by a simple hydrothermal reaction and applied as SPE sorbents to extract trace polycyclic aromatic hydrocarbons (PAHs) from environmental water samples. These sorbents possess high adsorption capacity and extraction efficiency due to strong adsorption ability of carbon materials and large specific surface area of nanoparticles, and only 10 mg of sorbents are required to extract PAHs from 100 mL water samples. Several condition parameters, such as eluent and its volume, adsorbent amount, sample volume, sample pH, and sample flow rate, were optimized to achieve good sensitivity and precision. Under the optimized extraction conditions, the method showed good linearity in the range of 1-100 μg/L, repeatability of the extraction (the RSDs were between 1.8 and 2.9%, n = 6), and satisfactory detection limits of 0.029-0.1 μg/L. The recoveries of PAHs spiked in environmental water samples ranged from 84.6 to 109.5%. All these results demonstrated that this new SPE technique was a viable alternative to conventional enrichment techniques for the extraction and analysis of PAHs in complex samples. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of tributyltin in whole water matrices under the European Water Framework Directive.

PubMed

Richter, Janine; Fettig, Ina; Philipp, Rosemarie; Jakubowski, Norbert; Panne, Ulrich; Fisicaro, Paola; Alasonati, Enrica

2016-08-12

Monitoring of water quality is important to control water pollution. Contamination of the aquatic system has a large effect on human health and the environment. Under the European Water Framework Directive (WFD) 2000/60/EC and the related directive on environmental quality standards (EQS) in the field of water policy 2008/105/EC, the need for sensitive reference methods was highlighted. Since tributyltin (TBT) is one of the WFD listed priority substances a method was developed which is capable to qualify and quantify the pollutant at the required low WFD EQS of 0.2ngL(-1) in whole water bodies, i.e. in non-filtered water samples with dissolved organic carbon and suspended particulate matter. Therefore special attention was paid on the interaction of TBT with the suspended particulate matter and humic substances to obtain a complete representation of the pollution in surface waters. Different water samples were investigated varying the content of organic dissolved and suspended matter. Quantification was performed using species-specific isotope dilution (SSID) and gas chromatography with inductively coupled plasma mass spectrometry (GC-ICP-MS). Different sample treatment strategies were evaluated and compared. The process of internal standard addition was investigated and optimized, hence the equilibrium between internal standards and matrix is of primary importance to perform accurate SSID. Samples spiked at EQS level were analyzed with a recovery between 95 and 105 %. Additionally real surface water samples were investigated and the TBT concentration for the whole water body was determined and compared with conventional routine analysis method. Copyright © 2016 Elsevier B.V. All rights reserved.

Authenticity screening of seized whiskey samples using electrophoresis microchips coupled with contactless conductivity detection.

PubMed

Rezende, Kariolanda C A; Moreira, Roger Cardoso; Logrado, Lucio Paulo Lima; Talhavini, Márcio; Coltro, Wendell K T

2016-10-01

This report describes for the first time the use of microchip electrophoresis (ME) devices integrated with capacitively coupled contactless conductivity detection (C 4 D) to investigate the authenticity of seized whiskey samples, which were probably adulterated by simple dilution with tap water. The proposed microfluidic platform was explored for the monitoring of anionic species (Cl - and F - ) in both original and tampered samples. The best separations were achieved within 70 s using a running buffer composed of lactic acid and histidine (pH = 5.9). ME-C 4 D devices were used to analyze samples from three different brands (five samples each). Based on the presence of inorganic anions like Cl - , F - , SO 4 2- and NO 2 - in different amounts, the authenticity of seized whiskeys was compared to original samples. According to the reported data, the proposed microfluidic platform can be useful to help regulatory authorities in the investigation and monitoring of authenticity of commercialized whiskey beverages. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fast analysis of quaternary ammonium pesticides in food and beverages using cation-exchange chromatography coupled with isotope-dilution high-resolution mass spectrometry.

PubMed

Nardin, Tiziana; Barnaba, Chiara; Abballe, Franco; Trenti, Gianmaria; Malacarne, Mario; Larcher, Roberto

2017-10-01

A fast separation based on cation-exchange liquid chromatography coupled with high-resolution mass spectrometry is proposed for simultaneous determination of chlormequat, difenzoquat, diquat, mepiquat and paraquat in several food and beverage commodities. Solid samples were extracted using a mixture of water/methanol/formic acid (69.6:30:0.4, v/v/v), while liquid samples were ten times diluted with the same solution. Separation was carried out on an experimental length-modified IonPac CS17 column (2 × 15 mm 2 ) that allowed the use of formic acid and acetonitrile as mobile phase. Detection limits for food and beverage matrices were established at 1.5 μg/L for chlormequat, difenzoquat and mepiquat, and 3 μg/L for diquat and paraquat, while for drinking water a pre-analytical sample concentration allowed detection limits of 9 and 20 ng/L, respectively. Precision, as repeatability (RSD%), ranged from 0.2 to 24%, with a median value of 6%, and trueness, as recovery, ranged from 64 to 118%, with a median value of 96%. The method developed was successfully applied to investigate the presence of herbicide residues in commercial commodities (mineral water, orange juice, beer, tea, green coffee bean, toasted coffee powder, cocoa bean, white corn flour, rice and sugar samples). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chitosan-based water-propelled micromotors with strong antibacterial activity.

PubMed

Delezuk, Jorge A M; Ramírez-Herrera, Doris E; Esteban-Fernández de Ávila, Berta; Wang, Joseph

2017-02-09

A rapid and efficient micromotor-based bacteria killing strategy is described. The new antibacterial approach couples the attractive antibacterial properties of chitosan with the efficient water-powered propulsion of magnesium (Mg) micromotors. These Janus micromotors consist of Mg microparticles coated with the biodegradable and biocompatible polymers poly(lactic-co-glycolic acid) (PLGA), alginate (Alg) and chitosan (Chi), with the latter responsible for the antibacterial properties of the micromotor. The distinct speed and efficiency advantages of the new micromotor-based environmentally friendly antibacterial approach have been demonstrated in various control experiments by treating drinking water contaminated with model Escherichia coli (E. coli) bacteria. The new dynamic antibacterial strategy offers dramatic improvements in the antibacterial efficiency, compared to static chitosan-coated microparticles (e.g., 27-fold enhancement), with a 96% killing efficiency within 10 min. Potential real-life applications of these chitosan-based micromotors for environmental remediation have been demonstrated by the efficient treatment of seawater and fresh water samples contaminated with unknown bacteria. Coupling the efficient water-driven propulsion of such biodegradable and biocompatible micromotors with the antibacterial properties of chitosan holds great considerable promise for advanced antimicrobial water treatment operation.

Investigation of drinking water quality in Kosovo.

PubMed

Berisha, Fatlume; Goessler, Walter

2013-01-01

In the recent years, not much environmental monitoring has been conducted in the territory of Kosovo. This study represents the first comprehensive monitoring of the drinking water situation throughout most of the territory of Kosovo. We present the distribution of major and minor trace elements in drinking water samples from Kosovo. During our study we collected 951 samples from four different sources: private-bored wells; naturally flowing artesian water; pumped-drilled wells; and public water sources (tap water). The randomly selected drinking water samples were investigated by routine water analyses using inductively coupled plasma mass spectrometry (ICPMS) for 32 elements (Li, Be, B, Na, Mg, Al, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Rb, Sr, Mo, Ag, Cd, Sn, Sb, Te, Ba, Tl, Pb, Bi, Th, U). Even though there are set guidelines for elemental exposure in drinking water worldwide, in developing countries, such as Kosovo, the lack of monitoring drinking water continues to be an important health concern. This study reports the concentrations of major and minor elements in the drinking water in Kosovo. Additionally, we show the variation of the metal concentration within different sources. Of the 15 regulated elements, the following five elements: Mn, Fe, Al, Ni, As, and U were the elements which most often exceeded the guidelines set by the EU and/or WHO.

Automation of preparation of nonmetallic samples for analysis by atomic absorption and inductively coupled plasma spectrometry

NASA Technical Reports Server (NTRS)

Wittmann, A.; Willay, G.

1986-01-01

For a rapid preparation of solutions intended for analysis by inductively coupled plasma emission spectrometry or atomic absorption spectrometry, an automatic device called Plasmasol was developed. This apparatus used the property of nonwettability of glassy C to fuse the sample in an appropriate flux. The sample-flux mixture is placed in a composite crucible, then heated at high temperature, swirled until full dissolution is achieved, and then poured into a water-filled beaker. After acid addition, dissolution of the melt, and filling to the mark, the solution is ready for analysis. The analytical results obtained, either for oxide samples or for prereduced iron ores show that the solutions prepared with this device are undistinguished from those obtained by manual dissolutions done by acid digestion or by high temperature fusion. Preparation reproducibility and analytical tests illustrate the performance of Plasmasol.

Geochemical modelling and speciation studies of metal pollutants present in selected water systems in South Africa

NASA Astrophysics Data System (ADS)

Magu, M. M.; Govender, P. P.; Ngila, J. C.

2016-04-01

Metal pollutants in water poses great threats to living beings and hence requires to be monitored regularly to avoid loss of lives. Various analytical methods are available to monitor these pollutants in water and can be improved with time. Modelling of metal pollutants in any water system helps chemists, engineers and environmentalists to greatly understand the various chemical processes in such systems. Water samples were collected from waste water treatment plant and river from highlands close to its source all the way to the ocean as it passing through areas with high anthropogenic activities. Pre-concentration of pollutants in the samples was done through acid digestion and metal pollutants were analysed using inductively coupled plasma-optical emission spectra (ICP-OES) to determine the concentration levels. Metal concentrations ranged between 0.1356-0.4658 mg/L for Al; 0.0031-0.0050 mg/L for Co, 0.0019-0.0956 mg/L for Cr; 0.0028-0.3484 mg/L for Cu; 0.0489-0.3474 mg/L for Fe; 0.0033-0.0285 mg/L for Mn; 0.0056-0.0222 mg/L for Ni; 0.0265-0.4753 mg/L for Pb and 0.0052-0.5594 mg/L for Zn. Modelling work was performed using PHREEQC couple with Geochemist's workbench (GWB) to determine speciation dynamics and bioavailability of these pollutants. Modelling thus adds value to analytical methods and hence a better complementary tool to laboratory-based experimental studies.

Arsenic species determination in human scalp hair by pressurized hot water extraction and high performance liquid chromatography-inductively coupled plasma-mass spectrometry.

PubMed

Morado Piñeiro, Andrés; Moreda-Piñeiro, Jorge; Alonso-Rodríguez, Elia; López-Mahía, Purificación; Muniategui-Lorenzo, Soledad; Prada-Rodríguez, Darío

2013-02-15

Analytical methods for the determination of total arsenic and arsenic species (mainly As(III) and As(V)) in human scalp hair have been developed. Inductively coupled plasma-mass spectrometry (ICP-MS) and high performance liquid chromatography (HPLC) coupled to ICP-MS have been used for total arsenic and arsenic species determination, respectively. The proposed methods include a "green", fast, high efficient and automated species leaching procedure by pressurized hot water extraction (PHWE). The operating parameters for PHWE including modifier concentration, extraction temperature, static time, extraction steps, pressure, mean particle size, diatomaceous earth (DE) mass/sample mass ratio and flush volume were studied using design of experiments (Plackett-Burman design PBD). Optimum condition implies a modifier concentration (acetic acid) of 150 mM and powdered hair samples fully mixed with diatomaceous earth (DE) as a dispersing agent at a DE mass/sample mass ratio of 5. The extraction has been carried out at 100°C and at an extraction pressure of 1500 psi for 5 min in four extraction step. Under optimised conditions, limits of quantification of 7.0, 6.3 and 50.3 ng g(-1) for total As, As(III) and As(V), respectively were achieved. Repeatability of the overall procedure (4.4, 7.2 and 2.1% for total As, As(III) and As(V), respectively) was achieved. The analysis of GBW-07601 (human hair) certified reference material was used for validation. The optimised method has been finally applied to several human scalp hair samples. Copyright © 2012 Elsevier B.V. All rights reserved.

MONITORING OF WATERWAYS FOR EMERGING CONTAMINANTS USING INTEGRATIVE SAMPLING COUPLED WITH LIQUID CHROMATOGRAPHY-ELECTROSPRAY/MASS SPECTROMETRY

EPA Science Inventory

Assessing the potential impact to the aquatic environment from emerging contaminants, entails monitoring a complex mixture (pharmaceuticals, polar pesticides, industrial by- products and degradation products) in natural waters. The presence of these chemicals, often at ultra-trac...

Open ocean pelago-benthic coupling: cyanobacteria as tracers of sedimenting salp faeces

NASA Astrophysics Data System (ADS)

Pfannkuche, Olaf; Lochte, Karin

1993-04-01

Coupling between surface water plankton and abyssal benthos was investigated during a mass development of salps ( Salpa fusiformis) in the Northeast Atlantic. Cyanobacteria numbers and composition of photosynthetic pigments were determined in faeces of captured salps from surface waters, sediment trap material, detritus from plankton hauls, surface sediments from 4500-4800 m depth and Holothurian gut contents. Cyanobacteria were found in all samples containing salp faeces and also in the guts of deep-sea Holothuria. The ratio between zeaxanthin (typical of cyanobacteria) and sum of chlorophyll a pigments was higher in samples from the deep sea when compared to fresh salp faeces, indicating that this carotenoid persisted longer in the sedimenting material than total chlorophyll a pigments. The microscopic and chemical observations allowed us to trace sedimenting salp faeces from the epipelagial to the abyssal benthos, and demonstrated their role as a fast and direct link between both systems. Cyanobacteria may provide a simple tracer for sedimenting phytodetritus.

Use of an ultra-clean sampling technique with inductively coupled plasma-mass spectrometry to determine trace-element concentrations in water from the Kirkwood-Cohansey Aquifer system, coastal plain, New Jersey

USGS Publications Warehouse

Ivahnenko, Tamara; Szabo, Zoltan; Hall, G.S.

1996-01-01

Water samples were collected during 1993 from 22 public supply wells screened in the Kirkwood-Cohansey aquifer system; concentrations of 18 trace elements were determined primarily by using inductively coupled plasma-mass spectrometry (ICP-MS) techniques, though graphite furnace atomic adsorption, hydride generation, and cold- vapor flameless atomic adsorption techniques were used for thallium, arsenic, and mercury, respectively, at the U.S. Geological Survey (USGS) National Water Quality Laboratory (NWQL). In addition, laboratory measurements of alkalinity and turbidity were made. The ground-water samples were collected by using ultra-clean sampling protocols developed by the USGS for collecting ground-water samples in areas with water containing low concentrations of trace elements. This technique is based on recently gained experience in sampling surface water for these elements. Field parameters (water temperature, specific conductance, pH, and dissolved-oxygen concentration) were monitored prior to sample collection. Three equipment blanks were collected to ensure that low-level trace-element contamination did not occur during sample collection. One split sample and a commercially- prepared reference standard were submitted to the NWQL o evaluate laboratory precision and accuracy, respectively. Trace-element concentrations in 10 sample splits and one equipment blank were also determined at the Rutgers University Chemistry Department laboratory. Results of the ICP-MS analyses and cold vapor flameless atomic absorption indicated that five trace elements-- cobalt, copper, lead, mercury, and nickel--were detectable in low concentrations (<0.1-29 mg/L) in most of the samples from the 22 wells, and four elements--aluminum, barium, manganese and zinc--were detected in higher concentrations than the other elements (30-710 mg/L for aluminum; 4-180 mg/L for barium, manganese, and zinc). The remaining nine trace elements were present in concentrations consistently lower than the minimum reporting limit. Turbidity was low (less than 1 nephelometric turbidity unit (NTU)), indicating that the trace-element concentrations were present in the dissolved phase and ideally would be reproducible in the absence of highly variable concentrations of particulates. The concentration of lead in one sample exceeded the U.S. Environmental Protection Agency (USEPA) action level of 15 mg/L; concentrations ranged from <1 to 16 mg/L. Mercury was frequently detected; concentrations ranged from <0.1 to 1.1 mg/L but did not exceed the USEPA maximum contaminant level. Results of analyses of the equipment blanks indicated that samples collected by using the new ultra-clean sampling protocols were free of low-level (< 1mg/L) trace-element contamination. The analysis of the split sample sent to the NWQL had a difference of 5 percent or less for all constituents except aluminum, for which the analysis had a difference of 10 percent. Results of ICP-MS analyses of split water samples sent to the Rutgers University Chemistry Department laboratory were, in general, in good agreement (within 10 percent) with those of the NWQL. Results of the analysis of the commercial standard agreed (within 5 percent) with the known concentrations of the trace elements. The quality-assurance data (three blanks, one split sample, and one standard), although not statistically evaluated because of the small data set, indicate that the measured trace-element concentrations are precise and accurate and that the samples were free of contamination at the microgram-per-liter level of contamination.

Speciation analysis of inorganic arsenic by magnetic solid phase extraction on-line with inductively coupled mass spectrometry determination.

PubMed

Montoro Leal, P; Vereda Alonso, E; López Guerrero, M M; Cordero, M T Siles; Cano Pavón, J M; García de Torres, A

2018-07-01

Arsenic, one of the main environmental pollutants and potent natural poison, is a chemical element that is spread throughout the Earth's crust. It is well known that the toxicity of arsenic is highly dependent on its chemical forms. Generally, the inorganic species are more toxic than its organics forms, and As(III) is 60 times more toxic than As(V). In environmental waters, arsenic exists predominantly in two chemical forms: As(III) and As(V). In view of these facts, fast, sensitive, accurate and simple analytical methods for the speciation of inorganic arsenic in environmental waters are required. In this work, a new magnetic solid phase extraction with a hydride generation system was coupled on line with inductively coupled plasma mass spectrometry (MSPE-HG-ICP-MS). The new system was based on the retention of As(III) and As(V) in two knotted reactors filled with (Fe 3 O 4 ) magnetic nanoparticles functionalized with [1,5-bis (2-pyridyl) 3-sulfophenylmethylene] thiocarbonohydrazide (PSTH-MNPs). As(III) and total inorganic As were sequentially eluted in different reduction conditions. The concentration of As(V) was obtained by subtracting As(III) from total As. The system runs in a fully automated way and the method has proved to have a wide linear range and to be precise, sensitive and fast. The detection limits found were 2.7 and 3.2 ng/L for As(III) and total As, respectively; with relative standard deviations (RSDs) of 2.5% and 2.7% and a sample throughput of 14.4 h -1 . In order to validate the developed method, several certified reference samples of environmental waters including sea water, were analyzed and the determined values were in good agreement with the certified values. The proposed method was successfully applied to the speciation analysis of inorganic arsenic in well-water and sea water. Copyright © 2018 Elsevier B.V. All rights reserved.

An analytical method for hydrogeochemical surveys: Inductively coupled plasma-atomic emission spectrometry after using enrichment coprecipitation with cobalt and ammonium pyrrolidine dithiocarbamate

USGS Publications Warehouse

Hopkins, D.M.

1991-01-01

Trace metals that are commonly associated with mineralization were concentrated and separated from natural water by coprecipitation with ammonium pyrollidine dithiocarbamate (APDC) and cobalt and determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The method is useful in hydrogeochemical surveys because it permits preconcentration near the sample sites, and selected metals are preserved shortly after the samples are collected. The procedure is relatively simple: (1) a liter of water is filtered; (2) the pH is adjusted; (3) Co chloride and APDC are added to coprecipitate the trace metals; and (4) later, the precipitate is filtered, dissolved, and diluted to 10 ml for a 100-fold concentration enrichment of the separated metals. Sb(III), As(III), Cd, Cr, Cu, Fe, Pb, Mo, Ni, Ag, V, and Zn can then be determined simultaneously by ICP-AES. In an experiment designed to measure the coprecipitation efficiency, Sb(III), Cd and Ag were recovered at 70 to 75% of their original concentration. The remaining metals were recovered at 85 to 100% of their original concentrations, however. The range for the lower limits of determination for the metals after preconcentration is 0.1 to 3.0 ??g/l. The precision of the method was evaluated by replicate analyses of a Colorado creek water and two simulated water samples. The accuracy of the method was estimated using a water reference standard (SRM 1643a) certified by the U.S. National Bureau of Standards. In addition, the method was evaluated by analyzing groundwater samples collected near a porphyry copper deposit in Arizona and by analyzing meltwater from glacier-covered areas favorable for mineralization in south-central Alaska. The results for the ICP-AES analyses compared favorably with those obtained using the sequential technique of GFAAS on the acidified but unconcentrated water samples. ICP-AES analysis of trace-metal preconcentrates for hydrogeochemical surveys is more efficient than GFAAS because a large suite of metals is simultaneously determined with acceptable analytical accuracy and precision. The proposed analytical technique can provide direct evidence of mineralization and is useful in the exploration for unknown ore deposits. ?? 1991.

Spectrophotometric and high performance liquid chromatographic methods for sensitive determination of bisphenol A

NASA Astrophysics Data System (ADS)

Zhuang, Yafeng; Zhou, Meng; Gu, Jia; Li, Xiangmei

2014-03-01

A new spectrophotometric method for the determination of trace amounts of bisphenol A based on a diazotization-coupling reaction was developed. In acidic solution, clenbuterol was first diazotized with sodium nitrite, then coupled with bisphenol A to from an azo-compound [I] in NH3-NH4Cl buffer, which shows a maximum absorption at 410 nm. The effects of the amount of sodium nitrite, diazo reaction time, the amount of clenbuterol, coupling reaction time and coupling reaction temperature have been examined. Under the optional conditions, the determination of the linear range of bisphenol A is 0.24-8.4 μg/mL, correlation coefficient is 0.9905 and detection limit of this method is 0.15 μg/mL. The spectrophotometric method is simple, rapid, high sensitivity with better accuracy. High performance liquid chromatography (HPLC) technique combined with this new spectrophotometric method has been also developed for the measurement of bisphenol A. The analysis was achieved on a C18 column using water and methanol as a mobile phase and the detection was done spectrophotometrically at 410 nm. These reported methods were applied to the determination of bisphenol A in hot water in contact with commercially available table-water bottle samples.

Preconcentration and determination of rare-earth elements in iron-rich water samples by extraction chromatography and plasma source mass spectrometry (ICP-MS).

PubMed

Hernández González, Carolina; Cabezas, Alberto J Quejido; Díaz, Marta Fernández

2005-11-15

A 100-fold preconcentration procedure based on rare-earth elements (REEs) separation from water samples with an extraction chromatographic column has been developed. The separation of REEs from matrix elements (mainly Fe, alkaline and alkaline-earth elements) in water samples was performed loading the samples, previously acidified to pH 2.0 with HNO(3), in a 2ml column preconditioned with 20ml 0.01M HNO(3). Subsequently, REEs were quantitatively eluted with 20ml 7M HNO(3). This solution was evaporated to dryness and the final residue was dissolved in 10ml 2% HNO(3) containing 1mugl(-1) of cesium used as internal standard. The solution was directly analysed by inductively coupled plasma mass spectrometry (ICP-MS), using ultrasonic nebulization, obtaining quantification limits ranging from 0.05 to 0.10 ngl(-1). The proposed method has been applied to granitic waters running through fracture fillings coated by iron and manganese oxy-hydroxides in the area of the Ratones (Cáceres, Spain) old uranium mine.

Extraction of trace tilmicosin in real water samples using ionic liquid-based aqueous two-phase systems.

PubMed

Pan, Ru; Shao, Dejia; Qi, Xueyong; Wu, Yun; Fu, Wenyan; Ge, Yanru; Fu, Haizhen

2013-01-01

The effective method of ionic liquid-based aqueous two-phase extraction, which involves ionic liquid (IL) (1-butyl-3-methyllimidazolium chloride, [C4mim]Cl) and inorganic salt (K2HPO4) coupled with high-performance liquid chromatography (HPLC), has been used to extract trace tilmicosin in real water samples which were passed through a 0.45 μm filter. The effects of the different types of salts, the concentration of K2HPO4 and of ILs, the pH value and temperature of the systems on the extraction efficiencies have all been investigated. Under the optimum conditions, the average extraction efficiency is up to 95.8%. This method was feasible when applied to the analysis of tilmicosin in real water samples within the range 0.5-40 μg mL(-1). The limit of detection was found to be 0.05 μg mL(-1). The recovery rate of tilmicosin was 92.0-99.0% from the real water samples by the proposed method. This process is suggested to have important applications for the extraction of tilmicosin.

Cisapride a green analytical reagent for rapid and sensitive determination of bromate in drinking water, bread and flour additives by oxidative coupling spectrophotometric methods

NASA Astrophysics Data System (ADS)

Al Okab, Riyad Ahmed

2013-02-01

Green analytical methods using Cisapride (CPE) as green analytical reagent was investigated in this work. Rapid, simple, and sensitive spectrophotometric methods for the determination of bromate in water sample, bread and flour additives were developed. The proposed methods based on the oxidative coupling between phenoxazine and Cisapride in the presence of bromate to form red colored product with max at 520 nm. Phenoxazine and Cisapride and its reaction products were found to be environmentally friendly under the optimum experimental condition. The method obeys beers law in concentration range 0.11-4.00 g ml-1 and molar absorptivity 1.41 × 104 L mol-1 cm-1. All variables have been optimized and the presented reaction sequences were applied to the analysis of bromate in water, bread and flour additive samples. The performance of these method was evaluated in terms of Student's t-test and variance ratio F-test to find out the significance of proposed methods over the reference method. The combination of pharmaceutical drugs reagents with low concentration create some unique green chemical analyses.

Field application of passive SBSE for the monitoring of pesticides in surface waters.

PubMed

Assoumani, A; Coquery, M; Liger, L; Mazzella, N; Margoum, C

2015-03-01

Spot sampling lacks representativeness for monitoring organic contaminants in most surface waters. Passive sampling has emerged as a cost-effective complementary sampling technique. We recently developed passive stir bar sorptive extraction (passive SBSE), with Twister from Gerstel, for monitoring moderately hydrophilic to hydrophobic pesticides (2.18 < log K ow < 5.11) in surface water. The aims of the present study were to assess this new passive sampler for the determination of representative average concentrations and to evaluate the contamination levels of two French rivers. Passive SBSE was evaluated for the monitoring of 16 pesticides in two rivers located in a small vineyard watershed during two 1-month field campaigns in spring 2010 and spring 2011. Passive SBSE was applied for periods of 1 or 2 weeks during the field campaigns and compared with spot sampling and weekly average automated sampling. The results showed that passive SBSE could achieve better time-representativeness than spot sampling and lower limits of quantification than automated sampling coupled with analytical SBSE for the pesticides studied. Finally, passive SBSE proved useful for revealing spatial and temporal variations in pesticide contamination of both rivers and the impact of rainfall and runoff on the river water quality.

Solid-phase extraction and separation procedure for trace aluminum in water samples and its determination by high-resolution continuum source flame atomic absorption spectrometry (HR-CS FAAS).

PubMed

Ciftci, Harun; Er, Cigdem

2013-03-01

In the present study, a separation/preconcentration procedure for determination of aluminum in water samples has been developed by using a new atomic absorption spectrometer concept with a high-intensity xenon short-arc lamp as continuum radiation source, a high-resolution double-echelle monochromator, and a charge-coupled device array detector. Sample solution pH, sample volume, flow rate of sample solution, volume, and concentration of eluent for solid-phase extraction of Al chelates with 4-[(dicyanomethyl)diazenyl] benzoic acid on polymeric resin (Duolite XAD-761) have been investigated. The adsorbed aluminum on resin was eluted with 5 mL of 2 mol L(-1) HNO(3) and its concentration was determined by high-resolution continuum source flame atomic absorption spectrometry (HR-CS FAAS). Under the optimal conditions, limit of detection obtained with HR-CS FAAS and Line Source FAAS (LS-FAAS) were 0.49 μg L(-1) and 3.91 μg L(-1), respectively. The accuracy of the procedure was confirmed by analyzing certified materials (NIST SRM 1643e, Trace elements in water) and spiked real samples. The developed procedure was successfully applied to water samples.

Determination of 99Tc in fresh water using TRU resin by ICP-MS.

PubMed

Guérin, Nicolas; Riopel, Remi; Kramer-Tremblay, Sheila; de Silva, Nimal; Cornett, Jack; Dai, Xiongxin

2017-10-02

Technetium-99 ( 99 Tc) determination at trace level by inductively coupled plasma mass spectrometry (ICP-MS) is challenging because there is no readily available appropriate Tc isotopic tracer. A new method using Re as a recovery tracer to determine 99 Tc in fresh water samples, which does not require any evaporation step, was developed. Tc(VII) and Re(VII) were pre-concentrated on a small anion exchange resin (AER) cartridge from one litre of water sample. They were then efficiently eluted from the AER using a potassium permanganate (KMnO 4 ) solution. After the reduction of KMnO 4 in 2 M sulfuric acid solution, the sample was passed through a small TRU resin cartridge. Tc(VII) and Re(VII) retained on the TRU resin were eluted using near boiling water, which can be directly used for the ICP-MS measurement. The results for method optimisation, validation and application were reported. Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

Development of a magnetic solid-phase extraction coupled with high-performance liquid chromatography method for the analysis of polyaromatic hydrocarbons.

PubMed

Ma, Yan; Xie, Jiawen; Jin, Jing; Wang, Wei; Yao, Zhijian; Zhou, Qing; Li, Aimin; Liang, Ying

2015-07-01

A novel magnetic solid phase extraction coupled with high-performance liquid chromatography method was established to analyze polyaromatic hydrocarbons in environmental water samples. The extraction conditions, including the amount of extraction agent, extraction time, pH and the surface structure of the magnetic extraction agent, were optimized. The results showed that the amount of extraction agent and extraction time significantly influenced the extraction performance. The increase in the specific surface area, the enlargement of pore size, and the reduction of particle size could enhance the extraction performance of the magnetic microsphere. The optimized magnetic extraction agent possessed a high surface area of 1311 m(2) /g, a large pore size of 6-9 nm, and a small particle size of 6-9 μm. The limit of detection for phenanthrene and benzo[g,h,i]perylene in the developed analysis method was 3.2 and 10.5 ng/L, respectively. When applied to river water samples, the spiked recovery of phenanthrene and benzo[g,h,i]perylene ranged from 89.5-98.6% and 82.9-89.1%, respectively. Phenanthrene was detected over a concentration range of 89-117 ng/L in three water samples withdrawn from the midstream of the Huai River, and benzo[g,h,i]perylene was below the detection limit. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rain water chemistry in Ankara, Turkey

NASA Astrophysics Data System (ADS)

Tuncel, Semra G.; Ungör, Sevgi

Samples of rain water were collected in Ankara for the period between September 1989 and May 1990, by using wet-only sampler. Concentrations of major cations (H +, Na + K + Ca 2+ and NH 4+) and major anions (Cl -, NO 3- and SO 42-) were determined for the first time in Turkey. The rain water was not acidic owing to high concentrations of alkaline soil particles in the atmosphere. However, the concentrations of acid forming ions, such as SO 4- and N03, were higher than the concentrations expected in a typical urban atmosphere. Most of the SO 4- in rain water was in the form of CaSO 4. Rain-aerosol coupling were examined by simultaneous sampling of aerosols with rain. The ions most efficiently scavenged from the atmosphere were found to be SO 42- and Ca 2+.

Uranium in Kosovo's drinking water.

PubMed

Berisha, Fatlume; Goessler, Walter

2013-11-01

The results of this paper are an initiation to capture the drinking water and/or groundwater elemental situation in the youngest European country, Kosovo. We aim to present a clear picture of the natural uranium concentration in drinking water and/or groundwater as it is distributed to the population of Kosovo. Nine hundred and fifty-one (951) drinking water samples were analyzed by inductively coupled plasma mass spectrometry (ICPMS). The results are the first countrywide interpretation of the uranium concentration in drinking water and/or groundwater, directly following the Kosovo war of 1999. More than 98% of the samples had uranium concentrations above 0.01 μg L(-1), which was also our limit of quantification. Concentrations up to 166 μg L(-1) were found with a mean of 5 μg L(-1) and median 1.6 μg L(-1) were found. Two point six percent (2.6%) of the analyzed samples exceeded the World Health Organization maximum acceptable concentration of 30 μg L(-1), and 44.2% of the samples exceeded the 2 μg L(-1) German maximum acceptable concentrations recommended for infant food preparations. Copyright © 2013 Elsevier Ltd. All rights reserved.

Simultaneous determination of four trace level endocrine disrupting compounds in environmental samples by solid-phase microextraction coupled with HPLC.

PubMed

Wang, Lingling; Zhang, Zhenzhen; Xu, Xu; Zhang, Danfeng; Wang, Fang; Zhang, Lei

2015-09-01

A simple, rapid, sensitive and effective method for the simultaneous determination of four endocrine disrupting compounds (EDCs) (bisphenol A (BPA), bisphenol F (BPF), bisphenol AF (BPAF) and bisphenol AP (BPAP)) in environment water samples based on solid-phase microextraction (SPME) coupled with high performance liquid chromatography (HPLC) was developed. Multi-wall carbon nanotubes (MWCNTs) adsorbents showed a good affinity to the target analytes. These compounds were rapidly extracted within 10 min. Various experimental parameters that could affect the extraction efficiencies had been investigated in detail. Under the optimum conditions, the enrichment factors of the method for the target EDCs were found to be 500. Satisfactory precision and accuracy of the method were obtained in a low concentration range of 2.0-500.0 ng mL(-1). The method detection limits were in the range of 0.10-0.30 ng mL(-1). The high pre-concentration rate and efficiency of the method ensure its successful application in extraction of trace EDCs from large volumes of environmental water samples. The extraction recoveries in real samples ranged from 85.3% to 102.5% with the relative standard deviations (n=5) less than 3.74%. Copyright © 2015 Elsevier B.V. All rights reserved.

(238)U and total radioactivity in drinking waters in Van province, Turkey.

PubMed

Selçuk Zorer, Özlem; Dağ, Beşir

2014-06-01

As part of the national survey to evaluate natural radioactivity in the environment, concentration levels of total radioactivity and natural uranium have been analysed in drinking water samples. A survey to study natural radioactivity in drinking waters was carried out in the Van province, East Turkey. Twenty-three samples of drinking water were collected in the Van province and analysed for total α, total β and (238)U activity. The total α and total β activities were counted by using the α/β counter of the multi-detector low background system (PIC MPC-9604), and the (238)U concentrations were determined by inductively coupled plasma-mass spectrometry (Thermo Scientific Element 2). The samples were categorised according to origin: tap, spring or mineral supply. The activity concentrations for total α were found to range from 0.002 to 0.030 Bq L(-1) and for total β from 0.023 to 1.351 Bq L(-1). Uranium concentrations ranging from 0.562 to 14.710 μg L(-1) were observed in drinking waters. Following the World Health Organisation rules, all investigated waters can be used as drinking water.

17O NMR Investigation of Water Structure and Dynamics

PubMed Central

Keeler, Eric G.; Michaelis, Vladimir K.; Griffin, Robert G.

2017-01-01

The structure and dynamics of the bound water in barium chlorate monohydrate were studied with 17O nuclear magnetic resonance (NMR) spectroscopy in samples that are stationary and spinning at the magic-angle in magnetic fields ranging from 14.1 to 21.1 T. 17O NMR parameters of the water were determined, and the effects of torsional oscillations of the water molecule on the 17O quadrupolar coupling constant (CQ) were delineated with variable temperature MAS NMR. With decreasing temperature and reduction of the librational motion, we observe an increase in the experimentally measured CQ explaining the discrepancy between experiments and predictions from density functional theory. In addition, at low temperatures and in the absence of 1H decoupling, we observe a well-resolved 1H–17O dipole splitting in the spectra, which provides information on the structure of the H2O molecule. The splitting arises because of the homogeneous nature of the coupling between the two 1H–17O dipoles and the 1H–1H dipole. PMID:27454747

Chemical dynamics of the first proton-coupled electron transfer of water oxidation on TiO2 anatase.

PubMed

Chen, Jia; Li, Ye-Fei; Sit, Patrick; Selloni, Annabella

2013-12-18

Titanium dioxide (TiO2) is a prototype, water-splitting (photo)catalyst, but its performance is limited by the large overpotential for the oxygen evolution reaction (OER). We report here a first-principles density functional theory study of the chemical dynamics of the first proton-coupled electron transfer (PCET), which is considered responsible for the large OER overpotential on TiO2. We use a periodic model of the TiO2/water interface that includes a slab of anatase TiO2 and explicit water molecules, sample the solvent configurations by first principles molecular dynamics, and determine the energy profiles of the two electronic states involved in the electron transfer (ET) by hybrid functional calculations. Our results suggest that the first PCET is sequential, with the ET following the proton transfer. The ET occurs via an inner sphere process, which is facilitated by a state in which one electronic hole is shared by the two oxygen ions involved in the transfer.

Comparison of in vitro estrogenic activity and estrogen concentrations in source and treated waters from 25 U.S. drinking water treatment plants.

PubMed

Conley, Justin M; Evans, Nicola; Mash, Heath; Rosenblum, Laura; Schenck, Kathleen; Glassmeyer, Susan; Furlong, Ed T; Kolpin, Dana W; Wilson, Vickie S

2017-02-01

In vitro bioassays have been successfully used to screen for estrogenic activity in wastewater and surface water, however, few have been applied to treated drinking water. Here, extracts of source and treated water samples were assayed for estrogenic activity using T47D-KBluc cells and analyzed by liquid chromatography-Fourier transform mass spectrometry (LC-FTMS) for natural and synthetic estrogens (including estrone, 17β-estradiol, estriol, and ethinyl estradiol). None of the estrogens were detected above the LC-FTMS quantification limits in treated samples and only 5 source waters had quantifiable concentrations of estrone, whereas 3 treated samples and 16 source samples displayed in vitro estrogenicity. Estrone accounted for the majority of estrogenic activity in respective samples, however the remaining samples that displayed estrogenic activity had no quantitative detections of known estrogenic compounds by chemical analyses. Source water estrogenicity (max, 0.47ng 17β-estradiol equivalents (E2Eq) L -1 ) was below levels that have been linked to adverse effects in fish and other aquatic organisms. Treated water estrogenicity (max, 0.078ngE2EqL -1 ) was considerably below levels that are expected to be biologically relevant to human consumers. Overall, the advantage of using in vitro techniques in addition to analytical chemical determinations was displayed by the sensitivity of the T47D-KBluc bioassay, coupled with the ability to measure cumulative effects of mixtures, specifically when unknown chemicals may be present. Published by Elsevier B.V.

[Determination of seven phenoxyacid herbicides in environmental water by high performance liquid chromatography coupled with three phase hollow fiber liquid phase microextraction].

PubMed

Peng, Xiaojun; Pang, Jinshan; Deng, Aihua

2011-12-01

A novel method for the simultaneous determination of seven phenoxyacid herbicides such as dicamba, fluroxypyr, 4-chlorophenoxyacetic acid (4-CPA), 2-methyl-4-chlorophenoxyacetic acid (MCPA), 2, 4-dichlorophenoxyacetic acid (2,4-D), 2,4-dichlorophenoxybutyric acid (2,4-DB) and 4-(2-methyl-4-chlorophenoxy) butyric acid (MCPB) in environmental water by three phase hollow fiber liquid phase microextraction (HF-LPME) coupled with high performance liquid chromatography (HPLC) was developed. In order to optimize the experimental conditions, the orthogonal test has been used. The effects of extraction solvent, pH of the donor phase and acceptor phase, extraction time, stirring speed and salt concentration on the detection were investigated. The optimal experimental conditions were as follows: octanol as organic solvent, pH 3 of donor phase, pH 12 of acceptor phase, extraction time of 30 min, stirring speed of 400 r/min. The results showed that the proposed method provided a wide linear range for 7 phenoxyacid herbicides with correlation coefficients of 0.995 3 - 0.998 8. The detection limits ranged from 0.2 to 1.0 microg/L. The enrichment factors were in the range of 76.7 - 121. The recoveries were in the range of 68% - 104% and the relative standard deviations (RSDs) were less than 8.1% for the environmental water samples. The method has the advantages of sensitivity, simplicity, fastness and the use of very small amounts of organic solvent. The method can meet the requirements of the determination of trace phenoxyacid herbicides in the environmental water samples, and the study provided a useful method for the analysis of trace substances in water samples.

Characterization of the corrosion resistance of several alloys to dilute biologically active solutions

NASA Technical Reports Server (NTRS)

Walsh, Daniel W.

1990-01-01

Sulfate reducing bacteria and acid producing bacteria/fungi detected in hygiene waters increased the corrosion rate in aluminum alloy. Biologically active media enhanced the formation of pits on metal coupons. Direct observation of gas evolved at the corrosion sample, coupled with scanning electron microscopy (SEM) and energy dispersive x-ray analysis of the corrosion products indicates that the corrosion rate is increased because the presence of bacteria favor the reduction of hydrogen as the cathodic reaction through the reaction of oxygen and water. SEM verifies the presence of microbes in a biofilm on the surface of corroding samples. The bacterial consortia are associated with anodic sites on the metal surface, aggressive pitting occurs adjacent to biofilms. Many pits are associated with triple points and inclusions in the aluminum alloy microstructure. Similar bacterial colonization was found on the stainless steel samples. Fourier transform Infrared Spectroscopy confirmed the presence of carbonyl groups in pitted areas of samples exposed to biologically active waters.

Determination of uranium in tap water by ICP-MS.

PubMed

El Himri, M; Pastor, A; de la Guardia, M

2000-05-01

A fast and accurate procedure has been developed for the determination of uranium at microg L(-1) level in tap and mineral water. The method is based on the direct introduction of samples, without any chemical pre-treatment, into an inductively coupled plasma mass spectrometer (ICP-MS). Uranium was determined at the mass number 238 using Rh as internal standard. The method provides a limit of detection of 2 ng L(-1) and a good repeatability with relative standard deviation values (RSD) about 3% for five independent analyses of samples containing 73 microg L(-1) of uranium. Recovery percentage values found for the determination of uranium in spiked natural samples varied between 91% and 106%. Results obtained are comparable with those found by radiochemical methods for natural samples and of the same order for the certified content of a reference material, thus indicating the accuracy of the ICP-MS procedure without the need of using isotope dilution. A series of mineral and tap waters from different parts of Spain and Morocco were analysed.

Enzymatic electrochemical detection coupled to multivariate calibration for the determination of phenolic compounds in environmental samples.

PubMed

Hernandez, Silvia R; Kergaravat, Silvina V; Pividori, Maria Isabel

2013-03-15

An approach based on the electrochemical detection of the horseradish peroxidase enzymatic reaction by means of square wave voltammetry was developed for the determination of phenolic compounds in environmental samples. First, a systematic optimization procedure of three factors involved in the enzymatic reaction was carried out using response surface methodology through a central composite design. Second, the enzymatic electrochemical detection coupled with a multivariate calibration method based in the partial least-squares technique was optimized for the determination of a mixture of five phenolic compounds, i.e. phenol, p-aminophenol, p-chlorophenol, hydroquinone and pyrocatechol. The calibration and validation sets were built and assessed. In the calibration model, the LODs for phenolic compounds oscillated from 0.6 to 1.4 × 10(-6) mol L(-1). Recoveries for prediction samples were higher than 85%. These compounds were analyzed simultaneously in spiked samples and in water samples collected close to tanneries and landfills. Published by Elsevier B.V.

Chemical and biological assessment of sediments and water of Khalid Khor, Sharjah, United Arab Emirates.

PubMed

Samara, Fatin; Elsayed, Yehya; Soghomonian, Balik; Knuteson, Sandra L

2016-10-15

Water and sediments were collected on March 2013 and April 2014 from Khalid Khor creek area in United Arab Emirates to assess their quality parameters. The pH and alkalinity of the water samples were measured and their values were similar to those of shallow saltwater ecosystems. In addition, elemental analyses and organic compounds were done using Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES) and Gas Chromatography-Mass Spectroscopy (GC-MS), respectively. The concentration of heavy and trace metals in the water samples were within the acceptable limits except for lead which showed high values, while the concentrations of metals in the sediment samples were relatively high and ranged from 6517 to 13,768mg/kg. GC-MS analysis showed the presence of polyaromatic heterocyclic (PAHs) compounds in sediments near the shipping area and in amounts classified as highly carcinogenic; however, no polychlorinated biphenyls (PCB) were identified. Moreover, fecal bacterial contamination in water was detected in concentrations that range between 300 and 10,140 organisms/100mL. Copyright © 2016 Elsevier Ltd. All rights reserved.

Optimisation of solid-phase microextraction coupled to HPLC-UV for the determination of organochlorine pesticides and their metabolites in environmental liquid samples.

PubMed

Torres Padrón, M E; Sosa Ferrera, Z; Santana Rodríguez, J J

2006-09-01

A solid-phase microextraction (SPME) procedure using two commercial fibers coupled with high-performance liquid chromatography (HPLC) is presented for the extraction and determination of organochlorine pesticides in water samples. We have evaluated the extraction efficiency of this kind of compound using two different fibers: 60-mum polydimethylsiloxane-divinylbenzene (PDMS-DVB) and Carbowax/TPR-100 (CW/TPR). Parameters involved in the extraction and desorption procedures (e.g. extraction time, ionic strength, extraction temperature, desorption and soaking time) were studied and optimized to achieve the maximum efficiency. Results indicate that both PDMS-DVB and CW/TPR fibers are suitable for the extraction of this type of compound, and a simple calibration curve method based on simple aqueous standards can be used. All the correlation coefficients were better than 0.9950, and the RSDs ranged from 7% to 13% for 60-mum PDMS-DVB fiber and from 3% to 10% for CW/TPR fiber. Optimized procedures were applied to the determination of a mixture of six organochlorine pesticides in environmental liquid samples (sea, sewage and ground waters), employing HPLC with UV-diode array detector.

Solid-phase microextraction-gas chromatography-mass spectrometry for the analysis of selective serotonin reuptake inhibitors in environmental water.

PubMed

Lamas, J Pablo; Salgado-Petinal, Carmen; García-Jares, Carmen; Llompart, María; Cela, Rafael; Gómez, Mariano

2004-08-13

The continuous contamination of surface waters by pharmaceuticals is of most environmental concern. Selective serotonin reuptake inhibitors (SSRIs) are drugs currently prescribed for the treatment of depressions and other psychiatric disorders and then, they are among the pharmaceuticals that can occur in environmental waters. Solid-phase microextraction (SPME) coupled to gas chromatography-mass spectrometry has been applied to the extraction of five SSRIs--venlafaxine, fluvoxamine, fluoxetine, citalopram and sertraline--from water samples. Some of the analytes were not efficiently extracted as underivatized compounds and so, an in situ acetylation step was introduced in the sample preparation procedure. Different parameters affecting extraction efficiency such as extraction mode, fiber coating and temperature were studied. A mixed-level fractional factorial design was also performed to simultaneously study the influence of other five experimental factors. Finally, a method based on direct SPME at 100 degrees C using polydimethylsiloxane-divinylbenzene fibers is proposed. The performance of the method was evaluated, showing good linearity and precision. The detection limits were in the sub-ng/mL level. Practical applicability was demonstrated through the analysis of real samples. Recoveries obtained for river water and wastewater samples were satisfactory in all cases. An important aspect of the proposed method is that no matrix effects were observed. Two of the target compounds, venlafaxine and citalopram, were detected and quantified in a sewage water sample.

Radionuclides and toxic elements transfer from the princess dump to water in Roodepoort, South Africa.

PubMed

Dlamini, S G; Mathuthu, M M; Tshivhase, V M

2016-03-01

High concentrations of radionuclides and toxic elements in gold mine tailings facilities present a health hazard to the environment and people living near that area. Soil and water samples from selected areas around the Princess Mine dump were collected. Soil sampling was done on the surface (15 cm) and also 100 cm below the surface. Water samples were taken from near the dump, mid-stream and the flowing part of the stream (drainage pipe) passing through Roodepoort from the mine dump. Soil samples were analyzed by gamma-ray spectroscopy using a HPGe detector to determine the activity concentrations of (238)U, (232)Th and (4) (​40)K from the activities of the daughter nuclides in the respective decay chains. The average activity concentrations for uranium and thorium in soil were calculated to be 129 ± 36.1 Bq/kg and 18.1 ± 4.01 Bq/kg, respectively. Water samples were analyzed using Inductively Coupled Plasma Mass Spectrometer. Transfer factors for uranium and thorium from soil to water (at point A closest to dump) were calculated to be 0.494 and 0.039, respectively. At point Z2, which is furthest from the dump, they were calculated to be 0.121 and 0.004, respectively. These transfer factors indicate that there is less translocation of the radionuclides as the water flows. Copyright © 2016 Elsevier Ltd. All rights reserved.

Natural fluoride levels in the drinking water, water fluoridation and estimated risk of dental fluorosis in a tropical region of Brazil.

PubMed

Sampaio, Fábio Correia; Silva, Fábia Danielle; Silva, Andréa Cristina; Machado, Ana Thereza; de Araújo, Demétrius Antônio; de Sousa, Erik Melo

2010-01-01

The aim of the present study was to determine the natural fluoride levels in the drinking water supplies of a tropical area of Brazil to identify the cities at risk of high prevalence of dental fluorosis and to provide data for future water fluoridation projects in the region. The present study was carried out in Paraíba, in the north-eastern region of Brazil. A total of 223 cities were selected, and local health workers were instructed to collect three samples of drinking water: one from the main public water supply and the other two from a public or residential tap with the same water source. Fluoride analyses were carried out in duplicate using a fluoride-specific electrode coupled to an ion analyser. A total of 167 cities (75%) provided water samples for analysis. Fluoride levels ranged from 0.1 to 1.0 ppm (mg/l). Samples from most of the cities (n = 163, 73%) presented low levels of fluoride (< 0.5 mg/l). Samples from three cities (a total estimate of 28,222 inhabitants exposed) presented 'optimum' fluoride levels (0.6 to 0.8 mg/l). Samples from one city (16,724 inhabitants) with 1.0 mg/l of fluoride in the water were above the recommended level (0.7 mg/l) for the local temperature. It can be concluded that the cities in this area of Brazil presented low natural fluoride levels in the drinking water and could implement controlled water fluoridation projects when technical requirements are accomplished. A high or a moderate prevalence of dental fluorosis due to the intake of natural fluoride in the drinking water is likely to take place in one city only.

Characterizing spatiotemporal variations of chromophoric dissolved organic matter in headwater catchment of a key drinking water source in China.

PubMed

Chen, Yihan; Yu, Kaifeng; Zhou, Yongqiang; Ren, Longfei; Kirumba, George; Zhang, Bo; He, Yiliang

2017-12-01

Natural surface drinking water sources with the increasing chromophoric dissolved organic matter (CDOM) have profound influences on the aquatic environment and drinking water safety. Here, this study investigated the spatiotemporal variations of CDOM in Fengshuba Reservoir and its catchments in China. Twenty-four surface water samples, 45 water samples (including surface water, middle water, and bottom water), and 15 pore water samples were collected from rivers, reservoir, and sediment of the reservoir, respectively. Then, three fluorescent components, namely two humic-like components (C1 and C2) and a tryptophan-like component (C3), were identified from the excitation-emission matrix coupled with parallel factor analysis (EEM-PARAFAC) for all samples. For spatial distributions, the levels of CDOM and two humic-like components in the reservoir were significantly lower than those in the upstream rivers (p < 0.01), indicating that the reservoir may act as a reactor to partly reduce the levels of exogenous input including CDOM and humic-like matters from the surrounding catchment. For temporal variations, the mean levels of CDOM and three fluorescent components did not significantly change in rivers, suggesting that perennial anthropic activity maybe an important factor impacting the concentration and composition of river CDOM but not the precipitation and runoff. However, these mean values of CDOM for the bulk waters of the reservoir changed markedly along with seasonal variations, indicating that the hydrological processes in the reservoir could control the quality and quantity of CDOM. The different correlations between the fluorescent components and primary water parameters in the river, reservoir, and pore water samples further suggest that the reservoir is an important factor regulating the migration and transformation of FDOM along with the variations of different environmental gradients.

Sensitivity-enhanced detection of non-labile proton and carbon NMR spectra on water resonances.

PubMed

Novakovic, Mihajlo; Martinho, Ricardo P; Olsen, Gregory L; Lustig, Michael S; Frydman, Lucio

2017-12-20

Chemical exchange saturation transfer (CEST) experiments enhance the NMR signals of labile protons by continuously transferring these protons' saturation to an abundant solvent pool like water. The present study expands these principles by fusing into these experiments homonuclear isotropic mixing sequences, enabling the water-enhanced detection of non-exchangeable species. Further opportunities are opened by the addition of coupling-mediated heteronuclear polarization transfers, which then impose on the water resonance a saturation stemming from non-labile heteronuclear species like 13 C. To multiplex the ensuing experiments, these relayed approaches are combined with time-domain schemes involving multiple Ramsey-labeling experiments imparting the frequencies of the non-labile sites on the water resonance, via chemical exchange. 13 C and 1 H NMR spectra were detected in this fashion with about two-fold SNR amplification vis-à-vis conventionally detected spectroscopies. When combined with non-uniform sampling principles, this methodology thus becomes a sensitive alternative to detect non-exchangeable species in biomolecules. Still, multiple parameters including the scalar couplings and solvent exchange rates, will affect the efficiency and consequently the practicality of the overall experiment.

Inductively coupled plasma-mass spectrometric method for the determination of dissolved trace elements in natural water

USGS Publications Warehouse

Garbarino, J.R.; Taylor, Howard E.

1996-01-01

An inductively coupled plasma-mass spectrometry method was developed for the determination of dissolved Al, As, B, Ba, Be, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Sr, Tl, U, V, and Zn in natural waters. Detection limits are generally in the 50-100 picogram per milliliter (pg/mL) range, with the exception of As which is in the 1 microgram per liter (ug/L) range. Interferences associated with spectral overlap from concomitant isotopes or molecular ions and sample matrix composition have been identified. Procedures for interference correction and reduction related to isotope selection, instrumental operating conditions, and mathematical data processing techniques are described. Internal standards are used to minimize instrumental drift. The average analytical precision attainable for 5 times the detection limit is about 16 percent. The accuracy of the method was tested using a series of U.S. Geological Survey Standard Reference Water Standards (SWRS), National Research Council Canada Riverine Water Standard, and National Institute of Standards and Technology (NIST) Trace Elements in Water Standards. Average accuracies range from 90 to 110 percent of the published mean values.

Rapid determination of glyphosate in cereal samples by means of pre-column derivatisation with 9-fluorenylmethyl chloroformate and coupled-column liquid chromatography with fluorescence detection.

PubMed

Hogendoorn, E A; Ossendrijver, F M; Dijkman, E; Baumann, R A

1999-02-12

A rapid procedure for the determination of glyphosate in cereals has been developed. Convenient sample pretreatment is carried out by (i) a overnight standing extraction of 1.0 g homogenized sample with 20 ml of water, (ii) centrifugation of the samples, (iii) a passing of 2.5 ml of the clear layer through a 100 mg C18 solid-phase extraction cartridge and (iv) collection of the last 1.5 ml of the eluent into a calibrated tube. For the instrumental analysis, the efficient approach developed earlier for environmental water samples [J.V. Sancho, F. Hernández, F.J. LUpez, E.A. Hogendoorn, E. Dijkman, P. van Zoonen, J. Chromatogr. A, 737 (1996) 75] was successfully adopted for the determination of glyphosate in the obtained cereal extracts. The procedure includes a 15 min derivatisation step of the analyte with 9-fluorenylmethyl chloroformate and a 16 times dilution step prior to instrumental analysis employing coupled-column LC with fluorescence detection. The developed procedure has a sample throughput of more than 25 samples per day and a limit of quantification of 0.5 mg/kg. The method was validated by analyzing freshly spiked cereal samples and samples with aged residues at levels between 1.0 and 10 mg/kg. The overall recovery of the freshly spiked samples was 86% (n = 10) with a repeatability of 6.5% and a reproducibility of 9.5%. For samples with aged residues recoveries performed at different time intervals (range 80-150 days) did not differ significantly; the overall recovery (n = 10) was 74% with a repeatability and reproducibility of 14 and 20%, respectively.

Chemical Speciation of Water Soluble Ions and Metals of Cloud and Rain Water During the Puerto Rico African Dust and Clouds Study (PRADACS) Campaigns

NASA Astrophysics Data System (ADS)

Torres, E.; Valle Diaz, C. J.; Lee, T.; Collett, J. L.; Fitzgerald, E.; Cuadra-Rodriguez, L. A.; Prather, K. A.; Sánchez, M.; McDowell, W. H.; Mayol-Bracero, O. L.

2013-05-01

The underlying physico-chemical processes of dust particles interactions are poorly understood; even less understood is how aging impacts cloud properties and climate as the particles travel from Africa to the Caribbean region. Caribbean landmasses have tropical montane cloud forests (TMCFs) that are tightly coupled to the atmospheric hydrologic cycle. TMCFs are ecosystems to study the effects African Dust (AD) on cloud formation and precipitation as these are very sensitive ecosystems that respond to small changes in climate. As part of the Puerto Rico African Dust and Clouds Study (PRADACS), chemical analyses were performed on cloud and rain water samples collected at Pico del Este (PE) station in Luquillo, PR (1051 masl) during campaigns held from 2010 to 2012. At PE, two cloud collectors (i.e., single stage (Aluminum version), a 2-stage (Teflon version) Caltech Active Strand Cloudwater Collector (CASCC)), a rainwater collector, and anAerosol Time-Of-Flight Mass Spectrometer (ATOFMS) were operated. Chemical analyses performed on collected samples include pH, conductivity, ion chromatography (IC), and inductive coupled plasma (ICP). Results from these campaigns showed that on days that had air masses with the influence of AD, cloud water samples had higher conductivity and pH values on average (up to 5.7 and 180μS/cm, respectively) than those with air masses without AD influence. An increase in the concentrations of water-soluble ions like non-sea salt calcium and magnesium, and metals like magnesium, calcium and aluminum was observed and the appearance of iron was seen on ICP analyses. The ATOFMS, showed an increase on the amount of particles during AD influence with composition of aluminum, silicates, potassium, iron and titanium aerosols. The increase on the aforementioned species was constant in the three years of sampling, which give us confidence in the identification of the chemical species that are present during the influence of AD.

Investigation of the marine boundary layer cloud and CCN properties under coupled and decoupled conditions over the Azores

DOE PAGES

Dong, Xiquan; Schwantes, Adam C.; Xi, Baike; ...

2015-06-10

Here, six coupled and decoupled marine boundary layer (MBL) clouds were chosen from the 19 month Atmospheric Radiation Measurement Mobile Facility data set over the Azores. Thresholds of liquid water potential temperature difference Δθ L < 0.5 K (>0.5 K) and total water mixing ratio difference Δq t < 0.5 g/kg (>0.5 g/kg) below the cloud base were used for selecting the coupled (decoupled) cases. A schematic diagram was given to demonstrate the coupled and decoupled MBL vertical structures and how they associate with nondrizzle, virga, and rain drizzle events. Out of a total of 2676 5 min samples, 34.5%more » were classified as coupled and 65.5% as decoupled, 36.2% as nondrizzle and 63.8% as drizzle (47.7% as virga and 16.1% as rain), and 33.4% as daytime and 66.6% as nighttime. The decoupled cloud layer is deeper (0.406 km) than coupled cloud layer (0.304 km), and its liquid water path and cloud droplet effective radius (r e) values (122.1 gm -2 and 13.0 µm) are higher than coupled ones (83.7 gm -2 and 10.4 µm). Conversely, decoupled stratocumuli have lower cloud droplet number concentration (N d) and surface cloud condensation nucleus (CCN) concentration (N CCN) (74.5 cm -3 and 150.9 cm -3) than coupled stratocumuli (111.7 cm -3 and 216.4 cm -3). The linear regressions between r e and N d with N CCN have demonstrated that coupled r e and N d strongly depend on N CCN and have higher correlations (-0.56 and 0.59) with N CCN than decoupled results (-0.14 and 0.25). The MBL cloud properties under nondrizzle and virga drizzle conditions are similar to each other but significantly different to those of rain drizzle.« less

Geochemical Variability and the Potential for Beneficial Use of Waste Water Coproduced with Oil from Permian Basin of the Southwest USA

NASA Astrophysics Data System (ADS)

Khan, N. A.; Holguin, F. O.; Xu, P.; Engle, M.; Dungan, B.; Hunter, B.; Carroll, K. C.

2014-12-01

The U.S. generates 21 billion barrels/year of coproduced water from oil and gas exploration, which is generally considered waste water. Growth in unconventional oil and gas production has spurred interest in beneficial uses of produced water, especially in arid regions such as the Permian Basin of Texas and New Mexico, the largest U.S. tight oil producer. Produced waters have variable chemistries, but generally contain high levels of organics and salts. In order to evaluate the environmental impact, treatment, and reuse potential, there is a need to characterize the compositional variability of produced water. In the present study, produced water samples were collected from 12 wells across the Permian Basin. Compositional analyses including coupled gas chromatography-time of flight-mass spectrometry and inductively coupled plasma-optical emission spectroscopy were conducted. The samples show elevated benzene, ethylbenzene, toluene, xylene, alkyl benzenes, propyl-benzene, and naphthalene compared to other heteroaromatics; they also contain complex hydrocarbon compounds containing oxygen, nitrogen, and sulfur. Van Krevelen diagrams show an increase in the concentration of heteroaromatic hydrocarbons with increasing well depth. The salinity, dominated by sodium-chloride, also increases with depth, ranging from 37-150 g/L TDS. Depth of wells (or producing formation) is a primary control on predicting water quality for treatment and beneficial use. Our results suggest that partial treatment by removing suspended solids and organic contaminants would support some beneficial uses such as onsite reuse, bioenergy production, and other industrial uses. Due to the high salinity, conventional desalination processes are not applicable or very costly, making beneficial uses requiring low salinity not feasible.

Hollow-fiber liquid-phase microextraction coupled with miniature capillary electrophoresis for the trace analysis of four aliphatic aldehydes in water samples.

PubMed

Li, Ying; Yi, Fan; Zheng, Yiliang; Wang, Yu; Ye, Jiannong; Chu, Qingcui

2015-08-01

An environmentally friendly method for the trace analysis of four aliphatic aldehydes as water disinfection byproducts has been developed based on hollow-fiber liquid-phase microextraction followed by miniature capillary electrophoresis with amperometric detection. After derivatization with 2-thiobarbituric acid, four aliphatic aldehydes (formaldehyde, acetaldehyde, propylaldehyde, and butyraldehyde) became detectable by the amperometric detector. Under the optimum conditions, four aliphatic aldehydes can be well separated from the coexisting interferents as well as their homologs (pentanal, glyoxal, and methyl-glyoxal), and the limits of detection (S/N = 3) could reach sub-nanogram-per-milliliter level based on hollow-fiber liquid-phase microextraction. The proposed method has been applied for the analyses of above four aliphatic aldehydes in different water samples such as drinking water, tap water, and river water, and the average recoveries were in the range of 90-113%, providing an alternative to conventional and microchip capillary electrophoresis approaches. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of trace heavy metals in harvested rainwater used for drinking in Hebron (south West Bank, Palestine) by ICP-MS.

PubMed

Malassa, Husam; Al-Rimawi, Fuad; Al-Khatib, Mahmoud; Al-Qutob, Mutaz

2014-10-01

Rainwater samples harvested for drinking from the west part of Hebron (south of West Bank in Palestine), the largest city in the West Bank, were analyzed for the content of different trace heavy metals (Cr, Mn, Co, Ni, Cu, Zn, Mo, Ag, Cd, Bi, and Pb) by inductively coupled plasma mass spectrometry (ICP-MS). This study was conducted to determine the water quality of harvested rainwater used for drinking of south West Bank (case study, Hebron area). A total of 44 water samples were collected in November 2012 from 44 house cisterns used to collect rainwater from the roofs of houses. The samples were analyzed for their pH, temperature, electrical conductivity, total dissolved solids, and different heavy metal contents. The pH of all water samples was within the US Environmental Protection Agency limits (6.5-8.5), while some water samples were found to exceed the allowed WHO limit for total dissolved solids (TDSs) in drinking water. Results showed that concentrations of the heavy metals vary significantly between the 44 samples. Results also showed that the concentration of five heavy metals (Cr, Mn, Ni, Ag, and Pb) is higher than the WHO limits for these heavy metals in drinking water. Overall, our findings revealed that harvested rainwater used for drinking of this part of south West Bank is contaminated with heavy metals that might affect human health.

PHOSPHORUS SORPTION DYNAMICS IN SOILS AND COUPLING WITH SURFACE AND PORE WATER IN RIVERINE WETLANDS

EPA Science Inventory

Adsorption to soils is one of the dominant mechanisms of P storage in wetlands. We examined P sorption dynamics in soils collected at 12 sample points with diverse hydrology, geomorphic position, mineralogy, and plant communities in two riverine wetlands in northern Minnesota and...

Metal analysis of cotton

USDA-ARS?s Scientific Manuscript database

Seven varieties of cotton were investigated for 8 metal ions (K, Na, Mg, Ca, Fe, Cu, Zn, and Mn) using Inductively Coupled Plasma-Optical Emission Spectroscopy. All of the varieties were grown at the same location. Half of the samples were dry (rain fed only) and the other were well-watered (irrigat...

Screen-printed electrode based electrochemical detector coupled with ionic liquid dispersive liquid-liquid microextraction and microvolume back-extraction for determination of mercury in water samples.

PubMed

Fernández, Elena; Vidal, Lorena; Martín-Yerga, Daniel; Blanco, María del Carmen; Canals, Antonio; Costa-García, Agustín

2015-04-01

A novel approach is presented, whereby gold nanostructured screen-printed carbon electrodes (SPCnAuEs) are combined with in-situ ionic liquid formation dispersive liquid-liquid microextraction (in-situ IL-DLLME) and microvolume back-extraction for the determination of mercury in water samples. In-situ IL-DLLME is based on a simple metathesis reaction between a water-miscible IL and a salt to form a water-immiscible IL into sample solution. Mercury complex with ammonium pyrrolidinedithiocarbamate is extracted from sample solution into the water-immiscible IL formed in-situ. Then, an ultrasound-assisted procedure is employed to back-extract the mercury into 10 µL of a 4 M HCl aqueous solution, which is finally analyzed using SPCnAuEs. Sample preparation methodology was optimized using a multivariate optimization strategy. Under optimized conditions, a linear range between 0.5 and 10 µg L(-1) was obtained with a correlation coefficient of 0.997 for six calibration points. The limit of detection obtained was 0.2 µg L(-1), which is lower than the threshold value established by the Environmental Protection Agency and European Union (i.e., 2 µg L(-1) and 1 µg L(-1), respectively). The repeatability of the proposed method was evaluated at two different spiking levels (3 and 10 µg L(-1)) and a coefficient of variation of 13% was obtained in both cases. The performance of the proposed methodology was evaluated in real-world water samples including tap water, bottled water, river water and industrial wastewater. Relative recoveries between 95% and 108% were obtained. Copyright © 2014 Elsevier B.V. All rights reserved.

Rapid detection of soils contaminated with heavy metals and oils by laser induced breakdown spectroscopy (LIBS).

PubMed

Kim, Gibaek; Kwak, Jihyun; Kim, Ki-Rak; Lee, Heesung; Kim, Kyoung-Woong; Yang, Hyeon; Park, Kihong

2013-12-15

A laser induced breakdown spectroscopy (LIBS) coupled with the chemometric method was applied to rapidly discriminate between soils contaminated with heavy metals or oils and clean soils. The effects of the water contents and grain sizes of soil samples on LIBS emissions were also investigated. The LIBS emission lines decreased by 59-75% when the water content increased from 1.2% to 7.8%, and soil samples with a grain size of 75 μm displayed higher LIBS emission lines with lower relative standard deviations than those with a 2mm grain size. The water content was found to have a more pronounced effect on the LIBS emission lines than the grain size. Pelletizing and sieving were conducted for all samples collected from abandoned mining areas and military camp to have similar water contents and grain sizes before being analyzed by the LIBS with the chemometric analysis. The data show that three types of soil samples were clearly discerned by using the first three principal components from the spectral data of soil samples. A blind test was conducted with a 100% correction rate for soil samples contaminated with heavy metals and oil residues. Copyright © 2013 Elsevier B.V. All rights reserved.

In situ ionic liquid dispersive liquid-liquid microextraction coupled to gas chromatography-mass spectrometry for the determination of organophosphorus pesticides.

PubMed

Cacho, J I; Campillo, N; Viñas, P; Hernández-Córdoba, M

2018-07-20

Nine organophosphorus pesticides (OPPs) were determined in environmental waters from different origins using in situ ionic liquid dispersive liquid microextraction (IL-DLLME). This preconcentration technique was coupled to gas chromatography-mass spectrometry (GC-MS) using microvial insert thermal desorption, an approach that uses a thermal desorption injector as sample introduction system. The parameters affecting both the microextraction and sample injection steps were optimized. The proposed method showed good precision, with RSD values ranging from 4.1 to 9.7%, accuracy with recoveries in the 85-118% range, and sensitivity with DLs ranging from 5 to 16 ng L -1 . Copyright © 2017 Elsevier B.V. All rights reserved.

The reach of human health risks associated with metals/metalloids in water and vegetables along a contaminated river catchment: South Africa and Mozambique.

PubMed

Genthe, Bettina; Kapwata, Thandi; Le Roux, Wouter; Chamier, Jessica; Wright, Caradee Y

2018-05-01

Anthropogenic pollution was identified as an environmental problem of concern when, in 2008, dozens of crocodiles died in the Olifants River catchment near the border of South Africa and Mozambique. Given the close proximity of households to the river and their making use of river water, we aimed to determine to what extent water pollution has an impact on health of indigent communities in South Africa and Mozambique in the catchment area. Water and vegetable samples were collected from the study areas. Biota samples were washed with double de-ionized Milli-Q water and freeze-dried. Heavy metal analyses in water and vegetables were done by means of Inductively Coupled Plasma Optical Emission Spectroscopy. Metal concentrations were applied in a human health risk assessment to estimate health risks. Mean concentrations of antimony, arsenic, cadmium, chromium, mercury, molybdenum, nickel and selenium in water samples from South Africa exceeded the World Health Organization guidelines for safe levels of intake. Only iron exceeded the recommended guidelines in water samples from Mozambique. Metals/metalloids were found in lower concentrations at Mozambique sites downstream of South African sites. In vegetables, uranium was between 10 and 20 times above safe guidelines in South Africa and between 3 and 6 times in Mozambique. Arsenic in water samples posed the highest cancer risk. Even with a reduction in the metal concentrations in river water from South Africa to Mozambique, the potential to cause adverse human health impacts from direct use of polluted river water is evident in both countries. Copyright © 2018 Elsevier Ltd. All rights reserved.

The choice of ultrasound assisted extraction coupled with spectrophotometric for rapid determination of gallic acid in water samples: Central composite design for optimization of process variables.

PubMed

Pooralhossini, Jaleh; Ghaedi, Mehrorang; Zanjanchi, Mohammad Ali; Asfaram, Arash

2017-01-01

A sensitive procedure namely ultrasound-assisted (UA) coupled dispersive nano solid-phase microextraction spectrophotometry (DNSPME-UV-Vis) was designed for preconcentration and subsequent determination of gallic acid (GA) from water samples, while the detailed of composition and morphology and also purity and structure of this new sorbent was identified by techniques like field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD) and Energy-dispersive X-ray spectroscopy (EDX) techniques. Among conventional parameters viz. pH, amount of sorbent, sonication time and volume of elution solvent based on Response Surface Methodology (RSM) and central composite design according to statistics based contour the best operational conditions was set at pH of 2.0; 1.5mg sorbent, 4.0min sonication and 150μL ethanol. Under these pre-qualified conditions the method has linear response over wide concentration range of 15-6000ngmL -1 with a correlation coefficient of 0.9996. The good figure of merits like acceptable LOD (S/N=3) and LOQ (S/N=10) with numerical value of 2.923 and 9.744ngmL -1 , respectively and relative recovery between 95.54 and 100.02% show the applicability and efficiency of this method for real samples analysis with RSDs below 6.0%. Finally the method with good performance were used for monitoring under study analyte in various real samples like tap, river and mineral waters. Copyright © 2016 Elsevier B.V. All rights reserved.

Investigation of Drinking Water Quality in Kosovo

PubMed Central

Berisha, Fatlume; Goessler, Walter

2013-01-01

In the recent years, not much environmental monitoring has been conducted in the territory of Kosovo. This study represents the first comprehensive monitoring of the drinking water situation throughout most of the territory of Kosovo. We present the distribution of major and minor trace elements in drinking water samples from Kosovo. During our study we collected 951 samples from four different sources: private-bored wells; naturally flowing artesian water; pumped-drilled wells; and public water sources (tap water). The randomly selected drinking water samples were investigated by routine water analyses using inductively coupled plasma mass spectrometry (ICPMS) for 32 elements (Li, Be, B, Na, Mg, Al, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Rb, Sr, Mo, Ag, Cd, Sn, Sb, Te, Ba, Tl, Pb, Bi, Th, U). Even though there are set guidelines for elemental exposure in drinking water worldwide, in developing countries, such as Kosovo, the lack of monitoring drinking water continues to be an important health concern. This study reports the concentrations of major and minor elements in the drinking water in Kosovo. Additionally, we show the variation of the metal concentration within different sources. Of the 15 regulated elements, the following five elements: Mn, Fe, Al, Ni, As, and U were the elements which most often exceeded the guidelines set by the EU and/or WHO. PMID:23509472

Improving Salmonella determination in Sinaloa rivers with ultrafiltration and most probable number methods.

PubMed

Jimenez, Maribel; Chaidez, Cristobal

2012-07-01

Monitoring of waterborne pathogens is improved by using concentration methods prior to detection; however, direct microbial enumeration is desired to study microbial ecology and human health risks. The aim of this work was to determine Salmonella presence in river water with an ultrafiltration system coupled with the ISO 6579:1993 isolation standard method (UFS-ISO). Most probable number (MPN) method was used directly in water samples to estimate Salmonella populations. Additionally, the effect between Salmonella determination and water turbidity was evaluated. Ten liters or three tenfold dilutions (1, 0.1, and 0.01 mL) of water were processed for Salmonella detection and estimation by the UFS-ISO and MPN methods, respectively. A total of 84 water samples were tested, and Salmonella was confirmed in 64/84 (76%) and 38/84 (44%) when UFS-ISO and MPN were used, respectively. Salmonella populations were less than 5 × 10(3) MPN/L in 73/84 of samples evaluated (87%), and only three (3.5%) showed contamination with numbers greater than 4.5 × 10(4) MPN/L. Water turbidity did not affect Salmonella determination regardless of the performed method. These findings suggest that Salmonella abundance in Sinaloa rivers is not a health risk for human infections in spite of its persistence. Thus, choosing the appropriate strategy to study Salmonella in river water samples is necessary to clarify its behavior and transport in the environment.

Incidence of heavy metal contamination in water supplies in northern Mexico.

PubMed

Wyatt, C J; Fimbres, C; Romo, L; Méndez, R O; Grijalva, M

1998-02-01

Contaminants in drinking water present public health risks. The objective of this study was to analyze water samples taken from wells or storage tanks, direct sources for domestic water in Northern Mexico, for the presence of lead (Pb), copper (Cu), cadmium (Cd), arsenic (As), and mercury (Hg). The samples were analyzed by atomic absorption coupled with a hydride generator or a graphite furnace. High levels of Pb (0.05-0.12 ppm) were found in Hermosillo, Guaymas, and Nacozari. Forty-three percent of the samples in Sonora exceeded the action level (0.015 ppm) established by the EPA for Pb. For As, 8.92% exceeded the limit with a range of 0.002-0.305 ppm. Several studies have indicated a possible link between As and fluoride (F) in drinking water. This study showed a positive correlation between F and As (r = 0.53, P = 0.01, and n = 116). One location in Hermosillo had 7.36 ppm of F and 0.117 ppm of As, 3.5 times the recommended F levels in drinking water and 2 times higher than the level permitted for As. Hg contamination was found in 42% of the samples. Based on the results of this study, it appears that As, Hg, and Pb contamination in the drinking water for some areas of the state of Sonora is a major concern.

Malignant human cell transformation of Marcellus shale gas drilling flow back water

PubMed Central

Yao, Yixin; Chen, Tingting; Shen, Steven S.; Niu, Yingmei; DesMarais, Thomas L; Linn, Reka; Saunders, Eric; Fan, Zhihua; Lioy, Paul; Kluz, Thomas; Chen, Lung-Chi; Wu, Zhuangchun; Costa, Max

2015-01-01

The rapid development of high-volume horizontal hydraulic fracturing for mining natural gas from shale has posed potential impacts on human health and biodiversity. The produced flow back waters after hydraulic stimulation is known to carry high levels of saline and total dissolved solids. To understand the toxicity and potential carcinogenic effects of these waste waters, flow back water from five Marcellus hydraulic fracturing oil and gas wells were analyzed. The physicochemical nature of these samples was analyzed by inductively coupled plasma mass spectrometry and scanning electron microscopy / energy dispersive X-ray spectroscopy. A cytotoxicity study using colony formation as the endpoint was carried out to define the LC50 values of test samples using human bronchial epithelial cells (BEAS-2B). The BEAS-2B cell transformation assay was employed to assess the carcinogenic potential of the samples. Barium and strontium were among the most abundant metals in these samples and the same metals were found elevated in BEAS-2B cells after long-term treatment. BEAS-2B cells treated for 6 weeks with flow back waters produced colony formation in soft agar that was concentration dependant. In addition, flow back water-transformed BEAS-2B cells show a better migration capability when compared to control cells. This study provides information needed to assess the potential health impact of post-hydraulic fracturing flow back waters from Marcellus Shale natural gas mining. PMID:26210350

Effects of abandoned arsenic mine on water resources pollution in north west of iran.

PubMed

Hajalilou, Behzad; Mosaferi, Mohammad; Khaleghi, Fazel; Jadidi, Sakineh; Vosugh, Bahram; Fatehifar, Esmail

2011-01-01

Pollution due to mining activities could have an important role in health and welfare of people who are living in mining area. When mining operation finishes, environ-ment of mining area can be influenced by related pollution e.g. heavy metals emission to wa-ter resources. The present study was aimed to evaluate Valiloo abandoned arsenic mine ef-fects on drinking water resources quality and possible health effects on the residents of min-ing area in the North West of Iran. Water samples and some limited composite wheat samples in downstream of min-ing area were collected. Water samples were analyzed for chemical parameters according to standard methods. For determination of arsenic in water samples, Graphite Furnace Atomic Absorption Spectrometric Method (GFAAS) and for wheat samples X - Ray Fluorescence (XRF) and Inductively Coupled Plasma Method (ICP) were used. Information about possible health effects due to exposure to arsenic was collected through interviews in studied villages and health center of Herris City. The highest concentrations of arsenic were measured near the mine (as high as 2000 µg/L in Valiloo mine opening water). With increasing distance from the mine, concentration was decreased. Arsenic was not detectable in any of wheat samples. Fortunately, no health effects had been reported between residents of studied area due to exposure to arsenic. Valiloo abandoned arsenic mine has caused release of arsenic to the around en-vironment of the mine, so arsenic concentration has been increased in the groundwater and also downstream river that requires proper measures to mitigate spread of arsenic.

Detection of heavy metals in water in Negeri Sembilan, Malaysia: From source to consumption

NASA Astrophysics Data System (ADS)

Khalaf, Baydaa; Abdullah, Md. Pauzi; Tahrim, Nurfaizah Abu

2018-04-01

Drinking water should be free from harmful levels of impurities, such as heavy metals. The aim of this study is to investigate the heavy metals concentrations in a water reticulation system of Negeri Sembilan. 25 stations were selected along Sungai Linggi (upstream of intake point) and through there reticulation system of Sungai Linggi Water Treatment Plant encompassing raw water through to the last point of use. Sampling activities were carried out in June and July 2016. The samples taken were analysed for heavymetals using an Inductively Coupled Plasma - Optical Emission Spectrometer (ICP-OES). In addition other water quality parameters were measured in situ (pH, water temperature, conductivity and dissolved oxygen) and analysed in the laboratory (BOD, COD, TSS, NH3-N, TOC and residual chlorine). The results showed a high level of Ca in the distribution system, while in the treatment plant it was normal, as well as Fe is decreased. Meanwhile Mn is decreased after treatment processes. The concentrations of DO and temperature in the tap water exceeded the standard concentrations.

A Water Mass Tracer Detected in Aerosols Demonstrates Ocean-Atmosphere Mass Transfer and Links Sea Spray Aerosol to Source Waters

NASA Astrophysics Data System (ADS)

Pendergraft, M.; Grimes, D. J.; Giddings, S. N.; Feddersen, F.; Prather, K. A.; Santander, M.; Lee, C.; Beall, C.

2016-12-01

During September and October of 2015 the Cross Surfzone/Inner-shelf Dye Exchange (CSIDE) project released rhodamine WT dye to study nearshore water movement and exchange offshore along a Southern California sandy beach. We utilized this opportunity to investigate ocean-atmosphere mass transfer via sea spray aerosol and linkage to source waters. Aerosol-concentrating sampling equipment was deployed at beachside and inland locations during three dye releases. Concentrated aerosol samples were analyzed for dye content using fluorescence spectroscopy. Here we present the ocean and atmosphere conditions associated with the presence and absence of dye in aerosol samples. Dye was identified in aerosol samples collected 0.1-0.3 km from the shoreline for 6 hs during the first and third dye releases of the CSIDE project. During these releases the dye persisted in the waters upwind of the sampling equipment. Dye was not detected in aerosol samples collected during the second release during which dye was moved away from waters upwind of the sampling equipment. Recovery of a chemical tracer in sea spray aerosol allows direct linkage to a known source area in the ocean that is independent of, but supported by, wind data. Our observations demonstrate: a tight ocean-atmosphere spatial coupling; a short residence time of coastal marine constituents before transfer to the atmosphere; that the ocean is both a sink for and a source of atmospheric and terrestrial material; and that human inputs to the ocean can return to us in sea spray aerosol.

Residues of selected antibiotics in the South Moravian Rivers, Czech Republic.

PubMed

Jarova, Katerina; Vavrova, Milada; Koleckarova, Alice

2015-01-01

The aim of this study was to assess the contamination level of aquatic ecosystems of the Oslava and the Jihlava Rivers, and of the Nove Mlyny Water Reservoir, situated in the South Moravian Region (Czech Republic), by residues of selected veterinary pharmaceuticals. We isolated and determined 10 sulfonamide antibiotics in samples of surface water and bottom sediments using optimized analytical methods. A representative number of sampling sites in the entire basin of selected waters were chosen. Samples were collected particularly near the larger cities in order to assess their possible impact to the aquatic ecosystems. Extraction, pre-concentration and purification of samples were performed using optimized methods of solid phase extraction and pressurized solvent extraction. Final identification and quantification were carried out by high-performance liquid chromatography coupled with diode array detector. The concentration of sulfonamides in water samples were all under the limit of detection. Regarding sediment samples, sulfadimidine was found at most sampling sites; its highest values were recorded in the Jihlava River (up to 979.8 µg.kg(-1) dry matter). Other frequently detected sulfonamides were sulfamethoxazole and sulfamerazine. Most other sulfonamides were under the limit of detection or limit of quantification. Monitoring of antibiotic residues in the environment, especially in the aquatic ecosystem, is a current topic due to the growing worldwide use in both human and veterinary medicine. According to obtained results, we document the pollution of selected rivers and water reservoir by particular sulfonamides which basically reflects their application in veterinary medicine.

Perchlorate in fish from a contaminated site in east-central Texas.

PubMed

Theodorakis, Christopher; Rinchard, Jacques; Anderson, Todd; Liu, Fujun; Park, June-Woo; Costa, Filipe; McDaniel, Leslie; Kendall, Ronald; Waters, Aaron

2006-01-01

Perchlorate, a known thyroid endocrine disruptor, contaminates surface waters near military instillations where solid fuel rocket motors are manufactured or assembled. To assess potential perchlorate exposure to fish and the human population which may feed on them, fish were collected around the Naval Weapons Industrial Reserve Plant in McLennan County, TX, and analyzed for the presence of the perchlorate anion. The sampling sites included Lake Waco and Belton Lake, and several streams and rivers within their watersheds. The general tendency was that perchlorate was only found in a few species sampled, and perchlorate was not detected in every individual within these species. When detected in the fish, perchlorate tissue concentrations were greater than that in the water. This may be due to highly variable perchlorate concentrations in the water coupled with individual-level variation in elimination from the body, or to routes of exposure other than water.

Using ion chromatography to monitor haloacetic acids in drinking water: a review of current technologies.

PubMed

Paull, Brett; Barron, Leon

2004-08-13

A review of the application of ion chromatography to the determination of haloacetic acids in drinking water is given. As it requires no sample derivatisation, ion chromatography in its various modes, such as ion-exchange, ion-interaction and ion-exclusion chromatography, is increasingly being investigated as a simpler alternative to gas chromatographic methods for the determination of polar disinfection by-products (DBPs) in drinking waters. Detection limits quoted for the regulated haloacetic acids (HAA5), are commonly in the mid to low microg/L range, however, in most cases analyte preconcentration is still necessary for detection at concentrations commonly found in actual drinking water samples. The coupling of ion chromatography to electrospray mass spectrometry provides a potential future direction, with improved sensitivity and selectivity compared to conductivity based detection, however associated cost and complexity for routine analysis is currently relatively high.

Development of a zoning-based environmental-ecological-coupled model for lakes to assess lake restoration effect

NASA Astrophysics Data System (ADS)

Xu, Mengjia; Zou, Changxin; Zhao, Yanwei

2017-04-01

Environmental/ecological models are widely used for lake management as they provide a means to understand physical, chemical and biological processes in highly complex ecosystems. Most research focused on the development of environmental (water quality) and ecological models, separately. Limited studies were developed to couple the two models, and in these limited coupled models, a lake was regarded as a whole for analysis (i.e., considering the lake to be one well-mixed box), which was appropriate for small-scale lakes and was not sufficient to capture spatial variations within middle-scale or large-scale lakes. This paper seeks to establish a zoning-based environmental-ecological-coupled model for a lake. The Baiyangdian Lake, the largest freshwater lake in Northern China, was adopted as the study case. The coupled lake models including a hydrodynamics and water quality model established by MIKE21 and a compartmental ecological model used STELLA software have been established for middle-sized Baiyangdian Lake to realize the simulation of spatial variations of ecological conditions. On the basis of the flow field distribution results generated by MIKE21 hydrodynamics model, four water area zones were used as an example for compartmental ecological model calibration and validation. The results revealed that the developed coupled lake models can reasonably reflected the changes of the key state variables although there remain some state variables that are not well represented by the model due to the low quality of field monitoring data. Monitoring sites in a compartment may not be representative of the water quality and ecological conditions in the entire compartment even though that is the intention of compartment-based model design. There was only one ecological observation from a single monitoring site for some periods. This single-measurement issue may cause large discrepancies particularly when sampled site is not representative of the whole compartment. The coupled models have been applied to simulate the spatial variation trends of ecological condition under ecological water supplement as an example to reflect the application effect in lake restoration and management. The simulation results indicate that the models can provide a useful tool for lake restoration and management. The simulated spatial variation trends can provide a foundation for establishing permissible ranges for a selected set of water quality indices for a series of management measures such as watershed pollution load control and ecological water transfer. Meanwhile, the coupled models can help us to understand processes taking place and the relations of interaction between components in the lake ecosystem and external conditions. Taken together, the proposed models we established show some promising applications as middle-scale or large-scale lake management tools for pollution load control and ecological water transfer. These tools quantify the implications of proposed future water management decisions.

Solid-phase microextraction coupled with high-performance liquid chromatography for the determination of phenylurea herbicides in aqueous samples.

PubMed

Lin, Hsin-Hang; Sung, Yu-Hsiang; Huang, Shang-Da

2003-09-12

Solid-phase microextraction coupled with high-performance liquid chromatography was successfully applied to the analysis of nine phenylurea herbicides (metoxuron, monuron, chlorotoluron, isoproturon, monolinuron, metobromuron, buturon, linuron, and chlorbromuron). Polydimethylsiloxane-divinylbenzene (PDMS-DVB, 60 microm) and Carbowax-templated resin (CW-TPR, 50 microm) fibers were selected from four commercial fibers for further study because of their better extraction efficiencies. The parameters of the desorption procedure were studied and optimized. The effects of the properties of analytes and fiber coatings, carryover, duration and temperature of absorption, pH, organic solvent and ionic strength of samples were also investigated. External calibration with an aqueous standard can be used for the analysis of environmental samples (lake water) using either PDMS-DVB or CW-TPR fibers. Good precisions (1.0-5.9%) are achieved for this method, and the detection limits are at the level of 0.5-5.1 ng/ml.

Spatially complex distribution of dissolved manganese in a fjord as revealed by high-resolution in situ sensing using the autonomous underwater vehicle Autosub.

PubMed

Statham, P J; Connelly, D P; German, C R; Brand, T; Overnell, J O; Bulukin, E; Millard, N; McPhail, S; Pebody, M; Perrett, J; Squire, M; Stevenson, P; Webb, A

2005-12-15

Loch Etive is a fjordic system on the west coast of Scotland. The deep waters of the upper basin are periodically isolated, and during these periods oxygen is lost through benthic respiration and concentrations of dissolved manganese increase. In April 2000 the autonomous underwater vehicle (AUV) Autosub was fitted with an in situ dissolved manganese analyzer and was used to study the spatial variability of this element together with oxygen, salinity, and temperature throughout the basin. Six along-loch transects were completed at either constant height above the seafloor or at constant depth below the surface. The ca. 4000 in situ 10-s-average dissolved Mn (Mnd) data points obtained provide a new quasi-synoptic and highly detailed view of the distribution of manganese in this fjordic environment not possible using conventional (water bottle) sampling. There is substantial variability in concentrations (<25 to >600 nM) and distributions of Mnd. Surface waters are characteristically low in Mnd reflecting mixing of riverine and marine end-member waters, both of which are low in Mnd. The deeper waters are enriched in Mnd, and as the water column always contains some oxygen, this must reflect primarily benthic inputs of reduced dissolved Mn. However, this enrichment of Mnd is spatially very variable, presumably as a result of variability in release of Mn coupled with mixing of water in the loch and removal processes. This work demonstrates how AUVs coupled with chemical sensors can reveal substantial small-scale variability of distributions of chemical species in coastal environments that would not be resolved by conventional sampling approaches. Such information is essential if we are to improve our understanding of the nature and significance of the underlying processes leading to this variability.

Using artificial sweeteners to identify contamination sources and infiltration zones in a coupled river-aquifer system

NASA Astrophysics Data System (ADS)

Bichler, Andrea; Muellegger, Christian; Hofmann, Thilo

2014-05-01

In shallow or unconfined aquifers the infiltration of contaminated river water might be a major threat to groundwater quality. Thus, the identification of possible contamination sources in coupled surface- and groundwater systems is of paramount importance to ensure water quality. Micropollutants like artificial sweeteners are promising markers for domestic waste water in natural water bodies. Compounds, such as artificial sweeteners, might enter the aquatic environment via discharge of waste water treatment plants, leaky sewer systems or septic tanks and are ubiquitously found in waste water receiving waters. The hereby presented field study aims at the (1) identification of contamination sources and (2) delineation of infiltration zones in a connected river-aquifer system. River bank filtrate in the groundwater body was assessed qualitatively and quantitatively using a combined approach of hydrochemical analysis and artificial sweeteners (acesulfame ACE) as waste water markers. The investigated aquifer lies within a mesoscale alpine head water catchment and is used for drinking water production. It is hypothesized that a large proportion of the groundwater flux originates from bank filtrate of a nearby losing stream. Water sampling campaigns in March and July 2012 confirmed the occurrence of artificial sweeteners at the investigated site. The municipal waste water treatment plant was identified as point-source for ACE in the river network. In the aquifer ACE was present in more than 80% of the monitoring wells. In addition, water samples were classified according to their hydrochemical composition, identifying two predominant types of water in the aquifer: (1) groundwater influenced by bank filtrate and (2) groundwater originating from local recharge. In combination with ACE concentrations a third type of water could be discriminated: (3) groundwater influence by bank filtrate but infiltrated prior to the waste water treatment plant. Moreover, the presence of ACE at elevated concentrations in aquifer zones dominated by local recharge indicated another point-source of domestic waste water. The combined analysis of ACE and conventional hydrochemical data proved to be useful to identify different sources of waste water. It is shown that the combination of physicochemical parameters and artificial sweeteners allow for a clear delineation of infiltration areas in the investigated aquifer system.

Electro-thermal vaporization direct analysis in real time-mass spectrometry for water contaminant analysis during space missions.

PubMed

Dwivedi, Prabha; Gazda, Daniel B; Keelor, Joel D; Limero, Thomas F; Wallace, William T; Macatangay, Ariel V; Fernández, Facundo M

2013-10-15

The development of a direct analysis in real time-mass spectrometry (DART-MS) method and first prototype vaporizer for the detection of low molecular weight (∼30-100 Da) contaminants representative of those detected in water samples from the International Space Station is reported. A temperature-programmable, electro-thermal vaporizer (ETV) was designed, constructed, and evaluated as a sampling interface for DART-MS. The ETV facilitates analysis of water samples with minimum user intervention while maximizing analytical sensitivity and sample throughput. The integrated DART-ETV-MS methodology was evaluated in both positive and negative ion modes to (1) determine experimental conditions suitable for coupling DART with ETV as a sample inlet and ionization platform for time-of-flight MS, (2) to identify analyte response ions, (3) to determine the detection limit and dynamic range for target analyte measurement, and (4) to determine the reproducibility of measurements made with the method when using manual sample introduction into the vaporizer. Nitrogen was used as the DART working gas, and the target analytes chosen for the study were ethyl acetate, acetone, acetaldehyde, ethanol, ethylene glycol, dimethylsilanediol, formaldehyde, isopropanol, methanol, methylethyl ketone, methylsulfone, propylene glycol, and trimethylsilanol.

Error Analysis of Clay-Rock Water Content Estimation with Broadband High-Frequency Electromagnetic Sensors—Air Gap Effect

PubMed Central

Bore, Thierry; Wagner, Norman; Delepine Lesoille, Sylvie; Taillade, Frederic; Six, Gonzague; Daout, Franck; Placko, Dominique

2016-01-01

Broadband electromagnetic frequency or time domain sensor techniques present high potential for quantitative water content monitoring in porous media. Prior to in situ application, the impact of the relationship between the broadband electromagnetic properties of the porous material (clay-rock) and the water content on the frequency or time domain sensor response is required. For this purpose, dielectric properties of intact clay rock samples experimental determined in the frequency range from 1 MHz to 10 GHz were used as input data in 3-D numerical frequency domain finite element field calculations to model the one port broadband frequency or time domain transfer function for a three rods based sensor embedded in the clay-rock. The sensor response in terms of the reflection factor was analyzed in time domain with classical travel time analysis in combination with an empirical model according to Topp equation, as well as the theoretical Lichtenecker and Rother model (LRM) to estimate the volumetric water content. The mixture equation considering the appropriate porosity of the investigated material provide a practical and efficient approach for water content estimation based on classical travel time analysis with the onset-method. The inflection method is not recommended for water content estimation in electrical dispersive and absorptive material. Moreover, the results clearly indicate that effects due to coupling of the sensor to the material cannot be neglected. Coupling problems caused by an air gap lead to dramatic effects on water content estimation, even for submillimeter gaps. Thus, the quantitative determination of the in situ water content requires careful sensor installation in order to reach a perfect probe clay rock coupling. PMID:27096865

Error Analysis of Clay-Rock Water Content Estimation with Broadband High-Frequency Electromagnetic Sensors--Air Gap Effect.

PubMed

Bore, Thierry; Wagner, Norman; Lesoille, Sylvie Delepine; Taillade, Frederic; Six, Gonzague; Daout, Franck; Placko, Dominique

2016-04-18

Broadband electromagnetic frequency or time domain sensor techniques present high potential for quantitative water content monitoring in porous media. Prior to in situ application, the impact of the relationship between the broadband electromagnetic properties of the porous material (clay-rock) and the water content on the frequency or time domain sensor response is required. For this purpose, dielectric properties of intact clay rock samples experimental determined in the frequency range from 1 MHz to 10 GHz were used as input data in 3-D numerical frequency domain finite element field calculations to model the one port broadband frequency or time domain transfer function for a three rods based sensor embedded in the clay-rock. The sensor response in terms of the reflection factor was analyzed in time domain with classical travel time analysis in combination with an empirical model according to Topp equation, as well as the theoretical Lichtenecker and Rother model (LRM) to estimate the volumetric water content. The mixture equation considering the appropriate porosity of the investigated material provide a practical and efficient approach for water content estimation based on classical travel time analysis with the onset-method. The inflection method is not recommended for water content estimation in electrical dispersive and absorptive material. Moreover, the results clearly indicate that effects due to coupling of the sensor to the material cannot be neglected. Coupling problems caused by an air gap lead to dramatic effects on water content estimation, even for submillimeter gaps. Thus, the quantitative determination of the in situ water content requires careful sensor installation in order to reach a perfect probe clay rock coupling.

Questa baseline and pre-mining ground-water quality investigation. 2. Low-flow (2001) and snowmelt (2002) synoptic/tracer water chemistry for the Red River, New Mexico

USGS Publications Warehouse

McCleskey, R. Blaine; Nordstrom, D. Kirk; Steiger, Judy I.; Kimball, Briant A.; Verplanck, Philip L.

2003-01-01

Water analyses are reported for 259 samples collected from the Red River, New Mexico, and its tributaries during low-flow(2001) and spring snowmelt (2002) tracer studies. Water samples were collected along a 20-kilometer reach of the Red River beginning just east of the town of Red River and ending at the U.S. Geological Survey streamflow-gaging station located east of Questa, New Mexico. The study area was divided into three sections where separate injections and synoptic sampling events were performed during the low-flow tracer study. During the spring snowmelt tracer study, three tracer injections and synoptic sampling events were performed bracketing the areas with the greatest metal loading into the Red River as determined from the low-flow tracer study. The lowflow tracer synoptic sampling events were August 17, 20, and 24, 2001. The synoptic sampling events for the spring snowmelt tracer were March 30, 31, and April 1, 2002. Stream and large inflow water samples were sampled using equal-width and depth-integrated sampling methods and composited into half-gallon bottles. Grab water samples were collected from smaller inflows. Stream temperatures were measured at the time of sample collection. Samples were transported to a nearby central processing location where pH and specific conductance were measured and the samples processed for chemical analyses. Cations, trace metals, iron redox species, and fluoride were analyzed at the U.S. Geological Survey laboratory in Boulder, Colorado. Cations and trace metal concentrations were determined using inductively coupled plasma-optical emission spectrometry and graphite furnace atomic absorption spectrometry. Arsenic concentrations were determined using hydride generation atomic absorption spectrometry, iron redox species were measured using ultraviolet-visible spectrometry, and fluoride concentrations were determined using an ion-selective electrode. Alkalinity was measured by automated titration, and sulfate, chloride, and bromide were analyzed by ion chromatography at the U.S. Geological Survey laboratory in Salt Lake City, Utah.

Organic Compounds, Trace Elements, Suspended Sediment, and Field Characteristics at the Heads-of-Tide of the Raritan, Passaic, Hackensack, Rahway, and Elizabeth Rivers, New Jersey, 2000-03

USGS Publications Warehouse

Bonin, Jennifer L.; Wilson, Timothy P.

2006-01-01

Concentrations of suspended sediment, particulate and dissolved organic carbon, trace elements, and organic compounds were measured in samples from the heads-of-tide of the five tributaries to the Newark and Raritan Bays during June 2000 to June 2003. The samples were collected as part of the New Jersey Department of Environmental Protection Toxics Reduction Workplan/Contaminant Assessment Reduction Program. Samples of streamwater were collected at water-quality sampling stations constructed near U.S. Geological Survey gaging stations on the Raritan, Passaic, Hackensack, Rahway, and Elizabeth Rivers. Sampling was conducted during base-flow conditions and storms. Constituent concentrations were measured to determine the water quality and to calculate the load of sediment and contaminants contributed to the bays from upstream sources. Water samples were analyzed for suspended sediment, dissolved organic carbon, particulate organic carbon, and specific conductance. Samples of suspended sediment and water were analyzed for 98 distinct polychlorinated biphenyl congeners, 7 dioxins, 10 furans, 27 pesticides, 26 polycyclic aromatic hydrocarbons, and the trace elements cadmium, lead, mercury, and methyl-mercury. Measurements of ultra-low concentrations of organic compounds in sediment and water were obtained by collecting 1 to 3 grams of suspended sediment on glass fiber filters and by passing at least 20 liters of filtered water through XAD-2 resin. The extracted sediment and XAD-2 resin were analyzed for organic compounds by high- and low-resolution gas chromatography mass-spectrometry that uses isotope dilution procedures. Trace elements in filtered and unfiltered samples were analyzed for cadmium, lead, mercury, and methyl-mercury by inductively coupled charged plasma and mass-spectrometry. All constituent concentrations are raw data. Interpretation of the data will be completed in the second phase of the study.

Simultaneous analysis of tropane alkaloids in teas and herbal teas by liquid chromatography coupled to high-resolution mass spectrometry (Orbitrap).

PubMed

Romera-Torres, Ana; Romero-González, Roberto; Martínez Vidal, José Luis; Garrido Frenich, Antonia

2018-05-01

A new method has been developed for the simultaneous determination of 13 tropane alkaloids in tea and herbal teas using high-performance liquid chromatography coupled to an Exactive-Orbitrap analyzer. A mixture of methanol, water, and formic acid was used for the extraction of the target compounds followed by a solid-phase extraction step. The validated method provided recoveries from 75 to 128% with intra- and interday precision lower than or equal to 24% (except for apoatropine). Limits of quantification ranged from 5 to 20 μg/kg. Eleven tea and herbal tea samples and two contaminated samples with Datura stramonium seeds were analyzed. Tropane alkaloids were detected in six samples with concentrations from 5 (apoatropine) to 4340 μg/kg (sum of physoperuvine, pseudotropine, and tropine), whereas concentrations from 5 (apoatropine) to 1725 μg/kg (sum of physoperuvine, pseudotropine, and tropine) were found in the contaminated samples. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Magnetic sulfur-doped porous carbon for preconcentration of trace mercury in environmental water prior to ICP-MS detection.

PubMed

Peng, Chuyu; He, Man; Chen, Beibei; Huang, Lijin; Hu, Bin

2017-11-20

A novel magnetic sulfur-doped porous carbon (MSPC) was fabricated via a simple one-step carbonization of a mixture of sucrose, basic magnesium sulfate whiskers and Fe 3 O 4 @SiO 2 nanoparticles. Due to the high S content, the prepared MSPC possessed high adsorption capacity for Hg 2+ (343 mg g -1 ) with good selectivity. Based on this, a method coupling magnetic solid phase extraction (MSPE) with inductively coupled plasma mass spectrometry (ICP-MS) was developed for the determination of trace Hg 2+ in environmental water samples. Various parameters such as pH, desorption solvent and its concentration, desorption volume and time, sample volume, and adsorption time that affect the determination have been optimized. Under the optimal conditions, a high enrichment factor of 100-fold was obtained, the limit of detection (LOD) was found to be 0.52 pg mL -1 with a relative standard deviation (c = 10 pg mL -1 , n = 7) of 7.1%, and a good linearity was obtained within the concentration range of 2-5000 pg mL -1 for Hg 2+ . Besides, the proposed method has very fast adsorption/desorption kinetics, target Hg 2+ could be rapidly adsorbed on the prepared MSPC in 2 min and desorbed from the MSPC in 2 min with the assistance of a permanent magnet. Therefore, the proposed method of MSPE-ICP-MS exhibits good application potential in the determination of trace Hg 2+ in environmental water samples.

Solid phase extraction of rare earth elements in seawater and estuarine water with 4-(2-thiazolylazo) resorcinol immobilized Chromosorb 106 for determination by inductively coupled plasma mass spectrometry

PubMed Central

Zereen, Fahmida; Yilmaz, Vedat; Arslan, Zikri

2013-01-01

A solid phase preconcentration method has been developed using new chelating resin prepared by immobilization of 4-(2-thiazolylazo) resorcinol (TAR) on Chromosorb 106. The method was optimized for determination of rare earth elements (REEs) in seawater and estuarine water samples by inductively coupled plasma mass spectrometry (ICP-MS). The effects of various experimental parameters, such as load pH, eluent concentration, sample and eluent flow rates were examined to find the optimum operating conditions. The REEs were quantitatively retained from saline solutions on a minicolumn Chromosorb 106-TAR resin at pH 5.0 and then eluted with 1.0 mL of 1% (v/v) HNO3. The resin possesses large sorption capacity for REEs ranging from 81.1 µmol g−1 for Lu and 108 µmol g−1 for Nd. Detection limits (3s) varied between 0.06 ng L−1 for Pr to 0.31 for Ce for preconcentration of 5.0 mL blank solutions (pH 5.0). The relative standard deviation for triplicate measurements was less than 5% at 0.1 µg L−1 level. The method was validated by analysis Nearshore seawater certified reference material (CASS–4). The elemental results were comparable with the values reported in literature. The method was verified by analysis of spiked and unspiked coastal seawater and estuarine water samples. PMID:24000264

Solid phase extraction of rare earth elements in seawater and estuarine water with 4-(2-thiazolylazo) resorcinol immobilized Chromosorb 106 for determination by inductively coupled plasma mass spectrometry.

PubMed

Zereen, Fahmida; Yilmaz, Vedat; Arslan, Zikri

2013-09-01

A solid phase preconcentration method has been developed using new chelating resin prepared by immobilization of 4-(2-thiazolylazo) resorcinol (TAR) on Chromosorb 106. The method was optimized for determination of rare earth elements (REEs) in seawater and estuarine water samples by inductively coupled plasma mass spectrometry (ICP-MS). The effects of various experimental parameters, such as load pH, eluent concentration, sample and eluent flow rates were examined to find the optimum operating conditions. The REEs were quantitatively retained from saline solutions on a minicolumn Chromosorb 106-TAR resin at pH 5.0 and then eluted with 1.0 mL of 1% (v/v) HNO 3 . The resin possesses large sorption capacity for REEs ranging from 81.1 µmol g -1 for Lu and 108 µmol g -1 for Nd. Detection limits (3s) varied between 0.06 ng L -1 for Pr to 0.31 for Ce for preconcentration of 5.0 mL blank solutions (pH 5.0). The relative standard deviation for triplicate measurements was less than 5% at 0.1 µg L -1 level. The method was validated by analysis Nearshore seawater certified reference material (CASS-4). The elemental results were comparable with the values reported in literature. The method was verified by analysis of spiked and unspiked coastal seawater and estuarine water samples.

Screening of pharmaceuticals and illicit drugs in wastewater and surface waters of Spain and Italy by high resolution mass spectrometry using UHPLC-QTOF MS and LC-LTQ-Orbitrap MS.

PubMed

Bade, Richard; Rousis, Nikolaos I; Bijlsma, Lubertus; Gracia-Lor, Emma; Castiglioni, Sara; Sancho, Juan V; Hernandez, Felix

2015-12-01

The existence of pharmaceuticals and illicit drugs (PIDs) in environmental waters has led many analytical chemists to develop screening methods for monitoring purposes. Water samples can contain a huge number of possible contaminants, commonly at low concentrations, which makes their detection and identification problematic. Liquid chromatography coupled with high resolution mass spectrometry (LC-HRMS) has proven itself effective in the screening of environmental contaminants. The present work investigates the use of the most popular HRMS instruments, quadrupole time-of-flight and linear trap quadrupole-Orbitrap, from two different laboratories. A suspect screening for PIDs was carried out on wastewater (influent and effluent) and surface water samples from Castellón, Eastern Spain, and Cremona, Northern Italy, incorporating a database of 107 PIDs (including 220 fragment ions). A comparison between the findings of both instruments and of the samples was made which highlights the advantages and drawbacks of the strategies applied in each case. In total, 28 compounds were detected and/or identified by either/both instruments with irbesartan, valsartan, benzoylecgonine and caffeine being the most commonly found compounds across all samples.

Practical and highly sensitive elemental analysis for aqueous samples containing metal impurities employing electrodeposition on indium-tin oxide film samples and laser-induced shock wave plasma in low-pressure helium gas.

PubMed

Kurniawan, Koo Hendrik; Pardede, Marincan; Hedwig, Rinda; Abdulmadjid, Syahrun Nur; Lahna, Kurnia; Idris, Nasrullah; Jobiliong, Eric; Suyanto, Hery; Suliyanti, Maria Margaretha; Tjia, May On; Lie, Tjung Jie; Lie, Zener Sukra; Kurniawan, Davy Putra; Kagawa, Kiichiro

2015-09-01

We have conducted an experimental study exploring the possible application of laser-induced breakdown spectroscopy (LIBS) for practical and highly sensitive detection of metal impurities in water. The spectrochemical measurements were carried out by means of a 355 nm Nd-YAG laser within N₂ and He gas at atmospheric pressures as high as 2 kPa. The aqueous samples were prepared as thin films deposited on indium-tin oxide (ITO) glass by an electrolysis process. The resulting emission spectra suggest that concentrations at parts per billion levels may be achieved for a variety of metal impurities, and it is hence potentially feasible for rapid inspection of water quality in the semiconductor and pharmaceutical industries, as well as for cooling water inspection for possible leakage of radioactivity in nuclear power plants. In view of its relative simplicity, this LIBS equipment offers a practical and less costly alternative to the standard use of inductively coupled plasma-mass spectrometry (ICP-MS) for water samples, and its further potential for in situ and mobile applications.

Simultaneous analysis of multiple classes of antimicrobials in environmental water samples using SPE coupled with UHPLC-ESI-MS/MS and isotope dilution.

PubMed

Tran, Ngoc Han; Chen, Hongjie; Do, Thanh Van; Reinhard, Martin; Ngo, Huu Hao; He, Yiliang; Gin, Karina Yew-Hoong

2016-10-01

A robust and sensitive analytical method was developed for the simultaneous analysis of 21 target antimicrobials in different environmental water samples. Both single SPE and tandem SPE cartridge systems were investigated to simultaneously extract multiple classes of antimicrobials. Experimental results showed that good extraction efficiencies (84.5-105.6%) were observed for the vast majority of the target analytes when extraction was performed using the tandem SPE cartridge (SB+HR-X) system under an extraction pH of 3.0. HPLC-MS/MS parameters were optimized for simultaneous analysis of all the target analytes in a single injection. Quantification of target antimicrobials in water samples was accomplished using 15 isotopically labeled internal standards (ILISs), which allowed the efficient compensation of the losses of target analytes during sample preparation and correction of matrix effects during UHPLC-MS/MS as well as instrument fluctuations in MS/MS signal intensity. Method quantification limit (MQL) for most target analytes based on SPE was below 5ng/L for surface waters, 10ng/L for treated wastewater effluents, and 15ng/L for raw wastewater. The method was successfully applied to detect and quantify the occurrence of the target analytes in raw influent, treated effluent and surface water samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Network analysis reveals multiscale controls on streamwater chemistry

Treesearch

Kevin J. McGuire; Christian E. Torgersen; Gene E. Likens; Donald C. Buso; Winsor H. Lowe; Scott W. Bailey

2014-01-01

By coupling synoptic data from a basin-wide assessment of streamwater chemistry with network-based geostatistical analysis, we show that spatial processes differentially affect biogeochemical condition and pattern across a headwater stream network. We analyzed a high-resolution dataset consisting of 664 water samples collected every 100 m throughout 32 tributaries in...

Cd-doped ZnO quantum dots-based immunoassay for the quantitative determination of bisphenol A.

PubMed

Zhang, Jun; Zhao, Su-Qing; Zhang, Kun; Zhou, Jian-Qing

2014-01-01

Bisphenol A (BPA) is a ubiquitous environmental contaminant in food products and aquatic ecosystems. Its endocrine and developmental toxicity presents a serious concern to human health and an effective high-throughput method for its detection is desirable. In this paper, water-soluble quantum dots (QDs) have been conjugated covalently with BPA antibodies and the conjugate has been utilized in a competitive fluorescence-linked immunoassay (FLISA). Cd-doped ZnO QDs were functionalized with poly(amidoamine) (PAMAM) dendrimers, as evidenced by ultraviolet absorption spectrum and fluorescence emission spectra analyses, and this led to their successful transfer into aqueous solution. Biological mass spectrometry demonstrated that the bisphenol A antibodies were successfully coupled to the water-soluble QDs, and the structures of these conjugates kept intact. The FLISA method allowed for BPA determination in a linear working range of 20.8-330.3 ng mL(-1) with the limit of detection (LOD) of 13.1 ng mL(-1). The recoveries of BPA from water samples were from 85.92% to 109.62%. In conclusion, a rapid and sensitive FLISA was developed by utilizing novel QD coupling method and validated for use in aqueous samples. Copyright © 2013 Elsevier Ltd. All rights reserved.

Investigation of pharmaceuticals in Missouri natural and drinking water using high performance liquid chromatography-tandem mass spectrometry.

PubMed

Wang, Chuan; Shi, Honglan; Adams, Craig D; Gamagedara, Sanjeewa; Stayton, Isaac; Timmons, Terry; Ma, Yinfa

2011-02-01

A comprehensive method has been developed and validated in two different water matrices for the analysis of 16 pharmaceutical compounds using solid phase extraction (SPE) of water samples, followed by liquid chromatography coupled with tandem mass spectrometry. These 16 compounds include antibiotics, hormones, analgesics, stimulants, antiepileptics, and X-ray contrast media. Method detection limits (MDLs) that were determined in both reagent water and municipal tap water ranged from 0.1 to 9.9 ng/L. Recoveries for most of the compounds were comparable to those obtained using U.S. EPA methods. Treated and untreated water samples were collected from 31 different water treatment facilities across Missouri, in both winter and summer seasons, and analyzed to assess the 16 pharmaceutical compounds. The results showed that the highest pharmaceutical concentrations in untreated water were caffeine, ibuprofen, and acetaminophen, at concentrations of 224, 77.2, and 70 ng/L, respectively. Concentrations of pharmaceuticals were generally higher during the winter months, as compared to those in the summer due, presumably, to smaller water quantities in the winter, even though pharmaceutical loadings into the receiving waters were similar for both seasons. © 2010 Elsevier Ltd. All rights reserved.

On-line determination of Sb(III) and total Sb using baker's yeast immobilized on polyurethane foam and hydride generation inductively coupled plasma optical emission spectrometry

NASA Astrophysics Data System (ADS)

Menegário, Amauri A.; Silva, Ariovaldo José; Pozzi, Eloísa; Durrant, Steven F.; Abreu, Cassio H.

2006-09-01

The yeast Saccharomyces cerevisiae was immobilized in cubes of polyurethane foam and the ability of this immobilized material to separate Sb(III) and Sb(V) was investigated. A method based on sequential determination of total Sb (after on-line reduction of Sb(V) to Sb(III) with thiourea) and Sb(III) (after on-line solid-liquid phase extraction) by hydride generation inductively coupled plasma optical emission spectrometry is proposed. A flow system assembled with solenoid valves was used to manage all stages of the process. The effects of pH, sample loading and elution flow rates on solid-liquid phase extraction of Sb(III) were evaluated. Also, the parameters related to on-line pre-reduction (reaction coil and flow rates) were optimized. Detection limits of 0.8 and 0.15 μg L - 1 were obtained for total Sb and Sb(III), respectively. The proposed method was applied to the analysis of river water and effluent samples. The results obtained for the determination of total Sb were in agreement with expected values, including the river water Standard Reference Material 1640 certified by the National Institute of Standards and Technology (NIST). Recoveries of Sb(III) and Sb(V) in spiked samples were between 81 ± 19 and 111 ±15% when 120 s of sample loading were used.

Determination of uranium in clinical and environmental samples by FIAS-ICPMS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Karpas, Z.; Lorber, A.; Halicz, L.

Uranium may enter the human body through ingestion or inhalation. Ingestion of uranium compounds through the diet, mainly drinking water, is a common occurrence, as these compounds are present in the biosphere. Inhalation of uranium-containing particles is mainly an occupational safety problem, but may also take place in areas where uranium compounds are abundant. The uranium concentration in urine samples may serve as an indication of the total uranium body content. A method based on flow injection and inductively coupled plasma mass spectrometry (FIAS-ICPMS) was found to be most suitable for determination of uranium in clinical samples (urine and serum),more » environmental samples (seawater, wells and carbonate rocks) and in liquids consumed by humans (drinking water and commercial beverages). Some examples of the application of the FIAS-ICPMS method are reviewed and presented here.« less

Simultaneous speciation and preservation of aqueous As, Sb and Se redox couples

NASA Astrophysics Data System (ADS)

Wu, D.; Pichler, T.

2014-12-01

We developed a new method for the simultaneous speciation analysis of inorganic arsenic (III, V), antimony (III, V) and selenium (IV, VI) in water samples via double-focusing sector field-inductively coupled plasma-mass spectrometry (SF-ICP-MS) coupled to high performance liquid chromatography (HPLC). A Hamilton PRX-X100 anion exchange column with EDTA (pH of 4.7) and 3% methanol as mobile phase was used for species separation. The flow rate was set to 1.5 mL min-1 and a solvent gradient (linear ramp from 5 mM to 30 mM) was applied. The overall analysis time for all six desired species was 11 minutes. The detection limits for As(III), As(V), Sb(III), Sb(V), Se(VI) and Se(IV) were 0.02 μg L-1, 0.06 μg L-1, 0.2 μg L-1, 0.02 μg L-1, 0.2 μg L-1 and 0.4 μg L-1 respectively. The retention times for As(III), As(V), Sb(III), Sb(V), Se(IV) and Se(VI) were 1.70, 2.94, 7.14, 2.28, 3.38 and 9.36 min, respectively. Subsequently, the stability of inorganic As(III, V), Sb(III, V) and Se(IV, VI) species in different water samples (groundwater, lake water and river water) was studied over a time scale of 11 weeks. High concentrations of Fe (25.0 mg/L) and Mn (25.0 mg/L) were added to different matrices to simulate Fe and Mn rich environments. All samples were spiked with 5.0 μg/L As(III, V) and Sb(III, V) and 15.0 μg/L Se(IV, VI).. We investigated several strategies for species preservation, i.e., EDTA only, EDTA combined with acidification (HCl, HNO3, formic acid and acetic acid). The preserved samples were stored at 4 °C in the dark. For comparison, another subsample without any preservation was stored at room temperature in the presence of light. The results showed that a combination EDTA acidified to pH of 3 can be used to preserve all species for at least 11 weeks. While EDTA only (pH = 6) failed to preserve As and Sb species, although Se species were preserved.

Hyperspectral Remote Sensing of the Coastal Ocean: Adaptive Sampling and Forecasting of In situ Optical Properties

DTIC Science & Technology

2003-09-30

We are developing an integrated rapid environmental assessment capability that will be used to feed an ocean nowcast/forecast system. The goal is to develop a capacity for predicting the dynamics in inherent optical properties in coastal waters. This is being accomplished by developing an integrated observation system that is being coupled to a data assimilative hydrodynamic bio-optical ecosystem model. The system was used adaptively to calibrate hyperspectral remote sensing sensors in optically complex nearshore coastal waters.

Aqueous heterogeneity at the air/water interface revealed by 2D-HD-SFG spectroscopy.

PubMed

Hsieh, Cho-Shuen; Okuno, Masanari; Hunger, Johannes; Backus, Ellen H G; Nagata, Yuki; Bonn, Mischa

2014-07-28

Water molecules interact strongly with each other through hydrogen bonds. This efficient intermolecular coupling causes strong delocalization of molecular vibrations in bulk water. We study intermolecular coupling at the air/water interface and find intermolecular coupling 1) to be significantly reduced and 2) to vary strongly for different water molecules at the interface--whereas in bulk water the coupling is homogeneous. For strongly hydrogen-bonded OH groups, coupling is roughly half of that of bulk water, due to the lower density in the near-surface region. For weakly hydrogen-bonded OH groups that absorb around 3500 cm(-1), which are assigned to the outermost, yet hydrogen-bonded OH groups pointing towards the liquid, coupling is further reduced by an additional factor of 2. Remarkably, despite the reduced structural constraints imposed by the interfacial hydrogen-bond environment, the structural relaxation is slow and the intermolecular coupling of these water molecules is weak. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrophilic interaction liquid chromatography coupled to high-resolution mass spectrometry to determine artificial sweeteners in environmental waters.

PubMed

Salas, Daniela; Borrull, Francesc; Fontanals, Núria; Marcé, Rosa Maria

2015-06-01

Artificial sweeteners are food additives employed as sugar substitutes which are now considered to be emerging organic contaminants. In the present study, a method is developed for the determination of a group of artificial sweeteners in environmental waters. Considering the polar and hydrophilic character of these compounds, hydrophilic interaction liquid chromatography is proposed for their separation as an alternative to traditional reversed-phase liquid chromatography. Two stationary phases with different chemistry were compared for this purpose. For the detection of the analytes, high-resolution mass spectrometry (Orbitrap) was employed to take advantage of its benefits in terms of reliable quantification and confirmation for the measurement of accurate masses. Solid-phase extraction was chosen as the sample treatment, in which the extract in a mixture of NH4OH:MeOH:ACN (1:4:15) was directly injected into the chromatographic system, simplifying the analytical procedure. The optimized method was validated on river and waste water samples. For example, in the case of effluent water samples, limits of detection ranged from 0.002 to 0.7 μg/L and limits of quantification ranged from 0.004 to 1.5 μg/L. Apparent (whole method) recoveries ranged from 57 to 74% with intra-day precision (%RSD, n = 5) ranging from 6 to 25%. The method was successfully applied to water samples from different rivers in Catalonia and different waste water treatment plants in Tarragona. Acesulfame, cyclamate, saccharine and sucralose were found in several samples.

Rapid Microcystin Determination Using a Paper Spray Ionization Method with a Time-of-Flight Mass Spectrometry System.

PubMed

Zhu, Xiaoqiang; Huang, Zhengxu; Gao, Wei; Li, Xue; Li, Lei; Zhu, Hui; Mo, Ting; Huang, Bao; Zhou, Zhen

2016-07-13

The eutrophication of surface water sources and climate changes have resulted in an annual explosion of cyanobacterial blooms in many irrigating and drinking water resources. To decrease health risks to the public, a rapid real time method for the synchronous determination of two usually harmful microcystins (MC-RR and MC-LR) in environmental water samples was built by employing a paper spray ionization method coupled with a time-of-flight mass spectrometer system. With this approach, direct analysis of microcystin mixtures without sample preparation has been achieved. Rapid detection was performed, simulating the release process of microcystins in reservoir water samples, and the routine detection frequency was every three minutes. The identification time of microcystins was reduced from several hours to a few minutes. The limit of detection is 1 μg/L, and the limit of quantitation is 3 μg/L. This method displays the ability for carrying out rapid, direct, and high-throughput experiments for determination of microcystins, and it would be of significant interest for environmental and food safety applications.

Dissolution kinetics of volatile organic compound vapors in water: An integrated experimental and computational study

NASA Astrophysics Data System (ADS)

Mahmoodlu, Mojtaba G.; Pontedeiro, Elizabeth M.; Pérez Guerrero, Jesús S.; Raoof, Amir; Majid Hassanizadeh, S.; van Genuchten, Martinus Th.

2017-01-01

In this study we performed batch experiments to investigate the dissolution kinetics of trichloroethylene (TCE) and toluene vapors in water at room temperature and atmospheric pressure. The batch systems consisted of a water reservoir and a connected headspace, the latter containing a small glass cylinder filled with pure volatile organic compound (VOC). Results showed that air phase concentrations of both TCE and toluene increased relatively quickly to their maximum values and then became constant. We considered subsequent dissolution into both stirred and unstirred water reservoirs. Results of the stirred experiments showed a quick increase in the VOC concentrations with time up to their solubility limit in water. VOC vapor dissolution was found to be independent of pH. In contrast, salinity had a significant effect on the solubility of TCE and toluene vapors. VOC evaporation and vapor dissolution in the stirred water reservoirs followed first-order rate processes. Observed data could be described well using both simplified analytical solutions, which decoupled the VOC dynamics in the air and water phases, as well as using more complete coupled solutions. However, the estimated evaporation (ke) and dissolution (kd) rate constants differed by up to 70% between the coupled and uncoupled formulations. We also numerically investigated the effects of fluid withdrawal from the small water reservoir due to sampling. While decoupling the VOC air and water phase mass transfer processes produced unreliable estimates of kd, the effects of fluid withdrawal on the estimated rate constants were found to be less important. The unstirred experiments showed a much slower increase in the dissolved VOC concentrations versus time. Molecular diffusion of the VOCs within the aqueous phase became then the limiting factor for mass transfer from air to water. Fluid withdrawal during sampling likely caused some minor convection within the reservoir, which was simulated by increasing the apparent liquid diffusion coefficient.

The biological pump and lower trophic level controls on carbon cycling in Lake Superior: Insights from a multi-pronged study

NASA Astrophysics Data System (ADS)

Schreiner, K. M.; Bramburger, A.; Ozersky, T.; Sheik, C.; Steinman, B. A.

2016-02-01

Lake Superior is the largest freshwater lake in the world, supporting economically important fisheries and providing drinking water to hundreds of thousands of people. In recent decades, summer surface water temperature and the intensity and duration of water column stratification in the lake has increased steadily. These physical changes have resulted in significant perturbations to lower trophic level ecosystem characteristics. Recent observations of Great Lakes plankton assemblages have revealed multi-decadal patterns of community reorganization, with increased relative abundance of taxa characteristic of warmer waters. These changes, coupled with changing nutrient concentrations and colonization by non-native taxa, threaten to shift trophic structure and carbon dynamics at the bottom of the food web. To this end, this study seeks to quantify the impacts of this ecosystem shift on carbon fixation, the biological pump, and organic carbon cycling in Lake Superior. Utilizing a combined sampling approach, in the summer of 2015 we collected water, sediment, and biological samples across a nearshore-to-offshore gradient in the western arm of Lake Superior. Analyses included the community composition of bacteria, archaea, phytoplankton, and zooplankton; water column carbon and nutrient speciation; algal pigments and pigment degradation products; and net primary productivity. The collection of surface sediments allowed for additional assessment of benthic-pelagic coupling. The novel combination of this wide-ranging set of analyses to a locally and globally important water body like Lake Superior allowed us to fully assess the interactions between lower trophic level biology and carbon and nutrient cycling throughout the water column. Preliminary data indicates that microbial community composition was variable across the western arm of Lake Superior and showed signs of stratification at individual stations (>100 m deep). Sample collection occurred soon after lake stratification in July 2015, and the presence of a deep chlorophyll maximum was noted. The results shed light on the functioning of the biological pump and nutrient and carbon dynamics in a changing ecosystem and provides insight on how further change in Lake Superior and other aquatic systems will affect ecosystem function and services.

Impact of industrial wastewater disposal on surface water bodies in Mostord area, north greater Cairo.

PubMed

Abdel-Sabour, M F; Rabie, F H; Mostafa, T; Hassan, S A

2001-10-01

The studied area (Shoubra El-Khima, Bahteem and Mostorod) lies in the industrial area north of Greater Cairo. The area suffers from several environmental problems such as sewage and disposal of pollutants from the surrounding factories into the surface water pathways in the area. Water samples were collected seasonally from different waterways found in the area, domestic and or industrial liquid wastes from 12 discharge tubes of different factories (as a point source of pollution). Chemical characteristics of different water samples and its heavy metals content were determined using ion coupled plasma technique (ICP). Results indicate that industrial and domestic wastewater samples contain several toxic levels of tested heavy metals (Cd, Co, Pb and Ni) which have a serious impact on surface waterways in the area. Shebin El-Qanater collector drain samples exhibited the highest levels of Cd, Co, Pb and Ni compared to other tested water bodies. Mostorod collector drain samples showed the highest levels of Zn and Cu. Industrial effluent samples collected from Cairo Company for Fabric industry had the highest amounts of total Zn Cu, Cd, Co and Pb, while Delta steel company discharges the highest amounts of total Fe and Mn. Al-Ahleya Plastic Company discharges the highest amounts of total-Ni. Generally, it is necessary to impose the environmental laws and its regulation regarding the industrial wastewater treatments and disposals to minimize the risk of the adverse effects of these pollutants.

High‐precision determination of lithium and magnesium isotopes utilising single column separation and multi‐collector inductively coupled plasma mass spectrometry

PubMed Central

Misra, Sambuddha; Lloyd, Nicholas; Elderfield, Henry; Bickle, Mike J.

2017-01-01

Rationale Li and Mg isotopes are increasingly used as a combined tool within the geosciences. However, established methods require separate sample purification protocols utilising several column separation procedures. This study presents a single‐step cation‐exchange method for quantitative separation of trace levels of Li and Mg from multiple sample matrices. Methods The column method utilises the macro‐porous AGMP‐50 resin and a high‐aspect ratio column, allowing quantitative separation of Li and Mg from natural waters, sediments, rocks and carbonate matrices following the same elution protocol. High‐precision isotope determination was conducted by multi‐collector inductively coupled plasma mass spectrometry (MC‐ICPMS) on the Thermo Scientific™ NEPTUNE Plus™ fitted with 1013 Ω amplifiers which allow accurate and precise measurements at ion beams ≤0.51 V. Results Sub‐nanogram Li samples (0.3–0.5 ng) were regularly separated (yielding Mg masses of 1–70 μg) using the presented column method. The total sample consumption during isotopic analysis is <0.5 ng Li and <115 ng Mg with long‐term external 2σ precisions of ±0.39‰ for δ7Li and ±0.07‰ for δ26Mg. The results for geological reference standards and seawater analysed by our method are in excellent agreement with published values despite the order of magnitude lower sample consumption. Conclusions The possibility of eluting small sample masses and the low analytical sample consumption make this method ideal for samples of limited mass or low Li concentration, such as foraminifera, mineral separates or dilute river waters. PMID:29078008

Hydrometric, Hydrochemical, and Hydrogeophysical Runoff Characterization Across Multiple Land Covers in the Agua Salud Project, Panama

NASA Astrophysics Data System (ADS)

Litt, Guy Finley

As the Panama Canal Authority faces sensitivity to water shortages, managing water resources becomes crucial for the global shipping industry's security. These studies address knowledge gaps in tropical water resources to aid hydrological model development and validation. Field-based hydrological investigations in the Agua Salud Project within the Panama Canal Watershed employed multiple tools across a variety of land covers to investigate hydrological processes. Geochemical tracers informed where storm runoff in a stream comes from and identified electrical conductivity (EC) as an economical, high sample frequency tracer during small storms. EC-based hydrograph separation coupled with hydrograph recession rate analyses identified shallow and deep groundwater storage-discharge relationships that varied by season and land cover. A series of plot-scale electrical resistivity imaging geophysical experiments coupled with rainfall simulation characterized subsurface flow pathway behavior and quantified respectively increasing infiltration rates across pasture, 10 year old secondary succession forest, teak (tectona grandis), and 30 year old secondary succession forest land covers. Additional soil water, groundwater, and geochemical studies informed conceptual model development in subsurface flow pathways and groundwater, and identified future research needs.

Determination of 4-tert-octylphenol in surface water samples of Jinan in China by solid phase extraction coupled with GC-MS.

PubMed

Yang, Xueyu; Liu, Mingren; Wang, Zhongpeng; Li, Qian; Zhang, Zhaoliang

2013-08-01

Octylphenols, considered as xenoestrogens, mainly exist as 4-tert-octylphenol (OP) in aquatic environments. The high stability and accumulation of OP in aquatic systems have caused endocrine disruption. The OP in surface water in Jinan, China was analyzed by gas chromatography-mass spectrometry (GC-MS) coupled with solid phase extraction (SPE). Water samples were extracted by SPE on a cartridge system containing C-18 as sorbent. To increase sensitivity and selectivity, OP was derivatized to 4-tert-octyl-phenoxy silane. With the use of phenanthrene-d10 as internal standard, the detection limit based on signal-to-noise ratio (S/N = 3) was 0.06 ng/mL. The average recovery was from 84.67% to 109.7%. The precision of the method given as the relative standard deviations (RSD) was within the range 6.24%-12.96%. In the target water samples, the concentrations of OP were as follows: 15.88-71.24 ng/L for Jinxiuchuan Reservoir, 3.850-26.68 ng/L for the city moat, 6.930-41.56 ng/L for Daming Lake, 66.03-474.2 ng/L for Xiaoqing River, 14.66-17.72 ng/L for the Yellow River, and 10.60-26.43 ng/L for Queshan Reservoir. The Xiaoqing River was seriously polluted due to the discharge of wastewater from Jinan. Jinxiuchuan Reservoir had a higher concentration of OP compared with the Yellow River and Queshan Reservoir, which is ascribed to the surrounding human activities. These data are reported for the first time, providing strong support for the control of OP pollution in Jinan.

Selective determination of semi-volatile thiophene compounds in water by molecularly imprinted polymer thin films with direct headspace gas chromatography sulfur chemiluminescence detection.

PubMed

Hijazi, Hassan Y; Bottaro, Christina S

2018-02-26

Water-compatible molecularly imprinted polymer (MIP) thin films are coupled with headspace gas chromatography sulfur chemiluminescence detection (HS-GC-SCD) to create a new approach for the determination of trace concentrations of thiophene compounds in water samples. Thiophene compounds are persistent, typically petrogenic, organic pollutants of concern due to their potential for biomagnification and bioaccumulation, mutagenicity, and carcinogenicity in terrestrial and aquatic fauna. Identification and quantitation in water, particularly following oil spills, is a priority. Following adsorption of the thiophenes to the MIPs, the MIP-bound analytes are analyzed directly by HS-GC-SCD, with minimal sample manipulation and virtually no organic solvent. Calibration curves of spiked seawater were linear from 5 μg L -1 to 100 μg L -1 and limits of detection (LOD) were in the range of 0.24-0.82 μg L -1 . Low matrix effects were observed in the analysis of thiophene compounds in seawater making the method suitable for use in fresh and saline waters without modification. Acceptable reproducibility was obtained for analysis of thiophene compounds from spiked seawater samples at RSDs ≤7.0% (n = 3).

Direct screening and confirmation of priority volatile organic pollutants in drinking water.

PubMed

Caro, J; Serrano, A; Gallego, M

2007-01-05

A screening tool was proposed for the rapid detection of eight priority volatile organic pollutants according to European standards in drinking water. The method is based on the direct coupling of a headspace sampler with a mass spectrometer, using a chromatographic column heated to 175 degrees C as an interface. The water sample was subjected to the headspace extraction process and the volatile fraction was introduced directly into the mass spectrometer, without prior chromatographic separation, achieving low detection limits (0.6-1.2 ng/ml) for all compounds. The mass spectrum resulting from the simultaneous ionization and fragmentation of the mixture of molecules constitutes the volatile profile of each sample. An appropriate chemometric treatment of these signals permitted them to be classified, on the basis of their volatile composition, as contaminated or uncontaminated with respect to the legally established concentration levels for these compounds in drinking water, and providing no false negatives. A conventional confirmation method was carried out to analyze positive water samples by using the same instrumental setup as in the screening method, but using an appropriate temperature program in the chromatographic column to separate, identify and quantify each analyte.

Chemical quality of tap water in Madrid: multicase control cancer study in Spain (MCC-Spain).

PubMed

Fernández-Navarro, Pablo; Villanueva, Cristina M; García-Pérez, Javier; Boldo, Elena; Goñi-Irigoyen, Fernando; Ulibarrena, Enrique; Rantakokko, Panu; García-Esquinas, Esther; Pérez-Gómez, Beatriz; Pollán, Marina; Aragonés, Nuria

2017-02-01

Chronic consumption of water, which contains contaminants, may give rise to adverse health effects. The Madrid region, covered by the population-based multicase-control (MCC-Spain) study, includes two drinking water supply areas. The different sources of the water, coupled together with the possible differences in water management, mean that there may be differences in drinking water quality. In the context of the MCC study, our aims were to describe contaminant concentrations in tap water drawn from various sampling points distributed around the region, assess these concentrations by reference to guideline values and study possible differences between the two supply areas. Tap water samples were collected from 34 sampling points in 7 towns in the Madrid region (19-29 April 2010), and 23 contaminants (metals, nitrates, disinfection by-product and Mutagen X levels) were quantified. We undertook a descriptive analysis of the contaminant concentrations in the water and compared them between the two water supply areas (Wilcoxon test). We created maps representing the distribution of the concentrations observed at water sampling points and assessed the correlations (Spearman's coefficient) between the different parameters measured. The concentrations of the contaminants were below guideline values. There were differences between the two supply areas in concentration of nitrates (p value = 0.0051) and certain disinfection by-products. While there were positive correlations (rho >0.70) among some disinfection by-products, no correlations were found in metals or nitrates. The differences in nitrate levels could be linked to differences in farming/industrial activities in the catchment areas and in disinfection by-products might be related to the existence of different treatment systems or bromine content in source waters.

Simultaneous determination of chlorinated organic compounds from environmental samples using gas chromatography coupled with a micro electron capture detector and micro-plasma atomic emission detector

NASA Astrophysics Data System (ADS)

Quan, Xie; Chen, Shuo; Platzer, Bernhard; Chen, Jingwen; Gfrerer, Marion

2002-01-01

Water and sediment samples were screened simultaneously for the presence of polychlorinated organic compounds using gas chromatography (GC) coupled with an micro electron capture detector (μ-ECD) and a newly developed helium plasma based on a micro-atomic emission detector (μ-AED). The GC column effluent was split 15:85 between two detectors. In this way, two chromatograms, one obtained by μ-ECD and another by μ-AED, were recorded simultaneously. α-, β-hexachlorocyclohexane and p, p'-DDE were detected. RSDs of the monitoring results from the two detection methods were <20% for the three compounds. A detection limit of 8.5 pg and at least 3 orders of magnitude of linear range for μ-AED was observed.

Cadmium, copper, lead, and zinc determination in precipitation: A comparison of inductively coupled plasma atomic emission spectrometry and graphite furnace atomization atomic absorption spectrometry

USGS Publications Warehouse

Reddy, M.M.; Benefiel, M.A.; Claassen, H.C.

1987-01-01

Selected trace element analysis for cadmium, copper, lead, and zinc in precipitation samples by inductively coupled plasma atomic emission Spectrometry (ICP) and by atomic absorption spectrometry with graphite furnace atomization (AAGF) have been evaluated. This task was conducted in conjunction with a longterm study of precipitation chemistry at high altitude sites located in remote areas of the southwestern United States. Coefficients of variation and recovery values were determined for a standard reference water sample for all metals examined for both techniques. At concentration levels less than 10 micrograms per liter AAGF analyses exhibited better precision and accuracy than ICP. Both methods appear to offer the potential for cost-effective analysis of trace metal ions in precipitation. ?? 1987 Springer-Verlag.

Changes in sample collection and analytical techniques and effects on retrospective comparability of low-level concentrations of trace elements in ground water

USGS Publications Warehouse

Ivahnenko, T.; Szabo, Z.; Gibs, J.

2001-01-01

Ground-water sampling techniques were modified to reduce random low-level contamination during collection of filtered water samples for determination of trace-element concentrations. The modified sampling techniques were first used in New Jersey by the US Geological Survey in 1994 along with inductively coupled plasma-mass spectrometry (ICP-MS) analysis to determine the concentrations of 18 trace elements at the one microgram-per-liter (μg/L) level in the oxic water of the unconfined sand and gravel Kirkwood-Cohansey aquifer system. The revised technique tested included a combination of the following: collection of samples (1) with flow rates of about 2L per minute, (2) through acid-washed single-use disposable tubing and (3) a single-use disposable 0.45-μm pore size capsule filter, (4) contained within portable glove boxes, (5) in a dedicated clean sampling van, (6) only after turbidity stabilized at values less than 2 nephelometric turbidity units (NTU), when possible. Quality-assurance data, obtained from equipment blanks and split samples, indicated that trace element concentrations, with the exception of iron, chromium, aluminum, and zinc, measured in the samples collected in 1994 were not subject to random contamination at 1μg/L.Results from samples collected in 1994 were compared to those from samples collected in 1991 from the same 12 PVC-cased observation wells using the available sampling and analytical techniques at that time. Concentrations of copper, lead, manganese and zinc were statistically significantly lower in samples collected in 1994 than in 1991. Sampling techniques used in 1994 likely provided trace-element data that represented concentrations in the aquifer with less bias than data from 1991 when samples were collected without the same degree of attention to sample handling.

Determination of phthalate esters from environmental water samples by micro-solid-phase extraction using TiO2 nanotube arrays before high-performance liquid chromatography.

PubMed

Zhou, Qingxiang; Fang, Zhi; Liao, Xiangkun

2015-07-01

We describe a highly sensitive micro-solid-phase extraction method for the pre-concentration of six phthalate esters utilizing a TiO2 nanotube array coupled to high-performance liquid chromatography with a variable-wavelength ultraviolet visible detector. The selected phthalate esters included dimethyl phthalate, diethyl phthalate, dibutyl phthalate, butyl benzyl phthalate, bis(2-ethylhexyl)phthalate and dioctyl phthalate. The factors that would affect the enrichment, such as desorption solvent, sample pH, salting-out effect, extraction time and desorption time, were optimized. Under the optimum conditions, the linear range of the proposed method was 0.3-200 μg/L. The limits of detection were 0.04-0.2 μg/L (S/N = 3). The proposed method was successfully applied to the determination of six phthalate esters in water samples and satisfied spiked recoveries were achieved. These results indicated that the proposed method was appropriate for the determination of trace phthalate esters in environmental water samples. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A vastly improved method for in situ stable isotope analysis of very small water samples.

NASA Astrophysics Data System (ADS)

Coleman, M. L.; Christensen, L. E.; Kriesel, J.; Kelly, J.; Moran, J.; Vance, S.

2016-12-01

The stable isotope compositions of hydrogen and oxygen in water, ice and hydrated minerals are key characteristics to determine the origin and history of the material. Originally, analyses were performed by separating hydrogen and preparing CO2 from the oxygen in water for stable isotope ratio mass spectrometry. Subsequently, infrared absorption spectrometry in either a Herriot cell or by cavity ring down allowed direct analysis of water vapor. We are developing an instrument, intended for spaceflight and in situ deployment, which will exploit Capillary Absorption Spectrometry (CAS) for the H and O isotope analysis and a laser to sample planetary ices and hydrated minerals. The Tunable Laser Spectrometer (TLS) instrument (part of SAM on the MSL rover Curiosity) works by infrared absorption and we use its performance as a benchmark for comparison. TLS has a relatively large sample chamber to contain mirrors which give a long absorption pathlength. CAS works on the same principle but utilizes a hollow optic fiber, greatly reducing the sample volume. The fiber is a waveguide, enhancing the laser - water-vapor interaction and giving more than four orders of magnitude increase in sensitivity, despite a shorter optical path length. We have calculated that a fiber only 2 m long will be able to analyze 5 nanomoles of water with a precision of less than 1 per mil for D?H. The fiber is coiled to minimize instrument volume. Our instrument will couple this analytical capability with laser sampling to free water from hydrated minerals and ice and ideally we would use the same laser via a beam-splitter both for sampling and analysis. The ability to analyze very small samples is of benefit in two ways. In this concept it will allow much faster analysis of small sub-samples, while the high spatial sampling resolution offered by the laser will allow analysis of the heterogeneity of isotopic composition within grains or crystals, revealing the history of their growth.

Flow injection on-line displacement/solid phase extraction system coupled with flame atomic absorption spectrometry for selective trace silver determination in water samples.

PubMed

Christou, Chrysoula K; Anthemidis, Aristidis N

2009-04-15

A novel flow injection (FI) on-line displacement solid phase extraction preconcentration and/or separation method coupled with FAAS in order to minimize interference from other metals was developed for trace silver determination. The proposed method involved the on-line formation and subsequently pre-sorption of lead diethyldithiocarbamate (Pb-DDTC) into a column packed with PTFE-turnings. The preconcentration and/or separation of the Ag(I) took place through a displacement reaction between Ag(I) and Pb(II) of the pre-sorbed Pb-DDTC. Finally, the retained analyte was eluted with isobutyl methyl ketone (IBMK) and delivered directly to nebulizer for measuring. Interference from co-existing ions with lower DDTC complex stability in comparison with Pb-DDTC, was eliminated without need for any masking reagent. With 120 s of preconcentration time at a sample flow rate of 7.6 mL min(-1), an enhancement factor of 110 and a detection limit (3s) of 0.2 microg L(-1) were obtained. The precision (RSD, n=10) was 3.1% at the 10 mug L(-1) level. The developed method was successfully applied to trace silver determination in a variety of environmental water samples and certified reference material.

Statistical Methods and Sampling Design for Estimating Step Trends in Surface-Water Quality

USGS Publications Warehouse

Hirsch, Robert M.

1988-01-01

This paper addresses two components of the problem of estimating the magnitude of step trends in surface water quality. The first is finding a robust estimator appropriate to the data characteristics expected in water-quality time series. The J. L. Hodges-E. L. Lehmann class of estimators is found to be robust in comparison to other nonparametric and moment-based estimators. A seasonal Hodges-Lehmann estimator is developed and shown to have desirable properties. Second, the effectiveness of various sampling strategies is examined using Monte Carlo simulation coupled with application of this estimator. The simulation is based on a large set of total phosphorus data from the Potomac River. To assure that the simulated records have realistic properties, the data are modeled in a multiplicative fashion incorporating flow, hysteresis, seasonal, and noise components. The results demonstrate the importance of balancing the length of the two sampling periods and balancing the number of data values between the two periods.

Applying multi-criteria analysis for preliminary assessment of the properties of alginate immobilized Myriophyllum spicatum in lake water samples.

PubMed

Milojković, Jelena V; Popović-Djordjević, Jelena B; Pezo, Lato L; Brčeski, Ilija D; Kostić, Aleksandar Ž; Milošević, Vladan D; Stojanović, Mirjana D

2018-05-11

The preliminary assessment of the properties of alginate immobilized aquatic weed Myriophyllum spicatum beads-MsAlg in a multi-element system of nine Serbian lakes water samples was done. Herein, the results obtained in the biosorption experiment with MsAlg contents of twenty-two elements analysed by inductively coupled plasma-optical emission spectrometry, biosorption capacity, element removal efficiency, total hardness (TH) and quality index of water (WQI) are presented. Scanning electron microscopy with energy dispersive X-ray spectroscopy was used for the characterization of M. spicatum and its beads. The study showed that aluminium, magnesium and strontium were adsorbed by MsAlg in the water samples from all examined lakes; barium and iron in the water samples from six lakes. The overall average efficiency of MsAlg in biosorption of elements was in the following order: Al > Ba > Sr > Fe > Mg (58.6, 51.7, 48.2, 23.9 and 17.7%, respectively). The increase of TH and WQI values after the biosorption was noticed in all studied lake water samples. The most significant correlations for pH were regarding the contents of B, Mg and Ca, whereas WQI was highly correlated to the contents of B and Mg, and pH. The complexity of the obtained data was explained by Cluster Analysis and Principal Component Analysis, which showed good discrimination capabilities between the water samples taken from different locations. Considering that the invasive M. spicatum is natural, widespread and that its immobilization is cheap and eco-friendly, presented findings could be helpful in further assessment of MsAlg beads for its potential use as biofilter. Copyright © 2018 Elsevier Ltd. All rights reserved.

Membrane assisted solvent extraction coupled with liquid chromatography tandem mass spectrometry applied to the analysis of alkylphenols in water samples.

PubMed

Salgueiro-González, N; Turnes-Carou, I; Muniategui-Lorenzo, S; López-Mahía, P; Prada-Rodríguez, D

2013-03-15

This work describes the development and validation of a novel, simple, sensitive and environmental friendly analytical method for the determination of alkylphenols in different types of water samples. The methodology was based on a membrane assisted solvent extraction of only 15 mL of water sample with 500 μL of hexane in combination with liquid chromatography-electrospray ionization tandem mass spectrometry in negative mode (LC-ESI-MS/MS). Acquisition was performed in the multiple reaction monitoring (MRM) mode recording two transitions for the identification of the target compounds. Quantitation is based on the use of deuterated labelled standards as surrogate standards. The figures of merit were satisfactory in all cases: absolute recoveries were close to 50% for most investigated compounds and relative recoveries varied between 81 and 108%. Repeatability and intermediate precision were <20% for all compounds. Uncertainty assessment of measurement was estimated on the basis of an in-house validation according to EURACHEM/CITAC guide. Quantitation limits of the method (MQL) were lower than 0.04 μg L(-1) in all cases, which allow the achievement of the limits established by the Directive 2008/105/EC for surface and seawater samples and by the new proposal COM (2011) 876 final. The feasibility of the proposed method was demonstrated analyzing seawater, surface water and drinking water samples from different areas of A Coruña (Northwest of Spain). The analyses evidenced the presence of nonylphenol in seawater (MQL-0.13 μg L(-1)) and surface water samples (0.12-0.19 μg L(-1)). The highest concentration was observed in drinking water (0.25 μg L(-1)). Copyright © 2013 Elsevier B.V. All rights reserved.

Interlaboratory comparability, bias, and precision for four laboratories measuring constituents in precipitation, November 1982-August 1983

USGS Publications Warehouse

Brooks, M.H.; Schroder, L.J.; Malo, B.A.

1985-01-01

Four laboratories were evaluated in their analysis of identical natural and simulated precipitation water samples. Interlaboratory comparability was evaluated using analysis of variance coupled with Duncan 's multiple range test, and linear-regression models describing the relations between individual laboratory analytical results for natural precipitation samples. Results of the statistical analyses indicate that certain pairs of laboratories produce different results when analyzing identical samples. Analyte bias for each laboratory was examined using analysis of variance coupled with Duncan 's multiple range test on data produced by the laboratories from the analysis of identical simulated precipitation samples. Bias for a given analyte produced by a single laboratory has been indicated when the laboratory mean for that analyte is shown to be significantly different from the mean for the most-probable analyte concentrations in the simulated precipitation samples. Ion-chromatographic methods for the determination of chloride, nitrate, and sulfate have been compared with the colorimetric methods that were also in use during the study period. Comparisons were made using analysis of variance coupled with Duncan 's multiple range test for means produced by the two methods. Analyte precision for each laboratory has been estimated by calculating a pooled variance for each analyte. Analyte estimated precisions have been compared using F-tests and differences in analyte precisions for laboratory pairs have been reported. (USGS)

Surface models for coupled modelling of runoff and sewer flow in urban areas.

PubMed

Ettrich, N; Steiner, K; Thomas, M; Rothe, R

2005-01-01

Traditional methods fail for the purpose of simulating the complete flow process in urban areas as a consequence of heavy rainfall and as required by the European Standard EN-752 since the bi-directional coupling between sewer and surface is not properly handled. The new methodology, developed in the EUREKA-project RisUrSim, solves this problem by carrying out the runoff on the basis of shallow water equations solved on high-resolution surface grids. Exchange nodes between the sewer and the surface, like inlets and manholes, are located in the computational grid and water leaving the sewer in case of surcharge is further distributed on the surface. Dense topographical information is needed to build a model suitable for hydrodynamic runoff calculations; in urban areas, in addition, many line-shaped elements like houses, curbs, etc. guide the runoff of water and require polygonal input. Airborne data collection methods offer a great chance to economically gather densely sampled input data.

Assessment of the acute toxicity of triclosan and methyl triclosan in wastewater based on the bioluminescence inhibition of Vibrio fischeri.

PubMed

Farré, Marinella; Asperger, Daniela; Kantiani, Lina; González, Susana; Petrovic, Mira; Barceló, Damià

2008-04-01

In this work, the contributions of triclosan and its metabolite methyl triclosan to the overall acute toxicity of wastewater were studied using Vibrio fischeri. The protocol used in this paper involved various steps. First, the aquatic toxicities of triclosan and methyl triclosan were determined for standard substances, and the 50% effective concentrations (EC(50)) were determined for these compounds. Second, the toxic responses to different mixtures of triclosan, methyl triclosan, and surfactants were studied in different water matrices, i.e., Milli-Q water, groundwater and wastewater, in order to evaluate (i) the antagonistic or synergistic effects, and (ii) the influence of the water matrices. Finally, chemical analysis was used in conjunction with the toxicity results in order to assess the aquatic toxicities of triclosan and its derivative in wastewaters. In this study, the toxicities of 45 real samples corresponding to the influents and effluents from eight wastewater treatment works (WWTW) were analyzed. Thirty-one samples were from a wastewater treatment plant (WWTP) equipped with two pilot-scale membrane bioreactors (MBR), and the influent and the effluent samples after various treatments were characterized via different chromatographic approaches, including solid-phase extraction (SPE), liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS), and SPE coupled to gas chromatography-mass spectrometry (GC-MS). The toxicity was determined by measuring the bioluminescence inhibition of Vibrio fischeri. In order to complete the study and to extrapolate the results to different WWTPs, the toxicity to V. fischeri of samples from seven more plants was analyzed, as were their triclosan and methyl triclosan concentrations. Good agreement was established between the overall toxicity values and concentrations of the biocides, indicating that triclosan is one of the major toxic organic pollutants currently found in domestic wastewaters.

Speciation analysis of mercury by dispersive solid-phase extraction coupled with capillary electrophoresis.

PubMed

Li, Jinhua; Liu, Junying; Lu, Wenhui; Gao, Fangfang; Wang, Liyan; Ma, Jiping; Liu, Huitao; Liao, Chunyang; Chen, Lingxin

2018-04-23

A pretreatment method of dispersive solid-phase extraction (DSPE) along with back-extraction followed by CE-UV detector was developed for the determination of mercury species in water samples. Sulfhydryl-functionalized SiO 2 microspheres (SiO 2 -SH) were synthesized and used as DSPE adsorbents for selective extraction and enrichment of three organic mercury species namely ethylmercury (EtHg), methylmercury (MeHg), and phenylmercury (PhHg), along with L-cysteine (L-cys) containing hydrochloric acid as back-extraction solvent. Several main extraction parameters were systematically investigated including sample pH, amount of adsorbent, extraction and back-extraction time, volume of eluent, and concentration of hydrochloric acid. Under optimal conditions, good linearity was achieved with correlation coefficients over 0.9990, in the range of 4-200 μg/L for EtHg, and 2-200 μg/L for MeHg and PhHg. The LODs were obtained of 1.07, 0.34, and 0.24 μg/L for EtHg, MeHg, and PhHg, respectively, as well as the LOQs were 3.57, 1.13, and 0.79 μg/L, respectively, with enrichment factors ranging from 109 to 184. Recoveries were attained with tap and lake water samples in a range of 62.3-107.2%, with relative standard deviations of 3.5-10.1%. The results proved that the method of SiO 2 -SH based DSPE coupled with CE-UV was a simple, rapid, cost-effective, and eco-friendly alternative for the determination of mercury species in water samples. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A surface enhanced Raman scattering quantitative analytical platform for detection of trace Cu coupled the catalytic reaction and gold nanoparticle aggregation with label-free Victoria blue B molecular probe.

PubMed

Li, Chongning; Ouyang, Huixiang; Tang, Xueping; Wen, Guiqing; Liang, Aihui; Jiang, Zhiliang

2017-01-15

With development of economy and society, there is an urgent need to develop convenient and sensitive methods for detection of Cu 2+ pollution in water. In this article, a simple and sensitive SERS sensor was proposed to quantitative analysis of trace Cu 2+ in water. The SERS sensor platform was prepared a common gold nanoparticle (AuNP)-SiO 2 sol substrate platform by adsorbing HSA, coupling with the catalytic reaction of Cu 2+ -ascorbic acid (H 2 A)-dissolved oxygen, and using label-free Victoria blue B (VBB) as SERS molecular probes. The SERS sensor platform response to the AuNP aggregations by hydroxyl radicals (•OH) oxidizing from the Cu 2+ catalytic reaction, which caused the SERS signal enhancement. Therefore, by monitoring the increase of SERS signal, Cu 2+ in water can be determined accurately. The results show that the SERS sensor platforms owns a linear response with a range from 0.025 to 25μmol/L Cu 2+ , and with a detection limit of 0.008μmol/L. In addition, the SERS method demonstrated good specificity for Cu 2+ , which can determined accurately trace Cu 2+ in water samples, and good recovery and accuracy are obtained for the water samples. With its high selectivity and good accuracy, the sensitive SERS quantitative analysis method is expected to be a promising candidate for determining copper ions in environmental monitoring and food safety. Copyright © 2016 Elsevier B.V. All rights reserved.

Blank and sample handling troubleshooting in ultratrace analysis of alkylphenols and bisphenol A by liquid chromatography tandem mass spectrometry.

PubMed

Salgueiro-González, N; Concha-Graña, E; Turnes-Carou, I; Muniategui-Lorenzo, S; López-Mahía, P; Prada-Rodríguez, D

2012-11-15

Blank contamination is a notorious problem in the ultratrace analysis of alkylphenols and bisphenol A. The achievement of low detection limits is complicated due to the high background signals. Furthermore, overestimations and underestimations in the analytical results can occur when blank levels are not stable. Thus, a review of sources of blank contamination in this type of analysis was carried out. Several sources of contamination were identified and useful guidelines are proposed for the determination of these compounds in water samples by liquid chromatography coupled with mass spectrometry. The system contamination was maintained below 0.09 ng (reagent blank) for all compounds and below 0.003 μg L(-1) (procedure blank). The main improvement was obtained by using LC-MS grade solvent in the mobile phase and PTFE syringe filters for the filtration of the sample extracts. Sample handling aspects such as filtration and storage of the water samples were also considered. The filtration of the samples should be avoided because both contamination and adsorption problems were observed when different kinds of filters were assayed. The refrigerated storage of water samples should be limited to 5 days (without addition of methanol) or 8 days (with 5% methanol). Copyright © 2012 Elsevier B.V. All rights reserved.

Determination of trace labile copper in environmental waters by magnetic nanoparticle solid phase extraction and high-performance chelation ion chromatography.

PubMed

Wei, Z; Sandron, S; Townsend, A T; Nesterenko, P N; Paull, B

2015-04-01

Cobalt magnetic nanoparticles surface functionalised with iminodiacetic acid were evaluated as a nano-particulate solid phase extraction absorbent for copper ions (Cu(2+)) from environmental water samples. Using an external magnetic field, the collector nanoparticles could be separated from the aqueous phase, and adsorbed ions simply decomplexed using dilute HNO3. Effects of pH, buffer concentration, sample and sorbent volume, extraction equilibrium time, and interfering ion concentration on extraction efficiency were investigated. Optimal conditions were then applied to the extraction of Cu(2+) ions from natural water samples, prior to their quantitation using high-performance chelation ion chromatography. The limits of detection (LOD) of the combined extraction and chromatographic method were ~0.1 ng ml(-1), based upon a 100-fold preconcentration factor (chromatographic performance; LOD=9.2 ng ml(-1) Cu(2+)), analytical linear range from 20 to 5000 ng mL(-1), and relative standard deviations=4.9% (c=1000 ng ml(-1), n=7). Accuracy and precision of the combined approach was verified using a certified reference standard estuarine water sample (SLEW-2) and comparison of sample determinations with sector field inductively coupled plasma mass spectrometry. Recoveries from the addition of Cu(2+) to impacted estuarine and rain water samples were 103.5% and 108.5%, respectively. Coastal seawater samples, both with and without prior UV irradiation and dissolved organic matter removal were also investigated using the new methodology. The effect of DOM concentration on copper availability was demonstrated. Copyright © 2015. Published by Elsevier B.V.

A combination of computational-experimental study on metal-organic frameworks MIL-53(Al) as sorbent for simultaneous determination of estrogens and glucocorticoids in water and urine samples by dispersive micro-solid-phase extraction coupled to UPLC-MS/MS.

PubMed

Gao, Guihua; Li, Sijia; Li, Shuo; Wang, Yudan; Zhao, Pan; Zhang, Xiangyu; Hou, Xiaohong

2018-04-01

In this work, computational and experimental methods were used to study the adsorption of estrogens and glucocorticoids on metal-organic frameworks (MOFs). Computer-aided molecular simulation was applied to predict the adsorption of eight analytes on four MOFs (MIL-101(Cr), MIL-100(Fe), MIL-53(Al), and UiO-66(Zr)) by examining molecular interactions and calculating free binding energies. Subsequently, the four water-stable MOFs were synthesized and evaluated as adsorbents for the target hormones in aqueous solution. As the MOF exhibiting the highest adsorption capacity in both computations and experiments, MIL-53(Al) was chosen as a sorbent to develop a dispersive micro-solid-phase extraction procedure coupled to ultra-performance liquid chromatography tandem mass spectrometry for simultaneous determination of the target analytes in water and human urine samples. Experimental parameters affecting the extraction recoveries, including pH, ionic strength, MIL-53(Al) amount, extraction time, desorption time, and desorption solvent, were optimized. The optimized method provided a linear range of 0.005025-368.6μg/L with good correlation coefficients (0.9982 ≤ r 2 ≤ 0.9992), and limits of detection (S/N = 3) and quantification (S/N = 10) of 0.0015-1.0μg/L and 0.005-1.8μg/L, respectively. The analyte recoveries were in the range of 80.6-98.4% in water samples and 88.4-93.2% in urine samples. Furthermore, MIL-53(Al) showed good stability over 10 extraction cycles (RSD < 10.0%). Good agreement between experimental measurements and computational results showed the potential of this approach for elucidating adsorption mechanisms and predicating extraction efficiencies for MOFs and targets, providing new directions for the development and utilization of MOFs. Copyright © 2017 Elsevier B.V. All rights reserved.

Rapid detection of Naegleria fowleri in water distribution pipeline biofilms and drinking water samples.

PubMed

Puzon, Geoffrey J; Lancaster, James A; Wylie, Jason T; Plumb, Iason J

2009-09-01

Rapid detection of pathogenic Naegleria fowler in water distribution networks is critical for water utilities. Current detection methods rely on sampling drinking water followed by culturing and molecular identification of purified strains. This culture-based method takes an extended amount of time (days), detects both nonpathogenic and pathogenic species, and does not account for N. fowleri cells associated with pipe wall biofilms. In this study, a total DNA extraction technique coupled with a real-time PCR method using primers specific for N. fowleri was developed and validated. The method readily detected N. fowleri without preculturing with the lowest detection limit for N. fowleri cells spiked in biofilm being one cell (66% detection rate) and five cells (100% detection rate). For drinking water, the detection limit was five cells (66% detection rate) and 10 cells (100% detection rate). By comparison, culture-based methods were less sensitive for detection of cells spiked into both biofilm (66% detection for <10 cells) and drinking water (0% detection for <10 cells). In mixed cultures of N. fowleri and nonpathogenic Naegleria, the method identified N. fowleri in 100% of all replicates, whereastests with the current consensus primers detected N. fowleri in only 5% of all replicates. Application of the new method to drinking water and pipe wall biofilm samples obtained from a distribution network enabled the detection of N. fowleri in under 6 h, versus 3+ daysforthe culture based method. Further, comparison of the real-time PCR data from the field samples and the standard curves enabled an approximation of N. fowleri cells in the biofilm and drinking water. The use of such a method will further aid water utilities in detecting and managing the persistence of N. fowleri in water distribution networks.

Design of a portable gas chromatography with a conducting polymer nanocomposite detector device and a method to analyze a gas mixture.

PubMed

Pirsa, Sajad

2017-04-01

A portable chromatography device and a method were developed to analyze a gas mixture. The device comprises a chromatographic column for separating components of a sample of the gas mixture. It has an air pump coupled to the inlet of a chromatographic column for pumping air and an injector coupled to the inlet of chromatographic column for feeding the sample using the air as a carrier gas. A detector is arranged downstream from and coupled to the outlet of the chromatographic column. The detector is a nanostructure semiconductive microfiber. The device further comprises an evaluation unit arranged and configured to evaluate each detected component to determine the concentration. The designed portable system was used for simultaneous detection of amines. The possibility of applying dispersive liquid-liquid microextraction for the determination of analytes in trace levels is demonstrated. The reproducibility of this method is acceptable, and good standard deviations were obtained. The relative standard deviation value is less than 6% for all analytes. Finally, the method was successfully applied to the extraction and determination of analytes in water samples. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Prevalence of Rotavirus Genogroup A and Norovirus Genogroup II in Bassaseachic Falls National Park Surface Waters in Chihuahua, Mexico.

PubMed

Delgado-Gardea, Ma Carmen E; Tamez-Guerra, Patricia; Gomez-Flores, Ricardo; Mendieta-Mendoza, Aurora; Zavala-Díaz de la Serna, Francisco Javier; Contreras-Cordero, Juan Francisco; Erosa-de la Vega, Gilberto; Pérez-Recoder, María Concepción; Sánchez-Ramírez, Blanca; González-Horta, Carmen; Infante-Ramírez, Rocío

2017-05-05

In areas lacking potable water treatment, drinking contaminated water may represent a public health threat. In addition to enteropathogenic bacteria and parasites, fecal contamination in water environments is associated with the transmission of enteric viruses and other causal agents of infectious disease. Rotavirus and norovirus are the main enteric viral agents responsible for diarrheic outbreaks. The aim of the present study was to detect seasonal variation of rotavirus and norovirus in the surface water at Bassaseachic Falls National Park during 2013. Rivers and streams within and nearby this park were sampled once in each season during 2013. Viral concentration was carried out by a handmade filtration equipment, using a commercial electropositive membrane coupled with the virus absortion elution technique (VIRADEL©). Detection of rotavirus and norovirus was performed by SYBR Green reverse transcription-real time polymerase chain reaction (SYBR GREEN© RT-qPCR) analyses. Norovirus genogroup II was detected in samples collected in June and October 2013. In the case of rotavirus, genogroup A was detected in March and June. The presence of rotavirus and norovirus was related to viral acute diarrhea in children less than five years of age, who were inhabiting the sampled areas. This may indicates that the contaminated water was potentially a risk factor for regional diarrheic outbreaks.

Anaerobic methane oxidation in two tropical freshwater systems

NASA Astrophysics Data System (ADS)

Roland, Fleur; Darchambeau, François; Crowe, Sean A.; Borges, Alberto V.

2014-05-01

Lake Kivu is one of the East African Great Lakes. It is located at the border between Rwanda and the Democratic Republic of the Congo. It is a deep meromictic lake characterized by huge amounts of methane (CH4) (60 km3 at 0° C and 1 atm) dissolved in its deep waters. Two thirds of the CH4 originates from anoxic bacterial reduction of dissolved carbon dioxide and one third from anaerobic degradation of settling organic material. CH4 then diffuses slowly from the monimolimnion to surface waters where many is oxidised by methanotrophic microorganisms. In Lake Kivu, this biological oxidation of CH4 could occur with different final electron acceptors: oxygen (aerobic oxidation) but also nitrate (NO3-), nitrite, sulfate (SO42-), iron (Fe) or manganese (Mn) in anaerobic conditions. If the anaerobic oxidation of CH4 (AOM) is generally coupled to SO42- reduction in marine waters, electron acceptors of the AOM were rarely investigated in freshwater systems. Five field campaigns were conducted from 2011 to 2013 during periods with contrasted ventilations of the upper water column. The dry season is characterized by a deeper mixing of surface waters ended by a steep gradient of physico-chemical conditions at the redox interface, while during the rainy season the mixed layer is shallower and ended at its deeper part by a NO3- accumulation zone. Sampling was conducted in the main basin of Lake Kivu but also in a particular sub-basin located northeast of the lake, the Kabuno Bay. Both systems are meromictic but differ in terms of morphometry and geochemistry with a shallower permanent chemocline and higher concentrations of CH4, Fe and Mn in the anoxic waters in Kabuno Bay compared to the main lake. Samples were collected for the measurements of CH4 concentrations and the various potential electron acceptors of the AOM. CH4 oxidation rates were measured along vertical profiles at 5 m and 0.5 m depth intervals respectively in the main basin and Kabuno bay water columns. Results indicate high rates of AOM in both main basin (up to 7 μmol L-1 d-1) and Kabuno bay (up to 16 μmol L-1 d-1). In the main basin, we observed a co-occurrence of the AOM and the SO42- reduction in the dry season. During the rainy season, higher oxidation rates occurred in the NO3- accumulation zone, which is in favour of a coupling between AOM and NO3- reduction. In Kabuno Bay, the higher AOM rates were observed at depths with highest particulate Fe concentrations. Our results suggest that AOM coupled with SO42-reduction may occur during the dry season in the main basin, whereas this oxidation could be coupled with NO3- reduction during the rainy season. In Kabuno Bay, the co-occurrence of the Fe [III] peak with high AOM suggests a coupling between the AOM and Fe reduction.

Field and laboratory arsenic speciation methods and their application to natural-water analysis

USGS Publications Warehouse

Bednar, A.J.; Garbarino, J.R.; Burkhardt, M.R.; Ranville, J.F.; Wildeman, T.R.

2004-01-01

The toxic and carcinogenic properties of inorganic and organic arsenic species make their determination in natural water vitally important. Determination of individual inorganic and organic arsenic species is critical because the toxicology, mobility, and adsorptivity vary substantially. Several methods for the speciation of arsenic in groundwater, surface-water, and acid mine drainage sample matrices using field and laboratory techniques are presented. The methods provide quantitative determination of arsenite [As(III)], arsenate [As(V)], monomethylarsonate (MMA), dimethylarsinate (DMA), and roxarsone in 2-8min at detection limits of less than 1??g arsenic per liter (??g AsL-1). All the methods use anion exchange chromatography to separate the arsenic species and inductively coupled plasma-mass spectrometry as an arsenic-specific detector. Different methods were needed because some sample matrices did not have all arsenic species present or were incompatible with particular high-performance liquid chromatography (HPLC) mobile phases. The bias and variability of the methods were evaluated using total arsenic, As(III), As(V), DMA, and MMA results from more than 100 surface-water, groundwater, and acid mine drainage samples, and reference materials. Concentrations in test samples were as much as 13,000??g AsL-1 for As(III) and 3700??g AsL-1 for As(V). Methylated arsenic species were less than 100??g AsL-1 and were found only in certain surface-water samples, and roxarsone was not detected in any of the water samples tested. The distribution of inorganic arsenic species in the test samples ranged from 0% to 90% As(III). Laboratory-speciation method variability for As(III), As(V), MMA, and DMA in reagent water at 0.5??g AsL-1 was 8-13% (n=7). Field-speciation method variability for As(III) and As(V) at 1??g AsL-1 in reagent water was 3-4% (n=3). ?? 2003 Elsevier Ltd. All rights reserved.

Multivariate analysis of the volatile components in tobacco based on infrared-assisted extraction coupled to headspace solid-phase microextraction and gas chromatography-mass spectrometry.

PubMed

Yang, Yanqin; Pan, Yuanjiang; Zhou, Guojun; Chu, Guohai; Jiang, Jian; Yuan, Kailong; Xia, Qian; Cheng, Changhe

2016-11-01

A novel infrared-assisted extraction coupled to headspace solid-phase microextraction followed by gas chromatography with mass spectrometry method has been developed for the rapid determination of the volatile components in tobacco. The optimal extraction conditions for maximizing the extraction efficiency were as follows: 65 μm polydimethylsiloxane-divinylbenzene fiber, extraction time of 20 min, infrared power of 175 W, and distance between the infrared lamp and the headspace vial of 2 cm. Under the optimum conditions, 50 components were found to exist in all ten tobacco samples from different geographical origins. Compared with conventional water-bath heating and nonheating extraction methods, the extraction efficiency of infrared-assisted extraction was greatly improved. Furthermore, multivariate analysis including principal component analysis, hierarchical cluster analysis, and similarity analysis were performed to evaluate the chemical information of these samples and divided them into three classifications, including rich, moderate, and fresh flavors. The above-mentioned classification results were consistent with the sensory evaluation, which was pivotal and meaningful for tobacco discrimination. As a simple, fast, cost-effective, and highly efficient method, the infrared-assisted extraction coupled to headspace solid-phase microextraction technique is powerful and promising for distinguishing the geographical origins of the tobacco samples coupled to suitable chemometrics. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DEVELOPMENT OF ARSENIC SPECIATION METHODOLOGY FOR DETERMINING BACKGROUND EXPOSURE LEVELS OF INORGANIC ARSENIC IN DIETARY SAMPLES AND APPLICATION TO IN VITRO BIOACCESSIBILITY STUDIES

EPA Science Inventory

Ingestion of arsenic is the primary route of exposure for most people, with dietary intake and drinking water as the primary sources of that exposure. Traditionally, measurements of arsenic dietary intake are based on food consumption data coupled with total arsenic data from a ...

Effects of varying water adsorption on a Cu3(BTC)2 metal-organic framework (MOF) as studied by 1H and 13C solid-state NMR spectroscopy.

PubMed

Gul-E-Noor, Farhana; Jee, Bettina; Pöppl, Andreas; Hartmann, Martin; Himsl, Dieter; Bertmer, Marko

2011-05-07

The process of water adsorption on a dehydrated Cu(3)(BTC)(2) (copper (II) benzene 1,3,5-tricarboxylate) metal-organic framework (MOF) was studied with (1)H and (13)C solid-state NMR. Different relative amounts of water (0.5, 0.75, 1, 1.5, 2, and 5 mole equivalents with respect to copper) were adsorbed via the gas phase. (1)H and (13)C MAS NMR spectra of dehydrated and water-loaded Cu(3)(BTC)(2) samples gave evidence on the structural changes due to water adsorption within the MOF material as well as information on water dynamics. The analysis of (1)H spinning sideband intensities reveals differences in the (1)H-(63/65)Cu hyperfine coupling between dehydrated and water-loaded samples. The investigation was continued for 60 days to follow the stability of the Cu(3)(BTC)(2) network under humid conditions. NMR data reveal that Cu(3)(BTC)(2) decomposes quite fast with the decomposition being different for different water contents. This journal is © the Owner Societies 2011

Groundwater and surface water exchange and resulting Nitrate dynamics in the Bogue Phalia Basin in northwestern Mississippi

USGS Publications Warehouse

Barlow, Jeannie R.; Coupe, Richard H.

2012-01-01

During April 2007 through September 2008, the USGS collected hydrogeologic and water-quality data from a site on the Bogue Phalia to evaluate the role of groundwater and surface-water interaction on the transport of nitrate to the shallow sand and gravel aquifer underlying the Mississippi Alluvial Plain in northwestern Mississippi. A two-dimensional groundwater/surface-water exchange model was developed using temperature and head data and VS2DH, a variably saturated flow and energy transport model. Results from this model showed that groundwater/surface-water exchange at the site occurred regularly and recharge was laterally extensive into the alluvial aquifer. Nitrate was consistently reported in surface-water samples (n = 52, median concentration = 39.8 μmol/L) although never detected in samples collected from in-stream piezometers or shallow monitoring wells adjacent to the stream (n = 46). These two facts, consistent detections of nitrate in surface water and no detections of nitrate in groundwater, coupled with model results that indicate large amounts of surface water moving through an anoxic streambed, support the case for denitrification and nitrate loss through the streambed.

Sensitive trace enrichment of environmental andiandrogen vinclozolin from natural waters and sediment samples using hollow-fiber liquid-phase microextraction.

PubMed

Lambropoulou, Dimitra A; Albanis, Triantafyllos A

2004-12-17

The presence of vinclozolin in the environment as far as the endocrine disruption effects in biota are concerned has raised interest in the environmental fate of this compound. In this respect, the present study attempts to investigate the feasibility of applying a novel quantitative method, liquid-phase microextraction (LPME), so as to determine this environmental andiandrogen in environmental samples such as water and sediment samples. The technique involved the use of a small amount (3 microL) of organic solvent impregnated in a hollow fiber membrane, which was attached to the needle of a conventional GC syringe. The extracted samples were analyzed by gas chromatography coupled with electron-capture detection. Experimental LPME conditions such as extraction solvent, stirring rate, content of NaCl and pH were tested. Once LPME was optimized, the performance of the proposed technique was evaluated for the determination of vinclozolin in different types of natural water samples. The recovery of spiked water samples was from 80 to 99%. The procedure was adequate for quantification of vinclozolin in waters at levels of 0.010 to 50 microg/L (r> 0.994) with a detection limit of 0.001 microg/L (S/N= 3). Natural sediment samples from the Aliakmonas River area (Macedonia, Greece) spiked with the target andiandrogen compound were liquid-liquid extracted and analyzed by the methodology developed in this work. No significant interferences from the samples matrix were noticed, indicating that the reported methodology is an innovative tactic for sample preparation in sediment analysis, with a considerable improvement in the achieved detection limits. The results demonstrated that apart from analyte enrichment, the proposed LPME procedure also serves as clean-up method and could be successfully performed to determine trace amounts of vinclozolin in water and sediment samples.

SYSTEM OPTIMIZATION FOR THE AUTOMATIC SIMULTANEOUS DETERMINATION OF ARSENIC, SELENIUM, AND ANTIMONY, USING HYDRIDE GENERATION INTRODUCTION TO AN INDUCTIVELY COUPLED PLASMA.

USGS Publications Warehouse

Pyen, Grace S.; Browner, Richard F.; Long, Stephen

1986-01-01

A fixed-size simplex has been used to determine the optimum conditions for the simultaneous determination of arsenic, selenium, and antimony by hydride generation and inductively coupled plasma emission spectrometry. The variables selected for the simplex were carrier gas flow rate, rf power, viewing height, and reagent conditions. The detection limit for selenium was comparable to the preoptimized case, but there were twofold and fourfold improvements in the detection limits for arsenic and antimony, respectively. Precision of the technique was assessed with the use of artificially prepared water samples.

Investigating water adsorption onto natural mineral dust particles: Linking DRIFTS experiments and BET theory

NASA Astrophysics Data System (ADS)

Joshi, Nitesh; Romanias, Manolis N.; Riffault, Veronique; Thevenet, Frederic

2017-08-01

The adsorption of water molecules on natural mineral dusts was investigated employing in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS). The natural dust samples originated from North and West Africa, Saudi Arabia and Gobi desert regions. Furthermore, the hygroscopicity of commercially available Arizona Test Dusts (ATDs) and Icelandic volcanic ash were examined. N2 sorption measurements, X-ray fluorescence and diffraction (XRF and XRD), as well as Inductively Coupled Plasma Mass Spectrometry (ICP-MS) analyses were performed to determine the physicochemical properties of the particles. The water adsorption experiments were conducted in an optical cell, at room temperature under the relative humidity (RH) range of 1.9-95%. Results were simulated using a modified three-parameter Brunauer-Emmett-Teller (BET) equation. Water monolayer (ML) was formed in the RH range of 15-25%, while additional water layers were formed at higher RH. Besides, the standard adsorption enthalpies of water onto natural mineral dust samples were determined. A thorough comparison of two commercially available ATD samples indicated that size distribution and/or porosity should play a key role in particle hygroscopicity. Regarding the natural mineral particles, Ca/Si ratios, and to a lesser extent Al/Si, Na/Si, Mg/Si ratios, were found to impact the minimum RH level required for water monolayer formation. These results suggest that the hygroscopic properties of investigated African dusts are quite similar over the whole investigated RH range. Furthermore, one of the major conclusions is that under most atmospheric relative humidity conditions, natural mineral samples are always covered with at least one layer of adsorbed water.

Analysis of perfluoroalkyl substances in waters from Germany and Spain.

PubMed

Llorca, Marta; Farré, Marinella; Picó, Yolanda; Müller, Jutta; Knepper, Thomas P; Barceló, Damià

2012-08-01

Water has been identified as one of the main routes of human exposure to perfluoroalkyl substances (PFASs). This work assessed the presence of 21 PFASs along the whole water cycle using a new fast and cost effective analytical method based on an online sample enrichment followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). The method was validated for different types of matrices (ultrapure water, tap water and treated wastewater). The quality parameters for the 21 selected compounds presented good limits of detection (LOD) and quantification (LOQ) ranging, in general, from 0.83-10 ng/L to 2.8-50 ng/L, respectively. The method was applied to assess the occurrence of PFASs in 148 water samples of different steps along the whole water cycle, including: mineral bottled water, tap water, river water and treated effluent wastewater, from Germany to Spain. In addition, in order to prove the good performance of the online analytical method, the analysis of PFASs was carried out in parallel using a method based on offline anionic solid phase extraction (SPE) followed by LC-MS/MS. Consistent results were obtained using both approaches. The more frequently found compounds were perfluoroalkyl acids, such as the perfluorobutanoic acid which was in the 54% of the tap water samples investigated with concentrations in the range between 2.4 and 27 ng/L, the perfluoroheptanoic acid (0.23-53 ng/L) and perfluorooctanoic acid (0.16-35 ng/L), and the sulphonate perfluorooctanesulfonate (0.04-258 ng/L) which was the second more frequent compound and also the compound found in with the higher concentration. It should be remarked that the 88% of the samples analyzed presented at least one of the compounds at quantifiable concentrations. In addition, PFASs including short chain compounds were proved to be prevalent in drinking water, and the 50% of the drinking water samples showed quantifiable concentrations of PFASs. It should be said that the great majority of the samples may not pose an immediate health risk to consumers, and just 6 of the drinking water samples presented concentrations of PFOS exceeding the Provisional Health Advisory (PHA) level established by the Office of Water from the USEPA for PFOS, which was set in 200 ng/L. Copyright © 2012 Elsevier B.V. All rights reserved.

Autonomous model protocell division driven by molecular replication.

PubMed

Taylor, J W; Eghtesadi, S A; Points, L J; Liu, T; Cronin, L

2017-08-10

The coupling of compartmentalisation with molecular replication is thought to be crucial for the emergence of the first evolvable chemical systems. Minimal artificial replicators have been designed based on molecular recognition, inspired by the template copying of DNA, but none yet have been coupled to compartmentalisation. Here, we present an oil-in-water droplet system comprising an amphiphilic imine dissolved in chloroform that catalyses its own formation by bringing together a hydrophilic and a hydrophobic precursor, which leads to repeated droplet division. We demonstrate that the presence of the amphiphilic replicator, by lowering the interfacial tension between droplets of the reaction mixture and the aqueous phase, causes them to divide. Periodic sampling by a droplet-robot demonstrates that the extent of fission is increased as the reaction progresses, producing more compartments with increased self-replication. This bridges a divide, showing how replication at the molecular level can be used to drive macroscale droplet fission.Coupling compartmentalisation and molecular replication is essential for the development of evolving chemical systems. Here the authors show an oil-in-water droplet containing a self-replicating amphiphilic imine that can undergo repeated droplet division.

Coupling asymmetric flow-field flow fractionation and fluorescence parallel factor analysis reveals stratification of dissolved organic matter in a drinking water reservoir.

PubMed

Pifer, Ashley D; Miskin, Daniel R; Cousins, Sarah L; Fairey, Julian L

2011-07-08

Using asymmetrical flow field-flow fractionation (AF4) and fluorescence parallel factor analysis (PARAFAC), we showed physicochemical properties of chromophoric dissolved organic matter (CDOM) in the Beaver Lake Reservoir (Lowell, AR) were stratified by depth. Sampling was performed at a drinking water intake structure from May to July 2010 at three depths (3-, 10-, and 18-m) below the water surface. AF4-fractograms showed that the CDOM had diffusion coefficient peak maximums between 3.5 and 2.8 x 10⁻⁶ cm² s⁻¹, which corresponded to a molecular weight range of 680-1950 Da and a size of 1.6-2.5 nm. Fluorescence excitation-emission matrices of whole water samples and AF4-generated fractions were decomposed with a PARAFAC model into five principal components. For the whole water samples, the average total maximum fluorescence was highest for the 10-m depth samples and lowest (about 40% less) for 18-m depth samples. While humic-like fluorophores comprised the majority of the total fluorescence at each depth, a protein-like fluorophore was in the least abundance at the 10-m depth, indicating stratification of both total fluorescence and the type of fluorophores. The results present a powerful approach to investigate CDOM properties and can be extended to investigate CDOM reactivity, with particular applications in areas such as disinfection byproduct formation and control and evaluating changes in drinking water source quality driven by climate change. Copyright © 2010 Elsevier B.V. All rights reserved.

A novel approach of periodate oxidation coupled with HPLC-FLD for the quantitative determination of 3-chloro-1,2-propanediol in water and vegetable oil.

PubMed

Hu, Zhixiong; Cheng, Peng; Guo, Mingli; Zhang, Weinong; Qi, Yutang

2013-07-10

A novel approach of periodate oxidation coupled with high-performance liquid chromatography (HPLC)-fluorescence detection (FLD) for the quantitative determination of 3-chloro-1,2-propanediol (3-MCPD) has been established. The essence of this approach lies in the production of chloroacetaldehyde by the oxidization cleavage of 3-MCPD with sodium periodate and the HPLC analysis of chloroacetaldehyde monitored by an FLD detector after fluorescence derivatization with adenine. The experimental parameters relating to the efficiency of the derivative reaction such as concentration of adenine, chloroacetaldehyde reaction temperature, and time were studied. Under the optimized conditions, the proposed method can provide high sensitivity, good linearity (r(2) = 0.999), and repeatability (percent relative standard deviations between 2.57% and 3.44%), the limits of detection and quantification were 0.36 and 1.20 ng/mL, respectively, and the recoveries obtained for water samples were in the range 93.39-97.39%. This method has been successfully applied to the analysis of real water samples. Also this method has been successfully used for the analysis of vegetable oil samples after pretreatment with liquid-liquid extraction; the recoveries obtained by a spiking experiment with soybean oil ranged from 96.27% to 102.42%. In comparison with gas chromatography or gas chromatography-mass spectrometry, the proposed method can provide the advantages of simple instrumental requirement, easy operation, low cost, and high efficiency, thus making this approach another good choice for the sensitive determination of 3-MCPD.

Sorptive extraction using polydimethylsiloxane/metal-organic framework coated stir bars coupled with high performance liquid chromatography-fluorescence detection for the determination of polycyclic aromatic hydrocarbons in environmental water samples.

PubMed

Hu, Cong; He, Man; Chen, Beibei; Zhong, Cheng; Hu, Bin

2014-08-22

In this work, metal-organic frameworks (MOFs, Al-MIL-53-NH₂) were synthesized via the hydrothermal method, and novel polydimethylsiloxane/metal-organic framework (PDMS/MOFs, PDMS/Al-MIL-53-NH₂)-coated stir bars were prepared by the sol-gel technique. The preparation reproducibility of the PDMS/MOFs-coated stir bar was good, with relative standard deviations (RSDs) ranging from 4.8% to 14.9% (n=7) within one batch and from 6.2% to 16.9% (n=6) among different batches. Based on this fact, a new method of PDMS/MOFs-coated stir bar sorptive extraction (SBSE) and ultrasonic-assisted liquid desorption (UALD) coupled with high performance liquid chromatography-fluorescence detection (HPLC-FLD) was developed for the determination of polycyclic aromatic hydrocarbons (PAHs) in environmental water samples. To obtain the best extraction performance for PAHs, several parameters affecting SBSE, such as extraction time, stirring rate, and extraction temperature, were investigated. Under optimal experimental conditions, wide linear ranges and good RSDs (n=7) were obtained. With enrichment factors (EFs) of 16.1- to 88.9-fold (theoretical EF, 142-fold), the limits of detection (LODs, S/N=3) of the developed method for the target PAHs were found to be in the range of 0.05-2.94 ng/L. The developed method was successfully applied to the analysis of PAHs in Yangtze River and East Lake water samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Determination of cadmium(II), cobalt(II), nickel(II), lead(II), zinc(II), and copper(II) in water samples using dual-cloud point extraction and inductively coupled plasma emission spectrometry.

PubMed

Zhao, Lingling; Zhong, Shuxian; Fang, Keming; Qian, Zhaosheng; Chen, Jianrong

2012-11-15

A dual-cloud point extraction (d-CPE) procedure has been developed for simultaneous pre-concentration and separation of heavy metal ions (Cd2+, Co2+, Ni2+, Pb2+, Zn2+, and Cu2+ ion) in water samples by inductively coupled plasma optical emission spectrometry (ICP-OES). The procedure is based on forming complexes of metal ion with 8-hydroxyquinoline (8-HQ) into the as-formed Triton X-114 surfactant rich phase. Instead of direct injection or analysis, the surfactant rich phase containing the complexes was treated by nitric acid, and the detected ions were back extracted again into aqueous phase at the second cloud point extraction stage, and finally determined by ICP-OES. Under the optimum conditions (pH=7.0, Triton X-114=0.05% (w/v), 8-HQ=2.0×10(-4) mol L(-1), HNO3=0.8 mol L(-1)), the detection limits for Cd2+, Co2+, Ni2+, Pb2+, Zn2+, and Cu2+ ions were 0.01, 0.04, 0.01, 0.34, 0.05, and 0.04 μg L(-1), respectively. Relative standard deviation (RSD) values for 10 replicates at 100 μg L(-1) were lower than 6.0%. The proposed method could be successfully applied to the determination of Cd2+, Co2+, Ni2+, Pb2+, Zn2+, and Cu2+ ion in water samples. Copyright © 2012 Elsevier B.V. All rights reserved.

Simultaneous determination of cadmium, lead and mercury ions at trace level by magnetic solid phase extraction with Fe@Ag@Dimercaptobenzene coupled to high performance liquid chromatography.

PubMed

Zhou, Qingxiang; Lei, Man; Liu, Yongli; Wu, Yalin; Yuan, Yongyong

2017-12-01

Pollution resulted from heavy metal ions have absorbed much attention, and it is of great importance to develop sensitive and simultaneous determination method for them with common technologies without highly sensitive instruments. We prepared a new and functional core-shell magnetic nano-material, Fe@Ag@dimercaptobenzene (Fe@Ag@DMB), by a one-step method with sodium borohydride as the reducing agent and transmission electron microscopy (TEM) and energy dispersive spectrometer (EDS) were used for characterisation. The mercapto functional groups on the newly synthesised magnetic nanoparticles could interact with Cd 2+ , Pb 2+ , and Hg 2+ ions in water samples and then efficient extraction for Cd 2+ , Pb 2+ , and Hg 2+ ions was achieved. DDTC-Na solution was a good elutent for elution of these ions from Fe@Ag@DMB nanoparticles. Based on these, a sensitive method was developed for simultaneous preconcentration and determination of the aforementioned ions using magnetic Fe@Ag@DMB nanoparticles as the magnetic solid phase extraction adsorbent prior to high performance liquid chromatography coupled with variable wavelength detection. Under the optimal conditions, the detection limits of the three metal ions were in the range of 0.011-0.031μgL -1 , and precisions were below 2.37% (n=6). The proposed method was evaluated with real water samples, and excellent spiked recoveries achieved indicated that the developed method would be a promising tool for monitoring these heavy metal ions in water samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Simultaneous determination of PPCPs, EDCs, and artificial sweeteners in environmental water samples using a single-step SPE coupled with HPLC-MS/MS and isotope dilution.

PubMed

Tran, Ngoc Han; Hu, Jiangyong; Ong, Say Leong

2013-09-15

A high-throughput method for the simultaneous determination of 24 pharmaceuticals and personal care products (PPCPs), endocrine disrupting chemicals (EDCs) and artificial sweeteners (ASs) was developed. The method was based on a single-step solid phase extraction (SPE) coupled with high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) and isotope dilution. In this study, a single-step SPE procedure was optimized for simultaneous extraction of all target analytes. Good recoveries (≥ 70%) were observed for all target analytes when extraction was performed using Chromabond(®) HR-X (500 mg, 6 mL) cartridges under acidic condition (pH 2). HPLC-MS/MS parameters were optimized for the simultaneous analysis of 24 PPCPs, EDCs and ASs in a single injection. Quantification was performed by using 13 isotopically labeled internal standards (ILIS), which allows correcting efficiently the loss of the analytes during SPE procedure, matrix effects during HPLC-MS/MS and fluctuation in MS/MS signal intensity due to instrument. Method quantification limit (MQL) for most of the target analytes was below 10 ng/L in all water samples. The method was successfully applied for the simultaneous determination of PPCPs, EDCs and ASs in raw wastewater, surface water and groundwater samples collected in a local catchment area in Singapore. In conclusion, the developed method provided a valuable tool for investigating the occurrence, behavior, transport, and the fate of PPCPs, EDCs and ASs in the aquatic environment. Copyright © 2013 Elsevier B.V. All rights reserved.

[Influence of organochlorine pesticides in wastewater on the soil along the channel].

PubMed

Xu, Liang; Zhang, Cai-Xiang; Liu, Min; Liao, Xiao-Ping; Yao, Lin-Lin; Li, Jia-Le; Xiang, Qing-Qing

2013-08-01

Nine profile soil samples and two sewage water samples were collected from Xiaodian sewage irrigation area in Taiyuan city, concentrations of organochlorine pesticides (OCPs) were determined by the gas chromatography coupled with electron capture detector (GC-ECD) to analyze the influence of the leakage of sewage water. The result shows that OCPs in sewage water were mainly composed of HCHs. Concentrations of DDTs and other organochlorine pesticides were very low or out of the detection limit. Concentrations of sigmaOCPs and HCHs in eight profiles near irrigation channels to some extend decreased with the increasing of the linear distance off the channel, which shows influences of the leakage of sewage water on the soil nearby. Concentrations of HCHs clearly decreased with the increasing of soil depth in most profile soils. For the horizontal direction, concentrations of HCHs also decreased with the increasing of the linear distance off the channel. The correlation between HCHs and TOC was positive, but no correlation between pH and HCHs was found.

Ultrafast quantitation of six quinolones in water samples by second-order capillary electrophoresis data modeling with multivariate curve resolution-alternating least squares.

PubMed

Alcaráz, Mirta R; Vera-Candioti, Luciana; Culzoni, María J; Goicoechea, Héctor C

2014-04-01

This paper presents the development of a capillary electrophoresis method with diode array detector coupled to multivariate curve resolution-alternating least squares (MCR-ALS) to conduct the resolution and quantitation of a mixture of six quinolones in the presence of several unexpected components. Overlapping of time profiles between analytes and water matrix interferences were mathematically solved by data modeling with the well-known MCR-ALS algorithm. With the aim of overcoming the drawback originated by two compounds with similar spectra, a special strategy was implemented to model the complete electropherogram instead of dividing the data in the region as usually performed in previous works. The method was first applied to quantitate analytes in standard mixtures which were randomly prepared in ultrapure water. Then, tap water samples spiked with several interferences were analyzed. Recoveries between 76.7 and 125 % and limits of detection between 5 and 18 μg L(-1) were achieved.

3D-printed, TiO2 NP-incorporated minicolumn coupled with ICP-MS for speciation of inorganic arsenic and selenium in high-salt-content samples.

PubMed

Su, Cheng-Kuan; Chen, Wei-Cheng

2018-04-25

To extend the applicability of solid phase extraction devices manufactured using 3D printing technologies, a stereolithographic 3D printer and resins incorporating titanium dioxide nanoparticles (TiO 2 NPs) were employed to fabricate a demountable minicolumn with TiO 2 NP-incorporated packing as a sample pretreatment device for the selective extraction of inorganic As and Se species from high-salt-content samples, and to facilitate their analyses when coupled to an inductively coupled plasma mass spectrometer. After optimization, the automatic system enabled highly sensitive determinations of As and Se species with detection limits as low as 0.004-0.033 μg L -1 for As and 0.061-0.128 μg L -1 for Se. Reliability was confirmed through analyses of the reference materials 1643f, SLEW-3, CASS-4, and 2670a, as well as spike analyses of samples of water and human urine. These 3D-printed minicolumns appear to be very useful for multi-elemental speciation of these elements from high-salt-content samples. Thus, the incorporation of active nanomaterials into raw printing resins can enable 3D printing technologies-not only to fabricate functionalized devices for diverse sample pretreatment applications but also to encourage the future development of multifunctional devices for analytical science. Graphical abstract Schematic presentation of a demountable minicolumn fabricated using a stereolithographic 3D printer and the resins incorporating with TiO 2 NPs. They were used to selectively extract As and Se species through controlling the sample acidities.

Bacterial community composition and structure in an Urban River impacted by different pollutant sources.

PubMed

Ibekwe, A Mark; Ma, Jincai; Murinda, Shelton E

2016-10-01

Microbial communities in terrestrial fresh water are diverse and dynamic in composition due to different environmental factors. The goal of this study was to undertake a comprehensive analysis of bacterial composition along different rivers and creeks and correlate these to land-use practices and pollutant sources. Here we used 454 pyrosequencing to determine the total bacterial community composition, and bacterial communities that are potentially of fecal origin, and of relevance to water quality assessment. The results were analyzed using UniFrac coupled with principal coordinate analysis (PCoA) to compare diversity, abundance, and community composition. Detrended correspondence analysis (DCA) and canonical correspondence analysis (CCA) were used to correlate bacterial composition in streams and creeks to different environmental parameters impacting bacterial communities in the sediment and surface water within the watershed. Bacteria were dominated by the phyla Proteobacteria, Bacteroidetes, Acidobacteria, and Actinobacteria, with Bacteroidetes significantly (P<0.001) higher in all water samples than sediment, where as Acidobacteria and Actinobacteria where significantly higher (P<0.05) in all the sediment samples than surface water. Overall results, using the β diversity measures, coupled with PCoA and DCA showed that bacterial composition in sediment and surface water was significantly different (P<0.001). Also, there were differences in bacterial community composition between agricultural runoff and urban runoff based on parsimony tests using 454 pyrosequencing data. Fecal indicator bacteria in surface water along different creeks and channels were significantly correlated with pH (P<0.01), NO2 (P<0.03), and NH4N (P<0.005); and in the sediment with NO3 (P<0.015). Our results suggest that microbial community compositions were influenced by several environmental factors, and pH, NO2, and NH4 were the major environmental factors driving FIB in surface water based on CCA analysis, while NO3 was the only factor in sediment. Published by Elsevier B.V.

Boron exposure assessment using drinking water and urine in the North of Chile.

PubMed

Cortes, S; Reynaga-Delgado, E; Sancha, A M; Ferreccio, C

2011-12-01

Boron is an essential trace element for plants and humans however it is still an open question what levels of boron are actually safe for humans. This study, conducted between 2006 and 2010, measured exposure levels of boron in drinking water and urine of volunteers in Arica, an area in the North of Chile with high levels of naturally occurring boron. Samples were taken of tap and bottled water (173 and 22, respectively), as well as urine from 22 volunteers, and subsequently analyzed by inductively coupled plasma spectroscopy (ICP-OES). Boron varied in public tap water from 0.22 to 11.3mgL(-1), with a median value of 2.9mgL(-1), while concentrations of boron in bottled water varied from 0.01 to 12.2mgL(-1). Neither tap nor bottled water samples had concentrations of boron within WHO recommended limits. The concentration of boron in urine varied between 0.45 and 17.4mgL(-1), with a median of 4.28mgL(-1) and was found to be correlated with tap water sampled from the homes of the volunteers (r=0.64). Authors highly recommend that in northern Chile - where levels of boron are naturally high - that the tap and bottled water supplies be monitored in order to protect public health and that regulatory standards also be established for boron in drinking water in order to limit exposure. Copyright © 2011 Elsevier B.V. All rights reserved.

Solid-phase microextraction of benzimidazole fungicides in environmental liquid samples and HPLC-fluorescence determination.

PubMed

López Monzón, A; Vega Moreno, D; Torres Padrón, M E; Sosa Ferrera, Z; Santana Rodríguez, J J

2007-03-01

Solid-phase microextraction (SPME) coupled with high-performance liquid chromatography (HPLC) with fluorescence detection was optimized for extraction and determination of four benzimidazole fungicides (benomyl, carbendazim, thiabendazole, and fuberidazole) in water. We studied extraction and desorption conditions, for example fiber type, extraction time, ionic strength, extraction temperature, and desorption time to achieve the maximum efficiency in the extraction. Results indicate that SPME using a Carboxen-polydimethylsiloxane 75 microm (CAR-PDMS) fiber is suitable for extraction of these types of compound. Final analysis of benzimidazole fungicides was performed by HPLC with fluorescence detection. Recoveries ranged from 80.6 to 119.6 with RSDs below 9% and limits of detection between 0.03 and 1.30 ng mL-1 for the different analytes. The optimized procedure was applied successfully to the determination of benzimidazole fungicides mixtures in environmental water samples (sea, sewage, and ground water).

A novel method for the determination of ascorbic acid and antioxidant capacity in Opuntia ficus indica using in vivo microdialysis.

PubMed

Pretti, L; Bazzu, G; Serra, P A; Nieddu, G

2014-03-15

A simple and rapid method was developed for in vivo simultaneous determination of ascorbic-acid and antioxidant capacity in microdialysates from cladodes of Opuntia ficus-indica (L.) Miller. The method is verified in water-stressed plants, as compared with a well-watered test controls. The microdialysis probe construction and insertion procedure was specifically developed to minimise the tissue trauma of the plant and to obtain optimal dialysis performance. Microdialysis was performed using a flow rate of 3 μL/min and the samples were analysed by HPLC coupled to electrochemical detection of ascorbic-acid and DPPH-determined antioxidant capacity. Our data indicate exponential decay of the concentrations of the analysed compounds as a function of microdialysis sampling time. Water-stressed Opuntia show decreased ascorbic acid levels and increased the others antioxidants. Copyright © 2013 Elsevier Ltd. All rights reserved.

Sediment Source Analysis at Malakoff Diggins State Historic Park, California

NASA Astrophysics Data System (ADS)

Ward, A. J., IV; Monohan, C.; Matiasek, S. J.; Alpers, C. N.; Curtis, J.; Campbell, K. M.; Roth, D. A.; Howle, J.

2016-12-01

This study aims to identify the sources of suspended sediment and trace metals which are discharged during storm events into Humbug Creek from Malakoff Diggins State Historic Park (MDSHP) in Nevada County, California. MDSHP includes a pit where approximately 32,000,000 cubic meters of auriferous Eocene gravel was mined by hydraulic and dredging methods during 1866-1884 and 1893-1910. High erosion rates within the pit contribute to water-quality impairment downstream; Humbug Creek is listed as an impaired water body under section 303(d) of the Clean Water Act because of suspended sediment, copper, mercury, and zinc. Sediment fingerprinting techniques (mineralogy and geochemistry) are being used to identify stratigraphic units in the pit responsible for delivering the greatest volume of sediment to the pit drain at Hiller Tunnel, which flows to Humbug Creek. In-situ sediment samples were collected in 2015 along four vertical transects located in the mine pit. Additionally, surface water samples were collected during 2015 and 2016 within the pit and Hiller Tunnel, targeting drainage networks below the in-situ sampling sites. In-situ and suspended sediment samples were analyzed for grain-size distribution, X-ray diffraction (XRD) to obtain quantitative mineralogy, inductively coupled plasma - mass spectrometry (ICP-MS) for trace elements, and inductively coupled plasma - optical emission spectroscopy (ICP-OES) for major elements. Preliminary XRD data indicate that the fine suspended sediment in Hiller Tunnel is composed predominantly of kaolinite and halloysite, with minor smectite, illite, and muscovite. Kaolinite is abundant in many of the samples from the in-situ vertical transects, but relatively few stratigraphic units have abundant halloysite. Quantitative erosion rates from a time series of terrestrial LiDAR measurements (2014-16) and from historical aerial photos will help to refine possible scenarios regarding sediment sources within the pit. Chemical and physical characterization of the in-situ sediments may reveal key indicators, or fingerprints, which will allow for a more efficient application of mitigation efforts in MDSHP by identifying which stratigraphic units are delivering high amounts of sediment to Humbug Creek.

Different Types of Heater-Cooler Units and Their Risk of Transmission of Mycobacterium chimaera During Open-Heart Surgery: Clues From Device Design.

PubMed

Kuehl, Richard; Banderet, Florian; Egli, Adrian; Keller, Peter M; Frei, Reno; Döbele, Thomas; Eckstein, Friedrich; Widmer, Andreas F

2018-05-28

OBJECTIVEWorldwide, Mycobacterium chimaera infections have been linked to contaminated aerosols from heater-cooler units (HCUs) during open-heart surgery. These infections have mainly been associated with the 3T HCU (LivaNova, formerly Sorin). The reasons for this and the risk of transmission from other HCUs have not been systematically assessed.DESIGNProspective observational study.SETTINGUniversity Hospital Basel, Switzerland.METHODSContinuous microbiological surveillance of 3 types of HCUs in use (3T from LivaNova/Sorin and HCU30 and HCU40 from Maquet) was initiated in June 2014, coupled with an epidemiologic workup. Monthly water and air samples were taken. Construction design was analyzed, and exhausted airflow was measured.RESULTS Mycobacterium chimaera grew in 8 of 12 water samples (66%) and 22 of 24 air samples (91%) of initial 3T HCUs in use, and in 2 of 83 water samples (2%) and 0 of 41 (0%) air samples of new replacement 3T HCUs. Moreover, 7 of 12 water samples (58%) and 0 of 4 (0%) air samples from the HCU30 were positive, and 0 of 64 (0%) water samples and 0 of 50 (0%) air samples from the HCU40 were positive. We identified 4 relevant differences in HCU design compared to the 3T: air flow direction, location of cooling ventilators, continuous cooling of the water tank at 4°C, and an electronic alarm in the HCU40 reminding the user of the next disinfection cycle.CONCLUSIONSAll infected patients were associated with a 3T HCU. The individual HCU design may explain the different risk of disseminating M. chimaera into the air of the operating room. These observations can help the construction of improved devices to ensure patient safety during cardiac surgery.Infect Control Hosp Epidemiol 2018;1-7.

Application of dispersion-solidification liquid-liquid microextraction for the determination of triazole fungicides in environmental water samples by high-performance liquid chromatography.

PubMed

Wang, Chun; Wu, Qiuhua; Wu, Chunxia; Wang, Zhi

2011-01-15

A simple, rapid and environmentally friendly method has been developed for the determination of four triazole fungicides (myclobutanil, tebuconazole, triadimenol, hexaconazole) in water samples by dispersion-solidification liquid-liquid microextraction coupled with high performance liquid chromatography-diode array detection. Several variables that affect the extraction efficiencies, including the type and volume of the extraction solvent and dispersive solvent, extraction time, effect of pH and salt addition, were investigated and optimized. Under the optimum conditions, the proposed method is sensitive and shows a good linearity within a range of 0.5-200 ng mL(-1), with the correlation coefficients (r) varying from 0.9992 to 0.9998. High enrichment factors were achieved ranging from 190 to 450. The recoveries of the target analytes from water samples at spiking levels of 1.0, 5.0 and 50.0 ng mL(-1) were between 84.8% and 110.2%. The limits of detection (LODs) for the analytes were ranged in 0.06-0.1 ng mL(-1), and the relative standard deviations (RSD) varied from 3.9% to 5.7%. The proposed method has been successfully applied for the determination of the triazole fungicides in real water samples. Copyright © 2010 Elsevier B.V. All rights reserved.

Ultra-trace levels analysis of microcystins and nodularin in surface water by on-line solid-phase extraction with high-performance liquid chromatography tandem mass spectrometry.

PubMed

Balest, Lydia; Murgolo, Sapia; Sciancalepore, Lucia; Montemurro, Patrizia; Abis, Pier Paolo; Pastore, Carlo; Mascolo, Giuseppe

2016-06-01

An on-line solid phase extraction coupled with high-performance liquid chromatography in tandem with mass spectrometry (on-line SPE/HPLC/MS-MS) method for the determination of five microcystins and nodularin in surface waters at submicrogram per liter concentrations has been optimized. Maximum recoveries were achieved by carefully optimizing the extraction sample volume, loading solvent, wash solvent, and pH of the sample. The developed method was also validated according to both UNI EN ISO IEC 17025 and UNICHIM guidelines. Specifically, ten analytical runs were performed at three different concentration levels using a reference mix solution containing the six analytes. The method was applied for monitoring the concentrations of microcystins and nodularin in real surface water during a sampling campaign of 9 months in which the ELISA method was used as standard official method. The results of the two methods were compared showing good agreement when the highest concentration values of MCs were found. Graphical abstract An on-line SPE/HPLC/MS-MS method for the determination of five microcystins and nodularin in surface waters at sub μg L(-1) was optimized and compared with ELISA assay method for real samples.

Chapter 1. Determination of elements in natural-water, biota, sediment, and soil samples using collision/reaction cell inductively coupled plasma-mass spectrometry

USGS Publications Warehouse

Garbarino, John R.; Kanagy, Leslie K.; Cree, Mark E.

2006-01-01

A new analytical method for the determination of elements in filtered aqueous matrices using inductively coupled plasma-mass spectrometry (ICP-MS) has been implemented at the U.S. Geological Survey National Water Quality Laboratory that uses collision/reaction cell technology to reduce molecular ion interferences. The updated method can be used to determine elements in filtered natural-water and other filtered aqueous matrices, including whole-water, biota, sediment, and soil digestates. Helium or hydrogen is used as the collision or reaction gas, respectively, to eliminate or substantially reduce interferences commonly resulting from sample-matrix composition. Helium is used for molecular ion interferences associated with the determination of As, Co, Cr, Cu, K, Mg, Na, Ni, V, W and Zn, whereas hydrogen is used for Ca, Fe, Se, and Si. Other elements that are not affected by molecular ion interference also can be determined simply by not introducing a collision/reaction gas into the cell. Analysis time is increased by about a factor of 2 over the previous method because of the additional data acquisition time in the hydrogen and helium modes. Method detection limits for As, Ca, Co, Cr, Cu, Fe, K, Mg, Na, Ni, Se, Si (as SiO2), V, W, and Zn, all of which use a collision/reaction gas, are 0.06 microgram per liter (?g/L) As, 0.04 milligram per liter (mg/L) Ca, 0.02 ?g/L Co, 0.02 ?g/L Cr, 0.04 ?g/L Cu, 1 ?g/L Fe, 0.007 mg/L K, 0.009 mg/L Mg, 0.09 mg/L Na, 0.05 ?g/L Ni, 0.04 ?g/L Se, 0.03 mg/L SiO2, 0.05 ?g/L V, 0.03 ?g/L W, and 0.04 ?g/L Zn. Most method detection limits are lower or relatively unchanged compared to earlier methods except for Co, K, Mg, Ni, SiO2, and Tl, which are less than a factor of 2 higher. Percentage bias for samples spiked at about one-third and two-thirds of the concentration of the highest calibration standard ranged from -8.1 to 7.9 percent for reagent water, -14 to 21 percent for surface water, and -16 to 16 percent for ground water. The percentage bias for reagent water spiked at trace-element concentrations of 0.5 to 3 ?g/L averaged 4.4 percent with a range of -6 to 16 percent, whereas the average percentage bias for Ca, K, Mg, Na, and SiO2 was 1.4 percent with a range of -4 to 10 percent for spikes of 0.5 to 3 mg/L. Elemental results for aqueous standard reference materials compared closely to the certified concentrations; all elements were within 1.5 F-pseudosigma of the most probable concentration. In addition, results from 25 filtered natural-water samples and 25 unfiltered natural-water digestates were compared with results from previously used methods using linear regression analysis. Slopes from the regression analyses averaged 0.98 and ranged from 0.87 to 1.29 for filtered natural-water samples; for unfiltered natural-water digestates, the average slope was 1.0 and ranged from 0.83 to 1.22. Tests showed that accurate measurements can be made for samples having specific conductance less than 7,500 microsiemens per centimeter (?S/cm) without dilution; earlier ICP-MS methods required dilution for samples with specific conductance greater than 2,500 ?S/cm.

Sunlight creates oxygenated species in water-soluble fractions of Deepwater Horizon oil.

PubMed

Ray, Phoebe Z; Chen, Huan; Podgorski, David C; McKenna, Amy M; Tarr, Matthew A

2014-09-15

In order to assess the impact of sunlight on oil fate, Macondo well oil from the Deepwater Horizon (DWH) rig was mixed with pure water and irradiated with simulated sunlight. After irradiation, the water-soluble organics (WSO) from the dark and irradiated samples were extracted and characterized by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Liquid-liquid extraction yielded two fractions from dark and irradiated water/oil mixtures: acidic WSOs (negative-ion electrospray (ESI)), and base/neutral WSOs (positive-ion ESI) coupled to FT-ICR MS to catalog molecular-level transformations that occur to Macondo-derived WSOs after solar irradiation. Such direct measure of oil phototransformation has not been previously reported. The most abundant heteroatom class detected in the irradiated WSO acid fractions correspond to molecules that contain five oxygens (O5), while the most abundant acids in the dark samples contain two oxygen atoms per molecule (O2). Higher-order oxygen classes (O5-O9) were abundant in the irradiated samples, but <1.5% relative abundance in the dark sample. The increased abundance of higher-order oxygen classes in the irradiated samples relative to the dark samples indicates that photooxidized components of the Macondo crude oil become water-soluble after irradiation. The base/neutral fraction showed decreased abundance of pyridinic nitrogen (N1) concurrent with an increased abundance of N1Ox classes after irradiation. The predominance of higher-order oxygen classes indicates that multiple photochemical pathways exist that result in oxidation of petroleum compounds. Copyright © 2014 Elsevier B.V. All rights reserved.

Multi-residue method for determination of 58 pesticides, pharmaceuticals and personal care products in water using solvent demulsification dispersive liquid-liquid microextraction combined with liquid chromatography-tandem mass spectrometry.

PubMed

Caldas, Sergiane Souza; Rombaldi, Caroline; Arias, Jean Lucas de Oliveira; Marube, Liziane Cardoso; Primel, Ednei Gilberto

2016-01-01

A rapid and efficient sample pretreatment using solvent-based de-emulsification dispersive liquid-liquid microextraction (SD-DLLME) coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) was studied for the extraction of 58 pharmaceuticals and personal care products (PPCPs) and pesticides from water samples. Type and volume of extraction and disperser solvents, pH, salt addition, amount of salt and type of demulsification solvent were evaluated. Limits of quantification (LOQ) in the range from 0.0125 to 1.25 µg L(-1) were reached, and linearity was in the range from the LOQ of each compound to 25 μg L(-1). Recoveries ranged from 60% to 120% for 84% of the compounds, with relative standard deviations lower than 29%. The proposed method demonstrated, for the first time, that sample preparation by SD-DLLME with determination by LC-MS/MS can be successfully used for the simultaneous extraction of 32 pesticides and 26 PPCPs from water samples. The entire procedure, including the extraction of 58 organic compounds from the aqueous sample solution and the breaking up of the emulsion after extraction with water, rather than with an organic solvent, was environmentally friendly. In addition, this technique was less expensive and faster than traditional techniques. Finally, the analytical method under study was successfully applied to the analysis of all 58 pesticides and PPCPs in surface water samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Ultra-Sensitive Elemental Analysis Using Plasmas 5.Speciation of Arsenic Compounds in Biological Samples by High Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry System

NASA Astrophysics Data System (ADS)

Kaise, Toshikazu

Arsenic originating from the lithosphere is widely distributed in the environment. Many arsenicals in the environment are in organic and methylated species. These arsenic compounds in drinking water or food products of marine origin are absorbed in human digestive tracts, metabolized in the human body, and excreted viatheurine. Because arsenic shows varying biological a spects depending on its chemical species, the biological characteristics of arsenic must be determined. It is thought that some metabolic pathways for arsenic and some arsenic circulation exist in aqueous ecosystems. In this paper, the current status of the speciation analysis of arsenic by HPLC/ICP-MS (High Performance Liquid Chromatography-Inductively Coupled Plasma Mass spectrometry) in environmental and biological samples is summarized using recent data.

Geochemical processes controlling selenium in ground water after mining, Powder River Basin, Wyoming, U.S.A.

USGS Publications Warehouse

Naftz, D.L.; Rice, J.A.

1989-01-01

Geochemical data for samples of overburden from three mines in the Powder River Basin indicate a statistically significant (0.01 confidence level) positive correlation (r = 0.74) between Se and organic C. Results of factor analysis with varimax rotation on the major and trace element data from the rock samples indicate large (>50) varimax loadings for Se in two of the three factors. In Factor 1, the association of Se with constituents common to detrital grains indicates that water transporting the detrital particles into the Powder River Basin also carried dissolved Se. The large (>50) varimax loadings of Se and organic C in Factor 2 probably are due to the organic affinities characteristic of Se. Dissolved Se concentrations in water samples collected at one coal mine are directly related to the dissolved organic C concentrations. Hydrophilic acid concentrations in the water samples from the mine ranged from 35 to 43% of the total dissolved organic C, and hydrophobic acid concentrations ranged from 40 to 49% of the total dissolved organic C. The largest dissolved organic C concentrations in water from the same mine (34-302 mg/l), coupled with the large proportion of acidic components, may saturate adsorption sites on geothite and similar minerals that comprise the aquifer material, thus decreasing the extent of selenite (SeO32-) adsorption as a sink for Se as the redox state of ground water decreases. ?? 1989.

Malignant human cell transformation of Marcellus Shale gas drilling flow back water.

PubMed

Yao, Yixin; Chen, Tingting; Shen, Steven S; Niu, Yingmei; DesMarais, Thomas L; Linn, Reka; Saunders, Eric; Fan, Zhihua; Lioy, Paul; Kluz, Thomas; Chen, Lung-Chi; Wu, Zhuangchun; Costa, Max; Zelikoff, Judith

2015-10-01

The rapid development of high-volume horizontal hydraulic fracturing for mining natural gas from shale has posed potential impacts on human health and biodiversity. The produced flow back waters after hydraulic stimulation are known to carry high levels of saline and total dissolved solids. To understand the toxicity and potential carcinogenic effects of these wastewaters, flow back waters from five Marcellus hydraulic fracturing oil and gas wells were analyzed. The physicochemical nature of these samples was analyzed by inductively coupled plasma mass spectrometry and scanning electron microscopy/energy dispersive X-ray spectroscopy. A cytotoxicity study using colony formation as the endpoint was carried out to define the LC50 values of test samples using human bronchial epithelial cells (BEAS-2B). The BEAS-2B cell transformation assay was employed to assess the carcinogenic potential of the samples. Barium and strontium were among the most abundant metals in these samples and the same metals were found to be elevated in BEAS-2B cells after long-term treatment. BEAS-2B cells treated for 6weeks with flow back waters produced colony formation in soft agar that was concentration dependent. In addition, flow back water-transformed BEAS-2B cells show better migration capability when compared to control cells. This study provides information needed to assess the potential health impact of post-hydraulic fracturing flow back waters from Marcellus Shale natural gas mining. Copyright © 2015 Elsevier Inc. All rights reserved.

Electrothermal vaporization of mineral acid solutions in inductively coupled plasma mass spectrometry: comparison with sample nebulization

NASA Astrophysics Data System (ADS)

Mora, Juan; Gras, Luis; van Veen, Eric H.; de Loos-Vollebregt, Margaretha T. C.

1999-06-01

The analytical behaviour of an electrothermal vaporization (ETV) device for the introduction of mineral acid solutions in inductively coupled plasma mass spectrometry (ICP-MS) was evaluated. Water, nitric acid, hydrochloric acid, perchloric acid and sulphuric acid in concentrations within the 0.05-1.0 mol l-1 range were studied. For all the acids tested, increasing the acid concentration increases the ion signal and deteriorates the precision. The magnitude of the signal enhancement depends on the analyte and on the acid considered. Acid solutions give rise to ion signals that are between 2 and 10 times higher than those with water. Among the acids tested, sulphuric acid provides the highest signals. The addition of palladium reduces matrix effects due to the acids and increases the signal in ETV ICP-MS. In comparison with conventional sample nebulization (CS), the ETV sample introduction system provides higher sensitivities (between 2 and 20 times higher) at the same acid concentration. The magnitude of this improvement is similar to that obtained with a microwave desolvation system (MWDS). The ETV sample introduction system gives rise to the lowest background signals from matrix-induced species. Due to this fact, the limits of detection (LODs) obtained for the isotopes affected by any interference are lower for ETV sample introduction than those obtained with the CS and the MWDS. For the isotopes that do not suffer from matrix-induced spectral interferences, the ETV gives rise to LODs higher than those obtained with the CS. For these isotopes the lowest LODs are obtained with MWDS.

An ionic liquid as a solvent for headspace single drop microextraction of chlorobenzenes from water samples.

PubMed

Vidal, Lorena; Psillakis, Elefteria; Domini, Claudia E; Grané, Nuria; Marken, Frank; Canals, Antonio

2007-02-12

A headspace single-drop microextraction (HS-SDME) procedure using room temperature ionic liquid and coupled to high-performance liquid chromatography capable of quantifying trace amounts of chlorobenzenes in environmental water samples is proposed. A Plackett-Burman design for screening was carried out in order to determine the significant experimental conditions affecting the HS-SDME process (namely drop volume, aqueous sample volume, stirring speed, ionic strength, extraction time and temperature), and then a central composite design was used to optimize the significant conditions. The optimum experimental conditions found from this statistical evaluation were: a 5 microL microdrop of 1-butyl-3-methylimidazolium hexafluorophosphate, exposed for 37 min to the headspace of a 10 mL aqueous sample placed in a 15 mL vial, stirred at 1580 rpm at room temperature and containing 30% (w/v) NaCl. The calculated calibration curves gave a high level of linearity for all target analytes with correlation coefficients ranging between 0.9981 and 0.9997. The repeatability of the proposed method, expressed as relative standard deviation, varied between 1.6 and 5.1% (n=5). The limits of detection ranged between 0.102 and 0.203 microg L(-1). Matrix effects upon extraction were evaluated by analysing spiked tap and river water as well as effluent water samples originating from a municipal wastewater treatment plant.

Dispersive liquid-liquid microextraction applied to isolation and concentration of alkylphenols and their short-chained ethoxylates in water samples.

PubMed

Zgoła-Grześkowiak, Agnieszka

2010-03-12

Dispersive liquid-liquid microextraction (DLLME) coupled with high-performance liquid chromatography with fluorescence detector was applied for the determination of alkylphenols and their short-chained ethoxylates in water samples. Development of DLLME procedure included optimisation of some important parameters such as kind and volume of extracting and dispersing solvents. Under optimised conditions 50 microL of trichloroethylene in 1.5 mL of acetone were rapidly injected into 5 mL of a water sample. After centrifuging the organic phase containing the analytes was taken for evaporation with a gentle nitrogen purge and reconstituted to 50 microL of acetonitrile. The aliquot of this solution was analysed with the use of HPLC. For octylphenol (OP) and octylphenol ethoxylates (OPEOs) linearity was satisfactory in the range 8-1000 microg L(-1) and for nonylphenol (NP) and nonylphenol ethoxylates (NPEOs) linearity was in the range from 50 to about 3000 microg L(-1). Limit of quantitation was 0.1 microg L(-1) for OP and OPEOs and 0.3 microg L(-1) for NP and NPEOs. Satisfactory recoveries between 66 and 79% were obtained for environmental samples. The results showed that DLLME is a simple, rapid and sensitive analytical method for the preconcentration of trace amounts of alkylphenols and their ethoxylates in environmental water samples. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Polydopamine-coated magnetic nanoparticles for isolation and enrichment of estrogenic compounds from surface water samples followed by liquid chromatography-tandem mass spectrometry determination.

PubMed

Capriotti, Anna Laura; Cavaliere, Chiara; La Barbera, Giorgia; Piovesana, Susy; Samperi, Roberto; Zenezini Chiozzi, Riccardo; Laganà, Aldo

2016-06-01

Estrogens, phytoestrogens, and mycoestrogens may enter into the surface waters from different sources, such as effluents of municipal wastewater treatment plants, industrial plants, and animal farms and runoff from agricultural areas. In this work, a multiresidue analytical method for the determination of 17 natural estrogenic compounds, including four steroid estrogens, six mycoestrogens, and seven phytoestrogens, in river water samples has been developed. (Fe3O4)-based magnetic nanoparticles coated by polydopamine (Fe3O4@pDA) were used for dispersive solid-phase extraction, and the final extract was analyzed by ultra-high performance liquid chromatography coupled with tandem mass spectrometry. The Fe3O4 magnetic nanoparticles were prepared by a co-precipitation procedure, coated by pDA, and characterized by scanning electron microscopy, infrared spectroscopy, and elemental analysis. The sample preparation method was optimized in terms of extraction recovery, matrix effect, selectivity, trueness, precision, method limits of detection, and method limits of quantification (MLOQs). For all the 17 analytes, recoveries were >70 % and matrix effects were below 30 % when 25 mL of river water sample was treated with 90 mg of Fe3O4@pDA nanoparticles. Selectivity was tested by spiking river water samples with 50 other compounds (mycotoxins, antibacterials, conjugated hormones, UV filters, alkylphenols, etc.), and only aflatoxins and some benzophenones showed recoveries >60 %. This method proved to be simple and robust and allowed the determination of natural estrogenic compounds belonging to different classes in surface waters with MLOQs ranging between 0.003 and 0.1 μg L(-1). Graphical Abstract Determination of natural estrogenic compounds in water by magnetic solid phase extraction followed by liquid chromatography-tandem mass spectrometry analysis.

Possible linkages between lignite aquifers, pathogenic microbes, and renal pelvic cancer in northwestern Louisiana, USA

USGS Publications Warehouse

Bunnell, J.E.; Tatu, C.A.; Bushon, R.N.; Stoeckel, D.M.; Brady, A.M.G.; Beck, M.; Lerch, H.E.; McGee, B.; Hanson, B.C.; Shi, R.; Orem, W.H.

2006-01-01

In May and September, 2002, 14 private residential drinking water wells, one dewatering well at a lignite mine, eight surface water sites, and lignite from an active coal mine were sampled in five Parishes of northwestern Louisiana, USA. Using a geographic information system (GIS), wells were selected that were likely to draw water that had been in contact with lignite; control wells were located in areas devoid of lignite deposits. Well water samples were analyzed for pH, conductivity, organic compounds, and nutrient and anion concentrations. All samples were further tested for presence of fungi (cultures maintained for up to 28 days and colonies counted and identified microscopically) and for metal and trace element concentration by inductively-coupled plasma mass spectrometry and atomic emission spectrometry. Surface water samples were tested for dissolved oxygen and presence of pathogenic leptospiral bacteria. The Spearman correlation method was used to assess the association between the endpoints for these field/laboratory analyses and incidence of cancer of the renal pelvis (RPC) based on data obtained from the Louisiana Tumor Registry for the five Parishes included in the study. Significant associations were revealed between the cancer rate and the presence in drinking water of organic compounds, the fungi Zygomycetes, the nutrients PO4 and NH3, and 13 chemical elements. Presence of human pathogenic leptospires was detected in four out of eight (50%) of the surface water sites sampled. The present study of a stable rural population examined possible linkages between aquifers containing chemically reactive lignite deposits, hydrologic conditions favorable to the leaching and transport of toxic organic compounds from the lignite into the groundwater, possible microbial contamination, and RPC risk. ?? Springer Science+Business Media B.V. 2006.

Coupling between the continental carbon and water cycles

NASA Astrophysics Data System (ADS)

Gentine, P.; Lemordant, L. A.; Green, J. K.

2017-12-01

The continental carbon adn water cycles are fundamentally coupled through leaf gas exchange at the stomata level. IN this presnetation we will emphasize the importance of this coupling for the future of the water cycle (runoff, evaporation, soil moisture) and in turn the implications for the carbon cycle and the capacity of continents to act as a carbon dioxyde sink in the future. Opprtunites from coupled carbon-water monitoring platforms will be then emphasized.

Depletion of Stem Water of Sclerocarya birrea Agroforestry Tree Precedes Start of Rainy Season in West African Sudanian Zone

NASA Astrophysics Data System (ADS)

Ceperley, Natalie; Mande, Theophile; Parlange, Marc B.

2013-04-01

Understanding water use by agroforestry trees in dry-land ecosystems is essential for improving water management. Agroforestry trees are valued and promoted for many of their ecologic and economic benefits but are often criticized as competing for valuable water resources. In order to understand the seasonal patterns of source water used by agroforestry trees, samples from rain, ground, and surface water were collected weekly in the subcatchment of the Singou watershed that is part of the Volta Basin. Soil and vegetation samples were collected from and under a Sclerocarya birrea agroforstry trees located in this catchment in sealed vials, extracted, and analyzed with a Picarro L2130-i CRDS to obtain both δO18 and δDH fractions. Meteorological measurements were taken with a network of wireless, autonomous stations that communicate through the GSM network (Sensorscope) and two complete eddy-covariance energy balance stations, in addition to intense monitoring of sub-canopy solar radiation, throughfall, stemflow, and soil moisture. Examination of the time series of δO18 concentrations confirm that values in soil and xylem water are coupled, both becoming enriched during the dry season and depleted during the rainy season. Xylem water δO18 levels drops to groundwater δO18 levels in early March when trees access groundwater for leafing out, however soil water does not reach this level until soil moisture increases in mid-June. The relationship between the δDH and δO18 concentrations of water extracted from soil and tree samples do not fall along the global meteoric water line. In order to explore whether this was a seasonally driven, we grouped samples into an "evaporated" group or a "meteoric" group based on the smaller residual to the respective lines. Although more soil samples were found along the m-line during the rainy season than tree samples or dry season soil samples, there was no significant difference in days since rain for any group This suggests that xylem water is always under stress from evapotranspiration and soil water underwent evaporation soon after a rain event. Visual observation of tree confirms conclusion that trees access deep ground water in March and April, before rain begins and before soil is connected to groundwater. Results from the research are being integrated into a local outreach project to improve use of agroforestry.

In-port derivatization coupled to different extraction techniques for the determination of alkylphenols in environmental water samples.

PubMed

Cavalheiro, J; Monperrus, M; Amouroux, D; Preud'Homme, H; Prieto, A; Zuloaga, O

2014-05-02

Large volume injection (LVI)-in port silylation coupled to gas chromatography-mass spectrometry (GC-MS) for the determination of alkylphenols (APs) in water samples applying four different extraction approaches was evaluated. Among the variables studied for in-port derivatization, vent time, cryo-focusing temperature and the ratio solvent volume/N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) volume were optimized using an experimental design approach. Regarding the extraction techniques, different approaches previously optimized in the research group were tested. On the one hand different polymeric materials were tested: silicon rod (SR), polyethersulfone (PES) and polydimethylsiloxane (PDMS), the latter in the stir-bar sorptive extraction format (SBSE-PDMS). PES was chosen among the polymeric materials due to the higher recoveries (compared with SR) and lower price (compared to PDMS in the stir-bar sorptive extraction, SBSE-PDMS). Both MASE and PES protocols were selected at this point for further method validation and application to real samples. Finally, the developed methods were validated and applied to the determination of target analytes in various aqueous environmental matrices, including estuarine water and wastewater. Acceptable repeatability in the case of MASE (5-17%) and PES (7-21%) procedures and method detection limits (MDLs, 5-123 and 28-328 ng L(-1) for PES and MASE, respectively) were obtained for most analytes. In terms of apparent recoveries in the presence of matrix, estuarine and effluent samples showed no significant matrix effect (apparent recoveries in the 73-121% for PES and 74-128% for MASE), while a stronger matrix effect was observed for influent wastewater samples (98-132% for PES and 65-156% for MASE). Both MASE and PES extractions combined with LVI-in-port derivatization-GC-MS were applied to the determination of APs in the estuary of Bilbao (Gulf of Biscay, Spain). Copyright © 2014 Elsevier B.V. All rights reserved.

A mobile and self-sufficient lab for high frequency measurements of stable water isotopes and chemistry of multiple water sources

NASA Astrophysics Data System (ADS)

Windhorst, David; Kraft, Philipp; Holly, Hartmut; Sahraei, Amir; Breuer, Lutz

2017-04-01

Technical advances over the last years have made instruments for stable water isotope and water chemistry measurements smaller, more durable and energy efficient. It is nowadays feasible to deploy such instruments in situ during field campaigns. Coupled to an automated sample delivery system, high temporal resolution online measurements of various sources are within the bounds of economic and technical possibility. However, the day to day operation of such equipment still requires either a lot of man power and infrastructure or the implementation of a quasi-self-sufficient system. The challenge remains on how to facilitate and remotely operate such a system. We present the design and implementation of the Water Analysis Trailer for Environmental Research (WATER), an autonomous platform consisting of instruments for stable water isotope and water chemistry analysis. The system takes and measures samples in high temporal resolution (<15 min) of up to 12 sources. To ensure an unmanned operation of up to one week several issues need to be addressed. The essential topics are: - self-sufficient power supply, - automated sample delivery and preparation, and - autonomous measurements and management interfacing all instruments. In addition to the basic requirements we implemented: - communication of all system states, alarm messages and measurement results to an internal as well as an external database via cellular telemetry, - automated storage of up to 300 frozen reference samples (100 mL, stored at -18°C), - climate control for temperature sensitive equipment (±1°C), - a local and remote (up to 20 km using radio telemetry) sensor network (i.e. to record states of the hydrological system and climate and soil conditions), also suitable to trigger specific measurements - automatic fire suppression and security system. The initial instrumentation includes a UV spectrometer (ProPs, Trios GmBH, Germany) to measure NO3-, COD, TOC and total suspended sediments, multiparameter water quality probe (YSI600R, YSI, USA) to measure electrical conductivity and pH, and a stable water isotope analyzer (L2130-i, Picarro, USA) coupled to a continuous water sampler (A0217, Picarro, USA). Fourty soil moisture, temperature and electrical conductivity sensors (5TE, Decagon, USA) are connect to the remote sensor network (A850, Adcon, Austria) and rain gauges and a climate station (WXT520, Vaisala, Finland) are connected to the local sensor network via SDI-12. In a first field trial starting in March 2017 the mobile laboratory will be used to study the hydrological processes in the developed landscape of the Schwingbach catchment (Germany). We are confident, that the unprecedented degree in detail, the measurements promise, will further accelerate our hydrological understanding and the interaction of various discharge generating sources.

Streaming Potential In Rocks Saturated With Water And Oil

NASA Astrophysics Data System (ADS)

Tarvin, J. A.; Caston, A.

2011-12-01

Fluids flowing through porous media generate electrical currents. These currents cause electric potentials, called "streaming potentials." Streaming potential amplitude depends on the applied pressure gradient, on rock and fluid properties, and on the interaction between rock and fluid. Streaming potential has been measured for rocks saturated with water (1) and with water-gas mixtures. (2) Few measurements (3) have been reported for rocks saturated with water-oil mixtures. We measured streaming potential for sandstone and limestone saturated with a mixture of brine and laboratory oil. Cylindrical samples were initially saturated with brine and submerged in oil. Saturation was changed by pumping oil from one end of a sample to the other and then through the sample in the opposite direction. Saturation was estimated from sample resistivity. The final saturation of each sample was determined by heating the sample in a closed container and measuring the pressure. Measurements were made by modulating the pressure difference (of oil) between the ends of a sample at multiple frequencies below 20 Hz. The observed streaming potential is a weak function of the saturation. Since sample conductivity decreases with increasing oil saturation, the electro-kinetic coupling coefficient (Pride's L (4)) decreases with increasing oil saturation. (1) David B. Pengra and Po-zen Wong, Colloids and Surfaces, vol., p. 159 283-292 (1999). (2) Eve S. Sprunt, Tony B. Mercer, and Nizar F. Djabbarah, Geophysics, vol. 59, p. 707-711 (1994). (3) Vinogradov, J., Jackson, M.D., Geophysical Res. L., Vol. 38, Article L01301 (2011). (4) Steve Pride, Phys. Rev. B, vol. 50, pp. 15678-15696 (1994).

Physicochemical properties and the concentration of anions, major and trace elements in groundwater, treated drinking water and bottled drinking water in Najran area, KSA

NASA Astrophysics Data System (ADS)

Brima, Eid I.

2017-03-01

Basic information about major elements in bottled drinking water is provided on product labels. However, more information is needed about trace elements in bottled drinking water and other sources of drinking water to assess its quality and suitability for drinking. This is the first such study to be carried out in Najran city in the Kingdom of Saudi Arabia (KSA). A total of 48 water samples were collected from different sources comprising wells, stations for drinking water treatment and bottled drinking water (purchased from local supermarkets). The concentrations of 24 elements [aluminum (Al), arsenic (As), barium (Ba), calcium (Ca), cadmium (Cd), cobalt (Co), chromium (Cr), cesium (Cs), copper (Cu), iron (Fe), potassium (K), magnesium (Mg), manganese (Mn), molydenum (Mo), sodium (Na), nickel (Ni), lead (Pb), rubidium (Rb), selenium (Se), strontium (Sr), titanium (Ti), vanadium (V), uranium (U) and zinc (Zn)] were determined by inductively coupled plasma-mass spectrometry (ICP-MS). Anions (chlorine (Cl-), fluoride (F-), sulfate (SO4 2-) and nitrate (NO3 -) were determined by ion chromatography (IC). Electrical conductivity (EC), pH, total dissolved salts (TDS) and total hardness (TH) were also measured. All parameters of treated drinking water and bottled drinking water samples did not exceed the World Health Organization (WHO) 2008, US Environmental Protection Agency (USEPA 2009), Gulf Cooperation Council Standardization Organization (GSO) 2008 and Saudi Arabian Standards Organization (SASO) 1984 recommended guidelines. It is noteworthy that groundwater samples were not used for drinking purpose. This study is important to raise public knowledge about drinking water, and to promote public health.

Rapid analysis of ultraviolet filters using dispersive liquid-liquid microextraction coupled to headspace gas chromatography and mass spectrometry.

PubMed

Pierson, Stephen A; Trujillo-Rodríguez, María J; Anderson, Jared L

2018-05-29

An ionic-liquid-based in situ dispersive liquid-liquid microextraction method coupled to headspace gas chromatography and mass spectrometry was developed for the rapid analysis of ultraviolet filters. The chemical structures of five ionic liquids were specifically designed to incorporate various functional groups for the favorable extraction of the target analytes. Extraction parameters including ionic liquid mass, molar ratio of ionic liquid to metathesis reagent, vortex time, ionic strength, pH, and total sample volume were studied and optimized. The effect of the headspace temperature and volume during the headspace sampling step was also evaluated to increase the sensitivity of the method. The optimized procedure is fast as it only required ∼7-10 min per extraction and allowed for multiple extractions to be performed simultaneously. In addition, the method exhibited high precision, good linearity, and low limits of detection for six ultraviolet filters in aqueous samples. The developed method was applied to both pool and lake water samples attaining acceptable relative recovery values. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mobility of major and trace elements in a coupled groundwater-surface water system: Merced River, CA

NASA Astrophysics Data System (ADS)

Wildman, R. A.; Domagalski, J. L.; Hering, J. G.

2004-12-01

Trace element transport in coupled surface water/groundwater systems is controlled not only by advective flow, but also by redox reactions that affect the partitioning of various elements between mobile and immobile phases. These processes have been examined in the context of a field project conducted by the U.S. Geological Survey (USGS) as part of the National Water-Quality Assessment (NAWQA) program. The Merced River flows out of Yosemite National Park and the Sierra Nevada foothills and into California's Central Valley, where it joins the San Joaquin River. Our field site is approximately twenty river kilometers from the confluence with the San Joaquin River. This deep alluvial plain has minimal topography. Agricultural development characterizes the land surrounding this reach of river; consequently, the hydrology is heavily influenced by irrigation. Riverbed groundwater samples were collected from ten wells aligned in two transects across the river located approximately 100 m apart. The wells were sampled from depths of 0.5 m, 1 m, and 3 m below the sediment-water interface. Groundwater flowpath samples were taken from wells positioned on a path perpendicular to the river and located 100 m, 500 m, and 1000 m from the river. The saturated groundwater system exists from 7 to 40 m below the surface and is confined below by a clay layer. Each well location samples from 3-5 depths in this surface aquifer. Samples were collected in December 2003, March-April, June-July, and October 2004. This served to provide an evenly-spaced sampling frequency over the course of a year, and also to allow observation of trends coinciding with the onset of winter, the spring runoff, and early and late summer irrigation. An initial survey of the elements in the riverbed samples was conducted using Inductively-Coupled Plasma Mass Spectrometry (ICP-MS). Elements for further study were selected based on variability in this survey, either with respect to depth or location, as well as to cover a range of expected geochemical behaviors. Further ICP-MS measurements focused on eight elements: strontium, barium, uranium, molybdenum, manganese, iron, phosphorus, and bromine. Bromine is a conservative tracer. Molybdenum, manganese, and iron will precipitate when oxidized, and uranium will precipitate when reduced. Strontium and barium are not redox-active but may be affected by dissolution-precipitation and sorption reactions. Phosphorus is a nutrient that will cycle actively in areas of biological productivity. Generally, these elements appear to behave as expected based on physical waterflow and assumed redox conditions. The two transects of wells across the river bracket a zone of known denitrification, which implies that sediment conditions favor oxidation upriver and reduction downriver. This trend is borne out both by the redox-sensitive elements at each transect, and by the strontium and barium, which bind to precipitated iron and manganese oxides in oxidizing conditions and are released into the dissolved state in reducing conditions. The flowpath samples appear to be enriched in strontium, phosphorus, and bromine when compared to the riverbed samples, and they are depleted in manganese and iron.

Water-mediated electron transfer between protein redox centers.

PubMed

Migliore, Agostino; Corni, Stefano; Felice, Rosa Di; Molinari, Elisa

2007-04-12

Recent experimental and theoretical investigations show that water molecules between or near redox partners can significantly affect their electron-transfer (ET) properties. Here we study the effects of intervening water molecules on the electron self-exchange reaction of azurin (Az), by performing a conformational sampling on the water medium and by using a newly developed ab initio method to calculate transfer integrals between molecular redox sites. We show that the insertion of water molecules at the interface between the copper active sites of Az dimers slightly increases the overall ET rate, while some favorable water conformations can considerably enhance the ET kinetics. These features are traced back to the interplay of two competing factors: the electrostatic interaction between the water and protein subsystems (mainly opposing the ET process for the water arrangements drawn from MD simulations) and the effectiveness of water in mediating ET coupling pathways. Such an interplay provides a physical basis for the found absence of correlation between the electronic couplings derived through ab initio electronic structure calculations and the related quantities obtained through the Empirical Pathways (EP) method. In fact, the latter does not account for electrostatic effects on the transfer integrals. Thus, we conclude that the water-mediated electron tunneling is not controlled by the geometry of a single physical pathway. We discuss the results in terms of the interplay between different ET pathways controlled by the conformational changes of one of the water molecules via its electrostatic influence. Finally, we examine the dynamical effects of the interfacial water and check the validity of the Condon approximation.

Endocrine disruptors in water filters used in the Rio dos Sinos Basin region, Southern Brazil.

PubMed

Furtado, C M; von Mühlen, C

2015-05-01

The activated carbon filter is used in residences as another step in the treatment of drinking water, based on a physical-chemical process to absorb pollutants that are not removed in conventional treatment. Endocrine disruptors (EDCs) are exogenous substances or mixtures of substances that acts on the endocrine system similarly to the endogenously produced hormones, triggering malfunctions and harmful changes to human and animal health. The objective of the present work was to study EDCs through semi-quantitative analysis of residential water filters collected in the region of Rio dos Sinos basin, focusing on two specific classes: hormones and phenols. The solid phase extraction principle was used for the extraction of compounds and gas chromatography coupled with mass spectrometry for the separation and characterization of EDCs. Four samples of residential filters collected from public water distribution and artesian wells, from the cities of Novo Hamburgo and São Leopoldo were analysed. Using the developed methodology, it was possible to detect and comparatively quantify selected EDCs in all studied samples, which indicates the presence of these contaminants in drinking water from different sources.

Determination of mycotoxins in different food commodities by ultra-high-pressure liquid chromatography coupled to triple quadrupole mass spectrometry.

PubMed

Beltrán, Eduardo; Ibáñez, María; Sancho, Juan Vicente; Hernández, Félix

2009-06-01

A rapid multianalyte-multiclass method with little sample manipulation has been developed for the simultaneous determination of eleven mycotoxins in different food commodities by using ultra-high-pressure liquid chromatography coupled to triple quadrupole mass spectrometry (UHPLC/MS/MS). Toxins were extracted from the samples with acetonitrile/water (80:20, v/v) 0.1% HCOOH and, after a two-fold dilution with water, directly injected into the system. Thanks to the fast high-resolution separation of UHPLC, the eleven mycotoxins were separated by gradient elution in only 4 min. The method has been validated in three food matrices (maize kernels, dry pasta (wheat), and eight-multicereal babyfood (wheat, maize, rice, oat, barley, rye, sorghum, millet)) at four different concentration levels. Satisfactory recoveries were obtained (70-110%) and precision (expressed as relative standard deviation) was typically below 15% with very few exceptions. Quantification of samples was carried out with matrix-matched standards calibration. The lowest concentration successfully validated in sample was as low as 0.5 microg/kg for aflatoxins and ochratoxin A in babyfood, and 20 microg/kg for the rest of the selected mycotoxins in all matrices tested. Deoxynivalenol could be only validated at 200 microg/kg, due the poor sensitivity for this mycotoxin analysis. With only two exceptions (HT-2 and deoxynivalenol), the limits of detection (LODs), estimated for a signal-to-noise ratio of 3 from the chromatograms of samples spiked at the lowest level validated, varied between 0.1 and 1 microg/kg in the three food matrices tested. The method was applied to the analysis of different kinds of samples. Positive findings were confirmed by acquiring two transitions (Q quantification, q confirmation) and evaluating the Q/q ratio. Copyright (c) 2009 John Wiley & Sons, Ltd.

Electrochemical preparation of composite polyaniline coating and its application in the determination of bisphenol A, 4-n-nonylphenol, 4-tert-octylphenol using direct solid phase microextraction coupled with high performance liquid chromatography.

PubMed

Huang, Minjia; Jiang, Guibin; Cai, Yaqi

2005-11-01

For SPME-HPLC, metal wires with better mechanical strength are preferred over the fused silica fibers. In this article, a novel composite polyaniline (CPANI) doped with PEG and polydimethylsiloxane coating (CPANI fiber) was prepared on a stainless steel wire by a three-electrode system: the fiber was used as the work electrode, a calomel electrode and a platinum electrode were used as the reference and the counter electrodes, respectively. To evaluate the new CPANI coating, the coating was used to extract three kinds of phenols (bisphenol A, 4-n-nonylphenol, and 4-tert-octylphenol) in water samples by direct-SPME mode and then desorbed in commercial SPME-HPLC interface to separation. The extraction procedure was also optimized. Five real water samples were investigated. Good recoveries were gained when environmental samples were analyzed.

Monitoring Pb in Aqueous Samples by Using Low Density Solvent on Air-Assisted Dispersive Liquid-Liquid Microextraction Coupled with UV-Vis Spectrophotometry.

PubMed

Nejad, Mina Ghasemi; Faraji, Hakim; Moghimi, Ali

2017-04-01

In this study, AA-DLLME combined with UV-Vis spectrophotometry was developed for pre-concentration, microextraction and determination of lead in aqueous samples. Optimization of the independent variables was carried out according to chemometric methods in three steps. According to the screening and optimization study, 86 μL of 1-undecanol (extracting solvent), 12 times syringe pumps, pH 2.0, 0.00% of salt and 0.1% DDTP (chelating agent) were chosen as the optimum independent variables for microextraction and determination of lead. Under the optimized conditions, R = 0.9994, and linearity range was 0.01-100 µg mL -1 . LOD and LOQ were 3.4 and 11.6 ng mL -1 , respectively. The method was applied for analysis of real water samples, such as tap, mineral, river and waste water.

Method for outlier detection: a tool to assess the consistency between laboratory data and ultraviolet-visible absorbance spectra in wastewater samples.

PubMed

Zamora, D; Torres, A

2014-01-01

Reliable estimations of the evolution of water quality parameters by using in situ technologies make it possible to follow the operation of a wastewater treatment plant (WWTP), as well as improving the understanding and control of the operation, especially in the detection of disturbances. However, ultraviolet (UV)-Vis sensors have to be calibrated by means of a local fingerprint laboratory reference concentration-value data-set. The detection of outliers in these data-sets is therefore important. This paper presents a method for detecting outliers in UV-Vis absorbances coupled to water quality reference laboratory concentrations for samples used for calibration purposes. Application to samples from the influent of the San Fernando WWTP (Medellín, Colombia) is shown. After the removal of outliers, improvements in the predictability of the influent concentrations using absorbance spectra were found.

Synthesis of cellulose functionalized with polyallylamine and its application to on-line collection/concentration and determination of phosphate by ICP/AES.

PubMed

Sumida, Takashi; Yamashita, Minoru; Okazaki, Yuka; Kawakita, Hirohisa; Fukutomi, Takashi

2012-01-01

A novel cellulose-based resin functionalized with polyallylamine was synthesized. It was applied to the collection of phosphate in environmental water samples, followed by concentration determination using an inductively coupled plasma-atomic emission spectrometer (ICP/AES). The synthesized resin, cellulose-glycidylmethacrylate-polyallylamine (CGP), showed good adsorption behavior toward trace amounts of phosphate over a wide pH range. The adsorbed-analyte can be easily eluted using 0.5 M hydrochloric acid; its recoveries was found to be 80 - 100%. The CGP resin synthesized was packed in a mini-column, which was then installed in a computer-controlled auto-pretreatment system for on-line collection/concentration and determination of trace phosphate by ICP/AES. The limit of detection for phosphate was found to be 0.6 µg P l(-1). The sample volumes were only 5 ml and the total analysis time was about 4 min. The developed method with CGP resin was successfully applied to the determination of phosphate in river water and tap water samples with satisfactory results. The recovery test showed that common matrices that may exist in environmental waters did not interfere with the determination of phosphate.

Studying the effect of the Semipalatinsk Test Site on radionuclide and elemental composition of water objects in the Irtysh River.

PubMed

Solodukhin, V; Аidarkhanov, A; Lukashenko, S; Gluchshenko, V; Poznyak, V; Lyahova, O

2015-06-01

The results of the field and laboratory studies of radiation and environmental state at the specific area of Irtysh River adjacent to the Semipalatinsk Test Site are provided. It was found that the radiation situation in this area is normal: equivalent dose of γ-radiation = (0.11-0.13) µSv h(-1). Determination of radionuclide composition of soil, bottom sediment and water samples was performed by the methods of instrumental γ-spectrometry, radiochemical analysis and the liquid scintillation β-spectrometry. It was found that concentrations of the studied natural and artificial radionuclides in these objects are very low; no contamination with radionuclides was detected in this segment of Irtysh River. The article provides the results of elemental composition determination for samples of soil and bottom sediment (by X-ray fluorescence method) and water samples (by inductively coupled plasma mass spectrometry method). It is shown that the content of some elements (Li, Be, B, V, Cu, Sr, Mo) in the water of Irtysh River increases downstream. The additional studies are required to explain this peculiarity. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

METHOD 200.5 - DETERMINATION OF TRACE ELEMENTS IN DRINKING WATER BY AXIALLY VIEWED INDUCTIVELY COUPLED PLASMA-ATOMIC EMISSION SPECTROMETRY

EPA Science Inventory

2.0 SUMMARY OF METHOD
2.1. A 50 mL aliquot of a well-mixed, non-filtered, acid preserved aqueous sample is accurately transferred to clean 50-mL plastic disposable digestion tube containing a mixture of nitric and hydrochloric acids. The aliquot is heated to 95 degrees C (+ o...

Latin hypercube approach to estimate uncertainty in ground water vulnerability

USGS Publications Warehouse

Gurdak, J.J.; McCray, J.E.; Thyne, G.; Qi, S.L.

2007-01-01

A methodology is proposed to quantify prediction uncertainty associated with ground water vulnerability models that were developed through an approach that coupled multivariate logistic regression with a geographic information system (GIS). This method uses Latin hypercube sampling (LHS) to illustrate the propagation of input error and estimate uncertainty associated with the logistic regression predictions of ground water vulnerability. Central to the proposed method is the assumption that prediction uncertainty in ground water vulnerability models is a function of input error propagation from uncertainty in the estimated logistic regression model coefficients (model error) and the values of explanatory variables represented in the GIS (data error). Input probability distributions that represent both model and data error sources of uncertainty were simultaneously sampled using a Latin hypercube approach with logistic regression calculations of probability of elevated nonpoint source contaminants in ground water. The resulting probability distribution represents the prediction intervals and associated uncertainty of the ground water vulnerability predictions. The method is illustrated through a ground water vulnerability assessment of the High Plains regional aquifer. Results of the LHS simulations reveal significant prediction uncertainties that vary spatially across the regional aquifer. Additionally, the proposed method enables a spatial deconstruction of the prediction uncertainty that can lead to improved prediction of ground water vulnerability. ?? 2007 National Ground Water Association.

Arsenic speciation analysis of urine samples from individuals living in an arsenic-contaminated area in Bangladesh.

PubMed

Hata, Akihisa; Yamanaka, Kenzo; Habib, Mohamed Ahsan; Endo, Yoko; Fujitani, Noboru; Endo, Ginji

2012-05-01

Chronic inorganic arsenic (iAs) exposure currently affects tens of millions of people worldwide. To accurately determine the proportion of urinary arsenic metabolites in residents continuously exposed to iAs, we performed arsenic speciation analysis of the urine of these individuals and determined whether a correlation exists between the concentration of iAs in drinking water and the urinary arsenic species content. The subjects were 165 married couples who had lived in the Pabna District in Bangladesh for more than 5 years. Arsenic species were measured using high-performance liquid chromatography and inductively coupled plasma mass spectrometry. The median iAs concentration in drinking water was 55 μgAs/L (range <0.5-332 μgAs/L). Speciation analysis revealed the presence of arsenite, arsenate, monomethylarsonic acid (MMA), and dimethylarsinic acid in urine samples with medians (range) of 16.8 (7.7-32.3), 1.8 (<0.5-3.3), 13.7 (5.6-25.0), and 88.6 μgAs/L (47.9-153.4 μgAs/L), respectively. No arsenobetaine or arsenocholine was detected. The concentrations of the 4 urinary arsenic species were significantly and linearly related to each other. The urinary concentrations of total arsenic and each species were significantly correlated with the iAs concentration of drinking water. All urinary arsenic species are well correlated with each other and with iAs in drinking water. The most significant linear relationship existed between the iAs concentration in drinking water and urinary iAs + MMA concentration. From these results, combined with the effects of seafood ingestion, the best biomarker of iAs exposure is urinary iAs + MMA concentration.

Magnetic solid phase extraction coupled with inductively coupled plasma mass spectrometry for the speciation of mercury in environmental water and human hair samples.

PubMed

Ma, Shishuai; He, Man; Chen, Beibei; Deng, Wenchao; Zheng, Qi; Hu, Bin

2016-01-01

In this work, γ-mercaptopropyltrimethoxysilane (γ-MPTS) modified Fe3O4@SiO2 magnetic nanoparticles (MNPs) was successfully prepared, and characterized by Fourier transform infrared spectrometer (FT-IR), Transmission electron microscope (TEM) and Vibrating sample magnetometer (VSM). The sorption performance of the prepared Fe3O4@SiO2@γ-MPTS MNPs towards methylmercury (CH3Hg(+)) and inorganic mercury (Hg(2+)) was investigated. It was found that CH3Hg(+) and Hg(2+) could be simultaneously retained on the prepared Fe3O4@SiO2@γ-MPTS MNPs, and the quantitative elution of CH3Hg(+) and total mercury (THg) was achieved by using 1.5 mol L(-1) HCl containing 0.01% and 3% thiourea (m/v), respectively. And the levels of Hg(2+) were obtained by subtracting CH3Hg(+) from THg. Based on the above facts, a method of magnetic solid phase extraction (MSPE) combined with inductively coupled plasma mass spectrometry (ICP-MS) was developed for the speciation of CH3Hg(+) and Hg(2+). Various experimental parameters affecting MSPE of CH3Hg(+) and Hg(2+) such as pH, eluent, sample volume, and co-existing ions have been studied. Under the optimized conditions, the limits of detection (LODs) for CH3Hg(+) and THg were 1.6 and 1.9 ng L(-1), respectively. The accuracy of the proposed method was validated by analysis of a Certified Reference Material NRCC DORM-2 dogfish muscle, and the determined values are in good agreement with the certified values. The proposed method has also been successfully applied for the speciation of CH3Hg(+) and Hg(2+) in environmental water and human hair samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Magnetic dummy molecularly imprinted polymers based on multi-walled carbon nanotubes for rapid selective solid-phase extraction of 4-nonylphenol in aqueous samples.

PubMed

Rao, Wei; Cai, Rong; Yin, Yuli; Long, Fang; Zhang, Zhaohui

2014-10-01

In this paper, a highly selective sample clean-up procedure combining magnetic dummy molecular imprinting with solid-phase extraction was developed for rapid separation and determination of 4-nonylphenol (NP) in the environmental water samples. The magnetic dummy molecularly imprinted polymers (mag-DMIPs) based on multi-walled carbon nanotubes were successfully synthesized with a surface molecular imprinting technique using 4-tert-octylphenol as the dummy template and tetraethylorthosilicate as the cross-linker. The maximum adsorption capacity of the mag-DMIPs for NP was 52.4 mg g(-1) and it took about 20 min to achieve the adsorption equilibrium. The mag-DMIPs exhibited the specific selective adsorption toward NP. Coupled with high performance liquid chromatography analysis, the mag-DMIPs were used to extract solid-phase and detect NP in real water samples successfully with the recoveries of 88.6-98.1%. Copyright © 2014 Elsevier B.V. All rights reserved.

Structural characterization of astaxanthin aggregates as revealed by analysis and simulation of optical spectra

NASA Astrophysics Data System (ADS)

Lu, Liping; Hu, Taoping; Xu, Zhigang

2017-10-01

Carotenoids can self-assemble in hydrated polar solvents to form J- or H-type aggregates, inducing dramatic changes in photophysical properties. Here, we measured absorption and emission spectra of astaxanthin in ethanol-water solution using ultraviolet-visible and fluorescence spectrometers. Two types of aggregates were distinguished in mixed solution at different water contents by absorption spectra. After addition of water, all probed samples immediately formed H-aggregates with maximum blue shift of 31 nm. In addition, J-aggregate was formed in 1:3 ethanol-water solution measured after an hour. Based on Frenkel exciton model, we calculated linear absorption and emission spectra of these aggregates to describe aggregate structures in solution. For astaxanthin, experimental results agreed well with the fitted spectra of H-aggregate models, which consisted of tightly packed stacks of individual molecules, including hexamers, trimers, and dimers. Transition moment of single astaxanthin in ethanol was obtained by Gaussian 09 program package to estimate the distance between molecules in aggregates. Intermolecular distance of astaxanthin aggregates ranges from 0.45 nm to 0.9 nm. Fluorescence analysis showed that between subbands, strong exciton coupling induced rapid relaxation of H-aggregates. This coupling generated larger Stokes shift than monomers and J-aggregates.

Improved coupled-column liquid chromatographic method for the determination of glyphosate and aminomethylphosphonic acid residues in environmental waters.

PubMed

Hidalgo, Carmén; Rios, Carolina; Hidalgo, Manuela; Salvadó, Victòria; Sancho, Juan V; Hernández, Félix

2004-04-30

An existing method for the determination of glyphosate and its main metabolite aminomethylphosphonic acid (AMPA) in water has been improved. It is based on precolumn derivatization with the fluorescent reagent 9-fluorenylmethylcloroformate (FMOC) followed by large-volume injection in a coupled-column LC system using fluorescence detection (LC-LC-FD). The derivatization step was slightly modified by changing parameters such as volume and/or concentration of sample and reagents to decrease the limits of quantification (LOQ) of glyphosate and AMPA to 0.1 microg/l. Additionally, the use of Amberlite IRA-900 for preconcentration of glyphosate, prior to the derivatization step, was investigated; the LOQ of glyphosate was lowered to 0.02 microg/l. Drinking, surface and ground water spiked with glyphosate and AMPA at 0.1-10 microg/l concentrations were analysed by the improved LC-LC-FD method. Recoveries were 87-106% with relative standard deviations lower than 8%. Drinking and ground water spiked with glyphosate at 0.02 and 0.1 microg/l were analysed after preconcentration on the anion-exchange resin with satisfactory recoveries (94-105%) and precision (better than 8%).

Development and application of a coupled bio-geochmical and hydrological model for point and non-point source river water pollution

NASA Astrophysics Data System (ADS)

Pohlert, T.

2007-12-01

The aim of this paper is to present recent developments of an integrated water- and N-balance model for the assessment of land use changes on water and N-fluxes for meso-scale river catchments. The semi-distributed water-balance model SWAT was coupled with algorithms of the bio-geochemical model DNDC as well as the model CropSyst. The new model that is further denoted as SWAT-N was tested with leaching data from a long- term lysimeter experiment as well as results from a 5-years sampling campaign that was conducted at the outlet of the meso-scale catchment of the River Dill (Germany). The model efficiency for N-load as well as the spatial representation of N-load along the river channel that was tested with results taken from longitudinal profiles show that the accuracy of the model has improved due to the integration of the aforementioned process-oriented models. After model development and model testing, SWAT-N was then used for the assessment of the EU agricultural policy (CAP reform) on land use change and consequent changes on N-fluxes within the Dill Catchment. giessen.de/geb/volltexte/2007/4531/

Gunshot residue (GSR) analysis by single particle inductively coupled plasma mass spectrometry (spICP-MS).

PubMed

Heringer, Rodrigo D; Ranville, James F

2018-05-25

Single particle inductively coupled plasma mass spectrometry (spICP-MS) was investigated as a screening-level technique for the analysis and characterization of inorganic gunshot residue (IGSR) nanoparticles. spICP-MS works with undigested samples whereby nanoparticles (NPs) in a suspension are individually atomized and ionized as they reach the plasma, each resulting in a pulse of analyte ions that can be quantified. The method is rapid, and signals from hundreds of NPs can be collected in 1-2min per sample. The technique is quantitative for NP mass and number concentration when only one element (single element mode) is measured using a quadrupole MS. Likewise, a qualitative elemental fingerprint can be obtained for individual NPs when peak-hopping between two elements (dual element mode). For this proof of concept study, each shooter's hand was sampled with ultrapure water or swab to obtain NPs suspensions. Measurements of antimony, barium, and lead were performed using both analysis modes. With no sample preparation and fully automated sample introduction, it is possible to analyze more than 100 samples in a day. Results show that this technique opens a new perspective for future research on GSR sample identification and characterization and can complement SEM/EDX analysis. Copyright © 2018 Elsevier B.V. All rights reserved.

Analysis of elemental concentration using ICP-AES and pathogen indicator in drinking water of Qasim Abad, District Rawalpindi, Pakistan.

PubMed

Sehar, Shama; Naz, Iffat; Ali, Naeem; Ahmed, Safia

2013-02-01

The present study was conducted to investigate drinking water quality (groundwater) from water samples taken from Qasim Abad, a locality of approximately 5,000 population, situated between twin cities Rawalpindi and Islamabad in Pakistan. The main sources of drinking water in this area are water bores which are dug upto the depth of 250-280 ft in almost every house. The study consists of the determination of physico-chemical properties, trace metals, heavy metals, rare earth elements and microbiological quality of drinking water. The data showed the variation of the investigated parameters in samples as follows: pH 6.75 to 8.70, electrical conductivity 540 to 855 μS/cm, total dissolved solids 325.46 to 515.23 ppm and dissolved oxygen 1.50 to 5.64 mg/L which are within the WHO guidelines for drinking water quality. The water samples were analysed for 30 elements (aluminium, iron, magnesium, manganese, silicon, zinc, molybdenum, titanium, chromium, nickel, tungsten, silver, arsenic, boron, barium, beryllium, cadmium, cobalt, copper, gallium, mercury, lanthanum, niobium, neodymium, lead, selenium, samarium, tin, vanadium and zirconium) by using inductively coupled plasma atomic emission spectroscopy. The organic contamination was detected in terms of most probable number (MPN) of faecal coliforms. Overall, elemental levels were lower than the recommended values but three water bores (B-1, B-6, B-7) had higher values of iron (1.6, 2.206, 0.65 ppm), two water bores (B-1, B-6) had higher values of aluminium (0.95, 1.92 ppm), respectively, and molybdenum was higher by 0.01 ppm only in one water bore (B-11). The total number of coliforms present in water samples was found to be within the prescribed limit of the WHO except for 5 out of 11 bore water samples (B-2, B-3, B-4, B-8, B-11), which were found in the range 5-35 MPN/100 mL, a consequence of infiltration of contaminated water (sewage) through cross connection, leakage points and back siphoning.

A laboratory rainfall simulator to study the soil erosion and runoff water

NASA Astrophysics Data System (ADS)

Cancelo González, Javier; Rial, M. E.; Díaz-Fierros, Francisco

2010-05-01

The soil erosion and the runoff water composition in some areas affected by forest fires or submitted to intensive agriculture are an important factor to keep an account, particularly in sensitive areas like estuary and rias that have a high importance in the socioeconomic development of some regions. An understanding of runoff production indicates the processes by which pollutants reach streams and also indicates the management techniques that might be uses to minimize the discharge of these materials into surface waters. One of the most methodology implemented in the soil erosion studies is a rainfall simulation. This method can reproduce the natural soil degradation processes in field or laboratory experiences. With the aim of improve the rainfall-runoff generation, a laboratory rainfall simulator which incorporates a fan-like intermittent water jet system for rainfall generation were modified. The major change made to the rainfall simulator consist in a system to coupling stainless steel boxes, whose dimensions are 12 x 20 x 45 centimeters, and it allows to place soil samples under the rainfall simulator. Previously these boxes were used to take soil samples in field with more of 20 centimeters of depth, causing the minimum disturbance in their properties and structure. These new implementations in the rainfall simulator also allow collect water samples of runoff in two ways: firstly, the rain water that constituted the overland flow or direct runoff and besides the rain water seeps into the soil by the process of infiltration and contributed to the subsurface runoff. Among main the variables controlled in the rainfall simulations were the soil slope and the intensity and duration of rainfall. With the aim of test the prototype, six soil samples were collected in the same sampling point and subjected to rainfall simulations in laboratory with the same intensity and duration. Two samples will constitute the control test, and they were fully undisturbed, and four samples were subjected to controlled burnings with different fire severity: two samples burnt to 250°C and the other two samples burnt to 450°C. Preliminary laboratory data of soil erosion and surface and subsurface runoff were obtained. The water parameters analysed were: pH, electrical conductivity, temperature (in the moment of sampling) and suspended sediments, ammonium, nitrates, total nitrogen (Kjeldahl method), within 24 hours after sampling.

Chemical, microbial and physical evaluation of commercial bottled waters in greater Houston area of Texas.

PubMed

Saleh, Mahmoud A; Abdel-Rahman, Fawzia H; Woodard, Brooke B; Clark, Shavon; Wallace, Cecil; Aboaba, Adetoun; Zhang, Wenluo; Nance, James H

2008-03-01

Due to the increased demand and consumption of bottled water in the United States, there has been a growing concern about the quality of this product. Retail outlets sell local as well as imported bottled water to consumers. Three bottles for each of 35 different brands of bottled water were randomly collected from local grocery stores in the greater Houston area. Out of the 35 different brands, 16 were designated as spring water, 11 were purified and/or fortified tap water, 5 were carbonated water and 3 were distilled water. Chemical, microbial and physical properties of all samples were evaluated including pH, conductivity, bacteria counts, anion concentration, trace metal concentration, heavy metal and volatile organics concentration were determined in all samples. Inductively coupled plasma/mass spectrometry (ICPMS) was used for elemental analysis, gas chromatography with electron capture detector (GCECD) as well as gas chromatography mass spectrometry (GCMS) were used for analysis of volatile organics, ion chromatography (IC) and selective ion electrodes were used for the analysis of anions. Bacterial identification was performed using the Biolog software (Biolog, Inc., Hayward, Ca, USA). The results obtained were compared with guidelines of drinking water recommended by the International Bottled Water Association (IBWA), United States Food and Drug Administration (FDA), United States Environmental Protection Agency (EPA) and the World Health Organization (WHO) drinking water standard. The majority of the analyzed chemicals were below their respective drinking water standards for maximum admissible concentrations (MAC). Volatile organic chemicals were found to be below detection limits. Four of the 35 brands of the bottled water samples analyzed were found to be contaminated with bacteria.

Prevalence of Rotavirus Genogroup A and Norovirus Genogroup II in Bassaseachic Falls National Park Surface Waters in Chihuahua, Mexico

PubMed Central

Delgado-Gardea, Ma. Carmen E.; Tamez-Guerra, Patricia; Gomez-Flores, Ricardo; Mendieta-Mendoza, Aurora; Zavala-Díaz de la Serna, Francisco Javier; Contreras-Cordero, Juan Francisco; Erosa-de la Vega, Gilberto; Pérez-Recoder, María Concepción; Sánchez-Ramírez, Blanca; González-Horta, Carmen; Infante-Ramírez, Rocío

2017-01-01

In areas lacking potable water treatment, drinking contaminated water may represent a public health threat. In addition to enteropathogenic bacteria and parasites, fecal contamination in water environments is associated with the transmission of enteric viruses and other causal agents of infectious disease. Rotavirus and norovirus are the main enteric viral agents responsible for diarrheic outbreaks. The aim of the present study was to detect seasonal variation of rotavirus and norovirus in the surface water at Bassaseachic Falls National Park during 2013. Rivers and streams within and nearby this park were sampled once in each season during 2013. Viral concentration was carried out by a handmade filtration equipment, using a commercial electropositive membrane coupled with the virus absortion elution technique (VIRADEL©). Detection of rotavirus and norovirus was performed by SYBR Green reverse transcription-real time polymerase chain reaction (SYBR GREEN© RT-qPCR) analyses. Norovirus genogroup II was detected in samples collected in June and October 2013. In the case of rotavirus, genogroup A was detected in March and June. The presence of rotavirus and norovirus was related to viral acute diarrhea in children less than five years of age, who were inhabiting the sampled areas. This may indicates that the contaminated water was potentially a risk factor for regional diarrheic outbreaks. PMID:28475152

Monitoring of Waterborne Parasites in Two Drinking Water Treatment Plants: A Study in Sarawak, Malaysia.

PubMed

Richard, Reena Leeba; Ithoi, Init; Abd Majid, Mohamad Azlan; Wan Sulaiman, Wan Yusoff; Tan, Tian Chye; Nissapatorn, Veeranoot; Lim, Yvonne Ai Lian

2016-06-28

The occurrence of waterborne parasites coupled with water parameters at various processing sites of two drinking water treatment plants (A and B) and seven distribution system (DS) sites in Sarawak, Malaysia were studied. Ten liters of water underwent immunomagnetic separation (IMS) technique to detect the presence of Giardia and Cryptosporidium (oo)cysts. The remaining supernatant was used to detect other parasites whilst 50 mL of water sample was each used in the detection of free-living amoebae and fecal coliforms. Sampled water was positive for Giardia (32.9%; 28/85), Cryptosporidium (18.8%; 16/85) followed by Spirometra ova-like (25.9%; 22/85), Blastocystis-like (25.9%; 22/85), nematode larvae-like (8.2%; 7/85) and Taenia ova-like (1.2%; 1/85). Meanwhile, 90.2% (55/61) samples were positive for Acanthamoeba and Naegleria via cultivation and of these, 11 isolates were confirmed as Acanthamoeba genotype T3 (5/7) and T4 (2/7) followed by Naegleria sp. (4/11), Naegleria italica (2/11), Naegleria australiensis (1/11), Naegleria angularis (1/11) and Vahlkampfia sp. (3/11). Cryptosporidium, Acanthamoeba and Naegleria were also detected in one of the seven tested DS sites. Only Giardia and Cryptosporidium showed significant correlations with fluoride and fecal coliforms. These results describe the occurrence of waterborne parasites that will assist key stakeholders in mitigating contamination at the specific sites.

Monitoring of Waterborne Parasites in Two Drinking Water Treatment Plants: A Study in Sarawak, Malaysia

PubMed Central

Richard, Reena Leeba; Ithoi, Init; Abd Majid, Mohamad Azlan; Wan Sulaiman, Wan Yusoff; Tan, Tian Chye; Nissapatorn, Veeranoot; Lim, Yvonne Ai Lian

2016-01-01

The occurrence of waterborne parasites coupled with water parameters at various processing sites of two drinking water treatment plants (A and B) and seven distribution system (DS) sites in Sarawak, Malaysia were studied. Ten liters of water underwent immunomagnetic separation (IMS) technique to detect the presence of Giardia and Cryptosporidium (oo)cysts. The remaining supernatant was used to detect other parasites whilst 50 mL of water sample was each used in the detection of free-living amoebae and fecal coliforms. Sampled water was positive for Giardia (32.9%; 28/85), Cryptosporidium (18.8%; 16/85) followed by Spirometra ova-like (25.9%; 22/85), Blastocystis-like (25.9%; 22/85), nematode larvae-like (8.2%; 7/85) and Taenia ova-like (1.2%; 1/85). Meanwhile, 90.2% (55/61) samples were positive for Acanthamoeba and Naegleria via cultivation and of these, 11 isolates were confirmed as Acanthamoeba genotype T3 (5/7) and T4 (2/7) followed by Naegleria sp. (4/11), Naegleria italica (2/11), Naegleria australiensis (1/11), Naegleria angularis (1/11) and Vahlkampfia sp. (3/11). Cryptosporidium, Acanthamoeba and Naegleria were also detected in one of the seven tested DS sites. Only Giardia and Cryptosporidium showed significant correlations with fluoride and fecal coliforms. These results describe the occurrence of waterborne parasites that will assist key stakeholders in mitigating contamination at the specific sites. PMID:27367710

Enrichment and determination of octylphenol and nonylphenol in environmental water samples by solid-phase microextraction with carboxylated carbon nano-spheres coating prior to gas chromatography-mass spectrometry.

PubMed

Gong, Sheng-Xiang; Wang, Xia; Li, Lei; Wang, Ming-Lin; Zhao, Ru-Song

2015-11-01

In this paper, a novel and simple method for the sensitive determination of endocrine disrupter compounds octylphenol (OP) and nonylphenol (NP) in environmental water samples has been developed using solid-phase microextraction (SPME) coupled with gas chromatography-mass spectrometry. Carboxylated carbon nano-spheres (CNSs-COOH) are used as a novel SPME coating via physical adhesion. The CNSs-COOH fiber possessed higher adsorption efficiency than 100 μm polydimethysiloxane (PDMS) fiber and was similar to 85 μm polyacrylate (PA) fiber for the two analytes. Important parameters, such as extraction time, pH, agitation speed, ionic strength, and desorption temperature and time, were investigated and optimized in detail. Under the optimal parameters, the developed method achieved low limits of detection of 0.13~0.14 ng·L(-1) and a wide linear range of 1~1000 ng·(-1) for OP and NP. The novel method was validated with several real environmental water samples, and satisfactory results were obtained.

Dry coupling for whole-body small-animal photoacoustic computed tomography

NASA Astrophysics Data System (ADS)

Yeh, Chenghung; Li, Lei; Zhu, Liren; Xia, Jun; Li, Chiye; Chen, Wanyi; Garcia-Uribe, Alejandro; Maslov, Konstantin I.; Wang, Lihong V.

2017-04-01

We have enhanced photoacoustic computed tomography with dry acoustic coupling that eliminates water immersion anxiety and wrinkling of the animal and facilitates incorporating complementary modalities and procedures. The dry acoustic coupler is made of a tubular elastic membrane enclosed by a closed transparent water tank. The tubular membrane ensures water-free contact with the animal, and the closed water tank allows pressurization for animal stabilization. The dry coupler was tested using a whole-body small-animal ring-shaped photoacoustic computed tomography system. Dry coupling was found to provide image quality comparable to that of conventional water coupling.

Determination of drugs in surface water and wastewater samples by liquid chromatography-mass spectrometry: Methods and preliminary results including toxicity studies with Vibrio fischeri

USGS Publications Warehouse

Farre, M.; Ferrer, I.; Ginebreda, A.; Figueras, M.; Olivella, L.; Tirapu, L.; Vilanova, M.; Barcelo, D.

2001-01-01

In the present work a combined analytical method involving toxicity and liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) was developed for the determination of pharmaceutical compounds in water samples. The drugs investigated were the analgesics: ibuprofen, ketoprofen, naproxen, and diclofenac, the decomposition product of the acetyl salicylic acid: salicylic acid and one lipid lowering agent, gemfibrozil. The selected compounds are acidic substances, very polar and all of them are analgesic compounds that can be purchased without medical prescription. The developed protocol consisted, first of all, on the use Microtox?? and ToxAlert??100 toxicity tests with Vibrio fischeri for the different pharmaceutical drugs. The 50% effective concentration (EC50) values and the toxicity units (TU) were determined for every compound using both systems. Sample enrichment of water samples was achieved by solid-phase extraction procedure (SPE), using the Merck LiChrolut?? EN cartridges followed by LC-ESI-MS. Average recoveries loading 1 l of samples with pH=2 varied from 69 to 91% and the detection limits in the range of 15-56 ng/l. The developed method was applied to real samples from wastewater and surface-river waters of Catalonia (north-east of Spain). One batch of samples was analyzed in parallel also by High Resolution Gas Chromatography coupled with Mass Spectrometry (HRGC-MS) and the results have been compared with the LC-ESI-MS method developed in this work. ?? 2001 Elsevier Science B.V. All rights reserved.

Evaluation of Hydrodynamic Chromatography Coupled with UV-Visible, Fluorescence and Inductively Coupled Plasma Mass Spectrometry Detectors for Sizing and Quantifying Colloids in Environmental Media

PubMed Central

Philippe, Allan; Schaumann, Gabriele E.

2014-01-01

In this study, we evaluated hydrodynamic chromatography (HDC) coupled with inductively coupled plasma mass spectrometry (ICP-MS) for the analysis of nanoparticles in environmental samples. Using two commercially available columns (Polymer Labs-PDSA type 1 and 2), a set of well characterised calibrants and a new external time marking method, we showed that flow rate and eluent composition have few influence on the size resolution and, therefore, can be adapted to the sample particularity. Monitoring the agglomeration of polystyrene nanoparticles over time succeeded without observable disagglomeration suggesting that even weak agglomerates can be measured using HDC. Simultaneous determination of gold colloid concentration and size using ICP-MS detection was validated for elemental concentrations in the ppb range. HDC-ICP-MS was successfully applied to samples containing a high organic and ionic background. Indeed, online combination of UV-visible, fluorescence and ICP-MS detectors allowed distinguishing between organic molecules and inorganic colloids during the analysis of Ag nanoparticles in synthetic surface waters and TiO2 and ZnO nanoparticles in commercial sunscreens. Taken together, our results demonstrate that HDC-ICP-MS is a flexible, sensitive and reliable method to measure the size and the concentration of inorganic colloids in complex media and suggest that there may be a promising future for the application of HDC in environmental science. Nonetheless the rigorous measurements of agglomerates and of matrices containing natural colloids still need to be studied in detail. PMID:24587393

Evaluation of hydrodynamic chromatography coupled with UV-visible, fluorescence and inductively coupled plasma mass spectrometry detectors for sizing and quantifying colloids in environmental media.

PubMed

Philippe, Allan; Schaumann, Gabriele E

2014-01-01

In this study, we evaluated hydrodynamic chromatography (HDC) coupled with inductively coupled plasma mass spectrometry (ICP-MS) for the analysis of nanoparticles in environmental samples. Using two commercially available columns (Polymer Labs-PDSA type 1 and 2), a set of well characterised calibrants and a new external time marking method, we showed that flow rate and eluent composition have few influence on the size resolution and, therefore, can be adapted to the sample particularity. Monitoring the agglomeration of polystyrene nanoparticles over time succeeded without observable disagglomeration suggesting that even weak agglomerates can be measured using HDC. Simultaneous determination of gold colloid concentration and size using ICP-MS detection was validated for elemental concentrations in the ppb range. HDC-ICP-MS was successfully applied to samples containing a high organic and ionic background. Indeed, online combination of UV-visible, fluorescence and ICP-MS detectors allowed distinguishing between organic molecules and inorganic colloids during the analysis of Ag nanoparticles in synthetic surface waters and TiO₂ and ZnO nanoparticles in commercial sunscreens. Taken together, our results demonstrate that HDC-ICP-MS is a flexible, sensitive and reliable method to measure the size and the concentration of inorganic colloids in complex media and suggest that there may be a promising future for the application of HDC in environmental science. Nonetheless the rigorous measurements of agglomerates and of matrices containing natural colloids still need to be studied in detail.

Surfactant-assisted emulsification dispersive liquid-liquid microextraction using 2-thenoyltrifluoroacetone as a chelating agent coupled with electrothermal atomic absorption spectrometry for the speciation of chromium in water and rice samples.

PubMed

Dokpikul, Nattawut; Chaiyasith, Wipharat Chuachuad; Sananmuang, Ratana; Ampiah-Bonney, Richmond J

2018-04-25

A novel method was developed by SAE-DLLME for chromium speciation in water and rice samples using 2-thenoyltrifluoroacetone (TTA) as a chelating reagent by ETAAS. The speciation of Cr(III) and Cr(VI) was achieved by complexation of Cr(III)-TTA and the total Cr was measured after reduction of Cr(VI) to Cr. The calibration graph was linear in the range of 0.02-2.50 µg L -1 , with a detection limit of 0.0052 µg L -1 . The %RSD was in range of 2.90-3.30% at 0.5, 1.5 and 2.5 µg L -1 of Cr(III), n = 5 and the EF was 54.47. The method was applied to chromium speciation and total chromium determination in real samples and gave recoveries in the range of 96.2-103.5% and 97.1-102.7% for Cr(III) and Cr(VI) in water samples and 93.7-103.5% of total Cr in rice samples. The accuracy of the method was evaluated by analysis of SRM 1573a with good agreement compared to the certified value. Copyright © 2017 Elsevier Ltd. All rights reserved.

Neuston Trawl and Whole Water Samples: A Comparison of Microplastic Sampling Techniques in The Gulf of Maine and Their Application to Citizen-Driven Science

NASA Astrophysics Data System (ADS)

Kautz, M.

2016-12-01

Microplastic research in aquatic environments has quickly evolved over the last decade. To have meaningful inter-study comparisons, it is necessary to define methodological criteria for both the sampling and sorting of microplastics. The most common sampling method used for sea surface samples has traditionally been a neuston net (NN) tow. Originally designed for plankton collection, neuston tows allow for a large volume of water to be sampled and can be coupled with phytoplankton monitoring. The widespread use of surface nets allows for easy comparison between data sets, but the units of measurement for calculating microplastic concentration vary, from surface area m2 and Km2, to volume of water sampled, m3. Contamination by the air, equipment, or sampler is a constant concern in microplastic research. Significant in-field contamination concerns for neuston tow sampling include air exposure time, microplastics in rinse water, sampler contact, and plastic net material. Seeking to overcome the lack of contamination control and the intrinsic instrumental size limitation associated with surface tow nets, we developed an alternative sampling method. The whole water (WW) method is a one-liter grab sample of surface water adapted from College of the Atlantic and Sea Education Association (SEA) student, Marina Garland. This is the only WW method that we are aware of being used to sample microplastic. The method addresses the increasing need to explore smaller size domains, to reduce potential contamination and to incorporate citizen scientists into data collection. Less water is analyzed using the WW method, but it allows for targeted sampling of point-source pollution, intertidal, and shallow areas. The WW methodology can easily be integrated into long-term or citizen science monitoring initiatives due to its simplicity and low equipment demands. The aim of our study was to demonstrate a practical and economically feasible method for sampling microplastic abundance at the micro (10-6m) and nano (10-8m) scale that can be used in a wide variety of environments, and for assessing spatial and temporal distributions. The method has been employed in a multi-year citizen science collaboration with Adventurers and Scientists for Conservation to study microplastic worldwide.

Determination of diphenylether herbicides in water samples by solid-phase microextraction coupled to liquid chromatography.

PubMed

Sheu, Hong-Li; Sung, Yu-Hsiang; Melwanki, Mahaveer B; Huang, Shang-Da

2006-11-01

Solid-phase microextraction (SPME) coupled to LC for the analysis of five diphenylether herbicides (aclonifen, bifenox, fluoroglycofen-ethyl, oxyfluorfen, and lactofen) is described. Various parameters of extraction of analytes onto the fiber (such as type of fiber, extraction time and temperature, pH, impact of salt and organic solute) and desorption from the fiber in the desorption chamber prior to separation (such as type and composition of desorption solvent, desorption mode, soaking time, and flush-out time) were studied and optimized. Four commercially available SPME fibers were studied. PDMS/divinylbenzene (PDMS/DVB, 60 microm) and carbowax/ templated resin (CW/TPR, 50 microm) fibers were selected due to better extraction efficiencies. Repeatability (RSD, < 7%), correlation coefficient (> 0.994), and detection limit (0.33-1.74 and 0.22-1.94 ng/mL, respectively, for PDMS/DVB and CW/TPR) were investigated. Relative recovery (81-104% for PDMS/DVB and 83-100% for CW/TPR fiber) values have also been calculated. The developed method was successfully applied to the analysis of river water and water collected from a vegetable garden.

Validation of a Sulfuric Acid Digestion Method for Inductively Coupled Plasma Mass Spectrometry Quantification of TiO2 Nanoparticles.

PubMed

Watkins, Preston S; Castellon, Benjamin T; Tseng, Chiyen; Wright, Moncie V; Matson, Cole W; Cobb, George P

2018-04-13

A consistent analytical method incorporating sulfuric acid (H 2 SO 4 ) digestion and ICP-MS quantification has been developed for TiO 2 quantification in biotic and abiotic environmentally relevant matrices. Sample digestion in H 2 SO 4 at 110°C provided consistent results without using hydrofluoric acid or microwave digestion. Analysis of seven replicate samples for four matrices on each of 3 days produced Ti recoveries of 97% ± 2.5%, 91 % ± 4.0%, 94% ± 1.8%, and 73 % ± 2.6% (mean ± standard deviation) from water, fish tissue, periphyton, and sediment, respectively. The method demonstrated consistent performance in analysis of water collected over a 1 month.

Assessment of heavy metals in seawater and fish tissues at Pulau Indah, Selangor, Malaysia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Md Yunus, Sabarina, E-mail: sabarina2020@salam.uitm.edu.m; Hamzah, Zaini; Wood, Ab. Khalik

This study focuses on the levels of heavy metals in seawater and selected fish tissue at Pulau Indah, Selangor, Malaysia. Pulau Indah primarily contains Westport (Malaysia’s major port), and a host of full scales factories. Therefore, it is important to monitor the levels of pollution in this water body and the aquatic organisms in the long term effects, due to the human activities in this area. Water samples in this study were taken from 8 locations along the coastal area. The water samples were collected using water sampler and sampling locations were determined using a Global Positioning system (GPS). Similarly,more » in situ water quality parameters including temperature, dissolve oxygen (DO), salinity, total suspended solid (TSS), pH and turbidity were measured by using portable multi probes meter. Then, the samples were acidified until pH 2 and filtered. Fish samples were purchased from local fisherman along the Pulau Indah coastal area and samples were digested using concentrated nitric acid in wet digestion method. The levels of selected heavy metals in four species of fish and seawater from Pulau Indah coastal area were determined using Inductive Coupled Plasma Mass Spectrometer (ICPMS) after dilution to the samples. In general, the quality of water at Pulau Indah is lower than Malaysia Marine Water Quality Standard except for few locations were higher than the maximum permissible levels. The concentration of heavy metals which are lead (Pb), copper (Cu), zinc (Zn) and uranium (U) in water samples are in the range of 0.36-5.43 µg/L, 75.20-621.58 µg/L, 11.92-30.52 µg/L, and 4.00-4.65 µg/L respectively. While the results of the four selected fish showed the following order of abundance Zn> U> Cu> Pb. Transfer factor (TF) of heavy metals in fish tissue of selected fish species from the water was discussed. However, the observed metal concentration in the sample tissue did not exceed the allowable limit of Malaysian Food Act (1983) and Regulation (1985). Therefore, it is safe for human consumption. Moreover, the pollution levels of these heavy metals were also compared with other studies. This present study can also be used to evaluate the safety dose uptake level of marine biota as well as to monitor environmental health.« less

Assessment of heavy metals in seawater and fish tissues at Pulau Indah, Selangor, Malaysia

NASA Astrophysics Data System (ADS)

Md Yunus, Sabarina; Hamzah, Zaini; Wood, Ab. Khalik; Ahmad

2015-04-01

This study focuses on the levels of heavy metals in seawater and selected fish tissue at Pulau Indah, Selangor, Malaysia. Pulau Indah primarily contains Westport (Malaysia's major port), and a host of full scales factories. Therefore, it is important to monitor the levels of pollution in this water body and the aquatic organisms in the long term effects, due to the human activities in this area. Water samples in this study were taken from 8 locations along the coastal area. The water samples were collected using water sampler and sampling locations were determined using a Global Positioning system (GPS). Similarly, in situ water quality parameters including temperature, dissolve oxygen (DO), salinity, total suspended solid (TSS), pH and turbidity were measured by using portable multi probes meter. Then, the samples were acidified until pH 2 and filtered. Fish samples were purchased from local fisherman along the Pulau Indah coastal area and samples were digested using concentrated nitric acid in wet digestion method. The levels of selected heavy metals in four species of fish and seawater from Pulau Indah coastal area were determined using Inductive Coupled Plasma Mass Spectrometer (ICPMS) after dilution to the samples. In general, the quality of water at Pulau Indah is lower than Malaysia Marine Water Quality Standard except for few locations were higher than the maximum permissible levels. The concentration of heavy metals which are lead (Pb), copper (Cu), zinc (Zn) and uranium (U) in water samples are in the range of 0.36-5.43 µg/L, 75.20-621.58 µg/L, 11.92-30.52 µg/L, and 4.00-4.65 µg/L respectively. While the results of the four selected fish showed the following order of abundance Zn> U> Cu> Pb. Transfer factor (TF) of heavy metals in fish tissue of selected fish species from the water was discussed. However, the observed metal concentration in the sample tissue did not exceed the allowable limit of Malaysian Food Act (1983) and Regulation (1985). Therefore, it is safe for human consumption. Moreover, the pollution levels of these heavy metals were also compared with other studies. This present study can also be used to evaluate the safety dose uptake level of marine biota as well as to monitor environmental health.

Worldwide drinking water occurrence and levels of newly-identified perfluoroalkyl and polyfluoroalkyl substances.

PubMed

Kaboré, Hermann A; Vo Duy, Sung; Munoz, Gabriel; Méité, Ladji; Desrosiers, Mélanie; Liu, Jinxia; Sory, Traoré Karim; Sauvé, Sébastien

2018-03-01

In the last decade or so, concerns have arisen with respect to the widespread occurrence of perfluoroalkyl acids (PFAAs) in the environment, food, drinking water, and humans. In this study, the occurrence and levels of a large range of perfluoroalkyl and polyfluoroalkyl substances (PFASs) were investigated in drinking water (bottled and tap water samples) from various locations around the world. Automated off-line solid phase extraction followed by ultra-high-performance liquid chromatography coupled to high-resolution mass spectrometry was used to analyze PFASs of various chain lengths and functional groups. In total, 29 target and 104 suspect-target PFASs were screened in drinking water samples (n=97) from Canada and other countries (Burkina Faso, Chile, Ivory Coast, France, Japan, Mexico, Norway, and the USA) in 2015-2016. Out of the 29 PFASs quantitatively analyzed, perfluorocarboxylates (PFCAs: C 4/14 ), perfluoroalkane sulfonates (PFSAs: C 4 , C 6 , C 8 ), and perfluoroalkyl acid precursors (e.g., 5:3 fluorotelomer carboxylate (5:3 FTCA)) were recurrently detected in drinking water samples (concentration range:

Anthropogenic pressure in a Portuguese river: Endocrine-disrupting compounds, trace elements and nutrients.

PubMed

Ribeiro, Cláudia M R; Maia, Alexandra S; Ribeiro, Ana R; Couto, Cristina; Almeida, Agostinho A; Santos, Mariana; Tiritan, Maria E

2016-10-14

Natural organic compounds such as phytoestrogens and phytosterols found in various plants, as well as mycotoxins produced by fungi, can be found in aquatic environments. The aim of this study was to investigate the occurrence of three different classes of natural estrogenic compounds, i.e., phytoestrogens, phytosterols and mycotoxins, in estuarine water samples from the Ave River estuary. For that, water samples were collected at five sampling points distributed along the estuary at low tide, during 1 year, processed by solid-phase extraction (SPE) and analyzed by gas chromatography coupled to mass spectrometry (GC-MS). To correlate the presence of phytoestrogens and phytosterols in the estuarine water, local flora was collected on riverside. Trace elements content and physicochemical parameters such as nutrients and dissolved oxygen were also determined seasonally at each sampling point, to give insights for the evaluation of water quality and anthropogenic pressure. Both phytoestrogens and phytosterols showed a seasonal variation, with the highest values observed in spring and summer and the lowest in winter. Daidzein (DAID) was found up to 404.0 ng L(-1) in spring and coumestrol (COUM) was found up to 165.0 ng L(-1) in summer. The mycotoxin deoxynivalenol (DON) was ubiquitously determined with values ranging from 59.5 to 642.4 ng L(-1). Nutrients and metals distribution and concentration varied among sampling stations and seasons. This study revealed for the first time the presence of mycotoxins, various classes of phytoestrogens and stigmasterol (STG) in estuarine water from the Ave River (Portugal), and the evaluation of the water quality confirmed that this estuary is still highly impacted by anthropogenic activities.

Hydrologic and Water-Quality Responses in Shallow Ground Water Receiving Stormwater Runoff and Potential Transport of Contaminants to Lake Tahoe, California and Nevada, 2005-07

USGS Publications Warehouse

Green, Jena M.; Thodal, Carl E.; Welborn, Toby L.

2008-01-01

Clarity of Lake Tahoe, California and Nevada has been decreasing due to inflows of sediment and nutrients associated with stormwater runoff. Detention basins are considered effective best management practices for mitigation of suspended sediment and nutrients associated with runoff, but effects of infiltrated stormwater on shallow ground water are not known. This report documents 2005-07 hydrogeologic conditions in a shallow aquifer and associated interactions between a stormwater-control system with nearby Lake Tahoe. Selected chemical qualities of stormwater, bottom sediment from a stormwater detention basin, ground water, and nearshore lake and interstitial water are characterized and coupled with results of a three-dimensional, finite-difference, mathematical model to evaluate responses of ground-water flow to stormwater-runoff accumulation in the stormwater-control system. The results of the ground-water flow model indicate mean ground-water discharge of 256 acre feet per year, contributing 27 pounds of phosphorus and 765 pounds of nitrogen to Lake Tahoe within the modeled area. Only 0.24 percent of this volume and nutrient load is attributed to stormwater infiltration from the detention basin. Settling of suspended nutrients and sediment, biological assimilation of dissolved nutrients, and sorption and detention of chemicals of potential concern in bottom sediment are the primary stormwater treatments achieved by the detention basins. Mean concentrations of unfiltered nitrogen and phosphorus in inflow stormwater samples compared to outflow samples show that 55 percent of nitrogen and 47 percent of phosphorus are trapped by the detention basin. Organic carbon, cadmium, copper, lead, mercury, nickel, phosphorus, and zinc in the uppermost 0.2 foot of bottom sediment from the detention basin were all at least twice as concentrated compared to sediment collected from 1.5 feet deeper. Similarly, concentrations of 28 polycyclic aromatic hydrocarbon compounds were all less than laboratory reporting limits in the deeper sediment sample, but 15 compounds were detected in the uppermost 0.2 foot of sediment. Published concentrations determined to affect benthic aquatic life also were exceeded for copper, zinc, benz[a]anthracene, phenanthrene, and pyrene in the shallow sediment sample. Isotopic composition of water (oxygen 18/16 and hydrogen 2/1 ratios) for samples of shallow ground water, lakewater, and interstitial water from Lake Tahoe indicate the lake was well mixed with a slight ground-water signature in samples collected near the lakebed. One interstitial sample from 0.8 foot beneath the lakebed was nearly all ground water and concentrations of nitrogen and phosphorus were comparable to concentrations in shallow ground-water samples. However, ammonium represented 65 percent of filtered nitrogen in this interstitial sample, but only 10 percent of the average nitrogen in ground-water samples. Nitrate was less than reporting limits in interstitial water, compared with mean nitrate concentration of 750 micrograms per liter in ground-water samples, indicating either active dissimilative nitrate reduction to ammonium by micro-organisms or hydrolysis of organic nitrogen to ammonium with concomitant nitrate reduction. The other interstitial sample falls along a mixing line between ground water and lake water and most of the nitrogen was organic nitrogen.

Endocrine-Disrupting Activities and Organic Contaminants Associated with Oil and Gas Operations in Wyoming Groundwater.

PubMed

Kassotis, Christopher D; Vu, Danh C; Vo, Phuc H; Lin, Chung-Ho; Cornelius-Green, Jennifer N; Patton, Sharyle; Nagel, Susan C

2018-04-05

Unconventional oil and natural gas (UOG) operations couple horizontal drilling with hydraulic fracturing to access previously inaccessible fossil fuel deposits. Hydraulic fracturing, a common form of stimulation, involves the high-pressure injection of water, chemicals, and sand to fracture the target layer and release trapped natural gas and/or oil. Spills and/or discharges of wastewater have been shown to impact surface, ground, and drinking water. The goals of this study were to characterize the endocrine activities and measure select organic contaminants in groundwater from conventional oil and gas (COG) and UOG production regions of Wyoming. Groundwater samples were collected from each region, solid-phase extracted, and assessed for endocrine activities (estrogen, androgen, progesterone, glucocorticoid, and thyroid receptor agonism and antagonism), using reporter gene assays in human endometrial cells. Water samples from UOG and conventional oil areas exhibited greater ER antagonist activities than water samples from conventional gas areas. Samples from UOG areas tended to exhibit progesterone receptor antagonism more often, suggesting there may be a UOG-related impact on these endocrine activities. We also report UOG-specific contaminants in Pavillion groundwater extracts, and these same chemicals at high concentrations in a local UOG wastewater sample. A unique suite of contaminants was observed in groundwater from a permitted drinking water well at a COG well pad and not at any UOG sites; high levels of endocrine activities (most notably, maximal estrogenic activity) were noted there, suggesting putative impacts on endocrine bioactivities by COG. As such, we report two levels of evidence for groundwater contamination by both UOG and COG operations in Wyoming.

Hygroscopic growth of water soluble organic carbon isolated from atmospheric aerosol collected at US national parks and Storm Peak Laboratory

NASA Astrophysics Data System (ADS)

Taylor, Nathan F.; Collins, Don R.; Lowenthal, Douglas H.; McCubbin, Ian B.; Gannet Hallar, A.; Samburova, Vera; Zielinska, Barbara; Kumar, Naresh; Mazzoleni, Lynn R.

2017-02-01

Due to the atmospheric abundance and chemical complexity of water soluble organic carbon (WSOC), its contribution to the hydration behavior of atmospheric aerosol is both significant and difficult to assess. For the present study, the hygroscopicity and CCN activity of isolated atmospheric WSOC particulate matter was measured without the compounding effects of common, soluble inorganic aerosol constituents. WSOC was extracted with high purity water from daily high-volume PM2.5 filter samples and separated from water soluble inorganic constituents using solid-phase extraction. The WSOC filter extracts were concentrated and combined to provide sufficient mass for continuous generation of the WSOC-only aerosol over the combined measurement time of the tandem differential mobility analyzer and coupled scanning mobility particle sizer-CCN counter used for the analysis. Aerosol samples were taken at Great Smoky Mountains National Park during the summer of 2006 and fall-winter of 2007-2008; Mount Rainier National Park during the summer of 2009; Storm Peak Laboratory (SPL) near Steamboat Springs, Colorado, during the summer of 2010; and Acadia National Park during the summer of 2011. Across all sampling locations and seasons, the hygroscopic growth of WSOC samples at 90 % RH, expressed in terms of the hygroscopicity parameter, κ, ranged from 0.05 to 0.15. Comparisons between the hygroscopicity of WSOC and that of samples containing all soluble materials extracted from the filters implied a significant modification of the hydration behavior of inorganic components, including decreased hysteresis separating efflorescence and deliquescence and enhanced water uptake between 30 and 70 % RH.

In-situ, time resolved monitoring of uranium in BFS:OPC grout. Part 2: Corrosion in water.

PubMed

Stitt, C A; Paraskevoulakos, C; Banos, A; Harker, N J; Hallam, K R; Pullin, H; Davenport, A; Street, S; Scott, T B

2018-06-18

To reflect potential conditions in a geological disposal facility, uranium was encapsulated in grout and submersed in de-ionised water for time periods between 2-47 weeks. Synchrotron X-ray Powder Diffraction and X-ray Tomography were used to identify the dominant corrosion products and measure their dimensions. Uranium dioxide was observed as the dominant corrosion product and time dependent thickness measurements were used to calculate oxidation rates. The effectiveness of physical and chemical grout properties to uranium corrosion and mobilisation is discussed and Inductively Coupled Plasma Mass Spectrometry was used to measure 238 U (aq) content in the residual water of several samples.

Application of picosecond laser-induced breakdown spectroscopy to quantitative analysis of boron in meatballs and other biological samples.

PubMed

Hedwig, Rinda; Lahna, Kurnia; Lie, Zener Sukra; Pardede, Marincan; Kurniawan, Koo Hendrik; Tjia, May On; Kagawa, Kiichiro

2016-11-10

This report presents the results of laser-induced breakdown spectroscopy (LIBS) study on biological and food samples of high water content using a picosecond (ps) laser at low output energy of 10 mJ and low-pressure helium ambient gas at 2 kPa. Evidence of excellent emission spectra of various analyte elements with very low background is demonstrated for a variety of samples without the need of sample pretreatment. Specifically, limits of detection in the range of sub-ppm are obtained for hazardous Pb and B impurities in carrots and meatballs. This study also shows the inferior performance of LIBS using a nanosecond laser and atmospheric ambient air for a soft sample of high water content and thereby explains its less successful applications in previous attempts. The present result has instead demonstrated the feasibility and favorable results of employing LIBS with a ps laser and low-pressure helium ambient gas as a less costly and more practical alternative to inductively coupled plasma for regular high sensitive inspection of harmful food preservatives and environmental pollutants.

Partial microwave-assisted wet digestion of animal tissue using a baby-bottle sterilizer for analyte determination by inductively coupled plasma optical emission spectrometry

NASA Astrophysics Data System (ADS)

Matos, Wladiana O.; Menezes, Eveline A.; Gonzalez, Mário H.; Costa, Letícia M.; Trevizan, Lilian C.; Nogueira, Ana Rita A.

2009-06-01

A procedure for partial digestion of bovine tissue is proposed using polytetrafluoroethylene (PTFE) micro-vessels inside a baby-bottle sterilizer under microwave radiation for multi-element determination by inductively coupled plasma optical emission spectrometry (ICP OES). Samples were directly weighed in laboratory-made polytetrafluoroethylene vessels. Nitric acid and hydrogen peroxide were added to the uncovered vessels, which were positioned inside the baby-bottle sterilizer, containing 500 mL of water. The hydrogen peroxide volume was fixed at 100 µL. The system was placed in a domestic microwave oven and partial digestion was carried out for the determination of Ca, Cu, Fe, Mg, Mn and Zn by inductively coupled plasma optical emission spectrometry. The single-vessel approach was used in the entire procedure, to minimize contamination in trace analysis. Better recoveries and lower residual carbon content (RCC) levels were obtained under the conditions established through a 2 4-1 fractional factorial design: 650 W microwave power, 7 min digestion time, 50 µL nitric acid and 50 mg sample mass. The digestion efficiency was ascertained according to the residual carbon content determined by inductively coupled plasma optical emission spectrometry. The accuracy of the proposed procedure was checked against two certified reference materials.

Methods for simultaneous detection of the cyanotoxins BMAA, DABA, and anatoxin-a in environmental samples.

PubMed

Al-Sammak, Maitham Ahmed; Hoagland, Kyle D; Snow, Daniel D; Cassada, David

2013-12-15

Blue-green algae, also known as cyanobacteria, can produce several different groups of toxins in the environment including hepatotoxins (microcystins), neurotoxic non-protein amino acids β-methylamino-l-alanine (BMAA), and 2,4-diaminobutyric (DABA), as well as the bicyclic amine alkaloid anatoxin-a. Few studies have addressed the methods necessary for an accurate determination of cyanotoxins in environmental samples, and none have been published that can detect these cyanotoxins together in a single sample. Cyanotoxins occur in a wide range of environmental samples including water, fish, and aquatic plant samples. Using polymeric cation exchange solid phase extraction (SPE) coupled with liquid chromatography and fluorescence detection (HPLC/FD), and liquid chromatography ion trap tandem mass spectrometry (LC/MS/MS), these compounds can for the first time be simultaneously quantified in a variety of environmental sample types. The extraction method for biological samples can distinguish bound and free cyanotoxins. Detection limits for water ranged from 5 to 7 μg/L using HPLC/FD, while detection limits for and LC/MS were in the range of 0.8-3.2 μg/L. Copyright © 2013 Elsevier Ltd. All rights reserved.

Salting-out assisted liquid-liquid extraction coupled with hydrophilic interaction chromatography for the determination of biguanides in biological and environmental samples.

PubMed

Alshishani, Anas; Salhimi, Salizawati Muhamad; Saad, Bahruddin

2018-01-15

A new salting-out assisted liquid-liquid extraction (SALLE) sample preparation method for the determination of the polar anti-diabetic biguanide drugs (metformin, buformin and phenformin) in blood plasma, urine and lake water samples were developed. The SALLE was performed by mixing samples (plasma (0.2mL), urine or lake water (1.0mL)) with acetonitrile (0.4mL for plasma, 0.5mL for urine or lake water), sodium hydroxide powder was then added for the phase separation. The effects of type of salting-out reagent, type of extraction solvent, volumes of acetonitrile and sample, amount of sodium hydroxide, vortexing and centrifugation times on the extraction efficiency were investigated. The upper layer, containing the biguanides, was directly injected into a HPLC unit using ZIC-HILIC column (150mm×2.1mm×3.5μm) and was detected at 236nm. The method was validated and calibration curves were linear with r 2 >0.99 over the range of 20-2000μgL -1 for plasma and 5-2000μgL -1 for urine and lake water samples. The limits of detection were in the range (3.8-5.6)μgL -1 , (0.8-1.5)μgL -1 and (0.3-0.8)μgL -1 for plasma, urine and lake water, respectively. The accuracies in the three matrices were within 87.3-103%, 87.4-109%, 82.2-109% of the nominal concentration for metformin, buformin and phenformin, respectively. The relative standard deviation for inter- and intra -day precision were in the range of 1.0-17% for all analytes in the three matrices. Copyright © 2017 Elsevier B.V. All rights reserved.

Chemical Analysis of Water-accommodated Fractions of Crude Oil Spills Using TIMS-FT-ICR MS.

PubMed

Benigni, Paolo; Marin, Rebecca; Sandoval, Kathia; Gardinali, Piero; Fernandez-Lima, Francisco

2017-03-03

Multiple chemical processes control how crude oil is incorporated into seawater and also the chemical reactions that occur overtime. Studying this system requires the careful preparation of the sample in order to accurately replicate the natural formation of the water-accommodated fraction that occurs in nature. Low-energy water-accommodated fractions (LEWAF) are carefully prepared by mixing crude oil and water at a set ratio. Aspirator bottles are then irradiated, and at set time points, the water is sampled and extracted using standard techniques. A second challenge is the representative characterization of the sample, which must take into consideration the chemical changes that occur over time. A targeted analysis of the aromatic fraction of the LEWAF can be performed using an atmospheric-pressure laser ionization source coupled to a custom-built trapped ion mobility spectrometry-Fourier transform-ion cyclotron resonance mass spectrometer (TIMS-FT-ICR MS). The TIMS-FT-ICR MS analysis provides high-resolution ion mobility and ultrahigh-resolution MS analysis, which further allow the identification of isomeric components by their collision cross-sections (CCS) and chemical formula. Results show that as the oil-water mixture is exposed to light, there is significant photo-solubilization of the surface oil into the water. Over time, the chemical transformation of the solubilized molecules takes place, with a decrease in the number of identifications of nitrogen- and sulfur-bearing species in favor of those with a greater oxygen content than were typically observed in the base oil.

Determination of human-use pharmaceuticals in filtered water by direct aqueous injection: high-performance liquid chromatography/tandem mass spectrometry

USGS Publications Warehouse

Furlong, Edward T.; Noriega, Mary C.; Kanagy, Christopher J.; Kanagy, Leslie K.; Coffey, Laura J.; Burkhardt, Mark R.

2014-01-01

This report describes a method for the determination of 110 human-use pharmaceuticals using a 100-microliter aliquot of a filtered water sample directly injected into a high-performance liquid chromatograph coupled to a triple-quadrupole tandem mass spectrometer using an electrospray ionization source operated in the positive ion mode. The pharmaceuticals were separated by using a reversed-phase gradient of formic acid/ammonium formate-modified water and methanol. Multiple reaction monitoring of two fragmentations of the protonated molecular ion of each pharmaceutical to two unique product ions was used to identify each pharmaceutical qualitatively. The primary multiple reaction monitoring precursor-product ion transition was quantified for each pharmaceutical relative to the primary multiple reaction monitoring precursor-product transition of one of 19 isotope-dilution standard pharmaceuticals or the pesticide atrazine, using an exact stable isotope analogue where possible. Each isotope-dilution standard was selected, when possible, for its chemical similarity to the unlabeled pharmaceutical of interest, and added to the sample after filtration but prior to analysis. Method performance for each pharmaceutical was determined for reagent water, groundwater, treated drinking water, surface water, treated wastewater effluent, and wastewater influent sample matrixes that this method will likely be applied to. Each matrix was evaluated in order of increasing complexity to demonstrate (1) the sensitivity of the method in different water matrixes and (2) the effect of sample matrix, particularly matrix enhancement or suppression of the precursor ion signal, on the quantitative determination of pharmaceutical concentrations. Recovery of water samples spiked (fortified) with the suite of pharmaceuticals determined by this method typically was greater than 90 percent in reagent water, groundwater, drinking water, and surface water. Correction for ambient environmental concentrations of pharmaceuticals hampered the determination of absolute recoveries and method sensitivity of some compounds in some water types, particularly for wastewater effluent and influent samples. The method detection limit of each pharmaceutical was determined from analysis of pharmaceuticals fortified at multiple concentrations in reagent water. The calibration range for each compound typically spanned three orders of magnitude of concentration. Absolute sensitivity for some compounds, using isotope-dilution quantitation, ranged from 0.45 to 94.1 nanograms per liter, primarily as a result of the inherent ionization efficiency of each pharmaceutical in the electrospray ionization process. Holding-time studies indicate that acceptable recoveries of pharmaceuticals can be obtained from filtered water samples held at 4 °C for as long as 9 days after sample collection. Freezing samples to provide for storage for longer periods currently (2014) is under evaluation by the National Water Quality Laboratory.

Histology, composition, and quality traits of chicken Pectoralis major muscle affected by wooden breast abnormality.

PubMed

Soglia, F; Mudalal, S; Babini, E; Di Nunzio, M; Mazzoni, M; Sirri, F; Cavani, C; Petracci, M

2016-03-01

Only a few years ago, the poultry industry began to face a recent abnormality in breast meat, known as wooden breast, which frequently overlaps with white striping. This study aimed to assess the impact of wooden breast abnormality on quality traits of meat. For this purpose, 32 normal (NRM), 32 wooden (WB), and 32 wooden and white-striped (WB/WS) Pectoralis major muscles were selected from the same flock of heavy broilers (males, Ross 708, weighing around 3.7 kg) in the deboning area of a commercial processing plant at 3 h postmortem and used to assess histology, proximate (moisture, protein, fat, ash, and collagen) and mineral composition (Mg, K, P, Na and Ca), sarcoplasmic and myofibrillar protein patterns, and technological traits of breast meat. Compared to the normal group, WB/WS fillets showed more severe histological lesions characterized by fiber degeneration, fibrosis, and lipidosis, coupled with a significantly harder texture. With regard to proximate and mineral composition, abnormal samples exhibited significantly (P < 0.001) higher moisture, fat, and collagen contents coupled with lower (P < 0.001) amounts of protein and ash. Furthermore, increased calcium (131 vs. 84 mg kg(-1); P < 0.05) and sodium (741 vs. 393 mg kg(-1); P < 0.001) levels were found in WB/WS meat samples. The SDS-PAGE analysis revealed a significantly lower amount of calcium-ATPase (SERCA, 114 kDa), responsible for the translocation of Ca ions across the membrane, in normal breasts compared to abnormal ones. As for meat quality traits, fillets affected by wooden abnormality exhibited significantly (P < 0.001) higher ultimate pH and lower water-holding/water-binding capacity. In particular, compared to normal, abnormal samples showed reduced marinade uptake coupled with increased drip loss and cooking losses as well. In conclusion, this study revealed that meat affected by wooden breast or both wooden breast and white striping abnormalities exhibit poorer nutritional value, harder texture, and impaired water-holding capacity. © 2015 Poultry Science Association Inc.

Electrochemical As(III) whole-cell based biochip sensor.

PubMed

Cortés-Salazar, Fernando; Beggah, Siham; van der Meer, Jan Roelof; Girault, Hubert H

2013-09-15

The development of a whole-cell based sensor for arsenite detection coupling biological engineering and electrochemical techniques is presented. This strategy takes advantage of the natural Escherichia coli resistance mechanism against toxic arsenic species, such as arsenite, which consists of the selective intracellular recognition of arsenite and its pumping out from the cell. A whole-cell based biosensor can be produced by coupling the intracellular recognition of arsenite to the generation of an electrochemical signal. Hereto, E. coli was equipped with a genetic circuit in which synthesis of beta-galactosidase is under control of the arsenite-derepressable arsR-promoter. The E. coli reporter strain was filled in a microchip containing 16 independent electrochemical cells (i.e. two-electrode cell), which was then employed for analysis of tap and groundwater samples. The developed arsenic-sensitive electrochemical biochip is easy to use and outperforms state-of-the-art bacterial bioreporters assays specifically in its simplicity and response time, while keeping a very good limit of detection in tap water, i.e. 0.8ppb. Additionally, a very good linear response in the ranges of concentration tested (0.94ppb to 3.75ppb, R(2)=0.9975 and 3.75 ppb to 30ppb, R(2)=0.9991) was obtained, complying perfectly with the acceptable arsenic concentration limits defined by the World Health Organization for drinking water samples (i.e. 10ppb). Therefore, the proposed assay provides a very good alternative for the portable quantification of As (III) in water as corroborated by the analysis of natural groundwater samples from Swiss mountains, which showed a very good agreement with the results obtained by atomic absorption spectroscopy. Copyright © 2013 Elsevier B.V. All rights reserved.

Determination of 90Sr and Pu isotopes in contaminated groundwater samples by inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Zoriy, Miroslav V.; Ostapczuk, Peter; Halicz, Ludwik; Hille, Ralf; Becker, J. Sabine

2005-04-01

A sensitive analytical method for determining the artificial radionuclides 90Sr, 239Pu and 240Pu at the ultratrace level in groundwater samples from the Semipalatinsk Test Site area in Kazakhstan by double-focusing sector field inductively coupled plasma mass spectrometry (ICP-SFMS) was developed. In order to avoid possible isobaric interferences at m/z 90 for 90Sr determination (e.g. 90Zr+, 40Ar50Cr+, 36Ar54Fe+, 58Ni16O2+, 180Hf2+, etc.), the measurements were performed at medium mass resolution under cold plasma conditions. Pu was separated from uranium by means of extraction chromatography using Eichrom TEVA resin with a recovery of 83%. The limits of detection for 90Sr, 239Pu and 240Pu in water samples were determined as 11, 0.12 and 0.1 fg ml-1, respectively. Concentrations of 90Sr and 239Pu in contaminated groundwater samples ranged from 18 to 32 and from 28 to 856 fg ml-1, respectively. The 240Pu/239Pu isotopic ratio in groundwater samples was measured as 0.17. This isotope ratio indicates that the most probable source of contamination of the investigated groundwater samples was the nuclear weapons tests at the Semipalatinsk Test Site conducted by the USSR in the 1960s.

Experimental evidence for chemo-mechanical coupling during carbon mineralization in ultramafic rocks

NASA Astrophysics Data System (ADS)

Lisabeth, H. P.; Zhu, W.; Kelemen, P. B.; Ilgen, A.

2017-09-01

Storing carbon dioxide in the subsurface as carbonate minerals has the benefit of long-term stability and immobility. Ultramafic rock formations have been suggested as a potential reservoir for this type of storage due to the availability of cations to react with dissolved carbon dioxide and the fast reaction rates associated with minerals common in ultramafic formations; however, the rapid reactions have the potential to couple with the mechanical and hydraulic behavior of the rocks and little is known about the extent and mechanisms of this coupling. In this study, we argue that the dissolution of primary minerals and the precipitation of secondary minerals along pre-existing fractures in samples lead to reductions in both the apparent Young's modulus and shear strength of aggregates, accompanied by reduction in permeability. Hydrostatic and triaxial deformation experiments were run on dunite samples saturated with de-ionized water and carbon dioxide-rich solutions while stress, strain, permeability and pore fluid chemistry were monitored. Sample microstructures were examined after reaction and deformation using scanning electron microscopy (SEM). The results show that channelized dissolution and carbonate mineral precipitation in the samples saturated with carbon dioxide-rich solutions modify the structure of grain boundaries, leading to the observed reductions in stiffness, strength and permeability. A geochemical model was run to help interpret fluid chemical data, and we find that the apparent reaction rates in our experiments are faster than rates calculated from powder reactors, suggesting mechanically enhanced reaction rates. In conclusion, we find that chemo-mechanical coupling during carbon mineralization in dunites leads to substantial modification of mechanical and hydraulic behavior that needs to be accounted for in future modeling efforts of in situ carbon mineralization projects.

Synergistic efficiency of the desilication of brackish underground water in Saudi Arabia by coupling γ-radiation and Fenton process: Membrane scaling prevention in reverse osmosis process

NASA Astrophysics Data System (ADS)

Aljohani, Mohammed S.

2017-12-01

One of the main water resources in arid Saudi Arabia is underground water. However, this brackish water has high silica content which can cause a recalcitrant deposit on the membrane in the reverse osmosis units during its desalination. In this study, we examined the synergistic efficiency of the removal of silica from the Buwaib water sample, when combining two advanced oxidation processes, γ-irradiation and the Fenton process, using hydrogen peroxide and zero valent metal iron as source of Fe3+. This latter adsorbs effectively on silica and co-precipitate. The influence of absorbed dose, iron dosage and pH effect were investigated. This preliminary study showed that these attractive and effective hybrid processes are very efficient in removing silica.

Mg/Ca ratios of the benthic foraminifera Oridorsalis umbonatus obtained by laser ablation from core top sediments: Relationship to bottom water temperature

NASA Astrophysics Data System (ADS)

Rathmann, SöHnke; Hess, Silvia; Kuhnert, Henning; Mulitza, Stefan

2004-12-01

A laser ablation system connected to an inductively coupled plasma mass spectrometer was used to determine Mg/Ca ratios of the benthic foraminifera Oridorsalis umbonatus. A set of modern core top samples collected along a depth transect on the continental slope off Namibia (320-2300 m water depth; 2.9° to 10.4°C) was used to calibrate the Mg/Ca ratio against bottom water temperature. The resulting Mg/Ca-bottom water temperature relationship of O. umbonatus is described by the exponential equation Mg/Ca = 1.528*e0.09*BWT. The temperature sensitivity of this equation is similar to previously published calibrations based on Cibicidoides species, suggesting that the Mg/Ca ratio of O. umbonatus is a valuable proxy for thermocline and deep water temperature.

Synchronized separation, concentration and determination of trace sulfadiazine and sulfamethazine in food and environment by using polyoxyethylene lauryl ether-salt aqueous two-phase system coupled to high-performance liquid chromatography.

PubMed

Lu, Yang; Cong, Biao; Tan, Zhenjiang; Yan, Yongsheng

2016-11-01

Polyoxyethylene lauryl ether (POELE10)-Na2C4H4O6 aqueous two-phase extraction system (ATPES) is a novel and green pretreatment technique to trace samples. ATPES coupled with high-performance liquid chromatography (HPLC) is used to analyze synchronously sulfadiazine (SDZ) and sulfamethazine (SMT) in animal by-products (i.e., egg and milk) and environmental water sample. It was found that the extraction efficiency (E%) and the enrichment factor (F) of SDZ and SMT were influenced by the types of salts, the concentration of salt, the concentration of POELE10 and the temperature. The orthogonal experimental design (OED) was adopted in the multi-factor experiment to determine the optimized conditions. The final optimal condition was as following: the concentration of POELE10 is 0.027gmL(-1), the concentration of Na2C4H4O6 is 0.180gmL(-1) and the temperature is 35°C. This POELE10-Na2C4H4O6 ATPS was applied to separate and enrich SDZ and SMT in real samples (i.e., water, egg and milk) under the optimal conditions, and it was found that the recovery of SDZ and SMT was 96.20-99.52% with RSD of 0.35-3.41%. The limit of detection (LOD) of this method for the SDZ and SMT in spiked samples was 2.52-3.64pgmL(-1), and the limit of quantitation (LOQ) of this method for the SDZ and SMT in spiked samples was 8.41-12.15pgmL(-1). Copyright © 2016 Elsevier Inc. All rights reserved.

An on-line push/pull perfusion-based hollow-fiber liquid-phase microextraction system for high-performance liquid chromatographic determination of alkylphenols in water samples.

PubMed

Chao, Yu-Ying; Jian, Zhi-Xuan; Tu, Yi-Ming; Wang, Hsaio-Wen; Huang, Yeou-Lih

2013-06-07

In this study, we employed a novel on-line method, push/pull perfusion hollow-fiber liquid-phase microextraction (PPP-HF-LPME), to extract 4-tert-butylphenol, 2,4-di-tert-butylphenol, 4-n-nonylphenol, and 4-n-octylphenol from river and tap water samples; we then separated and quantified the extracted analytes through high-performance liquid chromatography (HPLC). Using this approach, we overcame the problem of fluid loss across the porous HF membrane to the donor phase, permitting on-line coupling of HF-LPME to HPLC. In our PPP-HF-LPME system, we used a push/pull syringe pump as the driving source to perfuse the acceptor phase, while employing a heating mantle and an ultrasonic probe to accelerate mass transfer. We optimized the experimental conditions such as the nature of the HF supported intermediary phase and the acceptor phase, the composition of the donor and acceptor phases, the sample temperature, and the sonication conditions. Our proposed method provided relative standard deviations of 3.1-6.2%, coefficients of determination (r(2)) of 0.9989-0.9998, and limits of detection of 0.03-0.2 ng mL(-1) for the analytes under the optimized conditions. When we applied this method to analyses of river and tap water samples, our results confirmed that this microextraction technique allows reliable monitoring of alkylphenols in water samples.

Rapid analysis of pesticide residues in drinking water samples by dispersive solid-phase extraction based on multiwalled carbon nanotubes and pulse glow discharge ion source ion mobility spectrometry.

PubMed

Zou, Nan; Gu, Kejia; Liu, Shaowen; Hou, Yanbing; Zhang, Jialei; Xu, Xiang; Li, Xuesheng; Pan, Canping

2016-03-01

An analytical method based on dispersive solid-phase extraction with a multiwalled carbon nanotubes sorbent coupled with positive pulse glow discharge ion mobility spectrometry was developed for analysis of 30 pesticide residues in drinking water samples. Reduced ion mobilities and the mass-mobility correlation of 30 pesticides were measured. The pesticides were divided into five groups to verify the separation capability of pulse glow discharge in mobility spectrometry. The extraction conditions such as desorption solvent, ionic strength, conditions of adsorption and desorption, the amounts of multiwalled carbon nanotubes, and solution pH were optimized. The enrichment factors of pesticides were 5.4- to 48.7-fold (theoretical enrichment factor was 50-fold). The detection limits of pesticides were 0.01∼0.77 μg/kg. The linear range was 0.005-0.2 mg/L for pesticide standard solutions, with determination coefficients from 0.9616 to 0.9999. The method was applied for the analysis of practical and spiked drinking water samples. All results were confirmed by high-performance liquid chromatography with tandem mass spectrometry. The proposed method was proven to be a commendably rapid screening qualitative and semiquantitative technique for the analysis of pesticide residues in drinking water samples on site. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of organophosphorus pesticides in environmental water samples by dispersive liquid-liquid microextraction with solidification of floating organic droplet followed by high-performance liquid chromatography.

PubMed

Wu, Chunxia; Liu, Huimin; Liu, Weihua; Wu, Qiuhua; Wang, Chun; Wang, Zhi

2010-07-01

A simple dispersive liquid-liquid microextraction based on solidification of floating organic droplet coupled with high-performance liquid chromatography-diode array detection was developed for the determination of five organophosphorus pesticides (OPs) in water samples. In this method, the extraction solvent used is of low density, low toxicity, and proper melting point near room temperature. The extractant droplet could be collected easily by solidifying it in the lower temperature. Some important experimental parameters that affect the extraction efficiencies were optimized. Under the optimum conditions, the calibration curve was linear in the concentration range from 1 to 200 ng mL(-1) for the five OPs (triazophos, parathion, diazinon, phoxim, and parathion-methyl), with the correlation coefficients (r) varying from 0.9991 to 0.9998. High enrichment factors were achieved ranging from 215 to 557. The limits of detection were in the range between 0.1 and 0.3 ng mL(-1). The recoveries of the target analytes from water samples at spiking levels of 5.0 and 50.0 ng mL(-1) were 82.2-98.8% and 83.6-104.0%, respectively. The relative standard deviations fell in the range of 4.4% to 6.3%. The method was suitable for the determination of the OPs in real water samples.

Non-Contact Inspection of Composites Using Air-Coupled Ultrasound

NASA Astrophysics Data System (ADS)

Peters, J.; Kommareddy, V.; Liu, Z.; Fei, D.; Hsu, D.

2003-03-01

Conventional ultrasonic tests are conducted using water as a transmitting medium. Water coupled ultrasound cannot be applied to certain water-sensitive or porous materials and is more difficult to use in the field. In contrast, air-coupled ultrasound is non-contact and has clear advantages over water-coupled testing. The technology of air-coupled ultrasound has gained maturity in recent years. Some systems have become commercially available and researchers are pursuing several different modalities of air-coupled transduction. This paper reports our experience of applying air-coupled ultrasound to the inspection of flaws, damage, and normal internal structures of composite parts. Through-transmission C-scans at 400 kHz using a focused receiver has resolution sufficient to image honeycomb cells in the sandwich core. With the transmitter and receiver on the same side of a laminate. Lamb waves were generated and used for the imaging of substructures. Air-coupled scan results are presented for flaw detection and damage in aircraft composite structures.

Methane oxidation coupled to oxygenic photosynthesis in anoxic waters

PubMed Central

Milucka, Jana; Kirf, Mathias; Lu, Lu; Krupke, Andreas; Lam, Phyllis; Littmann, Sten; Kuypers, Marcel MM; Schubert, Carsten J

2015-01-01

Freshwater lakes represent large methane sources that, in contrast to the Ocean, significantly contribute to non-anthropogenic methane emissions to the atmosphere. Particularly mixed lakes are major methane emitters, while permanently and seasonally stratified lakes with anoxic bottom waters are often characterized by strongly reduced methane emissions. The causes for this reduced methane flux from anoxic lake waters are not fully understood. Here we identified the microorganisms and processes responsible for the near complete consumption of methane in the anoxic waters of a permanently stratified lake, Lago di Cadagno. Interestingly, known anaerobic methanotrophs could not be detected in these waters. Instead, we found abundant gamma-proteobacterial aerobic methane-oxidizing bacteria active in the anoxic waters. In vitro incubations revealed that, among all the tested potential electron acceptors, only the addition of oxygen enhanced the rates of methane oxidation. An equally pronounced stimulation was also observed when the anoxic water samples were incubated in the light. Our combined results from molecular, biogeochemical and single-cell analyses indicate that methane removal at the anoxic chemocline of Lago di Cadagno is due to true aerobic oxidation of methane fuelled by in situ oxygen production by photosynthetic algae. A similar mechanism could be active in seasonally stratified lakes and marine basins such as the Black Sea, where light penetrates to the anoxic chemocline. Given the widespread occurrence of seasonally stratified anoxic lakes, aerobic methane oxidation coupled to oxygenic photosynthesis might have an important but so far neglected role in methane emissions from lakes. PMID:25679533

Potential of capillary-column-switching liquid chromatography-tandem mass spectrometry for the quantitative trace analysis of small molecules. Application to the on-line screening of drugs in water.

PubMed

Pitarch, Elena; Hernandez, Felix; ten Hove, Jan; Meiring, Hugo; Niesing, Willem; Dijkman, Ellen; Stolker, Linda; Hogendoorn, Elbert

2004-03-26

We have investigated the potential of capillary-column-switching liquid chromatography coupled to tandem mass spectrometry (cLC-MS-MS) for the quantitative on-line trace analysis of target compounds in aqueous solutions. The technical design of the nano-scale cLC system developed at our Institute for peptide and protein identification has been tested and evaluated for the direct trace analysis of drugs in water samples. Sulphametoxazole, bezafibrate, metoprolol, carbamazepine and bisoprolol occurring frequently in Dutch waters, were selected as test compounds. Adequate conditions for trapping, elution and MS-MS detection were investigated by employing laboratory made 200 microm i.d. capillary columns packed with 5 microm aqua C18 material. In the final cLC-MS-MS conditions, a 1 cm length trapping column and a 4 cm length analytical column were selected. Under these conditions, the target compounds could be directly determined in water down to a level of around 50 ng/l employing only 25 microl of water sample. Validation was done by recovery experiments in ground-, surface- and drinking-water matrices as well as by the analysis of water samples with incurred residues and previously analyzed with a conventional procedure involving off-line solid-phase extraction and narrow-bore LC with MS-MS detection. The new methodology provided recoveries (50-500 ng/l level) between 50 and 114% with RSDs (n = 3, each level) below 20% for most of the compounds. Despite the somewhat less analytical performance in comparison to the conventional procedure, the on-line approach of the new methodology is very suitable for screening of drugs in aqueous samples.

Insights into streamflow generation mechanisms using high-frequency analysis of isotopes and water quality in streamflow and precipitation

NASA Astrophysics Data System (ADS)

von Freyberg, Jana; Kirchner, James W.

2017-04-01

In the pre-Alpine Alptal catchment in central Switzerland, snowmelt and rainfall events cause rapid changes not only in hydrological conditions, but also in water quality. A flood forecasting model for such a mountainous catchment thus requires process understanding that is informed by high-frequency monitoring of hydrological and hydrochemical parameters. Therefore, we installed a high-frequency sampling and analysis system near the outlet of the 0.7 km2 Erlenbach catchment, a headwater tributary of the Alp river. We measured stable water isotopes (δ18O, δ2H) in precipitation and streamwater using Picarro, Inc.'s (Santa Clara, CA, USA) newly developed Continuous Water Sampler Module (CWS) coupled to their L2130-i Cavity Ring-Down Spectrometer, at 30 min temporal resolution. Water quality was monitored with a dual-channel ion chomatograph (Metrohm AG, Herisau, Switzerland) for analysis of major cations and anions, as well as with a UV-Vis spectroscopy system and electrochemical probes (s::can Messtechnik GmbH, Vienna, Austria) for characterization of nutrients and basic water quality parameters. For quantification of trace elements and metals, we collected additional water samples for subsequent ICP-MS analysis in the laboratory. To illustrate the applicability of our newly developed automated analysis and sampling system under field conditions, we will present initial results from the 2016 fall and winter seasons at the Erlenbach catchment. During this period, river discharge was mainly fed by groundwater, as well as intermittent snowmelt and rain-on-snow events. Our high-frequency data set, along with spatially distributed sampling of snowmelt, enables a detailed analysis of source areas, flow pathways and biogeochemical processes that control chemical dynamics in streamflow and the discharge regime.

Determination of ultratrace levels of tributyltin in waters by isotope dilution and gas chromatography coupled to tandem mass spectrometry.

PubMed

Rodríguez-Cea, Andrés; Rodríguez-González, Pablo; Font Cardona, Nuria; Aranda Mares, José Luís; Ballester Nebot, Salomé; García Alonso, J Ignacio

2015-12-18

The current EU legislation lays down the Environmental Quality Standards (EQS) of 45 priority substances in surface water bodies. In particular, the concentration of tributyltin (TBT) must not exceed 0.2ngL(-1) and analytical methodologies with a Limit of Quantification (LOQ) equal or below 0.06ngL(-1) are urged to be developed. This work presents a procedure for the determination of ultratrace levels of TBT in water samples by Isotope Dilution and GC-MS/MS operating in Selected Reaction Monitoring (SRM) mode which meets current EU requirements. The method requires the monitorization of five consecutive transitions (287>175 to 291>179) for the sensitive and selective detection of TBT. The measured isotopic distribution of TBT fragment ions was in agreement with the theoretical values computed by a polynomial expansion algorithm. The combined use of Tandem Mass Spectrometry, a sample volume of 250mL, the preconcentration of 1mL of organic phase to 30μL and an injection volume of 25μL by Programmed Temperature Vaporization provided a LOQ of 0.0426ngL(-1) for TBT (calculated as ten times the standard deviation of nine independent blanks). The recovery for TBT calculated in Milli-Q water at the EQS level was 106.3±4%. A similar procedure was also developed for the quantification of dibutyltin (DBT) and monobutyltin (MBT) in water samples showing satisfactory results. The method was finally implemented in a routine testing laboratory to demonstrate its applicability to real samples obtaining quantitative recoveries for TBT at the EQS level in mineral water, river water and seawater. Copyright © 2015 Elsevier B.V. All rights reserved.

Integrated assessment of river water quality in contrasting catchments: Impact of urbanization on particle bound pollutant fluxes

NASA Astrophysics Data System (ADS)

Grathwohl, Peter; Ruegner, Hermann; Schwientek, Marc; Beckingham, Barbara

2013-04-01

Water quality in rivers typically depends on the degree of urbanization or the population density in a catchment. Transport of many pollutants in rivers is coupled to transport of suspended particles, potentially dominated by storm water overflows and mobilization of legacy contamination of sediments. Concentration of pollutants strongly sorbed to suspended particles cannot be diluted by water directly, but depends on the mixture of "polluted" urban and "clean" background particles. In the current study, the total concentration of polycyclic aromatic hydrocarbons (PAHs), the amount of total suspended solids (TSS) and turbidity were measured on a monthly basis in water samples from 5 neighbouring catchments with contrasting land use in Southwest Germany over 1.5 years. In addition, single flood events with large changes in turbidity were sampled at high temporal resolution. Linear correlations of turbidity and TSS where obtained over all catchments investigated. From linear regressions of turbidity vs. total PAH concentrations in water, robust mean concentrations of PAHs on suspended particles could be obtained, which were distinct for each catchment depending on urban influence. PAH concentrations on suspended particles were stable over a large turbidity range (up to 900 NTU) confirmed by samples taken during flood events. No pronounced effects due to changing particle size or origin have been observed for the catchments investigated (< 150 squared km). Regression of total concentrations of PAHs in water samples vs. turbidity thus comprises a robust measure of the average sediment quality in a given catchment and this correlates to the degree of urbanization represented by the number of inhabitants per total flux of suspended particles. The findings are very promising for other particle-bound contaminant fluxes (PCBs, phosphorus, etc.) and in terms of on-line monitoring of turbidity as a proxy for pollution.

Determination of trace-level haloacetic acids in drinking water by ion chromatography-inductively coupled plasma mass spectrometry.

PubMed

Liu, Yongjian; Mou, Shifen; Chen, Dengyun

2004-06-11

A new method for the determination of nine haloacetic acids (HAAs) with ion chromatography (IC) coupled to inductively coupled plasma mass spectrometry (ICP-MS) was developed. With the very hydrophilic anion-exchange column and steep gradient of sodium hydroxide, the nine HAAs could be well separated in 15 min. After suppression with an ASRS suppressor that was introduced in between IC and ICP-MS, the background was much decreased, the interference caused by sodium ion present in eluent was removed, and the sensitivities of HAAs were greatly improved. The chlorinated and brominated HAAs could be detected as 35ClO and 79Br without interference of the matrix due to the elemental selective ICP-MS. The detection limits for mono-, di-, trichloroacetic acids were between 15.6 and 23.6 microg/l. For the other six bromine-containing HAAs, the detection limits were between 0.34 and 0.99 microg/l. With the pretreatment of OnGuard Ag cartridge to remove high concentration of chloride in sample, the developed method could be applied to the determination of HAAs in many drinking water matrices.

Analysis of 22 Elements in Milk, Feed, and Water of Dairy Cow, Goat, and Buffalo from Different Regions of China.

PubMed

Zhou, Xuewei; Qu, Xueyin; Zhao, Shengguo; Wang, Jiaqi; Li, Songli; Zheng, Nan

2017-03-01

The objectives of this study were to measure the concentrations of elements in raw milk by inductively coupled plasma-mass spectrometry (ICP-MS) and evaluate differences in element concentrations among animal species and regions of China. Furthermore, drinking water and feed samples were analyzed to investigate whether the element concentrations in raw milk are correlated with those in water and feed. All samples were analyzed by ICP-MS following microwave-assisted acid digestion. The mean recovery of the elements was 98.7 % from milk, 103.7 % from water, and 93.3 % from a certified reference material (cabbage). Principal component analysis results revealed that element concentrations differed among animal species and regions. Correlation analysis showed that trace elements Mn, Fe, Ni, Ga, Se, Sr, Cs, U in water and Co, Ni, Cu, Se, U in feed were significantly correlated with those in milk (p < 0.05). Toxic and potential toxic elements Cr, As, Cd, Tl, Pb in water and Al, Cr, As, Hg, Tl in feed were significantly correlated with those in milk (p < 0.05). Results of correlation analysis revealed that elements in water and feed might contribute to the elements in milk.

Metal organic frameworks (MOFs) for magnetic solid-phase extraction of pyrazole/pyrrole pesticides in environmental water samples followed by HPLC-DAD determination.

PubMed

Ma, Jiping; Yao, Zhidan; Hou, Liwei; Lu, Wenhui; Yang, Qipeng; Li, Jinhua; Chen, Lingxin

2016-12-01

Magnetic metal-organic frameworks (MOFs, [MIL-101]) were prepared and used as magnetic solid-phase extraction (MSPE) adsorbents for preconcentration of four kinds of pyrazole/pyrrole pesticides (flusilazole, fipronil, chlorfenapyr, and fenpyroximate) in environmental water samples, followed by high-performance liquid chromatography-diode-array detector (HPLC-DAD) determination. Several variables affecting MSPE efficiency were systematically investigated, including amount of MIL-101, extraction time, sample pH, salt concentration, type of desorption solvent and desorption number of times. Under optimized conditions, excellent linearity was achieved in the range of 5.0-200.0μg/L for flusilazole and fipronil, and 2.0-200.0μg/L for chlorfenapyr and fenpyroximate, with correlation coefficients r>0.9911. Limits of detection and quantification were 0.3-1.5μg/L and 1.0-5.0μg/L, respectively. The intra-day and inter-day precision (relative standard deviation, n=6, %) at three spiked levels were 1.1-5.4% and 3.9-7.8% in terms of peak area, respectively. The method recoveries at three fortified concentration levels ranged from 81.8% to 107.5% for reservoir water samples, 81.0-99.5% for river water samples, and 80.2-106.5% for seawater samples. The developed MOFs based MSPE coupled with HPLC method proved to be a convenient, rapid and eco-friendly alternative to the sensitive determination of pyrazole/pyrrole pesticides with high repeatability and excellent practical applicability. Copyright © 2016 Elsevier B.V. All rights reserved.

Research on Coupling Method of Watershed Initial Water Rights Allocation in Daling River

NASA Astrophysics Data System (ADS)

Liu, J.; Fengping, W.

2016-12-01

Water scarcity is now a common occurrence in many countries. The situation of watershed initial water rights allocation has caused many benefit conflicts among regions and regional water sectors of domestic and ecology environment and industries in China. This study aims to investigate the method of watershed initial water rights allocation in the perspective of coupling in Daling River Watershed taking provincial initial water rights and watershed-level governmental reserved water as objects. First of all, regarding the allocation subsystem of initial water rights among provinces, this research calculates initial water rights of different provinces by establishing the coupling model of water quantity and quality on the principle of "rewarding efficiency and penalizing inefficiency" based on the two control objectives of water quantity and quality. Secondly, regarding the allocation subsystem of watershed-level governmental reserved water rights, the study forecasts the demand of watershed-level governmental reserved water rights by the combination of case-based reasoning and water supply quotas. Then, the bilaterally coupled allocation model on water supply and demand is designed after supply analysis to get watershed-level governmental reserved water rights. The results of research method applied to Daling River Watershed reveal the recommended scheme of watershed initial water rights allocation based on coordinated degree criterion. It's found that the feasibility of the iteration coupling model and put forward related policies and suggestions. This study owns the advantages of complying with watershed initial water rights allocation mechanism and meeting the control requirements of water quantity, water quality and water utilization efficiency, which help to achieve the effective allocation of water resources.

Remote Pulsed Laser Raman Spectroscopy System for Detecting Qater, Ice, and Hydrous Minerals

NASA Technical Reports Server (NTRS)

Garcia, Christopher S.; Abedin, M. Nuraul; Sharma, Shiv K.; Misra, Anupam K.; Ismail, Syed; Singh, Upendra; Refaat, Tamer F.; Elsayed-Ali, Hani; Sandford, Steve

2006-01-01

For exploration of planetary surfaces, detection of water and ice is of great interest in supporting existence of life on other planets. Therefore, a remote Raman spectroscopy system was demonstrated at NASA Langley Research Center in collaboration with University of Hawaii for detecting ice-water and hydrous minerals on planetary surfaces. In this study, a 532 nm pulsed laser is utilized as an excitation source to allow detection in high background radiation conditions. The Raman scattered signal is collected by a 4-inch telescope positioned in front of a spectrograph. The Raman spectrum is analyzed using a spectrograph equipped with a holographic super notch filter to eliminate Rayleigh scattering, and a holographic transmission grating that simultaneously disperses two spectral tracks onto the detector for higher spectral range. To view the spectrum, the spectrograph is coupled to an intensified charge-coupled device (ICCD), which allows detection of very weak Stokes line. The ICCD is operated in gated mode to further suppress effects from background radiation and long-lived fluorescence. The sample is placed at 5.6 m from the telescope, and the laser is mounted on the telescope in a coaxial geometry to achieve maximum performance. The system was calibrated using the spectral lines of a Neon lamp source. To evaluate the system, Raman standard samples such as calcite, naphthalene, acetone, and isopropyl alcohol were analyzed. The Raman evaluation technique was used to analyze water, ice and other hydrous minerals and results from these species are presented.

Supersonic molecular beam-hyperthermal surface ionisation coupled with time-of-flight mass spectrometry applied to trace level detection of polynuclear aromatic hydrocarbons in drinking water for reduced sample preparation and analysis time.

PubMed

Davis, S C; Makarov, A A; Hughes, J D

1999-01-01

Analysis of sub-ppb levels of polynuclear aromatic hydrocarbons (PAHs) in drinking water by high performance liquid chromatography (HPLC) fluorescence detection typically requires large water samples and lengthy extraction procedures. The detection itself, although selective, does not give compound identity confirmation. Benchtop gas chromatography/mass spectrometry (GC/MS) systems operating in the more sensitive selected ion monitoring (SIM) acquisition mode discard spectral information and, when operating in scanning mode, are less sensitive and scan too slowly. The selectivity of hyperthermal surface ionisation (HSI), the high column flow rate capacity of the supersonic molecular beam (SMB) GC/MS interface, and the high acquisition rate of time-of-flight (TOF) mass analysis, are combined here to facilitate a rapid, specific and sensitive technique for the analysis of trace levels of PAHs in water. This work reports the advantages gained by using the GC/HSI-TOF system over the HPLC fluorescence method, and discusses in some detail the nature of the instrumentation used.

Vortex-assisted surfactant-enhanced emulsification microextraction combined with LC-MS/MS for the determination of glucocorticoids in water with the aid of experimental design.

PubMed

Asati, Ankita; Satyanarayana, G N V; Patel, Devendra K

2017-04-01

An efficient and inexpensive method using vortex-assisted surfactant-enhanced emulsification microextraction (VASEME) based on solidification of floating organic droplet coupled with ultraperformance liquid chromatography-tandem mass spectrometry is proposed for the analysis of glucocorticoids in water samples (river water and hospital wastewater). VASEME was optimized by the experimental validation of Plackett-Burman design and central composite design, which has been co-related to experimental design. Plackett-Burman design showed that factors such as vortex time, surfactant concentration, and pH significantly affect the extraction efficiency of the method. Method validation was characterized by an acceptable calibration range of 1-1000 ng L -1 , and the limit of detection was in the range from 2.20 to 8.12 ng L -1 for glucocorticoids. The proposed method was applied to determine glucocorticoids in river water and hospital wastewater in Lucknow, India. It is reliable and rapid and has potential application for analysis of glucocorticoids in environmental aqueous samples. Graphical Abstract Low density based extraction of gluococorticoids by using design of experiment.

Pressurized capillary electrochromatographic analysis of water-soluble vitamins by combining with on-line concentration technique.

PubMed

Jia, Li; Liu, Yaling; Du, Yanyan; Xing, Da

2007-06-22

A pressurized capillary electrochromatography (pCEC) system was developed for the separation of water-soluble vitamins, in which UV absorbance was used as the detection method and a monolithic silica-ODS column as the separation column. The parameters (type and content of organic solvent in the mobile phase, type and concentration of electrolyte, pH of the electrolyte buffer, applied voltage and flow rate) affecting the separation resolution were evaluated. The combination of two on-line concentration techniques, namely, solvent gradient zone sharpening effect and field-enhanced sample stacking, was utilized to improve detection sensitivity, which proved to be beneficial to enhance the detection sensitivity by enabling the injection of large volumes of samples. Coupling electrokinetic injection with the on-line concentration techniques was much more beneficial for the concentration of positively charged vitamins. Comparing with the conventional injection mode, the enhancement in the detection sensitivities of water-soluble vitamins using the on-line concentration technique is in the range of 3 to 35-fold. The developed pCEC method was applied to evaluate water-soluble vitamins in corns.

Rapid determination of the volatile components in tobacco by ultrasound-microwave synergistic extraction coupled to headspace solid-phase microextraction with gas chromatography-mass spectrometry.

PubMed

Yang, Yanqin; Chu, Guohai; Zhou, Guojun; Jiang, Jian; Yuan, Kailong; Pan, Yuanjiang; Song, Zhiyu; Li, Zuguang; Xia, Qian; Lu, Xinbo; Xiao, Weiqiang

2016-03-01

An ultrasound-microwave synergistic extraction coupled to headspace solid-phase microextraction was first employed to determine the volatile components in tobacco samples. The method combined the advantages of ultrasound, microwave, and headspace solid-phase microextraction. The extraction, separation, and enrichment were performed in a single step, which could greatly simplify the operation and reduce the whole pretreatment time. In the developed method, several experimental parameters, such as fiber type, ultrasound power, and irradiation time, were optimized to improve sampling efficiency. Under the optimal conditions, there were 37, 36, 34, and 36 components identified in tobacco from Guizhou, Hunan, Yunnan, and Zimbabwe, respectively, including esters, heterocycles, alkanes, ketones, terpenoids, acids, phenols, and alcohols. The compound types were roughly the same while the contents were varied from different origins due to the disparity of their growing conditions, such as soil, water, and climate. In addition, the ultrasound-microwave synergistic extraction coupled to headspace solid-phase microextraction method was compared with the microwave-assisted extraction coupled to headspace solid-phase microextraction and headspace solid-phase microextraction methods. More types of volatile components were obtained by using the ultrasound-microwave synergistic extraction coupled to headspace solid-phase microextraction method, moreover, the contents were high. The results indicated that the ultrasound-microwave synergistic extraction coupled to headspace solid-phase microextraction technique was a simple, time-saving and highly efficient approach, which was especially suitable for analysis of the volatile components in tobacco. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of haloacetic acids, bromate, and dalapon in natural waters by ion chromatography-tandem mass spectrometry.

PubMed

Wu, Shimin; Anumol, Tarun; Gandhi, Jay; Snyder, Shane A

2017-03-03

The addition of oxidants for disinfecting water can lead to the formation of potentially carcinogenic compounds referred to as disinfection byproducts (DBPs). Haloacetic acids (HAAs) are one of the most widely detected DBPs in US water utilities and some of them are regulated by the US Environmental Protection Agency (USEPA). The present study developed a method to analyze all the compounds in the USEPA method 557 (nine HAAs, bromate and dalapon) plus four potentially more toxic iodinated HAAs in water by coupling ion chromatography with tandem mass spectrometry (IC-MS/MS). This aqueous direct injection method has significant advantages over traditional GC methods, which require a derivatization and sample extraction that are laborious, time-consuming, and can negatively impact reproducibility. The method developed in this study requires half the time of the current USEPA method 557 on IC-MS/MS while including more compounds and achieving sub-μg/L level method detection limits (MDLs) for all 15 target analytes. The single laboratory lowest concentration minimum reporting level (LCMRL) has also been determined in reagent water, which ranged from 0.011 to 0.62μg/L for the analytes. The mean recoveries of the analytes during matrix spike recovery tests were 77-125% in finished drinking water and 81-112% in surface water. This method was then applied to untreated, chlorinated, and chloraminated groundwater and surface water samples. Bromate and 9 HAAs were detected at different levels in some of these samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Continental paleothermometry and seasonality using the isotopic composition of aragonitic otoliths of freshwater fishes

NASA Astrophysics Data System (ADS)

Patterson, William P.; Smith, Gerald R.; Lohmann, Kyger C.

To investigate the applicability of oxygen isotope themometry using fish aragonite, the δ18O values of paired otolith and water samples were analyzed from six large modem temperate lakes. Otoliths are accretionaiy aragonitic structures which are precipitated within the sacculus of fish ears. Deep-water obligate benthic species from the hypolimnion of the Laurentian Great Lakes of North America and Lake Baikal, Siberia, provided cold-water end member values for aragonite δ18O. Warm-water values were obtained from naturally grown warm-water stenothermic species and from fish grown in aquaria under controlled conditions. These two groups, which represent growth over a temperature range of 3.2-30.3°C. were employed to determine the oxygen isotope temperature fractionation relationship for aragonite-water: 103lnα = 18.56 (±0.319)·(103)T-1 K -33.49 (±0.307). Empirical calibration of a fish aragonite thennometry equation allows its direct application to studies of paleoclimate. For example, high-resolution sampling of shallow-water eurythermic species coupled with a knowledge of the isotopic composition of meteoric waters can be used to determine seasonal temperature variation. This approach was tested using a modem shallow-water eurythermic species from Sandusky Bay, Lake Erie. Temperatures calculated from carbonate composition agree with meteorological records from the Sandusky Bay weather station for the same time period.

Condensed Phase Membrane Introduction Mass Spectrometry with Direct Electron Ionization: On-line Measurement of PAHs in Complex Aqueous Samples

NASA Astrophysics Data System (ADS)

Termopoli, Veronica; Famiglini, Giorgio; Palma, Pierangela; Cappiello, Achille; Vandergrift, Gregory W.; Krogh, Erik T.; Gill, Chris G.

2016-02-01

Polycyclic aromatic hydrocarbons (PAHs) are USEPA regulated priority pollutants. Their low aqueous solubility requires very sensitive analytical methods for their detection, typically involving preconcentration steps. Presented is the first demonstrated `proof of concept' use of condensed phase membrane introduction mass spectrometry (CP-MIMS) coupled with direct liquid electron ionization (DEI) for the direct, on-line measurement of PAHs in aqueous samples. DEI is very well suited for the ionization of PAHs and other nonpolar compounds, and is not significantly influenced by the co-elution of matrix components. Linear calibration data for low ppb levels of aqueous naphthalene, anthracene, and pyrene is demonstrated, with measured detection limits of 4 ppb. Analytical response times (t10%-90% signal rise) ranged from 2.8 min for naphthalene to 4.7 min for pyrene. Both intra- and interday reproducibility has been assessed (<3% and 5% RSD, respectively). Direct measurements of ppb level PAHs spiked in a variety of real, complex environmental sample matrices is examined, including natural waters, sea waters, and a hydrocarbon extraction production waste water sample. For these spiked, complex samples, direct PAH measurement by CP-MIMS-DEI yielded minimal signal suppression from sample matrix effects (81%-104%). We demonstrate the use of this analytical approach to directly monitor real-time changes in aqueous PAH concentrations with potential applications for continuous on-line monitoring strategies and binding/adsorption studies in heterogeneous samples.

Preparation and characterization of chitosan membranes by using a combined freeze gelation and mild crosslinking method.

PubMed

Orrego, Carlos E; Valencia, Jesús S

2009-02-01

When gelification is performed by freezing-thawing repeated cycles, the resultant gel-like polymer systems are called cryogels. This work aims to assess the effect of the addition of glutaraldehyde and 18 Crown Ether-6 on surface properties and protein loading of dried chitosan cryogel films. Residual water content of treated chitosan membranes ranged between 11.93 and 13.86%, while their water activities vary from 0.5 to 0.7 (measured from 4 to 60 degrees C). Based on thermal data, water evaporation peak and degradation temperatures of chitosan membranes shifted to a higher temperature for crosslinked samples. X-ray diffractograms provide high values of crystallinity for all the samples (70.67-92.86%), the highest value being for the glutaraldehyde-treated membrane. Candida rugosa lipase can be immobilized successfully on chitosan membranes. Lipase immobilized on glutaraldehyde-crosslinked chitosan yielded the highest efficiency in terms of total coupled protein and protein loading efficiency.

Continuous flow analysis combined with a light-absorption ratio variation approach for determination of copper at ng/ml level in natural water.

PubMed

Gao, Hong-Wen; Wang, Chun-Lei; Jia, Jiang-Yan; Zhang, Ya-Lei

2007-06-01

The complexation between Cu(II) and naphthochrome green (NG) is very sensitive at pH 4.09 with the formation of complex ion [Cu(NG)2(H2O)2](2-). It can thus used for the determination of Cu(II) by the light-absorption ratio variation approach (LARVA) with a good selectivity. Both the ordinary detection procedure and continuous flow analysis (CFA) were carried out, where the latter is fit for continuous and rapid analysis of samples. The limit of detection (LOD) of Cu(II) is only 1 ng/ml, which is favorable for direct monitoring of natural water. About 30 samples could be analyzed per hour by CFA. Cu(II) contents in Yangtze River, West Lake, Taihu Lake of China and seawater near Shanghai were determined with satisfactory results. The CFA-LARVA spectrophotometry was the first to be coupled and it will play an important role in the in-situ analysis of natural water quality.

Determination of endocrine-disrupting compounds in water samples by magnetic nanoparticle-assisted dispersive liquid-liquid microextraction combined with gas chromatography-tandem mass spectrometry.

PubMed

Pérez, Rosa Ana; Albero, Beatriz; Tadeo, José Luis; Sánchez-Brunete, Consuelo

2016-11-01

A rapid extraction procedure is presented for the determination of five endocrine-disrupting compounds, estrone, ethinylestradiol, bisphenol A, triclosan, and 2-ethylhexylsalicylate, in water samples. The analysis involves a two-step extraction procedure that combines dispersive liquid-liquid microextraction (DLLME) with dispersive micro-solid phase extraction (D-μ-SPE), using magnetic nanoparticles, followed by in situ derivatization in the injection port of a gas chromatograph coupled to triple quadrupole mass spectrometry. The use of uncoated or oleate-coated Fe 3 O 4 nanoparticles as sorbent in the extraction process was evaluated and compared. The main parameters involved in the extraction process were optimized applying experimental designs. Uncoated Fe 3 O 4 nanoparticles were selected in order to simplify and make more cost-effective the procedure. DLLME was carried out at pH 3, during 2 min, followed by the addition of the nanoparticles for D-μ-SPE employing 1 min in the extraction. Analysis of spiked water samples of different sources gave satisfactory recovery results for all the compounds with detection limits ranging from 7 to 180 ng l -1 . Finally, the procedure was applied in tap, well, and river water. Graphical abstract Diagram of the extraction method using magnetic nanoparticles (MNPs).

Organic compounds in produced waters from shale gas wells.

PubMed

Maguire-Boyle, Samuel J; Barron, Andrew R

2014-01-01

A detailed analysis is reported of the organic composition of produced water samples from typical shale gas wells in the Marcellus (PA), Eagle Ford (TX), and Barnett (NM) formations. The quality of shale gas produced (and frac flowback) waters is a current environmental concern and disposal problem for producers. Re-use of produced water for hydraulic fracturing is being encouraged; however, knowledge of the organic impurities is important in determining the method of treatment. The metal content was determined by inductively coupled plasma optical emission spectrometry (ICP-OES). Mineral elements are expected depending on the reservoir geology and salts used in hydraulic fracturing; however, significant levels of other transition metals and heavier main group elements are observed. The presence of scaling elements (Ca and Ba) is related to the pH of the water rather than total dissolved solids (TDS). Using gas chromatography mass spectrometry (GC/MS) analysis of the chloroform extracts of the produced water samples, a plethora of organic compounds were identified. In each water sample, the majority of organics are saturated (aliphatic), and only a small fraction comes under aromatic, resin, and asphaltene categories. Unlike coalbed methane produced water it appears that shale oil/gas produced water does not contain significant quantities of polyaromatic hydrocarbons reducing the potential health hazard. Marcellus and Barnett produced waters contain predominantly C6-C16 hydrocarbons, while the Eagle Ford produced water shows the highest concentration in the C17-C30 range. The structures of the saturated hydrocarbons identified generally follows the trend of linear > branched > cyclic. Heterocyclic compounds are identified with the largest fraction being fatty alcohols, esters, and ethers. However, the presence of various fatty acid phthalate esters in the Barnett and Marcellus produced waters can be related to their use in drilling fluids and breaker additives rather than their presence in connate fluids. Halogen containing compounds are found in each of the water samples, and although the fluorocarbon compounds identified are used as tracers, the presence of chlorocarbons and organobromides formed as a consequence of using chlorine containing oxidants (to remove bacteria from source water), suggests that industry should concentrate on non-chemical treatments of frac and produced waters.

Ultrasensitive determination of cadmium in seawater by hollow fiber supported liquid membrane extraction coupled with graphite furnace atomic absorption spectrometry

NASA Astrophysics Data System (ADS)

Peng, Jin-feng; Liu, Rui; Liu, Jing-fu; He, Bin; Hu, Xia-lin; Jiang, Gui-bin

2007-05-01

A new procedure, based on hollow fiber supported liquid membrane preconcentration coupled with graphite furnace atomic absorption spectrometry (GFAAS) detection, was developed for the determination of trace Cd in seawater samples. With 1-octanol that contained a mixture of dithizone (carrier) and oleic acid immobilized in the pores of the polypropylene hollow fiber as a liquid membrane, Cd was selectively extracted from water samples into 0.05 M HNO 3 that filled the lumen of the hollow fiber as a stripping solution. The main extraction related parameters were optimized, and the effects of salinity and some coexisting interferants were also evaluated. Under the optimum extraction conditions, an enrichment factor of 387 was obtained for a 100-mL sample solution. In combination with graphite furnace atomic absorption spectrometry, a very low detection limit (0.8 ng L - 1 ) and a relative standard deviation (2.5% at 50 ng L - 1 level) were achieved. Five seawater samples were analyzed by the proposed method without dilution, with detected Cd concentration in the range of 56.4-264.8 ng L - 1 and the relative spiked recoveries over 89%. For comparison, these samples were also analyzed by the Inductively Coupled Plasma Mass Spectrometry (ICP-MS) method after a 10-fold dilution for matrix effect elimination. Statistical analysis with a one-way ANOVA shows no significant differences (at 0.05 level) between the results obtained by the proposed and ICP-MS methods. Additionally, analysis of certified reference materials (GBW (E) 080040) shows good agreement with the certified value. These results indicate that this present method is very sensitive and reliable, and can effectively eliminate complex matrix interferences in seawater samples.

Wear behaviour of the couple polyethylene Ti6Al4V: Effects of the metallic surface preparation and nitrogen implantation

NASA Astrophysics Data System (ADS)

Martinella, R.; Giovanardi, S.; Palombarini, G.; Corchia, M.; Delogu, P.; Giorgi, R.; Tosello, C.

The wear behaviour improvement of the tribological couple Ti6Al4V-UHMWPE is of great interest to the medical field. Wear tests were carried out in water on a reciprocating UHMWPE annulus on implanted Ti6Al4V disc tribotestcr, with loads and velocities simulating those of hip joints. A comparison of wear behaviours was also carried out between untreated Ti6Al4V samples and Ti6Al4V subjected to a special lapping procedure. UHMWPE worn against ion-implanted and especially lapped Ti alloy showed the lowest wear rate, while, the highest (about one order of magnitude) was shown by the UHMWPE against untreated Ti6Al4V samples. XPS and AES surface analyses were carried out on metallic discs to examine the chemical composition of the surface before wear tests. Moreover depth distribution of nitrogen in implanted samples was determined using the same techniques. SEM observations displayed a polyethylene transfer film on all metallic surfaces, particularly on untreated Ti6Al4V samples. A discussion about uselessness of more conventional surface treatments for the Ti alloy is also reported.

Assessment of Sulphate and Iron Contamination and Seasonal Variations in the Water Resources of a Damodar Valley Coalfield, India: A Case Study.

PubMed

Tiwari, Ashwani Kumar; De Maio, Marina

2018-02-01

The aim of the present study was to assess the sulphate [Formula: see text] and iron (Fe) contamination and seasonal variations in the water resources (groundwater, surface water, and mine water) of the West Bokaro coalfield region, India. One hundred and twenty-four water resources samples were collected from the coalfield during the post- and pre-monsoon seasons. The concentrations of [Formula: see text] were determined using ion chromatography and Fe concentrations were analyzed using inductively coupled plasma mass spectrometry. A statistical analysis was used to easily understand the seasonal variations of the elements in the water resources of the area. The concentrations of [Formula: see text] and Fe in the water resources were higher in the pre-monsoon season than in the post-monsoon season, irrespective of location. The water resources of the coalfield were contaminated with high concentrations of [Formula: see text] and Fe, and would require suitable treatment before drinking, domestic and industrial uses.

2Q NMR of 2H2O ordering at solid interfaces

NASA Astrophysics Data System (ADS)

Krivokhizhina, Tatiana V.; Wittebort, R. J.

2014-06-01

Solvent ordering at an interface can be studied by multiple-quantum NMR. Quantitative studies of 2H2O ordering require clean double-quantum (2Q) filtration and an analysis of 2Q buildup curves that accounts for relaxation and, if randomly oriented samples are used, the distribution of residual couplings. A pulse sequence with absorption mode detection is extended for separating coherences by order and measuring relaxation times such as the 2Q filtered T2. Coherence separation is used to verify 2Q filtration and the 2Q filtered T2 is required to extract the coupling from the 2Q buildup curve when it is unresolved. With our analysis, the coupling extracted from the buildup curve in 2H2O hydrated collagen was equivalent to the resolved coupling measured in the usual 1D experiment and the 2Q to 1Q signal ratio was in accord with theory. Application to buildup curves from 2H2O hydrated elastin, which has an unresolved coupling, revealed a large increase in the 2Q signal upon mechanical stretch that is due to an increase in the ordered water fraction while changes in the residual coupling and T2 are small.

Dissolved organic matter dynamics in surface waters affected by oil spill pollution: Results from the Serious Game exercise

NASA Astrophysics Data System (ADS)

Gonnelli, M.; Galletti, Y.; Marchetti, E.; Mercadante, L.; Retelletti Brogi, S.; Ribotti, A.; Sorgente, R.; Vestri, S.; Santinelli, C.

2016-11-01

Dissolved organic carbon (DOC), chromophoric and fluorescent dissolved organic matter (CDOM and FDOM, respectively) surface distribution was studied during the Serious Game exercise carried out in the Eastern Ligurian Sea, where an oil spill was localized by using satellite images and models. This paper reports the first DOC, CDOM and FDOM data for this area together with an evaluation of fluorescence as a fast and inexpensive tool for early oil spill detection in marine waters. The samples collected in the oil spill showed a fluorescence intensity markedly higher ( 5 fold) than all the other samples. The excitation-emission matrixes, coupled with parallel factor analysis (PARAFAC), allowed for the identification in the FDOM pool of a mixture of polycyclic aromatic hydrocarbons, humic-like and protein-like fluorophores.

[Studies on GC fingerprint of volatile oil of Houttuynia cordata].

PubMed

Yang, Bin; Wang, Ruo-Jing; Wang, Qian-Peng; Lu, Dong-Mei; Li, Hua; Xiao, Yong-Qing; Wang, Yong-Yan

2006-12-01

To establish a GC fingerprint of the volatile oil of Houttuynia cordata. The volatile oil was extracted from H. cordata by water stream distillation method, and analyzed by GC coupled with FID. 12 bathes of samples collected from different regions were analyzed; the GC fingerprint of the volatile oil of H. cordata was subsequently established. The established GC fingerprint can be used for the identification of H. cordata.

Spatiotemporal Variation in Environmental Vibrio cholerae in an Estuary in Southern Coastal Ecuador.

PubMed

Ryan, Sadie J; Stewart-Ibarra, Anna M; Ordóñez-Enireb, Eunice; Chu, Winnie; Finkelstein, Julia L; King, Christine A; Escobar, Luis E; Lupone, Christina; Heras, Froilan; Tauzer, Erica; Waggoner, Egan; James, Tyler G; Cárdenas, Washington B; Polhemus, Mark

2018-03-10

Cholera emergence is strongly linked to local environmental and ecological context. The 1991-2004 pandemic emerged in Perú and spread north into Ecuador's El Oro province, making this a key site for potential re-emergence. Machala, El Oro, is a port city of 250,000 inhabitants, near the Peruvian border. Many livelihoods depend on the estuarine system, from fishing for subsistence and trade, to domestic water use. In 2014, we conducted biweekly sampling for 10 months in five estuarine locations, across a gradient of human use, and ranging from inland to ocean. We measured water-specific environmental variables implicated in cholera growth and persistence: pH, temperature, salinity, and algal concentration, and evaluated samples in five months for pathogenic and non-pathogenic Vibrio cholerae , by polymerase chain reaction (PCR). We found environmental persistence of pandemic strains O1 and O139, but no evidence for toxigenic strains. Vibrio cholerae presence was coupled to algal and salinity concentration, and sites exhibited considerable seasonal and spatial heterogeneity. This study indicates that environmental conditions in Machala are optimal for cholera re-emergence, with risk peaking during September, and higher risk near urban periphery low-income communities. This highlights a need for surveillance of this coupled cholera-estuarine system to anticipate potential future cholera outbreaks.

Spatiotemporal Variation in Environmental Vibrio cholerae in an Estuary in Southern Coastal Ecuador

PubMed Central

Stewart-Ibarra, Anna M.; Ordóñez-Enireb, Eunice; Chu, Winnie; Finkelstein, Julia L.; King, Christine A.; Escobar, Luis E.; Lupone, Christina; Heras, Froilan; Tauzer, Erica; Waggoner, Egan; Polhemus, Mark

2018-01-01

Cholera emergence is strongly linked to local environmental and ecological context. The 1991–2004 pandemic emerged in Perú and spread north into Ecuador’s El Oro province, making this a key site for potential re-emergence. Machala, El Oro, is a port city of 250,000 inhabitants, near the Peruvian border. Many livelihoods depend on the estuarine system, from fishing for subsistence and trade, to domestic water use. In 2014, we conducted biweekly sampling for 10 months in five estuarine locations, across a gradient of human use, and ranging from inland to ocean. We measured water-specific environmental variables implicated in cholera growth and persistence: pH, temperature, salinity, and algal concentration, and evaluated samples in five months for pathogenic and non-pathogenic Vibrio cholerae, by polymerase chain reaction (PCR). We found environmental persistence of pandemic strains O1 and O139, but no evidence for toxigenic strains. Vibrio cholerae presence was coupled to algal and salinity concentration, and sites exhibited considerable seasonal and spatial heterogeneity. This study indicates that environmental conditions in Machala are optimal for cholera re-emergence, with risk peaking during September, and higher risk near urban periphery low-income communities. This highlights a need for surveillance of this coupled cholera–estuarine system to anticipate potential future cholera outbreaks. PMID:29534431

Determination of acidic non-steroidal anti-inflammatory drugs in aquatic samples by liquid chromatography-triple quadrupole mass spectrometry combined with carbon nanotubes-based solid-phase extraction.

PubMed

Reinholds, I; Pugajeva, I; Zacs, Dz; Lundanes, E; Rusko, J; Perkons, I; Bartkevics, V

2017-10-18

A solid-phase extraction (SPE) method based on multi-walled carbon nanotubes (CNT) was developed for the determination of 12 acidic non-steroidal anti-inflammatory drugs (NSAIDs) in surface waters and tap water. Pristine and functionalised CNTs were evaluated as sorbent materials. Batch experiments were used to optimise sorption and desorption conditions (sorbent type and amount, adsorption time, pH). The adsorption equilibrium was reached after 8 to 48 h duration, which increased with the pH of solution. Non-agglomerated pristine CNTs (20 mg) showed the most optimal adsorption (94 to 100%) for all of the analytes after a 30-min contact period in acidified water solutions (100 mL). The compounds retained at those conditions were recovered by 40 to 95% by using 5% ammonium hydroxide in methanol as the desorbing solution at ambient conditions. A comprehensive liquid chromatography coupled to triple quadrupole mass spectrometry (LC-QqQ-MS/MS) was used for the analysis of real water samples. The method showed sufficient recovery (65-125%) and good precision (2-14% relative standard deviation (RSD)). The limits of detection and quantification ranged between 0.01 and 1.3 ng L -1 and 0.04 and 3.9 ng L -1 . Only diclofenac and ibuprofen were found in the analysed surface water samples from Latvia (n = 10) and Norway (n = 14). Diclofenac was found at 1.7-8.4 ng L -1 concentration in two samples of surface waters, whereas the concentrations of ibuprofen ranged between 1.0 and 9.2 ng L -1 in seven samples collected in Norway and 3.9-17 ng L -1 in three samples from Latvia.

Concentrations of mercury and other metals in black bass (Micropterus spp.) from Whiskeytown Lake, Shasta County, California, 2005

USGS Publications Warehouse

May, Jason T.; Hothem, Roger L.; Bauer, Marissa L.; Brown, Larry R.

2012-01-01

This report presents the results of a reconnaissance study conducted by the U.S. Geological Survey (USGS) to determine mercury (Hg) and other selected metal concentrations in Black bass (Micropterus spp.) from Whiskeytown Lake, Shasta County, California. Total mercury concentrations were determined by cold-vapor atomic absorption spectroscopy (CVAAS) in fillets and whole bodies of each sampled fish. Selected metals scans were performed on whole bodies (less the fillets) by inductively coupled plasma–mass spectroscopy (ICP-MS) and inductively coupled plasma–optical emission spectroscopy (ICP-OES). Mercury concentrations in fillet samples ranged from 0.06 to 0.52 micrograms per gram (μg/g) wet weight (ww). Total mercury (HgT) in the same fish whole-body samples ranged from 0.04 to 0.37 (μg/g, ww). Mercury concentrations in 17 percent of "legal catch size" (≥305 millimeters in length) were above the U.S. Environmental Protection Agency water-quality criterion for the protection of human health of 0.30 μg/g (ww). These data will serve as a baseline for future monitoring efforts within Whiskeytown Lake.

Linking Land-Use to Submarine Groundwater Discharge Nutrient Fluxes on Maui, Hawaii

NASA Astrophysics Data System (ADS)

Bishop, J. M.; Glenn, C. R.; Amato, D. W.; Dulaiova, H.

2014-12-01

Fertilized agricultural lands, wastewater injection, and areas with high septic system density each have substantial potential for contributing excess nutrients to the coastal waters of islands via submarine groundwater discharge (SGD). We evaluated the coastal impacts of such land-use around the island of Maui using stable isotopes (δ15N of NO3-; δ18O and δ2H of H2O) and nutrient concentrations from wells, springs, beach seeps, SGD, and coastal waters, and coupled these to coastal water SGD and nutrient fluxes using 222Rn mass balance. Flowpaths and recharge elevations for groundwater samples were determined using the δ18OH2O of samples, recharge data, modeled groundwater head, and published local meteoric water lines. Coastal groundwater samples whose flowpaths transect sugarcane plots showed highest dissolved inorganic nitrogen (DIN - NO3- + NO2-) concentrations, ranging from 225 - 450 µM, and the δ15N of those samples was on average 3.3 ± 0.6 ‰ (n = 15), as expected for urea fertilizers applied to commercial sugarcane. Samples whose flowpaths transect large amounts of septic sources showed moderate DIN concentrations (max. 100 µM), but had higher δ15N values (9.7 ± 4.8 ‰, n = 5), reflecting their sewage influence. Due to nitrate reduction during subterranean transit, groundwater and coastal waters proximal to deep, near-coast wastewater injection (Kahului) display the highest average δ15N values encountered (δ15NNO3- 18.8 ± 11.1 ‰, n = 19) and moderate DIN concentrations (max 90 µM). Average SGD nutrient fluxes among the different field sites ranged from 700 - 1,500,000 µmol/d/m of shoreline for DIN and 600 - 22,000 µmol/d/m for orthophosphate. These results indicate that areas with the highest N and P fluxes are areas where coastal groundwater flowpaths transect large tracts of sugarcane production. Although highest SGD rates occur near the Kahului wastewater injection wells (~ 2800 m3/day) the relatively low nutrient concentrations in the groundwater end member lead to comparatively modest nutrient fluxes of 270,000 and 13,000 μmol/d/m for DIN and orthophosphate, respectively. This study demonstrates the utility of coupling stable isotope and SGD-radioisotope tracers to (1) determine the source of nutrients in SGD as well as (2) the trajectories and specific fluxes of those nutrients to the coast.

Regional-scale, fully coupled modelling of stream aquifer interaction in a tropical catchment

NASA Astrophysics Data System (ADS)

Werner, Adrian D.; Gallagher, Mark R.; Weeks, Scott W.

2006-09-01

SummaryThe planning and management of water resources in the Pioneer Valley, north-eastern Australia requires a tool for assessing the impact of groundwater and stream abstractions on water supply reliabilities and environmental flows in Sandy Creek (the main surface water system studied). Consequently, a fully coupled stream-aquifer model has been constructed using the code MODHMS, calibrated to near-stream observations of watertable behaviour and multiple components of gauged stream flow. This model has been tested using other methods of estimation, including stream depletion analysis and radon isotope tracer sampling. The coarseness of spatial discretisation, which is required for practical reasons of computational efficiency, limits the model's capacity to simulate small-scale processes (e.g., near-stream groundwater pumping, bank storage effects), and alternative approaches are required to complement the model's range of applicability. Model predictions of groundwater influx to Sandy Creek are compared with baseflow estimates from three different hydrograph separation techniques, which were found to be unable to reflect the dynamics of Sandy Creek stream-aquifer interactions. The model was also used to infer changes in the water balance of the system caused by historical land use change. This led to constraints on the recharge distribution which can be implemented to improve model calibration performance.

State of the art in on-line techniques coupled to flow injection analysis FIA/on-line- a critical review

PubMed Central

Puchades, R.; Maquieira, A.; Atienza, J.; Herrero, M. A.

1990-01-01

Flow injection analysis (FIA) has emerged as an increasingly used laboratory tool in chemical analysis. Employment of the technique for on-line sample treatment and on-line measurement in chemical process control is a growing trend. This article reviews the recent applications of FlA. Most papers refer to on-line sample treatment. Although FIA is very well suited to continuous on-line process monitoring, few examples have been found in this areamost of them have been applied to water treatment or fermentation processes. PMID:18925271

Focusing particle concentrator with application to ultrafine particles

DOEpatents

Hering, Susanne; Lewis, Gregory; Spielman, Steven R.

2013-06-11

Technology is presented for the high efficiency concentration of fine and ultrafine airborne particles into a small fraction of the sampled airflow by condensational enlargement, aerodynamic focusing and flow separation. A nozzle concentrator structure including an acceleration nozzle with a flow extraction structure may be coupled to a containment vessel. The containment vessel may include a water condensation growth tube to facilitate the concentration of ultrafine particles. The containment vessel may further include a separate carrier flow introduced at the center of the sampled flow, upstream of the acceleration nozzle of the nozzle concentrator to facilitate the separation of particle and vapor constituents.

Determination of uranium isotopes in food and environmental samples by different techniques: a comparison.

PubMed

Forte, M; Rusconi, R; Margini, C; Abbate, G; Maltese, S; Badalamenti, P; Bellinzona, S

2001-01-01

The uranium concentration in 59 samples of bottled and tap water, mainly from northern Italy, was measured by different techniques. Results obtained by inductively coupled plasma mass spectrometry (ICP-MS), semiconductor alpha spectrometry and low level liquid scintillation counting with alpha/beta discrimination (LSC) have been compared. High resolution gamma spectrometry and semiconductor alpha spectrometry have been used to analyse uranium in a variety of organic and inorganic samples. Isotopic secular equilibrium in the 238U series may be lacking or hidden by auto-absorption phenomena, so caution should be used in evaluating gamma spectrometry data. Alpha spectrometry has also been used to ascertain the possible pollution from depleted uranium in the environment.

Packed in-tube solid phase microextraction with graphene oxide supported on aminopropyl silica: Determination of target triazines in water samples.

PubMed

De Toffoli, Ana L; Fumes, Bruno H; Lanças, Fernando M

2018-02-22

On-line in-tube solid phase microextraction (in-tube SPME) coupled to high performance liquid chromatography and tandem mass spectrometry (HPLC-MS/MS) was successfully applied to the determination of selected triazines in water samples. The method based on the employment of a packed column containing graphene oxide (GO) supported on aminopropyl silica (Si) showed that the extraction phase has a high potential for triazines extraction aiming to its physical-chemical properties including ultrahigh specific surface area, good mechanical and thermal stability and high fracture strength. Injection volume and loading time were both investigated and optimized. The method validation using Si-GO to extract and concentrate the analytes showed satisfactory results, good sensitivity, good linearity (0.2-4.0 µg L -1 ) and low detection limits (1.1-2.9 ng L -1 ). The high extraction efficiency was determined with enrichment factors ranging from 1.2-2.9 for the lowest level, 1.3-4.9 intermediate level and 1.2-3.0 highest level (n = 3). Although the analytes were not detected in the real samples evaluated, the method has demonstrated to be efficient through its application in the analysis of spiked triazines in ground and mineral water samples.

Determination of rhodium in metallic alloy and water samples using cloud point extraction coupled with spectrophotometric technique

NASA Astrophysics Data System (ADS)

Kassem, Mohammed A.; Amin, Alaa S.

2015-02-01

A new method to estimate rhodium in different samples at trace levels had been developed. Rhodium was complexed with 5-(4‧-nitro-2‧,6‧-dichlorophenylazo)-6-hydroxypyrimidine-2,4-dione (NDPHPD) as a complexing agent in an aqueous medium and concentrated by using Triton X-114 as a surfactant. The investigated rhodium complex was preconcentrated with cloud point extraction process using the nonionic surfactant Triton X-114 to extract rhodium complex from aqueous solutions at pH 4.75. After the phase separation at 50 °C, the surfactant-rich phase was heated again at 100 °C to remove water after decantation and the remaining phase was dissolved using 0.5 mL of acetonitrile. Under optimum conditions, the calibration curve was linear for the concentration range of 0.5-75 ng mL-1 and the detection limit was 0.15 ng mL-1 of the original solution. The enhancement factor of 500 was achieved for 250 mL samples containing the analyte and relative standard deviations were ⩽1.50%. The method was found to be highly selective, fairly sensitive, simple, rapid and economical and safely applied for rhodium determination in different complex materials such as synthetic mixture of alloys and environmental water samples.

Determination of alkylphenols and alkylphenol mono- and diethoxylates in environmental samples by high-performance liquid chromatography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahel, M.; Giger, W.

1985-07-01

A routine method is described for the quantitative determination of 4-nonylphenol (NP) and 4-nonylphenol mono-(NP1EO) and diethoxylate (NP2EO) in samples from wastewater and sludge treatment and from the aquatic environment. An exhaustive steam-distillation/solvent-extraction procedure was employed to enrich the analytes from aqueous and solid samples. Quantitative determinations were performed by normal-phase high-performance liquid chromatography (HP-LC) using aminosilica columns. Relative standard deviations were 3.0-4.4% in a river water containing 3.9 ..mu..g/L NP, 23.4 ..mu..g/L NP1EO, and 9.4 ..mu..g/L NP2EO. A digested sewage sludge with 1.6 g of NP/kg of dry matter was analyzed with a relative standard deviation of 3.7%. Recoveriesmore » were higher than 80%, and the estimated detection limit in water samples was 0.5 ..mu..g/L. Reversed-phase HPLC on octylsilica provided complementary qualitative data, particularly on homologous alkylphenolic compounds. Good agreement was found between quantitative determinations by HPLC and by high-resolution gas chromatography with flame ionization detection and directly coupled mass spectrometry. Municipal wastewater effluents, sewage sludges, and natural waters were analyzed to demonstrate the method's broad applicability. 19 references, 4 tables, 4 figures.« less

Use of Dialysis Multi-level Samplers to Examine Microbial Processes in a Shallow Alluvial Aquifer of the Rio Grande, New Mexico

NASA Astrophysics Data System (ADS)

Crossey, L. J.; Vinson, D. S.; Block, S. E.; Dahm, C. N.; Spilde, M.; Pershall, A. D.

2001-12-01

The riparian zone of the Rio Grande near Belen, New Mexico, hosts a shallow sand-dominated aquifer with discharge - recharge events occurring on time scales ranging from hours to months. Using a multi-level sampler with dialysis cells (DMLS), we have sampled the upper 1.5 m of the water table at 10 cm vertical resolution. The DMLS system provides a passive means of water sampling at high resolution and with minimal disturbance to the environment being studied. Water samples have been analyzed for major ion chemistry as well as redox-sensitive parameters (iron, manganese, dissolved oxygen, sulfur, organic carbon, and redox potential). Depth-related trends emerge through the DMLS approach that are not evident from traditional well sampling methods. Vertical hydrochemical profiles reveal substantial seasonal variability, as well as changes related to major infiltration events during monsoon rains. In conjunction with continuously recorded water table data, we can assess redox-related biogeochemical and microbiological processes in terms of groundwater-surface water interaction. In addition, we have examined mineral products and bacterial growths within the dialysis cells. Cells with membrane pore size of 10†m serve as microcosms to investigate solid products that would be difficult to isolate from the natural sediments. Over a period of several weeks, sufficient microbial/mineral growth occurs. These samples have been imaged with scanning electron microscopy and chemically inspected by energy-dispersive X-ray spectroscopy. Notable products include iron sulfides; iron and manganese oxides (crystalline and amorphous); and tentatively authigenic phosphates, some containing rare earth elements. DMLS is a useful tool for coupling high-resolution chemical investigation of groundwater with examination of microbial activity in this shallow aquifer. The approach may have applications in other environments where good vertical resolution is needed.

Rapid analysis of chlorinated anilines in environmental water samples using ultrasound assisted emulsification microextraction with solidification of floating organic droplet followed by HPLC-UV detection.

PubMed

Ramkumar, Abilasha; Ponnusamy, Vinoth Kumar; Jen, Jen-Fon

2012-08-15

The present study demonstrates a simple, rapid and efficient method for the determination of chlorinated anilines (CAs) in environmental water samples using ultrasonication assisted emulsification microextraction technique based on solidification of floating organic droplet (USAEME-SFO) coupled with high performance liquid chromatography-ultraviolet (HPLC-UV) detection. In this extraction method, 1-dodecanol was used as extraction solvent which is of lower density than water, low toxicity, low volatility, and low melting point (24 °C). After the USAEME, extraction solvent could be collected easily by keeping the extraction tube in ice bath for 2 min and the solidified organic droplet was scooped out using a spatula and transferred to another glass vial and allowed to thaw. Then, 10 μL of extraction solvent was diluted with mobile phase (1:1) and taken for HPLC-UV analysis. Parameters influencing the extraction efficiency, such as the kind and volume of extraction solvent, volume of sample, ultrasonication time, pH and salt concentration were thoroughly examined and optimized. Under the optimal conditions, the method showed good linearity in the concentration range of 0.05-500 ng mL(-1) with correlation coefficients ranging from 0.9948 to 0.9957 for the three target CAs. The limit of detection based on signal to noise ratio of 3 ranged from 0.01 to 0.1 ng mL(-1). The relative standard deviations (RSDs) varied from 2.1 to 6.1% (n=3) and the enrichment factors ranged from 44 to 124. The proposed method has also been successfully applied to analyze real water samples and the relative recoveries of environmental water samples ranged from 81.1 to 116.9%. Copyright © 2012 Elsevier B.V. All rights reserved.

Feasibility and technology for making remote measurements of solutes in water

USGS Publications Warehouse

Goldberg, Marvin C.; Weiner, Eugene R.

1977-01-01

An indepth evaluation of the available technology in the field of laser-Raman spectroscopy indicates that a TV-type detector, a single monochromator with a holographic grating, an entrance slit filter blocking the Rayleigh light, and a pulsed laser coupled to signal averaging electronics is the best combination of commercial equipment that is presently available for building a remote water-quality sensor. The resultant sensor would be capable of measuring oxyanions in water at concentrations from 10 to 50 milligrams per liter at distances from ground level to 30 meters above the sample. The main interferences would be ambient light, bioluminescence, and natural fluorescence, all of which are minimized when taking advantage of the signal generating and readout capability contained in this equipment package.

Molecularly imprinted polymer cartridges coupled on-line with high performance liquid chromatography for simple and rapid analysis of dextromethorphan in human plasma samples.

PubMed

Moein, Mohammad Mahdi; Javanbakht, Mehran; Akbari-Adergani, Behrouz

2011-04-01

In this paper, a novel method is described for automated determination of dextromethorphan in biological fluids using molecularly imprinted solid-phase extraction (MISPE) as a sample clean-up technique combined with high performance liquid chromatography (HPLC). The water-compatible molecularly imprinted polymers (MIPs) were prepared using methacrylic acid as functional monomer, ethylene glycol dimethacrylate as cross-linker, chloroform as porogen and dextromethorphan as template molecule. These imprinted polymers were used as solid-phase extraction sorbent for the extraction of dextromethorphan from human plasma samples. Various parameters affecting the extraction efficiency of the MIP cartridges were evaluated. The high selectivity of the sorbent coupled to the high performance liquid chromatographic system permitted a simple and rapid analysis of this drug in plasma samples with limits of detection (LOD) and quantification (LOQ) of 0.12 ng/mL and 0.35 ng/mL, respectively. The MIP selectivity was evaluated by analyzing of the dextromethorphan in presence of several substances with similar molecular structures and properties. Results from the HPLC analyses showed that the recoveries of dextromethorphan using MIP cartridges from human plasma samples in the range of 1-50 ng/mL were higher than 87%. Copyright © 2011 Elsevier B.V. All rights reserved.

On-line Differential Thermal Isotope Analysis: A New Method for Measuring Oxygen and Hydrogen Isotopes of Hydration Water in Minerals

NASA Astrophysics Data System (ADS)

Bauska, T.; Hodell, D. A.; Walters, G.

2016-12-01

Oxygen (16O,17O,18O) and hydrogen (H,D) isotopes of hydration water in minerals provide a rich source of information about the conditions under which hydrated minerals form on Earth and other planetary bodies (e.g. Mars). We have developed a new method for measuring different types of bonded water (e.g., molecular, hydroxyl) contained in hydrated minerals by coupling a thermal gravimeter (TG) and a cavity ringdown laser spectrometer (CRDS). The method involves step heating a mineral sample, precisely measuring the weight loss and enthalpy as the sample undergoes dehydration and dehydroxylation, whilst simultaneously determining the oxygen and hydrogen isotopes of the water vapor evolved from the mineral sample by cavity ring-down laser spectroscopy (CRDS). Nitrogen carrier gas is used to transfer the sample from the TG to the CRDS via a heated line and interface box. The interface includes the capability of (i) cryogenic trapping discrete types of water for samples containing small amounts of water; (ii) injecting small quantities of water of known isotopic value for calibration; and (iii) converting volatile organic compounds to nascent amounts of water using a catalyst. The CRDS continually measures water vapor concentration in the optical cavity and hydrogen and oxygen isotope ratios. Isotopic values are calculated by integrating the product of the water amount and its isotopic value for the separated peaks after correcting for background. Precision of the method was estimated by comparing isotope results of total water for gypsum measured by DTIA with our conventional method of extraction and analysis (Gázquez et al., 2015. Rapid Communications in Mass Spectrometry, 29, 1997-2006). Errors for the isotopic values of total hydration water vary between ±0.08 and ±0.34 ‰ for δ18O and between ±0.16 and ±0.86 ‰ for δD. We demonstrate the application of the DTIA method to a variety of hydrous minerals and mineraloids including gypsum, clays, and amorphous silica (opal, glass, chert). The DTIA method has wide ranging application for addressing fundamental problems across many disciplines in Earth and Planetary Sciences, including: paleoclimatology, sedimentology, volcanology, water exchange between the solid earth and hydrosphere, and water on Mars and other planetary bodies.

Application of multiwalled carbon nanotubes as sorbents for the extraction of mycotoxins in water samples and infant milk formula prior to high performance liquid chromatography mass spectrometry analysis.

PubMed

Socas-Rodríguez, Bárbara; González-Sálamo, Javier; Hernández-Borges, Javier; Rodríguez Delgado, Miguel Ángel

2016-05-01

In this work, a simple and environmental friendly methodology has been developed for the analysis of a group of six mycotoxins with estrogenic activity produced by Fusarium species (i.e. zearalanone, zearalenone, α-zearalanol, β-zearalanol, α-zearalenol, and β-zearalenol), using microdispersive SPE the symbol micro should de before dSPE with multiwalled carbon nanotubes as sorbent. Separation, determination, and quantification were achieved by HPLC coupled to ion trap MS with an ESI interface. Parameters affecting the extraction efficiency of µ-dSPE such as pH of the sample, amount of multiwalled carbon nanotubes, and type and volume of elution solvent, were studied and optimized. The methodology was validated for mineral, pond, and wastewater as well as for powdered infant milk using 17β-estradiol-2,4,16,16,17-d5 (17β-E2 -D5 ) as internal standard, obtaining recoveries ranging from 85 to 120% for the three types of water samples and from 77 to 115% for powdered infant milk. RSD values were lower than 10%. The LOQs achieved were in the range 0.05-2.90 μg/L for water samples and 2.02-31.9 μg/L for powdered infant milk samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Degradation products from naturally aged paper leaves of a 16th-century-printed book: a spectrochemical study.

PubMed

Bronzato, Maddalena; Calvini, Paolo; Federici, Carlo; Bogialli, Sara; Favaro, Gabriella; Meneghetti, Moreno; Mba, Miriam; Brustolon, Marina; Zoleo, Alfonso

2013-07-15

In this work, we present a wide-range spectrochemical analysis of the degradation products from naturally aged paper. The samples obtained from wash waters used during the de-acidification treatment of leaves from a 16th-century-printed book were analysed through NMR, IR, Raman UV/Vis, EPR and X-ray fluorescence (XRF) spectroscopy and HPLC-MS and inductively coupled plasma (ICP) analysis. By these methods we also studied some of the previous samples treated by acidification (sample AP) and catalytic hydrogenation (sample HP). Crossing all the data, we obtained precise indications about the main functional groups occurring on the degraded, water-soluble cellulose oligomers. These results point out that the chromophores responsible for browning are conjugated carbonyl and carboxyl compounds. As a whole, we show that the analysis of wash waters, used in the usual conservation treatments of paper de-acidification, gives much valuable information about both the conservation state of the book and the degradation reactions occurring on the leaves, due to the huge amount of cellulose by-products contained in the samples. We propose therefore this procedure as a new very convenient general method to obtain precious and normally unavailable information on the cellulose degradation by-products from naturally aged paper. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultra-sensitive speciation analysis of mercury by CE-ICP-MS together with field-amplified sample stacking injection and dispersive solid-phase extraction.

PubMed

Chen, YiQuan; Cheng, Xian; Mo, Fan; Huang, LiMei; Wu, Zujian; Wu, Yongning; Xu, LiangJun; Fu, FengFu

2016-04-01

A simple dispersive solid-phase extraction (DSPE) used to extract and preconcentrate ultra-trace MeHg, EtHg and Hg(2+) from water sample, and a sensitive method for the simultaneous analysis of MeHg, EtHg and Hg(2+) by using capillary electrophoresis-inductively coupled plasma mass spectrometry (CE-ICP-MS) with field-amplified sample stacking injection (FASI) were first reported in this study. The DSPE used thiol cotton particles as adsorbent, and is simple and effective. It can be used to extract and preconcentrate ultra-trace mercury compounds in water samples within 30 min with a satisfied recovery and no mercury species alteration during the process. The FASI enhanced the sensitivity of CE-ICP-MS with 25-fold, 29-fold and 27-fold for MeHg, EtHg and Hg(2+) , respectively. Using FASI-CE-ICP-MS together with DSPE, we have successfully determined ultra-trace MeHg, EtHg and Hg(2+) in tap water with a limits of quantification (LOQs) of 0.26-0.45 pg/mL, an RSD (n = 3) < 6% and a recovery of 92-108%. Ultra-high sensitivity, as well as much less sample and reagent consumption and low operating cost, make our method a valuable technique to the speciation analysis of ultra-trace mercury. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Size exclusion chromatography with online ICP-MS enables molecular weight fractionation of dissolved phosphorus species in water samples.

PubMed

Venkatesan, Arjun K; Gan, Wenhui; Ashani, Harsh; Herckes, Pierre; Westerhoff, Paul

2018-04-15

Phosphorus (P) is an important and often limiting element in terrestrial and aquatic ecosystem. A lack of understanding of its distribution and structures in the environment limits the design of effective P mitigation and recovery approaches. Here we developed a robust method employing size exclusion chromatography (SEC) coupled to an ICP-MS to determine the molecular weight (MW) distribution of P in environmental samples. The most abundant fraction of P varied widely in different environmental samples: (i) orthophosphate was the dominant fraction (93-100%) in one lake, two aerosols and DOC isolate samples, (ii) species of 400-600 Da range were abundant (74-100%) in two surface waters, and (iii) species of 150-350 Da range were abundant in wastewater effluents. SEC-DOC of the aqueous samples using a similar SEC column showed overlapping peaks for the 400-600 Da species in two surface waters, and for >20 kDa species in the effluents, suggesting that these fractions are likely associated with organic matter. The MW resolution and performance of SEC-ICP-MS agreed well with the time integrated results obtained using conventional ultrafiltration method. Results show that SEC in combination with ICP-MS and DOC has the potential to be a powerful and easy-to-use method in identifying unknown fractions of P in the environment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Micromachined ultrasonic transducers for air-coupled nondestructive evaluation

NASA Astrophysics Data System (ADS)

Hansen, Sean T.; Degertekin, F. Levent; Khuri-Yakub, Butrus T.

1999-01-01

Conventional methods of ultrasonic non-destructive evaluation (NDE) use liquids to couple sound waves into the test samples. This either requires immersion of the parts to be examined or the use of complex and bulky water squirting systems that must be scanned over the structure. Air-coupled ultrasonic systems eliminate these requirements if the losses at air-solid interfaces are tolerable. Micromachined capacitive ultrasonic transducers (cMUTs) have been shown to have more than 100 dB dynamic range when used in the bistatic transmission mode. In this paper, we present results of a pitch-catch transmission system using cMUTs that achieves a 103 dB dynamic range. Each transducer consists of 10,000 silicon nitride membranes of 100 micrometers diameter connected in parallel. This geometry result in transducers with a resonant frequency around 2.3 MHz. These transducers can be used in transmission experiments at normal incident to the sample or to excite and detect guided waves in aluminum and composite plates. In this paper we present ultrasonic defect detection results from both through transmission and guided Lamb wave experiments in aluminum and composite plates, such as those used in aircraft.

Fast Determination of Toxic Arsenic Species in Food Samples Using Narrow-bore High-Performance Liquid-Chromatography Inductively Coupled Plasma Mass Spectrometry.

PubMed

Terol, Amanda; Marcinkowska, Monika; Ardini, Francisco; Grotti, Marco

2016-01-01

A new method for the speciation analysis of arsenic in food using narrow-bore high-performance liquid-chromatography inductively coupled plasma mass spectrometry (HPLC-ICP-MS) has been developed. Fast separation of arsenite, arsenate, monomethylarsonic acid and dimethylarsinic acid was carried out in 7 min using an anion-exchange narrow-bore Nucleosil 100 SB column and 12 mM ammonium dihydrogen phosphate of pH 5.2 as the mobile phase, at a flow rate of 0.3 mL min(-1). A PFA-ST micronebulizer jointed to a cyclonic spray chamber was used for HPLC-ICP-MS coupling. Compared with standard-bore HPLC-ICP-MS, the new method has provided higher sensitivity, reduced mobile-phase consumption, a lower matrix plasma load and a shorter analysis time. The achieved instrumental limits of detection were in the 0.3 - 0.4 ng As mL(-1) range, and the precision was better than 3%. The arsenic compounds were efficiently (>80%) extracted from various food samples using a 1:5 methanol/water solution, with additional ultrasonic treatment for rice products. The applicability of this method was demonstrated by the analysis of several samples, such as seafood (fish, mussels, shrimps, edible algae) and rice-based products (Jasmine and Arborio rice, spaghetti, flour, crackers), including three certified reference materials.

ACCELERATED SOLVENT EXTRACTION COMBINED WITH ...

EPA Pesticide Factsheets

A research project was initiated to address a recurring problem of elevated detection limits above required risk-based concentrations for the determination of semivolatile organic compounds in high moisture content solid samples. This project was initiated, in cooperation with the EPA Region 1 Laboratory, under the Regional Methods Program administered through the ORD Office of Science Policy. The aim of the project was to develop an approach for the rapid removal of water in high moisture content solids (e.g., wetland sediments) in preparation for analysis via Method 8270. Alternative methods for water removal have been investigated to enhance compound solid concentrations and improve extraction efficiency, with the use of pressure filtration providing a high-throughput alternative for removal of the majority of free water in sediments and sludges. In order to eliminate problems with phase separation during extraction of solids using Accelerated Solvent Extraction, a variation of a water-isopropanol extraction method developed at the USGS National Water Quality Laboratory in Denver, CO is being employed. The concentrations of target compounds in water-isopropanol extraction fluids are subsequently analyzed using an automated Solid Phase Extraction (SPE)-GC/MS method developed in our laboratory. The coupled approaches for dewatering, extraction, and target compound identification-quantitation provide a useful alternative to enhance sample throughput for Me

Analysis of PAEs contaminants in water sources for agriculture, industrial and residential areas from local city district

NASA Astrophysics Data System (ADS)

Chen, Qidan; Chen, Qixian; Wu, Fei; Liao, Jia; Zhao, Xi

2018-02-01

The technology of DEHP and DBP detection by high performance liquid chromatography coupled with ultraviolet detection (HPLC-UV) was developed and applied in analysis of local water sources from agriculture, industrial and residential areas. Under the optimized sample pretreatment and detection conditions, DEHP and DBP were well separated and detected in 4 mins. The detection limit of DBP was 0.002 mg/L and DEHP was 0.006 mg/L, and it meets the Chinese National Standard limitations for drinking water quality. The linear correlation coefficient of DBP and DEHP standard calibration curves was 0.9998 and 0.9995. The linear range of DBP was 0.020 mg/L ∼20.0 mg/L, with the standard deviation of 0.560% ∼5.07%, and the linear range of DEHP was 0.060 mg/L ∼15.0 mg/L, with the standard deviation of 0.546% ∼5.74%. Ten water samples from Jinwan district of Zhuhai in Guangdong province of China were analyzed. However, the PAEs amounts found in the water sources from industrial areas were higher than the agriculture and residential areas, industries grow incredibly fast in the district in recently years and more attention should be paid to the increasing risks of water sources pollution.

Coupling of the hydration water dynamics and the internal dynamics of actin detected by quasielastic neutron scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fujiwara, Satoru, E-mail: fujiwara.satoru@jaea.go.jp; Plazanet, Marie; Oda, Toshiro

2013-02-15

Highlights: ► Quasielastic neutron scattering spectra of F-actin and G-actin were measured. ► Analysis of the samples in D{sub 2}O and H{sub 2}O provided the spectra of hydration water. ► The first layer hydration water around F-actin is less mobile than around G-actin. ► This difference in hydration water is in concert with the internal dynamics of actin. ► Water outside the first layer behaves bulk-like but influenced by the first layer. -- Abstract: In order to characterize dynamics of water molecules around F-actin and G-actin, quasielastic neutron scattering experiments were performed on powder samples of F-actin and G-actin, hydratedmore » either with D{sub 2}O or H{sub 2}O, at hydration ratios of 0.4 and 1.0. By combined analysis of the quasielastic neutron scattering spectra, the parameter values characterizing the dynamics of the water molecules in the first hydration layer and those of the water molecules outside of the first layer were obtained. The translational diffusion coefficients (D{sub T}) of the hydration water in the first layer were found to be 1.2 × 10{sup −5} cm{sup 2}/s and 1.7 × 10{sup −5} cm{sup 2}/s for F-actin and G-actin, respectively, while that for bulk water was 2.8 × 10{sup −5} cm{sup 2}/s. The residence times were 6.6 ps and 5.0 ps for F-actin and G-actin, respectively, while that for bulk water was 0.62 ps. These differences between F-actin and G-actin, indicating that the hydration water around G-actin is more mobile than that around F-actin, are in concert with the results of the internal dynamics of F-actin and G-actin, showing that G-actin fluctuates more rapidly than F-actin. This implies that the dynamics of the hydration water is coupled to the internal dynamics of the actin molecules. The D{sub T} values of the water molecules outside of the first hydration layer were found to be similar to that of bulk water though the residence times are strongly affected by the first hydration layer. This supports the recent observation on intracellular water that shows bulk-like behavior.« less

Solid-phase microextraction based on polyaniline doped with perfluorooctanesulfonic acid coupled to HPLC for the quantitative determination of chlorophenols in water samples.

PubMed

He, Huan; Zhuang, Yuan; Peng, Ying; Gao, Zhanqi; Yang, Shaogui; Sun, Cheng

2014-02-01

A porous and highly efficient polyaniline-based solid-phase microextraction (SPME) coating was successfully prepared by the electrochemical deposition method. A method based on headspace SPME followed by HPLC was established to rapidly determine trace chlorophenols in water samples. Influential parameters for the SPME, including extraction mode, extraction temperature and time, pH and ionic strength procedures, were investigated intensively. Under the optimized conditions, the proposed method was linear in the range of 0.5-200 μg/L for 4-chlorophenol and 2,4,6-trichlorophenol, 0.2-200 μg/L for 2,4-dichlorophenol and 2-200 μg/L for 2,3,4,6-tetrachlorophenol and pentachlorophenol, with satisfactory correlation coefficients (>0.99). RSDs were <15% (n = 5) and LODs were relatively low (0.10-0.50 μg/L). Compared to commercial 85 μm polyacrylate and 60 μm polydimethylsiloxane/divinylbenzene fibers, the homemade polyaniline fiber showed a higher extraction efficiency. The proposed method has been successfully applied to the determination of chlorophenols in water samples with satisfactory recoveries. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Exogenous contamination of uranium in human scalp hair.

PubMed

Muikku, Maarit; Heikkinen, Tarja

2012-06-01

The use of human scalp hair as a bioindicator of occupational or environmental exposure has been the subject of some debate over the years. One problem is how to distinguish internal contamination from external contamination. In this study, possibility that elevated levels of natural uranium in human hair are partly due to the exogenously bound uranium from uranium-rich household water was tested. Hair samples from six adult volunteers were cut and then exposed externally to uranium by using washing water with highly elevated levels of natural uranium. After that, and before making the analysis using inductively coupled plasma mass spectrometry (ICP-MS), the samples were washed using two commonly used washing procedures in order to remove external contamination. No quantitative information was gained in the tests, but it was shown that the use of uranium-rich water when washing hair affects the uranium concentration in hair. Although the samples were cleaned according to widely used washing procedures before the analysis, the uranium concentrations in hair were about three orders of magnitude higher after the tests. The possibility of external contamination should be kept in mind, especially when considering hair as an excretion pathway for estimating internal dose.

Combination of artificial neural network and genetic algorithm method for modeling of methylene blue adsorption onto wood sawdust from water samples.

PubMed

Khajeh, Mostafa; Sarafraz-Yazdi, Ali; Natavan, Zahra Bameri

2016-03-01

The aim of this research was to develop a low price and environmentally friendly adsorbent with abundant of source to remove methylene blue (MB) from water samples. Sawdust solid-phase extraction coupled with high-performance liquid chromatography was used for the extraction and determination of MB. In this study, an experimental data-based artificial neural network model is constructed to describe the performance of sawdust solid-phase extraction method for various operating conditions. The pH, time, amount of sawdust, and temperature were the input variables, while the percentage of extraction of MB was the output. The optimum operating condition was then determined by genetic algorithm method. The optimized conditions were obtained as follows: 11.5, 22.0 min, 0.3 g, and 26.0°C for pH of the solution, extraction time, amount of adsorbent, and temperature, respectively. Under these optimum conditions, the detection limit and relative standard deviation were 0.067 μg L(-1) and <2.4%, respectively. The Langmuir and Freundlich adsorption models were applied to describe the isotherm constant and for the removal and determination of MB from water samples. © The Author(s) 2013.

Graphene oxide bonded fused-silica fiber for solid-phase microextraction-gas chromatography of polycyclic aromatic hydrocarbons in water.

PubMed

Xu, Lili; Feng, Juanjuan; Li, Jubai; Liu, Xia; Jiang, Shengxiang

2012-01-01

A novel chemically bonded graphene oxide/fused-silica fiber was prepared and applied in solid-phase microextraction of six polycyclic aromatic hydrocarbons from water samples coupled with gas chromatography. It exhibited high extraction efficiency and excellent stability. Effects of extraction time, extraction temperature, ionic strength, stirring rate and desorption conditions were investigated and optimized in our work. Detection limits to the six polycyclic aromatic hydrocarbons were less than 0.08 μg/L, and their calibration curves were all linear (R(2)≥0.9954) in the range from 0.05 to 200 μg/L. Single fiber repeatability and fiber-to-fiber reproducibility were less than 6.13 and 15.87%, respectively. This novel fiber was then utilized to analyze two real water samples from the Yellow River and local waterworks, and the recoveries of samples spiked at 1 and 10 μg/L ranged from 84.48 to 118.24%. Compared with other coating materials, this graphene oxide-coated fiber showed many advantages: wide linear range, low detection limit, and good stability in acid, alkali, organic solutions and at high temperature. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coupling of solvent-based de-emulsification dispersive liquid-liquid microextraction with high performance liquid chromatography for simultaneous simple and rapid trace monitoring of 2,4-dichlorophenoxyacetic acid and 2-methyl-4-chlorophenoxyacetic acid.

PubMed

Behbahani, Mohammad; Najafi, Fatemeh; Bagheri, Saman; Bojdi, Majid Kalate; Hassanlou, Parmoon Ghareh; Bagheri, Akbar

2014-04-01

A simple, rapid, and efficient sample pretreatment technique, based on solvent-based de-emulsification dispersive liquid-liquid microextraction (SD-DLLME), followed by high performance liquid chromatography (HPLC) has been developed for simultaneous preconcentration and trace detection of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2-methyl-4-chlorophenoxyacetic acid (MCPA) in water and urine samples. Some parameters such as acidity of solution, the amount of salt, type, and volume of extraction solvents, type of disperser/de-emulsifier solvent, and its volume were investigated and optimized. Under optimum extraction conditions, the limits of detections (LODs) of this method for MCPA and 2,4-D were 0.2 and 0.6 μg L(-1) (based on 3S(b)/m) in water and 0.4 and 1.6 μg L(-1) in urine, respectively. Furthermore, dynamic linear range of this method for MCPA and 2,4-D was 1-300 and 2-400 μg L(-1), repectively. Finally, the applicability of the proposed method was evaluated by extraction and determination of the herbicides in urine and different water samples.

Fast automated dual-syringe based dispersive liquid-liquid microextraction coupled with gas chromatography-mass spectrometry for the determination of polycyclic aromatic hydrocarbons in environmental water samples.

PubMed

Guo, Liang; Tan, Shufang; Li, Xiao; Lee, Hian Kee

2016-03-18

An automated procedure, combining low density solvent based solvent demulsification dispersive liquid-liquid microextraction (DLLME) with gas chromatography-mass spectrometry analysis, was developed for the determination of polycyclic aromatic hydrocarbons (PAHs) in environmental water samples. Capitalizing on a two-rail commercial autosampler, fast solvent transfer using a large volume syringe dedicated to the DLLME process, and convenient extract collection using a small volume microsyringe for better GC performance were enabled. Extraction parameters including the type and volume of extraction solvent, the type and volume of dispersive solvent and demulsification solvent, extraction and demulsification time, and the speed of solvent injection were investigated and optimized. Under the optimized conditions, the linearity ranged from 0.1 to 50 μg/L, 0.2 to 50 μg/L, and 0.5 to 50 μg/L, depending on the analytes. Limits of detection were determined to be between 0.023 and 0.058 μg/L. The method was applied to determine PAHs in environmental water samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Comparison pesticide residue levels in the surface of Bertam River in Cameron Highlands, Pahang

NASA Astrophysics Data System (ADS)

Haron, S. H.; Ismail B., S.

2015-09-01

The presence of pesticide residues in the surface water of Bertam River in the agricultural areas of Cameron Highlands in Pahang, Malaysia was monitored from May to October 2014. The sampling sites were located at 10 sampling points along the Bertam River in the vegetable planting areas. The extraction method of the pesticide (organophosphate/pyrethroid) from the river samples used solid phase extraction followed by gas chromatography (with electron capture detector, ECD). Insecticides, cypermethrin and chlorpyrifos were found in the surface water of Bertam River. High level concentrations of those insecticides in the river were observed during the period from May to October 2014, a period which included both seasons (wet and dry seasons). The highest concentration of 2.66 µg/mL and 1.23 µg/mL of cypermethrin was observed during the wet and dry seasons respectively. This could be due to the frequent usage of the above-mentioned insecticides coupled with contamination that could have originated from the application sites. Meanwhile, the lowest concentration detected in the surface water was chlorpyrifos (0.11 µg/mL and 0.17 µg/mL) during the dry and wet seasons, respectively.

Optimizations of packed sorbent and inlet temperature for large volume-direct aqueous injection-gas chromatography to determine high boiling volatile organic compounds in water.

PubMed

Yu, Bofan; Song, Yonghui; Han, Lu; Yu, Huibin; Liu, Yang; Liu, Hongliang

2014-08-22

For the expanded application area, fast trace analysis of certain high boiling point (i.e., 150-250 °C) volatile organic compounds (HVOCs) in water, a large volume-direct aqueous injection-gas chromatography (LV-DAI-GC) method was optimized for the following parameters: packed sorbent for sample on-line pretreatment, inlet temperature and detectors configuration. Using the composite packed sorbent self-prepared with lithium chloride and a type of diatomite, the method enabled safe injection of an approximately 50-100 μL sample at an inlet temperature of 150 °C in the splitless mode and separated HVOCs from water matrix in 2 min. Coupled with a flame ionization detector (FID), an electron capture detector (ECD) and a flame photometric detector (FPD), the method could simultaneously quantify 27 HVOCs that belong to seven subclasses (i.e., halogenated aliphatic hydrocarbons, chlorobenzenes, nitrobenzenes, anilines, phenols, polycyclic aromatic hydrocarbons and organic sulfides) in 26 min. Injecting a 50 μL sample without any enrichment step, such as cryotrap focusing, the limits of quantification (LOQs) for the 27 HVOCs was 0.01-3 μg/L. Replicate analyses of the 27 HVOCs spiked source and river water samples exhibited good precision (relative standard deviations ≤ 11.3%) and accuracy (relative errors ≤ 17.6%). The optimized LV-DAI-GC was robust and applicable for fast determination and automated continuous monitoring of HVOCs in surface water. Copyright © 2014 Elsevier B.V. All rights reserved.

Development of an automated method for determining oil in water by direct aqueous supercritical fluid extraction coupled on-line with infrared spectroscopy.

PubMed

Minty, B; Ramsey, E D; Davies, I

2000-12-01

A direct aqueous supercritical fluid extraction (SFE) system was developed which can be directly interfaced to an infrared spectrometer for the determination of oil in water. The technique is designed to provide an environmentally clean, automated alternative to established IR methods for oil in water analysis which require the use of restricted organic solvents. The SFE-FTIR method involves minimum sample handling stages, with on-line analysis of a 500 ml water sample being complete within 15 min. Method accuracy for determining water samples spiked with gasoline, white spirit, kerosene, diesel or engine oil was 81-100% with precision (RSD) ranging from 3 to 17%. An independent evaluation determined a 2 ppm limit of quantification for diesel in industrial effluents. The results of a comparative study involving an established IR method and the SFE-FTIR method indicate that oil levels calculated using an accepted equation which includes coefficients derived from reference hydrocarbon standards may result in significant errors. A new approach permitted the derivation of quantification coefficients for the SFE-FTIR analyses which provided improved results. In situations where the identity of the oil to be analysed is known, a rapid off-line SFE-FTIR system calibration procedure was developed and successfully applied to various oils. An optional in-line silica gel clean-up procedure incorporated within the SFE-FTIR system enables the same water sample to be analysed for total oil content including vegetable oils and selectively for petroleum oil content within a total of 20 min. At the end of an analysis the SFE system is cleaned using an in situ 3 min clean cycle.

Effect of Sodium Bisulfite Injection on the Microbial Community Composition in a Brackish-Water-Transporting Pipeline▿†

PubMed Central

Park, Hyung Soo; Chatterjee, Indranil; Dong, Xiaoli; Wang, Sheng-Hung; Sensen, Christoph W.; Caffrey, Sean M.; Jack, Thomas R.; Boivin, Joe; Voordouw, Gerrit

2011-01-01

Pipelines transporting brackish subsurface water, used in the production of bitumen by steam-assisted gravity drainage, are subject to frequent corrosion failures despite the addition of the oxygen scavenger sodium bisulfite (SBS). Pyrosequencing of 16S rRNA genes was used to determine the microbial community composition for planktonic samples of transported water and for sessile samples of pipe-associated solids (PAS) scraped from pipeline cutouts representing corrosion failures. These were obtained from upstream (PAS-616P) and downstream (PAS-821TP and PAS-821LP, collected under rapid-flow and stagnant conditions, respectively) of the SBS injection point. Most transported water samples had a large fraction (1.8% to 97% of pyrosequencing reads) of Pseudomonas not found in sessile pipe samples. The sessile population of PAS-616P had methanogens (Methanobacteriaceae) as the main (56%) community component, whereas Deltaproteobacteria of the genera Desulfomicrobium and Desulfocapsa were not detected. In contrast, PAS-821TP and PAS-821LP had lower fractions (41% and 0.6%) of Methanobacteriaceae archaea but increased fractions of sulfate-reducing Desulfomicrobium (18% and 48%) and of bisulfite-disproportionating Desulfocapsa (35% and 22%) bacteria. Hence, SBS injection strongly changed the sessile microbial community populations. X-ray diffraction analysis of pipeline scale indicated that iron carbonate was present both upstream and downstream, whereas iron sulfide and sulfur were found only downstream of the SBS injection point, suggesting a contribution of the bisulfite-disproportionating and sulfate-reducing bacteria in the scale to iron corrosion. Incubation of iron coupons with pipeline waters indicated iron corrosion coupled to the formation of methane. Hence, both methanogenic and sulfidogenic microbial communities contributed to corrosion of pipelines transporting these brackish waters. PMID:21856836

What is safe and clean water in rural Bolivian communities? A preliminary investigation of heavy metal contamination in rural community water systems in the Bolivian Altiplano

NASA Astrophysics Data System (ADS)

Borella, M.; Guido, Z.; Borella, P.; Ketron, T.

2009-12-01

A proliferation of potable water systems utilizing groundwater is currently underway in the Lake Titicaca region of the Bolivian Altiplano. With the aid of national and international organizations, rural communities are developing groundwater sources because the region’s surface water is highly contaminated with waterborne pathogens—the primary factor contributing to high child mortality rates in developing nations. According to UNICEF, 86 percent of Bolivian families have access to “improved” water systems, which predominantly take the form of deep groundwater wells or contained natural springs. While the water systems have worked well to reduce pathogens in drinking water systems that cause illnesses such as dysentery, the water is rarely tested for heavy metal contamination, such as arsenic and lead. While bacteria analysis is essential, it is not the only component of healthy drinking water. Testing for heavy metals is especially important in the Bolivian Altiplano because abundant volcanic deposits and massive sulfide deposits suggest that in some areas it is likely that the water contains elevated concentrations of heavy metals. In this study, Terra Resource Development International, A California-based 502(c)3 nonprofit organization, partnered with Stanford University, the Technical University of Bolivia, and the Bolivian Geologic and Mining Survey to collect water samples in 36 rural community situated in four watersheds feeding into Lake Titicaca. Water was collected from shallow, hand dug wells, deep groundwater wells, springs, and small rivers in the Tiwanku, Laja, Batallas, Achacachi watersheds and were analyzed for inorganic contaminants. Samples were analyzed at Stanford’s Environmental Measurements Facility using the Inductively Coupled Plasma (ICP) Spectrometer for major ions and heavy metals. Results will help determine which, if any, community water systems are at risk of heavy metal contamination, where more comprehensive sampling is needed, and will inform Bolivian water managers of the potential need for heavy metal analysis.

Interventions and Interactions: Understanding Coupled Human-Water Dynamics for Improved Water Resources Management in the Himalayas

NASA Astrophysics Data System (ADS)

Crootof, A.

2017-12-01

Understanding coupled human-water dynamics offers valuable insights to address fundamental water resources challenges posed by environmental change. With hydropower reshaping human-water interactions in mountain river basins, there is a need for a socio-hydrology framework—which examines two-way feedback loops between human and water systems—to more effectively manage water resources. This paper explores the cross-scalar interactions and feedback loops between human and water systems in river basins affected by run-of-the-river hydropower and highlights the utility of a socio-hydrology perspectives to enhance water management in the face of environmental change. In the Himalayas, the rapid expansion of run-of-the-river hydropower—which diverts streamflow for energy generation—is reconfiguring the availability, location, and timing of water resources. This technological intervention in the river basin not only alters hydrologic dyanmics but also shapes social outcomes. Using hydropower development in the highlands of Uttarakhand, India as a case study, I first illustrate how run-of-the-river projects transform human-water dynamics by reshaping the social and physical landscape of a river basin. Second, I emphasize how examining cross-scalar feedbacks among structural dynamics, social outcomes, and values and norms in this coupled human-water system can inform water management. Third, I present hydrological and social literature, raised separately, to indicate collaborative research needs and knowledge gaps for coupled human-water systems affected by run-of-the-river hydropower. The results underscore the need to understand coupled human-water dynamics to improve water resources management in the face of environmental change.

The optical lens coupled X-ray in-line phase contrast imaging system for the characterization of low Z materials

NASA Astrophysics Data System (ADS)

Wang, Kai; Lin, Wei; Dai, Fei; Li, Jun; Qi, Xiaobo; Lei, Haile; Liu, Yuanqiong

2018-05-01

Due to the high spatial resolution and contrast, the optical lens coupled X-ray in-line phase contrast imaging system with the secondary optical magnification is more suitable for the characterization of the low Z materials. The influence of the source to object distance and the object to scintillator distance on the image resolution and contrast is studied experimentally. A phase correlation algorithm is used for the image mosaic of a serial of X-ray phase contrast images acquired with high resolution, the resulting resolution is less than 1.0 μm, and the whole field of view is larger than 1.4 mm. Finally, the geometric morphology and the inner structure of various weakly absorbing samples and the evaporation of water in the plastic micro-shell are in situ characterized by the optical lens coupled X-ray in-line phase contrast imaging system.

Deciphering groundwater quality for irrigation and domestic purposes - a case study in Suri I and II blocks, Birbhum District, West Bengal, India

NASA Astrophysics Data System (ADS)

Das, Shreya; Nag, S. K.

2015-07-01

Assessment of the hydrochemical characteristics of water and aquifer hydraulic properties is important for groundwater planning and management in the study area. It is not only the basic need for human existence but also a vital input for all development activities. The present hydro-geochemical study of groundwater samples from the Suri I and II blocks of Birbhum district, West Bengal (23.76 ∘-23.99 ∘N; 87.42 ∘-87.64 ∘E) was carried out to assess their suitability for agricultural, domestic and drinking purposes. For this study, samples were collected from 26 locations during the post-monsoon and pre-monsoon sessions spanning over 2012 and 2013. Groundwater samples were analyzed for their physical and chemical properties using standard laboratory methods. Physical and chemical parameters of groundwater such as pH, electrical conductivity, total dissolved solids, Na, K, Ca, Mg, Fe, Cl, HCO3, SO4 and F were determined. Various water quality indices like SAR, SSP, PI, RSC, MAR and KR have been calculated for each water sample to identify the irrigational suitability standard. According to most of these parameters, the groundwater has been found to be well to moderately suitable for irrigation. In the post-monsoon session exceptionally high RSC values for around 80% samples indicate an alkaline hazard to the soil. The ion balance histogram for post-monsoon indicates undesirable ion balance values according to fresh water standards whereas in pre-monsoon, the samples show good ion balance in water. For determination of the drinking suitability standard of groundwater, three parameters have been considered - total hardness (TH), Piper's trilinear diagram and water quality index study. Groundwater of the present study area has been found to be moderately-hard to hard during both sampling sessions and hence poses no health risk which could arise due to excess consumption of calcium or magnesium. Hydrogeochemical facies in the form of Piper's trilinear diagram plot which helps in identification of the water `type' which can render a particular taste or odour to water, indicates that groundwater in the study area is majorly of CaMgHCO 3 and NaHCO 3 type (fresh type) during both post-monsoon and pre-monsoon sessions barring a couple of samples which are of CaMgSO 4/CaMgClSO 4 type in pre-monsoon. Water quality index study reveals that close to 90% of the water samples are suitable for drinking during post-monsoon compared to pre-monsoon during which period only 60% of water samples fall under the suitable drinking water category. Gibbs' diagrams, which help in identification of natural processes controlling hydrogeochemistry of groundwater indicates that for both post-monsoon and pre-monsoon sessions, the overall hydrogeochemistry of the study area is dominated by rock-water interaction processes.

Assessment of drinking water quality using ICP-MS and microbiological methods in the Bholakpur area, Hyderabad, India.

PubMed

Abdul, Rasheed M; Mutnuri, Lakshmi; Dattatreya, Patil J; Mohan, Dayal A

2012-03-01

A total of 16 people died and over 500 people were hospitalized due to diarrhoeal illness in the Bholakpur area of Hyderabad, India on 6th May 2009. A study was conducted with immediate effect to evaluate the quality of municipal tap water of the Bholakpur locality. The study consists of the determination of physico-chemical properties, trace metals, heavy metals, rare earth elements and microbiological quality of drinking water. The data showed the variation of the investigated parameters in samples as follows: pH 7.14 to 8.72, EC 455 to 769 μS/cm, TDS 303.51 to 515.23 ppm and DO 1.01 to 6.83 mg/L which are within WHO guidelines for drinking water quality. The water samples were analyzed for 27 elements (Li, Be, B, Na, Mg, Al, Si, K, Ca, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, As, Se, Rb, Sr, Mo, Ag, Cd, Sb, Ba and Pb) using inductively coupled plasma-mass spectrometry (ICP-MS). The concentrations of Fe (0.12 to 1.13 mg/L), Pb (0.01 to 0.07 mg/L), Cu (0.01 to 0.19 mg/L), Ni (0.01 to 0.15 mg/L), Al (0.16 to 0.49 mg/L), and Na (38.36 to 68.69 mg/L) were obtained, which exceed the permissible limits of the World Health Organization (WHO) for drinking water quality guidelines. The remaining elements were within the permissible limits. The microbiological quality of water was tested using standard plate count, membrane filtration technique, thermotolerant coliform (TTC), and most probable number (MPN) methods. The total heterotrophic bacteria ranged from 1.0 × 10(5) to 18 × 10(7 )cfu/ml. Total viable bacteria in all the water samples were found to be too numerable to count and total number of coliform bacteria in all water samples were found to be of order of 1,100 to >2,400 MPN index/100 ml. TTC tested positive for coliform bacteria at 44.2°C. All the water samples of the study area exceeded the permissible counts of WHO and that (zero and minimal counts) of the control site (National Geophysical Research Institute) water samples. Excessively high colony numbers indicate that the water is highly contaminated with microorganisms and is hazardous for drinking purposes. Bacteriological pollution of drinking water supplies caused diarrhoeal illness in Bholakpur, which is due to the infiltration of contaminated water (sewage) through cross connection, leakage points, and back siphoning.

Authentication of Kalix (N.E. Sweden) vendace caviar using inductively coupled plasma-based analytical techniques: evaluation of different approaches.

PubMed

Rodushkin, I; Bergman, T; Douglas, G; Engström, E; Sörlin, D; Baxter, D C

2007-02-05

Different analytical approaches for origin differentiation between vendace and whitefish caviars from brackish- and freshwaters were tested using inductively coupled plasma double focusing sector field mass spectrometry (ICP-SFMS) and multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). These approaches involve identifying differences in elemental concentrations or sample-specific isotopic composition (Sr and Os) variations. Concentrations of 72 elements were determined by ICP-SFMS following microwave-assisted digestion in vendace and whitefish caviar samples from Sweden (from both brackish and freshwater), Finland and USA, as well as in unprocessed vendace roe and salt used in caviar production. This data set allows identification of elements whose contents in caviar can be affected by salt addition as well as by contamination during production and packaging. Long-term method reproducibility was assessed for all analytes based on replicate caviar preparations/analyses and variations in element concentrations in caviar from different harvests were evaluated. The greatest utility for differentiation was demonstrated for elements with varying concentrations between brackish and freshwaters (e.g. As, Br, Sr). Elemental ratios, specifically Sr/Ca, Sr/Mg and Sr/Ba, are especially useful for authentication of vendace caviar processed from brackish water roe, due to the significant differences between caviar from different sources, limited between-harvest variations and relatively high concentrations in samples, allowing precise determination by modern analytical instrumentation. Variations in the 87Sr/86Sr ratio for vendace caviar from different harvests (on the order of 0.05-0.1%) is at least 10-fold less than differences between caviar processed from brackish and freshwater roe. Hence, Sr isotope ratio measurements (either by ICP-SFMS or by MC-ICP-MS) have great potential for origin differentiation. On the contrary, it was impossible to differentiate between Swedish caviar processed from brackish water roe and Finnish freshwater caviar based solely on 187Os/188Os ratios.

Co-occurrence profiles of trace elements in potable water systems: a case study.

PubMed

Andra, Syam S; Makris, Konstantinos C; Charisiadis, Pantelis; Costa, Costas N

2014-11-01

Potable water samples (N = 74) from 19 zip code locations in a region of Greece were profiled for 13 trace elements composition using inductively coupled plasma mass spectrometry. The primary objective was to monitor the drinking water quality, while the primary focus was to find novel associations in trace elements occurrence that may further shed light on common links in their occurrence and fate in the pipe scales and corrosion products observed in urban drinking water distribution systems. Except for arsenic at two locations and in six samples, rest of the analyzed elements was below maximum contaminant levels, for which regulatory values are available. Further, we attempted to hierarchically cluster trace elements based on their covariances resulting in two groups; one with arsenic, antimony, zinc, cadmium, and copper and the second with the rest of the elements. The grouping trends were partially explained by elements' similar chemical activities in water, underscoring their potential for co-accumulation and co-mobilization phenomena from pipe scales into finished water. Profiling patterns of trace elements in finished water could be indicative of their load on pipe scales and corrosion products, with a corresponding risk of episodic contaminant release. Speculation was made on the role of disinfectants and disinfection byproducts in mobilizing chemically similar trace elements of human health interest from pipe scales to tap water. It is warranted that further studies may eventually prove useful to water regulators from incorporating the acquired knowledge in the drinking water safety plans.

Factorial design optimization of experimental variables in the on-line separation/preconcentration of copper in water samples using solid phase extraction and ICP-OES determination.

PubMed

Escudero, Luis A; Cerutti, S; Olsina, R A; Salonia, J A; Gasquez, J A

2010-11-15

An on-line preconcentration procedure using solid phase extraction (SPE) for the determination of copper in different water samples by inductively coupled plasma optical emission spectrometry (ICP-OES) is proposed. The copper was retained on a minicolumn filled with ethyl vinyl acetate (EVA) at pH 8.0 without using any complexing reagent. The experimental optimization step was performed using a two-level full factorial design. The results showed that pH, sample loading flow rate, and their interaction (at the tested levels) were statistically significant. In order to determine the best conditions for preconcentration and determination of copper, a final optimization of the significant factors was carried out using a central composite design (CCD). The calibration graph was linear with a regression coefficient of 0.995 at levels near the detection limit up to at least 300 μg L(-1). An enrichment factor (EF) of 54 with a preconcentration time of 187.5 s was obtained. The limit of detection (3σ) was 0.26 μg L(-1). The sampling frequency for the developed methodology was about 15 samples/h. The relative standard deviation (RSD) for six replicates containing 50 μg L(-1) of copper was 3.76%. The methodology was successfully applied to the determination of Cu in tap, mineral, river water samples, and in a certified VKI standard reference material. Copyright © 2010 Elsevier B.V. All rights reserved.

Field-Integrated Studies of Long-Term Sustainability of Chromium Bioreduction at Hanford 100H Site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Long, Philip E.

2006-06-01

The objectives of the project are to investigate coupled hydraulic, geochemical, and microbial conditions, and to determine the critical biogeochemical parameters necessary to maximize the extent of Cr(VI) bioreduction and minimize Cr(III) reoxidation in groundwater. Specific goals of the project are as follows: (1) Field testing and monitoring of Cr(VI) bioreduction in ground water and its transformation into insoluble species of Cr(III) at the Hanford 100H site, to develop the optimal strategy of water sampling for chemical, microbial, stable isotope analyses, and noninvasive geophysical monitoring; (2) Bench-scale flow and transport investigations using columns of undisturbed sediments to obtain diffusion andmore » kinetic parameters needed for the development of a numerical model, predictions of Cr(VI) bioreduction, and potential of Cr(III) reoxidation; and (3) Development of a multiphase, multi-component 3D reactive transport model and a code, TOUGHREACT-BIO, to predict coupled biogeochemical-hydrological processes associated with bioremediation, and to calibrate and validate the developed code based on the results of bench-scale and field-scale Cr(VI) biostimulation experiments in ground water at the Hanford Site.« less

Zero valent Fe-reduced graphene oxide quantum dots as a novel magnetic dispersive solid phase microextraction sorbent for extraction of organophosphorus pesticides in real water and fruit juice samples prior to analysis by gas chromatography-mass spectrometry.

PubMed

Akbarzade, Samaneh; Chamsaz, Mahmoud; Rounaghi, Gholam Hossein; Ghorbani, Mahdi

2018-01-01

A selective and sensitive magnetic dispersive solid-phase microextraction (MDSPME) coupled with gas chromatography-mass spectrometry was developed for extraction and determination of organophosphorus pesticides (Sevin, Fenitrothion, Malathion, Parathion, and Diazinon) in fruit juice and real water samples. Zero valent Fe-reduced graphene oxide quantum dots (rGOQDs@ Fe) as a new and effective sorbent were prepared and applied for extraction of organophosphorus pesticides using MDSPME method. In order to study the performance of this new sorbent, the ability of rGOQDs@ Fe was compared with graphene oxide and magnetic graphene oxide nanocomposite by recovery experiments of the organophosphorus pesticides. Several affecting parameters in the microextraction procedure, including pH of donor phase, donor phase volume, stirring rate, extraction time, and desorption conditions such as the type and volume of solvents and desorption time were thoroughly investigated and optimized. Under the optimal conditions, the method showed a wide linear dynamic range with R-square between 0.9959 and 0.9991. The limit of detections, the intraday and interday relative standard deviations (n = 5) were less than 0.07 ngmL -1 , 4.7, and 8.6%, respectively. The method was successfully applied for extraction and determination of organophosphorus pesticides in real water samples (well, river and tap water) and fruit juice samples (apple and grape juice). The obtained relative recoveries were in the range of 82.9%-113.2% with RSD percentages of less than 5.8% for all the real samples.

Small Scale Characterization of the Presence of the Explosive Octahydro-1,3,5,7-tetranitro- 1,3,5,7 tetrazocine (HMX) Near Former Naval Sites on Vieques Island, Puerto Rico

NASA Astrophysics Data System (ADS)

Simmons, C. C.; Carvalho-Knighton, K. M.; Pyrtle, A. J.

2007-12-01

Octahydro-1,3,5,7-tetranitro-1,3,5,7 tetrazocine (HMX) is a synthetic energetic compounds that has been commonly used in military munitions. The presence and movement of HMX through the environment is of growing concern because of potential civilian exposure and impacts on human health. HMX remains in the environment unreactive with little degradation. It can be transported great distances in water thus having the possibility for migrating into groundwater. The former naval sites in Vieques were used for weapons training and housed several disposal sites. Previous studies around these sites indicate the presence of radioactive materials produced through thermal fission, such as Cs-137. Since HMX was primarily used to implode fissionable materials in nuclear devices, evaluating the release of HMX and consequent movement through the environment at these sites is essential. Surface water and soil samples as well as core and pore water samples were collected from two sites in Vieques; Kiani Lagoon and Mosquito Bay. All samples were extracted using EPA method 8330 and analyzed using RP-HPLC analysis with a C-18 column. HMX was undetected in samples collected from both Kiani Lagoon and Mosquito Bay. The development of a model that studies the flow rates and fate of water runoff in these areas of interest, coupled with data on groundwater testing inside the actual former naval facilities, is being explored for further sample collection and analysis.

MCX based solid phase extraction combined with liquid chromatography tandem mass spectrometry for the simultaneous determination of 31 endocrine-disrupting compounds in surface water of Shanghai.

PubMed

Zhang, Hong-Chang; Yu, Xue-jun; Yang, Wen-chao; Peng, Jin-feng; Xu, Ting; Yin, Da-Qiang; Hu, Xia-lin

2011-10-15

A novel analytical method employing MCX (mixed-mode cationic exchange) based solid phase extraction (SPE) coupled with liquid chromatography tandem mass spectrometry (LC-MS/MS) was developed to detect 31 endocrine-disrupting compounds (EDCs) in surface water samples simultaneously. The target EDCs belong to five classes, including seven estrogens, eight androgens, six progesterones, five adrenocortical hormones and five industrial compounds. In order to simultaneously concentrate the target EDCs and eliminate matrix interferences in the water samples, MCX SPE cartridges were employed for SPE, and then followed by a simple and highly efficient three-step sequential elution procedure. Two electrospray ionization (ESI) detection modes, positive (ESI+) and (ESI-), were optimized for HPLC-MS/MS analysis to obtain the highest sensitivity for all the EDCs. The limits of detection (LODs) were 0.02-1.9 ng L(-1), which are lower than or comparable to these reported in references. Wide linear ranges (LOD-100 ng L(-1) for ESI+ mode, and LOD-200 ng L(-1) for ESI- mode) were obtained with determination coefficients (R(2)) higher than 0.99 for all the compounds. With five internal standards, good recoveries (84.4-103.0%) of all the target compounds were obtained in selected surface water samples. The developed method was successfully applied to investigate the EDCs occurrence in the surface water of Shanghai by analyzing surface water samples from 11 sites. The results showed that nearly all the target compounds (30 in 31) were present in the surface water samples of Shanghai, of which three industrial compounds (4-t-OP, BPA, and BPF) showed the highest concentrations (median concentrations were 11.88-23.50 ng L(-1)), suggesting that industrial compounds were the dominating EDCs in the surface water of Shanghai, and much more attention should be paid on these compounds. Our present research demonstrated that SPE with MCX cartridges combined with HPLC-MS/MS was convenient, efficient and reliable for multiclass analysis of EDCs in surface water. Copyright © 2011 Elsevier B.V. All rights reserved.

Study on the Relationship between Manganese Concentrations in Rural Drinking Water and Incidence and Mortality Caused by Cancer in Huai'an City

PubMed Central

Zhang, Qin; Pan, Enchun; Liu, Linfei; Hu, Wei; He, Yuan; Xu, Qiujin; Liang, Cunzhen

2014-01-01

Background. Cancer is a significant disease burden in the world. Many studies showed that heavy metals or their compounds had connection with cancer. But the data conflicting about the relationship of manganese (Mn) to cancer are not enough. In this paper, the relationship was discussed between Mn concentrations in drinking water for rural residents and incidence and mortality caused by malignant tumors in Huai'an city. Methods. A total of 158 water samples from 28 villages of 14 towns were, respectively, collected during periods of high flow and low flow in 3 counties of Huai'an city, along Chinese Huai'he River. The samples of deep groundwater, shallow groundwater, and surface water were simultaneously collected in all selected villages. Mn concentrations in all water samples were determined by inductively coupled plasma-mass spectrometry (ICP-MS 7500a). The correlation analysis was used to study the relationship between the Mn concentration and cancer incidence and mortality. Results. Mn concentrations detectable rate was 100% in all water samples. The mean concentration was 452.32 μg/L ± 507.76 μg/L. There was significant difference between the high flow period and low flow period (t = −5.23, P < 0.05) and also among deep groundwater, shallow groundwater, and surface water (F = 5.02, P < 0.05). The ratio of superscale of Mn was 75.32%. There was significant difference of Mn level between samples in the high flow period and low flow period (χ 2 = 45.62, P < 0.05) and also among deep groundwater, shallow groundwater, and surface water (χ 2 = 10.66, P < 0.05). And also we found that, during the low flow period, Mn concentration has positive correlation with cancer incidence and mortality; for a 1 μg/L increase in Mn concentration, there was a corresponding increase of 0.45/100000 new cancer cases and 0.35/100000 cancer deaths (P < 0.05). Conclusions. In Huai'an city, the mean concentration of Mn in drinking water was very high. Mn concentration correlated with cancer incidence and mortality. PMID:25530966

Study on the relationship between manganese concentrations in rural drinking water and incidence and mortality caused by cancer in Huai'an city.

PubMed

Zhang, Qin; Pan, Enchun; Liu, Linfei; Hu, Wei; He, Yuan; Xu, Qiujin; Liang, Cunzhen

2014-01-01

Cancer is a significant disease burden in the world. Many studies showed that heavy metals or their compounds had connection with cancer. But the data conflicting about the relationship of manganese (Mn) to cancer are not enough. In this paper, the relationship was discussed between Mn concentrations in drinking water for rural residents and incidence and mortality caused by malignant tumors in Huai'an city. A total of 158 water samples from 28 villages of 14 towns were, respectively, collected during periods of high flow and low flow in 3 counties of Huai'an city, along Chinese Huai'he River. The samples of deep groundwater, shallow groundwater, and surface water were simultaneously collected in all selected villages. Mn concentrations in all water samples were determined by inductively coupled plasma-mass spectrometry (ICP-MS 7500a). The correlation analysis was used to study the relationship between the Mn concentration and cancer incidence and mortality. Mn concentrations detectable rate was 100% in all water samples. The mean concentration was 452.32 μg/L ± 507.76 μg/L. There was significant difference between the high flow period and low flow period (t = -5.23, P < 0.05) and also among deep groundwater, shallow groundwater, and surface water (F = 5.02, P < 0.05). The ratio of superscale of Mn was 75.32%. There was significant difference of Mn level between samples in the high flow period and low flow period (χ(2) = 45.62, P < 0.05) and also among deep groundwater, shallow groundwater, and surface water (χ(2) = 10.66, P < 0.05). And also we found that, during the low flow period, Mn concentration has positive correlation with cancer incidence and mortality; for a 1 μg/L increase in Mn concentration, there was a corresponding increase of 0.45/100000 new cancer cases and 0.35/100000 cancer deaths (P < 0.05). In Huai'an city, the mean concentration of Mn in drinking water was very high. Mn concentration correlated with cancer incidence and mortality.

Spatial Variability of Benthic-Pelagic Coupling in an Estuary Ecosystem: Consequences for Microphytobenthos Resuspension Phenomenon

PubMed Central

Ubertini, Martin; Lefebvre, Sébastien; Gangnery, Aline; Grangeré, Karine; Le Gendre, Romain; Orvain, Francis

2012-01-01

The high degree of physical factors in intertidal estuarine ecosystem increases material processing between benthic and pelagic compartments. In these ecosystems, microphytobenthos resuspension is a major phenomenon since its contribution to higher trophic levels can be highly significant. Understanding the sediment and associated microphytobenthos resuspension and its fate in the water column is indispensable for measuring the food available to benthic and pelagic food webs. To identify and hierarchize the physical/biological factors potentially involved in MPB resuspension, the entire intertidal area and surrounding water column of an estuarine ecosystem, the Bay des Veys, was sampled during ebb tide. A wide range of physical parameters (hydrodynamic regime, grain size of the sediment, and suspended matter) and biological parameters (flora and fauna assemblages, chlorophyll) were analyzed to characterize benthic-pelagic coupling at the bay scale. Samples were collected in two contrasted periods, spring and late summer, to assess the impact of forcing variables on benthic-pelagic coupling. A mapping approach using kriging interpolation enabled us to overlay benthic and pelagic maps of physical and biological variables, for both hydrological conditions and trophic indicators. Pelagic Chl a concentration was the best predictor explaining the suspension-feeders spatial distribution. Our results also suggest a perennial spatio-temporal structure of both benthic and pelagic compartments in the ecosystem, at least when the system is not imposed to intense wind, with MPB distribution controlled by both grain size and bathymetry. The benthic component appeared to control the pelagic one via resuspension phenomena at the scale of the bay. Co-inertia analysis showed closer benthic-pelagic coupling between the variables in spring. The higher MPB biomass observed in summer suggests a higher contribution to filter-feeders diets, indicating a higher resuspension effect in summer than in spring, in turn suggesting an important role of macrofauna bioturbation and filter feeding (Cerastoderma edule). PMID:22952910

In tube-solid phase microextraction-nano liquid chromatography: Application to the determination of intact and degraded polar triazines in waters and recovered struvite.

PubMed

Serra-Mora, P; Jornet-Martinez, N; Moliner-Martinez, Y; Campíns-Falcó, P

2017-09-01

In-tube solid-phase microextraction (IT-SPME) coupled to miniaturized liquid chromatography (LC) techniques are attractive mainly due to the column efficiency improvement, sensitivity enhancement and reduction of solvent consumption. In addition, the nanomaterials based sorbents can play a key role in the improvement of the extraction efficiency taking into account their interesting physical and chemical properties. Thus, in this work the performance of IT-SPME coupled to nano LC (NanoLC) has been compared with the performance of IT-SPME coupled to capillary LC (CapLC) with similar configurations for the determination of polar triazines including their degradation products. In both cases, a DAD detector was used. Different extractive phases such as TRB-5, TRB-5/c-SWNTs, TRB-5/c-MWNTs capillary columns have been tested. The dimensions of the capillary columns were 0.32mm id×40cm length and 0.1 or 0.075mm i.d.×15cm length for the couplings with CapLC and NanoLC, respectively. The processed volume was 4mL for CapLC and 0.5mL for NanoLC. The elution was carried out with ACN:H 2 O (30:70, v/v). IT-SPME-NanoLC has shown a higher performance than IT-SPME-CapLC for the target analytes demonstrating the enhancement of the extraction efficiency with the former configuration. A new phase TEOS-MTEOS-SiO 2 NPs has been also proposed for IT-SPME-NanoLC, which improves the retention of polar compounds. Compared with previously published works, improved LODs were achieved (0.025-0.5μgL -1 ). The practical application of the proposed procedure has been demonstrated for the analysis of water samples and recovered struvite samples from wastewater treatment plants. Therefore, the proposed procedure can be an alternative method for regulatory purposes. Copyright © 2017 Elsevier B.V. All rights reserved.

Hot-water and solid-phase extraction of fluorescent whitening agents in paper materials and infant clothes followed by unequivocal determination with ion-pair chromatography-tandem mass spectrometry.

PubMed

Chen, Hsin-Chang; Ding, Wang-Hsien

2006-03-10

A comprehensive method for the determination of four stilbene-type disulfonate and one distyrylbiphenyl-type fluorescent whitening agents (FWAs) in paper materials (napkin and paper tissue) and infant clothes was developed. FWAs were extracted from paper material and cloth samples using a hot-water extraction, and the aqueous extracts were then preconcentrated with the newly developed Oasis WAX (mixed-mode of weak anion exchange and reversed-phase sorbent) solid-phase extraction cartridge. The analytes were unequivocal determined by ion pair chromatography coupled with negative electrospray ionization-tandem mass spectrometry (HPLC-ESI-MS-MS), applying a di-n-hexyl-ammonium acetate (DHAA) as the ion-pairing reagent in mobile phase. Limits of quantitation (LOQ) were established between 0.2 and 0.9 ng/g in 2 g of samples. Recovery of five FWAs in spiked commercial samples was between 42 and 95% and RSD (n = 3) ranging from 2 to 11%. The method was finally applied to commercial samples, showing that two stilbene-type disulfonates were predominant FWAs detected in napkin and infant cloth samples.

Magnetic solid phase extraction and static headspace gas chromatography-mass spectrometry method for the analysis of polycyclic aromatic hydrocarbons.

PubMed

Cai, Ying; Yan, Zhihong; Wang, Lijia; NguyenVan, Manh; Cai, Qingyun

2016-01-15

A magnetic solid phase extraction (MSPE) protocol combining a static headspace gas chromatography coupled to mass spectrometry (HS-GC-MS) method has been developed for extraction, and determination of 16 polycyclic aromatic hydrocarbons (PAHs) in drinking water samples. Magnetic nanoparticles (MNPs) were coated with 3-aminopropyltriethoxysilane and modified by cholesterol chloroformate. Transmission electron microscope, vibrating sample magnetometer, Fourier transform infrared spectrometry and X-ray photoelectron spectroscopy were used to characterize the cholesterol-functionalized sorbents, and the main parameters affecting the extraction as well as HS sampling, such as sorbent amount, extraction time, oven temperature and equilibration time have been investigated and established. Combination with HS sampling, the MSPE procedure was simple, fast and environmentally friendly, without need of any organic solvent. Method validation proved the feasibility of the developed sorbents for the quantitation of the investigated analytes at trace levels obtaining the limit of detection (S/N=3) ranging from 0.20 to 7.8 ng/L. Good values for intra and inter-day precision were obtained (RSDs ≤ 9.9%). The proposed method was successfully applied to drinking water samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Condenser-type diffusion denuders for the collection of sulfur dioxide in a cleanroom.

PubMed

Chang, In-Hyoung; Lee, Dong Soo; Ock, Soon-Ho

2003-02-01

High-efficiency condenser-type diffusion denuders of cylindrical and planar geometries are described. The film condensation of water vapor onto a cooled denuder surface can be used as a method for collecting water-soluble gases. By using SO(2) as the test gas, the planar design offers quantitative collection efficiency at air sampling rates up to 5 L min(-1). Coupled to ion chromatography, the limit of detection (LOD) for SO(2) is 0.014 ppbv with a 30-min successive analysis sequence. The method has been successfully applied to the analysis of temperature- and humidity-controlled cleanroom air.

Dual-cloud point extraction coupled to high performance liquid chromatography for simultaneous determination of trace sulfonamide antimicrobials in urine and water samples.

PubMed

Nong, Chunyan; Niu, Zongliang; Li, Pengyao; Wang, Chunping; Li, Wanyu; Wen, Yingying

2017-04-15

Dual-cloud point extraction (dCPE) was successfully developed for simultaneous extraction of trace sulfonamides (SAs) including sulfamerazine (SMZ), sulfadoxin (SDX), sulfathiazole (STZ) in urine and water samples. Several parameters affecting the extraction were optimized, such as sample pH, concentration of Triton X-114, extraction temperature and time, centrifugation rate and time, back-extraction solution pH, back-extraction temperature and time, back-extraction centrifugation rate and time. High performance liquid chromatography (HPLC) was applied for the SAs analysis. Under the optimum extraction and detection conditions, successful separation of the SAs was achieved within 9min, and excellent analytical performances were attained. Good linear relationships (R 2 ≥0.9990) between peak area and concentration for SMZ and STZ were optimized from 0.02 to 10μg/mL, for SDX from 0.01 to 10μg/mL. Detection limits of 3.0-6.2ng/mL were achieved. Satisfactory recoveries ranging from 85 to 108% were determined with urine, lake and tap water spiked at 0.2, 0.5 and 1μg/mL, respectively, with relative standard deviations (RSDs, n=6) of 1.5-7.7%. This method was demonstrated to be convenient, rapid, cost-effective and environmentally benign, and could be used as an alternative tool to existing methods for analysing trace residues of SAs in urine and water samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Trace analysis of glyphosate in water by capillary electrophoresis on a chip with high sample volume loadability.

PubMed

Horčičiak, Michal; Masár, Marián; Bodor, Róbert; Danč, Ladislav; Bel, Peter

2012-03-01

A new method for the determination of trace glyphosate (GLYP), non-selective pesticide, by CZE with online ITP pre-treatment of drinking waters on a column-coupling (CC) chip has been developed. CC chip was equipped with two injection channels of 0.9 and 9.9 μL volumes, two separation channels of 9.3 μL total volume and a pair of conductivity detectors. A very effective ITP sample clean-up performed in the first channel at low pH (3.2) was introduced for quick CZE resolution and detection of GLYP carried out at higher pH (6.1) in the second channel on the CC chip. The LOD for GLYP was estimated at 2.5 μg/L (15 nmol/L) using a 9.9 |mL volume of the injection channel. ITP-CZE analyses of model and real samples have provided very favorable intra-day (0.1-1.2% RSD) and inter-day (2.9% RSD) repeatabilities of the migration time for GLYP while 0.2-6.9% RSD values were typical for the peak area data. Recoveries of GLYP in spiked drinking water varied in the range of 99-109%. A minimum pre-treatment of drinking water (degassing and dilution) and a short analysis time (ca. 10 min) were distinctive features of ITP-CZE determinations of GLYP on the CC chip with high sample volume loaded, as well. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of C18 composite solid-phase microextraction fiber and its application to the determination of organochlorine pesticides in water samples.

PubMed

Li, Siyan; Lu, Chengwei; Zhu, Fang; Jiang, Ruifen; Ouyang, Gangfeng

2015-05-11

In this work, a C18 composite solid-phase microextraction (SPME) fiber was prepared with a new method and applied to the analysis of organochlorine pesticides (OCPs) in water sample. A stainless steel wire (o.d. 127 μm) was used as the substrate, and a mixture of the C18 particle (3.5 μm) and the 184 silicone was used as the coating material. During the process of fiber preparation, a section of capillary column was used to fix the mixture onto the stainless steel wire and to ensure the constant of coating thickness. The prepared fiber showed excellent thermal stability and solvent resistance. By coupling with gas chromatography-mass spectrometry (GC-MS), the fiber exhibited wide linearity (2-500 ng L(-1)) and good sensitivity for the determination of six OCPs in water samples, the OCPs tested included hexachlorobezene, trans-chlordane, cis-chlordane, o,p-DDT, p,p-DDT and mirex. Not only the extraction performance of the newly prepared fiber was more than seven times higher than those of commercial fibers, the limits of detections (LODs) (0.059-0.151 ng L(-1)) for OCPs achieved under optimized conditions were also lower than those of reported SPME methods. The fiber was successfully applied to the determination of OCPs in real water samples by using developed SPME-GC-MS method. Copyright © 2015 Elsevier B.V. All rights reserved.

Online analysis of five organic ultraviolet filters in environmental water samples using magnetism-enhanced monolith-based in-tube solid phase microextraction coupled with high-performance liquid chromatography.

PubMed

Mei, Meng; Huang, Xiaojia

2017-11-24

Due to the endocrine disrupting properties, organic UV filters have been a great risk for humans and other organisms. Therefore, development of accurate and effective analytical methods is needed for the determination of UV filters in environmental waters. In this work, a fast, sensitive and environmentally friendly method combining magnetism-enhanced monolith-based in-tube solid phase microextraction with high-performance liquid chromatography with diode array detection (DAD) (ME-MB-IT/SPME-HPLC-DAD) for the online analysis of five organic UV filters in environmental water samples was developed. To extract UV filters effectively, an ionic liquid-based monolithic capillary column doped with magnetic nanoparticles was prepared by in-situ polymerization and used as extraction medium of online ME-MB-IT/SPME-HPLC-DAD system. Several extraction conditions including the intensity of magnetic field, sampling and desorption flow rate, volume of sample and desorption solvent, pH value and ionic strength of sample matrix were optimized thoroughly. Under the optimized conditions, the extraction efficiencies for five organic UV filters were in the range of 44.0-100%. The limits of detection (S/N=3) and limits of quantification (S/N=10) were 0.04-0.26μg/L and 0.12-0.87μg/L, respectively. The precisions indicated by relative standard deviations (RSDs) were less than 10% for both intra- and inter-day variabilities. Finally, the developed method was successfully applied to the determination of UV filters in three environmental water samples and satisfactory results were obtained. Copyright © 2017 Elsevier B.V. All rights reserved.

A simple distillation method to extract bromine from natural water and salt samples for isotope analysis by multi-collector inductively coupled plasma mass spectrometry.

PubMed

Eggenkamp, H G M; Louvat, P

2018-04-30

In natural samples bromine is present in trace amounts, and measurement of stable Br isotopes necessitates its separation from the matrix. Most methods described previously need large samples or samples with high Br/Cl ratios. The use of metals as reagents, proposed in previous Br distillation methods, must be avoided for multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) analyses, because of risk of cross-contamination, since the instrument is also used to measure stable isotopes of metals. Dedicated to water and evaporite samples with low Br/Cl ratios, the proposed method is a simple distillation that separates bromide from chloride for isotopic analyses by MC-ICP-MS. It is based on the difference in oxidation potential between chloride and bromide in the presence of nitric acid. The sample is mixed with dilute (1:5) nitric acid in a distillation flask and heated over a candle flame for 10 min. The distillate (bromine) is trapped in an ammonia solution and reduced to bromide. Chloride is only distilled to a very small extent. The obtained solution can be measured directly by MC-ICP-MS for stable Br isotopes. The method was tested for a variety of volumes, ammonia concentrations, pH values and distillation times and compared with the classic ion-exchange chromatography method. The method more efficiently separates Br from Cl, so that samples with lower Br/Cl ratios can be analysed, with Br isotope data in agreement with those obtained by previous methods. Unlike other Br extraction methods based on oxidation, the distillation method presented here does not use any metallic ion for redox reactions that could contaminate the mass spectrometer. It is efficient in separating Br from samples with low Br/Cl ratios. The method ensures reproducible recovery yields and a long-term reproducibility of ±0.11‰ (1 standard deviation). The distillation method was successfully applied to samples with low Br/Cl ratios and low Br amounts (down to 20 μg). Copyright © 2018 John Wiley & Sons, Ltd.

Determination of cadmium and lead at low levels by using preconcentration at fullerene coupled to thermospray flame furnace atomic absorption spectrometry

NASA Astrophysics Data System (ADS)

Pereira, M. G.; Pereira-Filho, E. R.; Berndt, H.; Arruda, M. A. Z.

2004-04-01

A new and sensitive method for Cd and Pb determinations, based on the coupling of thermospray flame furnace atomic absorption spectrometry and a preconcentrator system, was developed. The procedure comprised the chelating of Cd and Pb with ammonium pyrrolidinedithiocarbamate with posterior adsorption of the chelates on a mixture (40 mg) of C 60 and C 70 at a flow rate of 2.0 ml min -1. These chelates were eluted from the adsorbent by passing a continuous flow of ethanol (80% v/v) at 0.9 ml min -1 to a nickel tube placed in an air/acetylene flame. After sample introduction into the tube by using a ceramic capillary (0.5 mm i.d.), the analytical signals were registered as peak height. Under these conditions, improvement factors in detectability of 675 and 200 were obtained for Cd and Pb, respectively, when compared to conventional flame atomic absorption spectrometry. Spiked samples (mineral and tap waters) and drinking water containing natural concentrations of Cd were employed for evaluating accuracy by comparing the results obtained from the proposed methodology with those using electrothermal atomic absorption spectrometry. In addition, certified reference materials (rye grass, CRM 281 and pig kidney, CRM 186) were also adopted for the accuracy tests. Due to the good linearity ranges for Cd (0.5-5.0 μg l -1) and Pb (10-250 μg l -1), samples with different concentrations could be analyzed. Detection limits of 0.1 and 2.4 μg l -1 were obtained for Cd and Pb, respectively, and RSD values <4.5% were observed ( n=10). Finally, a sample throughput of 24 determinations per hour was possible.

Application of dispersive liquid-liquid microextraction coupled with vortex-assisted hydrophobic magnetic nanoparticles based solid-phase extraction for determination of aflatoxin M1 in milk samples by sensitive micelle enhanced spectrofluorimetry.

PubMed

Amoli-Diva, Mitra; Taherimaslak, Zohreh; Allahyari, Mehdi; Pourghazi, Kamyar; Manafi, Mohammad Hanif

2015-03-01

An efficient, simple and fast low-density solvent based dispersive liquid-liquid microextraction (LDS-DLLME) followed by vortex-assisted dispersive solid phase extraction (VA-D-SPE) has been developed as a new approach for extraction and preconcentration of aflatoxin M1 in milk samples prior to its micelle enhanced spectrofluorimetic determination. In this LDS-DLLME coupled VA-D-SPE method, milk samples were first treated with methanol/water (80:20, v/v) after removing the fat layer. This solvent was directly used as the dispersing solvent in DLLME along with using 1-heptanol (as a low-density solvent with respect to water) as the extracting solvent. In VA-D-SPE approach, hydrophobic oleic acid modified Fe3O4 nanoparticles were used to retrieve the analyte from the DLLME step. It is considerably that the target of VA-D-SPE was 1-heptanol rather than the aflatoxin M1 directly. The main parameters affecting the efficiency of LDS-DLLME and VA-D-SPE procedures and signal enhancement of aflatoxin M1 were investigated and optimized. Under the optimum conditions, the method was linear in the range from 0.02 to 200 µg L(-1) with the correlation coefficient (R(2)) of 0.9989 and detection limit of 13 ng L(-1). The intra-day precision was 2.9 and 4.3% and the inter-day precision was 2.1 and 3.3% for concentration of 2 and 50 µg L(-1) respectively. The developed method was applied for extraction and preconcentration of AFM1 in three commercially available milk samples and the results were compared with the official AOAC method. Copyright © 2014 Elsevier B.V. All rights reserved.

Membrane filtration immobilization technique-a simple and novel method for primary isolation and enrichment of bacteriophages.

PubMed

Ghugare, G S; Nair, A; Nimkande, V; Sarode, P; Rangari, P; Khairnar, K

2017-02-01

To develop a method for the isolation and enrichment of bacteriophages selectively against specific bacteria coupled with a membrane filtration technique. Rapid isolation and concentration of host-specific bacteriophages was achieved by exposure of the sample suspected to contain bacteriophages to a specific host immobilized on a 0·45 μm membrane in a membrane filtration unit. The principle behind this method is the exploitation of host-specific interaction of bacteriophages with their host and maximizing this interaction using a classic membrane filtration method. This provides a chance for each bacteriophage in the sample to interact with the specific host on the membrane filter fitted with a vacuum pump. Specific bacteriophages of the host are retained on the membrane along with its host cells due to the effect of adsorption and these adsorbed bacteriophages (along with their hosts) on the filter disc are then amplified and enriched in regular nutritive broth tryptose soya broth by incubation. With the help of the plaque assay method, host-specific phages of various bacterial species were isolated, segregated and enriched. The phage concentration method coupled with membrane filtration immobilization of host bacteria was able to isolate and enrich the host-specific bacteriophages by several fold using a lower quantity of an environmental water sample, or other phage suspensions. Enrichment of phages from single plaques was also achieved. The isolation and detection of host-specific bacteriophages from a low density bacteriophage water sample in a single step by the use of a simple and basic microbiological technique can be achieved. Enrichment of phages from low phage titre suspensions is also achieved very effectively. © 2016 The Society for Applied Microbiology.

Perfluoroalkyl substances assessment in drinking waters from Brazil, France and Spain.

PubMed

Schwanz, Thiago G; Llorca, Marta; Farré, Marinella; Barceló, Damià

2016-01-01

Human exposure to perfluoroalkyl substances (PFASs) occurs primarily via dietary intake and drinking water. In this study, 16 PFASs have been assessed in 96 drinking waters (38 bottled waters and 58 samples of tap water) from Brazil, France and Spain. The total daily intake and the risk index (RI) of 16 PFASs through drinking water in Brazil, France and Spain have been estimated. This study was carried out using an analytical method based on an online sample enrichment followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). The quality parameters of the analytical method were satisfactory for the analysis of the 16 selected compounds in drinking waters. Notably, the method limits of detection (MLOD) and method limits of quantification (MLOQ) were in the range of 0.15 to 8.76ng/l and 0.47 to 26.54ng/l, respectively. The results showed that the highest PFASs concentrations were found in tap water samples and the more frequently found compound was perfluorooctanesulfonic acid (PFOS), with mean concentrations of 7.73, 15.33 and 15.83ng/l in French, Spanish and Brazilian samples, respectively. In addition, PFOS was detected in all tap water samples from Brazil. The highest level of PFASs contamination in a single sample was 140.48ng/l in a sample of Spanish tap water. In turn, in bottled waters the highest levels were detected in a French sample with 116ng/l as the sum of PFASs. Furthermore, the most frequent compounds and those at higher concentrations were perfluoroheptanoic acid (PFHpA) with a mean of frequencies in the three countries of 51.3%, followed by perfluorobutanesulfonic acid (PFBS) (27.2%) and perfluorooctanoic acid (PFOA) (23.0%). Considering that bottled water is approximately 38% of the total intake, the total PFASs exposure through drinking water intake for an adult man was estimated to be 54.8, 58.0 and 75.6ng/person per day in Spain, France and Brazil, respectively. However, assuming that the water content in other beverages has at least the same levels of contamination as in bottled drinking water, these amounts were increased to 72.2, 91.4 and 121.0ng/person per day for an adult man in Spain, France and Brazil, respectively. The results of total daily intake in different gender/age groups showed that children are the most exposed population group through hydration with maximum values in Brazil of 2.35 and 2.01ng/kg body weight (BW)/day for male and female, respectively. Finally, the RI was calculated. In spite of the highest values being found in Brazil, it was demonstrated that, in none of the investigated countries, drinking water pose imminent risk associated with PFASs contamination. Copyright © 2015 Elsevier B.V. All rights reserved.

Magnetic susceptibility as a proxy for the hydrobiogeochemical cycling of iron within the water table fluctuation zone at hydrocarbon contaminated sites

NASA Astrophysics Data System (ADS)

Atekwana, E. A.; Enright, A.; Atekwana, E. A.; Beaver, C. L.; Rossbach, S.; Slater, L. D.; Ntarlagiannis, D.

2016-12-01

Sharp redox gradients are indicative of enhanced biogeochemical activity and occur at or near the water table. Hydrologic forcing drives changes in redox state and oxygen levels, enhancing the elemental cycling of metals, and coupling different biogeochemical cycles. These coupled hydrobiogeochemical cycles are often difficult to study in the field using geochemical and microbial proxies because of direct sampling limitations, the costs associated with these techniques, and because the dynamic nature of these processes complicates the interpretation of single time point measurements, which may not give accurate representations of prevailing conditions. Geophysical techniques can provide both the spatial and temporal resolution needed to elucidate these processes. Here we investigated the use of magnetic susceptibility (c) as a viable proxy for understanding the biogeochemical cycling of iron at several hydrocarbon contaminated sites where active intrinsic bioremediation is occurring. We performed borehole c logging using a Bartington c probe in the field as well as made c measurements on core samples retrieved from the field sites. Our results show the following: (1) in both sulfate-rich and sulfate-poor aquifers, excursions in c are coincident with zones of free product contamination and are limited to the water table fluctuation (smear) zone; (2) c values within the free product plume and contamination source zones are higher compared to values within the dissolved product plume; (3) high c coincides with zones of elevated Fe (II) and Fe (III) concentrations extracted from aquifer solids; and (4) the mixed valence magnetite and greigite were the dominant magnetic minerals. The c excursions are limited to the water table fluctuation zones because fluctuating water level conditions are hot beds for microbial activity due to the steep hydrocarbon and nutrients and consequently redox gradients. High water levels during periods of recharge favor anaerobic conditions enhancing iron reduction, while low water conditions during drought periods favor iron oxidation due to increased oxygen penetration. Such conditions favor mixed valent iron minerals such as magnetite and greigite. We conclude that c measurements are a low cost, rapid monitoring tool for assessing the elemental cycling of iron.

Malignant human cell transformation of Marcellus Shale gas drilling flow back water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yao, Yixin; Department of Environmental Medicine, New York University School of Medicine, Tuxedo, NY 10987; Chen, Tingting

The rapid development of high-volume horizontal hydraulic fracturing for mining natural gas from shale has posed potential impacts on human health and biodiversity. The produced flow back waters after hydraulic stimulation are known to carry high levels of saline and total dissolved solids. To understand the toxicity and potential carcinogenic effects of these wastewaters, flow back waters from five Marcellus hydraulic fracturing oil and gas wells were analyzed. The physicochemical nature of these samples was analyzed by inductively coupled plasma mass spectrometry and scanning electron microscopy/energy dispersive X-ray spectroscopy. A cytotoxicity study using colony formation as the endpoint was carriedmore » out to define the LC{sub 50} values of test samples using human bronchial epithelial cells (BEAS-2B). The BEAS-2B cell transformation assay was employed to assess the carcinogenic potential of the samples. Barium and strontium were among the most abundant metals in these samples and the same metals were found to be elevated in BEAS-2B cells after long-term treatment. BEAS-2B cells treated for 6 weeks with flow back waters produced colony formation in soft agar that was concentration dependent. In addition, flow back water-transformed BEAS-2B cells show better migration capability when compared to control cells. This study provides information needed to assess the potential health impact of post-hydraulic fracturing flow back waters from Marcellus Shale natural gas mining. - Highlights: • This is the first report of potential cytotoxicity and transforming activity of Marcellus shale gas mining flow back to mammalian cells. • Barium and Strontium were elevated in flow back water exposed cells. • Flow back water malignantly transformed cells and formed tumor in athymic nude mice. • Flow back transformed cells exhibited altered transcriptome with dysregulated cell migration pathway and adherent junction pathway.« less

Considerations on ultra-trace analysis of phthalates in drinking water.

PubMed

Serôdio, P; Nogueira, J M F

2006-07-01

Stir bar sorptive extraction with liquid desorption followed by large volume injection and capillary gas chromatography coupled to mass spectrometry (SBSE-LD/LVI-GC-MS), had been applied for the determination of ultra-traces of seven-phthalates (dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, butyl benzyl phthalate, bis(2-ethylhexyl) adipate, bis(2-ethylhexyl) phthalate and bis(1-octyl) phthalate) in drinking water samples, which are included in the priority lists set by several international regulatory organizations. Instrumental calibration under the selected-ion monitoring mode acquisition (LVI-GC-MS(SIM)), experimental parameters that could affect the SBSE-LD efficiency, as well as, the control of the contamination profile are fully discussed. Throughout systematic assays on 30 mL water samples spiked at the 0.40 microg/L level, it had been established that stir bars coated with 47 microL of polydimethylsiloxane, an equilibrium time of 60 min (1,000 rpm) and methanol as back extraction solvent, allowed the best analytical performance to monitor phthalates in water matrices. From the data obtained, good accuracy and a remarkable reproducibility (< 14.8%) were attained, providing experimental recovery data in agreement with the theoretical equilibrium described by the octanol-water partition coefficients (K(PDMS/W) approximately K(O/W)), with the exception of bis(2-ethylhexyl) adipate, bis(2-ethylhexyl) phthalate and bis(1-octyl) phthalate, for which lower yields were measured. Additionally, a remarkable linear dynamic range between 25 and 2,000 ng/L (r(2)>0.99) and low detection limits (3-40 ng/L) were also achieved for the seven-phthalates studied. The application of the present method to monitor phthalates in tap and bottled mineral water samples, allowed convenient selectivity and high sensitivity up to 1.0 microg/L level, using the standard addition methodology. The proposed method showed to be feasible and sensitive with a low sample volume requirement to monitor phthalates in drinking water matrices at the ultra-trace level, in compliance with international regulatory directives on water quality.

Occurrence of Emerging Micropollutants in Water Systems in Gauteng, Mpumalanga, and North West Provinces, South Africa.

PubMed

Wanda, Elijah M M; Nyoni, Hlengilizwe; Mamba, Bhekie B; Msagati, Titus A M

2017-01-13

The ubiquitous occurrence of emerging micropollutants (EMPs) in water is an issue of growing environmental-health concern worldwide. However, there remains a paucity of data regarding their levels and occurrence in water. This study determined the occurrence of EMPs namely: carbamazepine (CBZ), galaxolide (HHCB), caffeine (CAF), tonalide (AHTN), 4-nonylphenol (NP), and bisphenol A (BPA) in water from Gauteng, Mpumalanga, and North West provinces, South Africa using comprehensive two-dimensional gas chromatography coupled to high resolution time-of-flight mass spectrometry (GCxGC-HRTOFMS). Kruskal-Wallis test and ANOVA were performed to determine temporal variations in occurrence of the EMPs. Principal component analysis (PCA) and Surfer Golden Graphics software for surface mapping were used to determine spatial variations in levels and occurrence of the EMPs. The mean levels ranged from 11.22 ± 18.8 ng/L for CAF to 158.49 ± 662 ng/L for HHCB. There was no evidence of statistically significant temporal variations in occurrence of EMPs in water. Nevertheless, their levels and occurrence vary spatially and are a function of two principal components (PCs, PC1 and PC2) which controlled 89.99% of the variance. BPA was the most widely distributed EMP, which was present in 62% of the water samples. The detected EMPs pose ecotoxicological risks in water samples, especially those from Mpumalanga province.

Occurrence of Emerging Micropollutants in Water Systems in Gauteng, Mpumalanga, and North West Provinces, South Africa

PubMed Central

Wanda, Elijah M. M.; Nyoni, Hlengilizwe; Mamba, Bhekie B.; Msagati, Titus A. M.

2017-01-01

The ubiquitous occurrence of emerging micropollutants (EMPs) in water is an issue of growing environmental-health concern worldwide. However, there remains a paucity of data regarding their levels and occurrence in water. This study determined the occurrence of EMPs namely: carbamazepine (CBZ), galaxolide (HHCB), caffeine (CAF), tonalide (AHTN), 4-nonylphenol (NP), and bisphenol A (BPA) in water from Gauteng, Mpumalanga, and North West provinces, South Africa using comprehensive two-dimensional gas chromatography coupled to high resolution time-of-flight mass spectrometry (GCxGC-HRTOFMS). Kruskal-Wallis test and ANOVA were performed to determine temporal variations in occurrence of the EMPs. Principal component analysis (PCA) and Surfer Golden Graphics software for surface mapping were used to determine spatial variations in levels and occurrence of the EMPs. The mean levels ranged from 11.22 ± 18.8 ng/L for CAF to 158.49 ± 662 ng/L for HHCB. There was no evidence of statistically significant temporal variations in occurrence of EMPs in water. Nevertheless, their levels and occurrence vary spatially and are a function of two principal components (PCs, PC1 and PC2) which controlled 89.99% of the variance. BPA was the most widely distributed EMP, which was present in 62% of the water samples. The detected EMPs pose ecotoxicological risks in water samples, especially those from Mpumalanga province. PMID:28098799

Coupled diffusion in lipid bilayers upon close approach

DOE PAGES

Pronk, Sander; Lindahl, Erik; Kasson, Peter M.

2014-12-23

Biomembrane interfaces create regions of slowed water dynamics in their vicinity. When two lipid bilayers come together, this effect is further accentuated, and the associated slowdown can affect the dynamics of larger-scale processes such as membrane fusion. We have used molecular dynamics simulations to examine how lipid and water dynamics are affected as two lipid bilayers approach each other. These two interacting fluid systems, lipid and water, both slow and become coupled when the lipid membranes are separated by a thin water layer. We show in particular that the water dynamics become glassy, and diffusion of lipids in the apposedmore » leaflets becomes coupled across the water layer, while the “outer” leaflets remain unaffected. This dynamic coupling between bilayers appears mediated by lipid–water–lipid hydrogen bonding, as it occurs at bilayer separations where water–lipid hydrogen bonds become more common than water–water hydrogen bonds. We further show that such coupling occurs in simulations of vesicle–vesicle fusion prior to the fusion event itself. As a result, such altered dynamics at membrane–membrane interfaces may both stabilize the interfacial contact and slow fusion stalk formation within the interface region.« less

On-line hydrogen-isotope measurements of organic samples using elemental chromium: An extension for high temperature elemental-analyzer techniques

USGS Publications Warehouse

Gehre, Matthias; Renpenning, Julian; Gilevska, Tetyana; Qi, Haiping; Coplen, Tyler B.; Meijer, Harro A.J.; Brand, Willi A.; Schimmelmann, Arndt

2015-01-01

The high temperature conversion (HTC) technique using an elemental analyzer with a glassy carbon tube and filling (temperature conversion/elemental analysis, TC/EA) is a widely used method for hydrogen isotopic analysis of water and many solid and liquid organic samples with analysis by isotope-ratio mass spectrometry (IRMS). However, the TC/EA IRMS method may produce inaccurate δ2H results, with values deviating by more than 20 mUr (milliurey = 0.001 = 1‰) from the true value for some materials. We show that a single-oven, chromium-filled elemental analyzer coupled to an IRMS substantially improves the measurement quality and reliability for hydrogen isotopic compositions of organic substances (Cr-EA method). Hot chromium maximizes the yield of molecular hydrogen in a helium carrier gas by irreversibly and quantitatively scavenging all reactive elements except hydrogen. In contrast, under TC/EA conditions, heteroelements like nitrogen or chlorine (and other halogens) can form hydrogen cyanide (HCN) or hydrogen chloride (HCl) and this can cause isotopic fractionation. The Cr-EA technique thus expands the analytical possibilities for on-line hydrogen-isotope measurements of organic samples significantly. This method yielded reproducibility values (1-sigma) for δ2H measurements on water and caffeine samples of better than 1.0 and 0.5 mUr, respectively. To overcome handling problems with water as the principal calibration anchor for hydrogen isotopic measurements, we have employed an effective and simple strategy using reference waters or other liquids sealed in silver-tube segments. These crimped silver tubes can be employed in both the Cr-EA and TC/EA techniques. They simplify considerably the normalization of hydrogen-isotope measurement data to the VSMOW-SLAP (Vienna Standard Mean Ocean Water-Standard Light Antarctic Precipitation) scale, and their use improves accuracy of the data by eliminating evaporative loss and associated isotopic fractionation while handling water as a bulk sample. The calibration of organic samples, commonly having high δ2H values, will benefit from the availability of suitably 2H-enriched reference waters, extending the VSMOW-SLAP scale above zero.

DETERMINATION OF BROMATE IN DRINKING WATERS BY ION CHROMATOGRAPHY WITH INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRIC DETECTION

EPA Science Inventory

Bromate is a disinfection by-product in drinking water, formed during the ozonation of source water containing bromide. An inductively coupled plasma mass spectrometer is combined with an ion chromatograph for the analysis of bromate in drinking waters. Three chromatographic colu...

Comparison of various liquid chromatographic methods involving UV and atmospheric pressure chemical ionization mass spectrometric detection for the efficient trace analysis of phenylurea herbicides in various types of water samples.

PubMed

van der Heeft, E; Dijkman, E; Baumann, R A; Hogendoorn, E A

2000-05-19

The performance of mass spectrometric (MS) detection and UV detection in combination with reversed-phase liquid chromatography without and with the use of coupled column RPLC (LC-LC) has been compared for the trace analysis of phenylurea herbicides in environmental waters. The selected samples of this comparative study originated from an inter-laboratory study. For both detection modes, a 50 mm x 4.6 mm I.D. column and a 100 mm x 4.6 mm I.D. column packed with 3 microm C18 were used as the first (C-1) and second (C-2) column, respectively. Atmospheric pressure chemical ionization mass spectrometry was performed on a magnetic sector instrument. The LC-LC-MS analysis was carried out on-line by means of direct large volume (11.7 ml) injection (LVI). The performance of both on-line (LVI, 4 ml of sample) and off-line LC-LC-UV (244 nm) analysis was investigated. The latter procedure consisted of a solid-phase extraction (SPE) of 250 ml of water sample on a 500 mg C18 cartridge. The comparative study showed that LC-LC-MS is more selective then LC-LC-UV and, in most cases, more sensitive. The LVI-LC-LC-MS approach combines direct quantification and confirmation of most of the analytes down to a level of 0.01 microg/l in water samples in less then 30 min. As regards LC-LC-UV, the off-line method appeared to be a more viable approach in comparison with the on-line procedure. This method allows the screening of phenylurea's in various types of water samples down to a level of at least 0.05 microg/l. On-line analysis with LVI provided marginal sensitivity (limits of detection of about 0.1 microg/l) and selectivity was sometimes less in case of surface water samples. Both the on-line LVI-LC-LC-MS method and the LC-LC-UV method using off-line SPE were validated by analysing a series of real-life reference samples. These samples were part of an inter-laboratory test and contained residues of herbicides ranging from 0.02 to 0.8 microg/l. Beside good correlation between the methods the data agreed very well with the true values of the samples.

Water-chemistry and on-site sulfur-speciation data for selected springs in Yellowstone National Park, Wyoming, 1994-1995

USGS Publications Warehouse

Ball, James W.; Nordstrom, D. Kirk; Cunningham, Kirk M.; Schoonen, Martin A.; Xu, Yong; DeMonge, Jennifer M.

1998-01-01

Forty-two water analyses are reported for samples collected at 8 hot springs and their overflow drainages, two geysers, and two ambient-temperature acid streams in Yellowstone National Park during 1994-95. These water samples were collected and analyzed as part of the initial research investigations on sulfur redox speciation in the hot springs of Yellowstone and to document chemical changes in overflows that affect major ions, redox species, and trace elements. The sulfur redox speciation research is a collaboration between the State University of New York (SUNY) at Stony Brook and the U.S. Geological Survey (USGS). Four hot springs, Ojo Caliente, Azure, Frying Pan, and Angel Terrace, were studied in detail. Analyses were performed adjacent to the sampling site or in an on-site mobile lab truck constructed by the USGS, or later in a USGS laboratory. Water temperature, specific conductance, pH, Eh, D.O., and dissolved H2S were determined adjacent to the sample source at the time of sampling. Alkalinity and F- were determined on-site on the day of sample collection. Thiosulfate and polythionates were determined as soon as possible (minutes to hours later) by ion chromatography (IC). Other major anions (Cl-, SO4 2-, Br-) also were determined on-site by IC within two days of sample collection. Ammonium, Fe(II), and Fe(total) were determined on-site by ultraviolet/visible spectrophotometry within two days of sample collection. Later in the USGS laboratory, densities were determined. Concentrations of Ca, Mg, Li, Na, and K were determined by flame atomic absorption and emission (Na, K) spectrometry. Concentrations of Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe(total), K, Mg, Mn, Na, Ni, Pb, Si, Sr, V, and Zn were determined by inductively-coupled plasma optical emission spectrometry. Trace concentrations of Al and Mg were determined by Zeeman-corrected graphite furnace atomic absorption spectrometry. Three important conclusions from the sampling and analyses are: (1) variability in H2S concentrations can be caused as much by sampling and preservation artifacts as by actual variations in water composition over time, (2) historical determinations of S2O3 2- were subject to overestimation, most likely because of inadequate preservation leading to H2S oxidation, and (3) S2O3 2- is a common constituent of hot spring waters.

Analysis of δ18O and δD values of environmental waters at high temporal and spatial resolution by continuous diffusion sampling cavity ring-down spectrometry

NASA Astrophysics Data System (ADS)

Munksgaard, Niels; Bass, Adrian; Wurster, Chris; Bird, Michael

2013-04-01

A novel sampling device utilises diffusion through porous PTFE tubing to deliver water vapour continuously from a liquid water source for analysis of δ18O and δD values by Cavity Ring-Down Spectrometry (CRDS). Comparison of isotopic data for a range of water samples analysed by Diffusion Sampling-CRDS (DS-CRDS) and Isotope Ratio Mass Spectrometry (IRMS) shows significant linear correlations between the two methods allowing for accurate standardisation of DS-CRDS data. The internal precision for an integration period of 3 min (standard deviation = 0.1 ‰ and 0.3 ‰ for δ18O and δD values, respectively) is similar to analysis of water by injection/evaporation CRDS of discrete water samples. The isotopic effects of variable air and water temperature, water vapour concentration and water pumping rate were found to be either negligible or correctable by analysis of water standards. Separation of the analysed water vapour from non-volatile dissolved and particulate contaminants in the liquid sample minimises interferences associated with CRDS analyses of many aqueous samples. Coupling of the DS-CRDS instrument to an auto sampler enables rapid analysis (10 min) of discrete water samples. The DS-CRDS system was used in the first continuous shipboard measurement of δ18O and δD of water. Combined with continuous salinity recordings, a data set of nearly 6,000 isotope measurements was made at 30-s intervals during a 3-day voyage through the Great Barrier Reef Lagoon. Precise identification of river plumes within the Great Barrier Reef Lagoon was possible because unique δ18O/δD-salinity relationships of individual plumes were measured at high spatial and temporal resolution. Continuous shipboard measurement of δ18O/δD values by DS-CRDS provides additional discriminatory power for assessing water mass formation processes and histories at a small fraction of the cost of traditional isotope analysis of discrete samples. In a second application of DS-CRDS, continuous real-time analysis, at 30-s intervals, of precipitation at an Australian tropical location revealed extreme and rapidly changing δ18O and δD values related to variations in moisture source areas, transport paths and precipitation histories. The range of δ18O (-19.6 ‰ to +2.6 ‰) and δD (-140 ‰ to +13 ‰) values from almost 6,000 measurements of nine rain events over 15 days during an 8-month period at a single location was comparable with the range measured in 1532 monthly samples from all seven Australian Global Network of Isotopes in Precipitation stations from 1962 to 2002. Extreme variations in δ18O (-8.7 ‰ to -19.6 ‰) and δD (-54 ‰ to -140 ‰) were recorded within a single 4-h period. Real-time stable isotope monitoring of environmental waters at high temporal and spatial resolution enables new and powerful tracer applications in climatology, hydrology, eco-physiology and palaeo-climatology.

Magnetic ionic liquid aqueous two-phase system coupled with high performance liquid chromatography: A rapid approach for determination of chloramphenicol in water environment.

PubMed

Yao, Tian; Yao, Shun

2017-01-20

A novel organic magnetic ionic liquid based on guanidinium cation was synthesized and characterized. A new method of magnetic ionic liquid aqueous two-phase system (MILATPs) coupled with high-performance liquid chromatography (HPLC) was established to preconcentrate and determine trace amount of chloramphenicol (CAP) in water environment for the first time. In the absence of volatile organic solvents, MILATPs not only has the excellent properties of rapid extraction, but also exhibits a response to an external magnetic field which can be applied to assist phase separation. The phase behavior of MILATPs was investigated and phase equilibrium data were correlated by Merchuk equation. Various influencing factors on CAP recovery were systematically investigated and optimized. Under the optimal conditions, the preconcentration factor was 147.2 with the precision values (RSD%) of 2.42% and 4.45% for intra-day (n=6) and inter-day (n=6), respectively. The limit of detection (LOD) and limit of quantitation (LOQ) were 0.14ngmL -1 and 0.42ngmL -1 , respectively. Fine linear range of 12.25ngmL -1 -2200ngmL -1 was obtained. Finally, the validated method was successfully applied for the analysis of CAP in some environmental waters with the recoveries for the spiked samples in the acceptable range of 94.6%-99.72%. Hopefully, MILATPs is showing great potential to promote new development in the field of extraction, separation and pretreatment of various biochemical samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Ultra high performance liquid chromatography tandem mass spectrometry for rapid analysis of trace organic contaminants in water

PubMed Central

2013-01-01

Background The widespread utilization of organic compounds in modern society and their dispersion through wastewater have resulted in extensive contamination of source and drinking waters. The vast majority of these compounds are not regulated in wastewater outfalls or in drinking water while trace amounts of certain compounds can impact aquatic wildlife. Hence it is prudent to monitor these contaminants in water sources until sufficient toxicological data relevant to humans becomes available. A method was developed for the analysis of 36 trace organic contaminants (TOrCs) including pharmaceuticals, pesticides, steroid hormones (androgens, progestins, and glucocorticoids), personal care products and polyfluorinated compounds (PFCs) using a single solid phase extraction (SPE) technique with ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). The method was applied to a variety of water matrices to demonstrate method performance and reliability. Results UHPLC-MS/MS in both positive and negative electrospray ionization (ESI) modes was employed to achieve optimum sensitivity while reducing sample analysis time (<20 min) compared with previously published methods. The detection limits for most compounds was lower than 1.0 picogram on the column while reporting limits in water ranged from 0.1 to 15 ng/L based on the extraction of a 1 L sample and concentration to 1 mL. Recoveries in ultrapure water for most compounds were between 90-110%, while recoveries in surface water and wastewater were in the range of 39-121% and 38-141% respectively. The analytical method was successfully applied to analyze samples across several different water matrices including wastewater, groundwater, surface water and drinking water at different stages of the treatment. Among several compounds detected in wastewater, sucralose and TCPP showed the highest concentrations. Conclusion The proposed method is sensitive, rapid and robust; hence it can be used to analyze a large variety of trace organic compounds in different water matrixes. PMID:23777604

Vanadium Recovery from Oil Fly Ash by Carbon Removal and Roast-Leach Process

NASA Astrophysics Data System (ADS)

Jung, Myungwon; Mishra, Brajendra

2018-02-01

This research mainly focuses on the recovery of vanadium from oil fly ash by carbon removal and the roast-leach process. The oil fly ash contained about 85% unburned carbon and 2.2% vanadium by weight. A vanadium-enriched product was obtained after carbon removal, and the vanadium content of this product was 19% by weight. Next, the vanadium-enriched product was roasted with sodium carbonate to convert vanadium oxides to water-soluble sodium metavanadate. The roasted sample was leached with water at 60°C, and the extraction percentage of vanadium was about 92% by weight. Several analytical techniques, such as inductively coupled plasma atomic emission spectroscopy (ICP-AES), x-ray fluorescence (XRF), and thermogravimetric and differential thermal analysis (TG-DTA), were utilized for sample analyses. Thermodynamic modeling was also conducted with HSC chemistry software to explain the experimental results.

Low level detection of Cs-135 and Cs-137 in environmental samples by ICP-MS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liezers, Martin; Farmer, Orville T.; Thomas, Linda MP

2009-10-01

The measurement of the fission product cesium isotopes 135Cs and 137Cs at low femtogram (fg) 10-15 levels in ground water by Inductively Coupled Plasma-Mass Spectrometry ICP-MS is reported. To eliminate the potential natural barium isobaric interference on the cesium isotopes, in-line chromatographic separation of the cesium from barium was performed followed by high sensitivity ICP-MS analysis. A high efficiency desolvating nebulizer system was employed to maximize ICP-MS sensitivity ~10cps/femtogram. The three sigma detection limit measured for 135Cs was 2fg/ml (0.1uBq/ml) and for 137Cs 0.9fg/ml (0.0027Bq/ml) with analysis time of less than 30 minutes/sample. Cesium detection and 135/137 isotope ratio measurementmore » at very low femtogram levels using this method in a ground water matrix is also demonstrated.« less

Heavy metals in red crabs, Chaceon quinquedens, from the Gulf of Mexico.

PubMed

Perry, Harriet; Isphording, Wayne; Trigg, Christine; Riedel, Ralf

2015-12-30

The red crab, Chaceon quinquedens, is distributed in deep waters of the Gulf of Mexico (GOM) and is most abundant in an area associated with sediment deposition from the Mississippi River. Sediment geochemistry and biological and ecological traits of red crabs favor accumulation of contaminants. Red crabs, sediment, and bottom water samples were taken from three distinct geographic locations representing areas with differing exposure to contaminant laden effluents from the Mississippi River. Inductively coupled plasma spectrophotometry and atomic absorption spectrophotometry were employed to determine levels of heavy metals in red crab muscle tissue. Ion site partitioning was used to determine metal speciation in sediments. Red crabs showed evidence of heavy metal bioaccumulation in all sample areas with high variability in contaminant levels in individual crabs for some metals. Bioavailability of metals in sediment did not always result in accumulation in muscle tissue. Copyright © 2015 Elsevier Ltd. All rights reserved.

IM-CRDS for the analysis of matrix-bound water isotopes: a streamlined (and updated) tool for ecohydrologists to probe small-scale variability in plants Yasuhara, S. (syasuhara@picarro.com)1,Carter, J.A. (jcarter@picarro.com)1, Dennis, K.J. (kdennis@picarro.com)1 1Picarro Inc., 3105 Patrick Henry Drive, Santa Clara, CA 95054

NASA Astrophysics Data System (ADS)

Yasuhara, S.

2013-12-01

The ability to measure the isotopic composition of matrix-bound water is valuable to many facets of earth and environmental sciences. For example, ecohydrologists use stable isotopes of oxygen and hydrogen in plant and soil water, in combination with measurements of atmospheric water vapor, surface water and precipitation, to estimate budgets of evapotranspiration. Likewise, water isotopes of oceanic water, brines and other waters with high total dissolved solids (TDS, e.g., juices) are relevant to studying large-scale oceanic circulation, small-scale mixing, groundwater contamination, the balance of evaporation to precipitation, and the provenance of food. Conventionally matrix-bound water has been extracted using cryogenic distillation, whereby water is distilled from the material in question (e.g., a leaf sample) by heating under vacuum and collecting the resultant water vapor using liquid nitrogen. The water can then be analyzed for its stable isotopic composition by a variety of methods, including isotope ratio mass spectrometry and laser techniques, such as Cavity Ring-Down Spectroscopy (CRDS). Here we present recent improvements in an alternative, and stream-lined, solution for integrated sample extraction and isotopic measurement using a Picarro Induction Module (IM) coupled to commercially-available CRDS analyzer from Picarro. This technique is also valuable for waters with high TDS, which can have detrimental effects on flash vaporization process, typically used for the introduction of water to Picarro CRDS water isotope analyzers. The IM works by inductively heating a sample held within a metal sample holder in a glass vial flushed with dry air. Tested samples include leaves, stems, twigs, calibration water, juices, and salt water. The heating process evolves water vapor which is then swept through the system at approximately 150 standard cubic centimeters per minute. The evolved water vapor passes through an activated charcoal cartridge for removal of large organics, and then through Picarro's Micro-Combustion Cartridge that acts to oxidize interfering organics to CO2 and H2O. Using an open-split, the IM is interfaced directly with a CRDS system (in this case, an L2130-i) for the measurement of δ18O and δD. Based on replicate measurements of water introduced to the system using glass filter paper, the precision of the system is better than 0.35 and 1.5 ‰ for δ18O and δD, respectively. We will present improvements in system operation that have reduced systematic errors associated with (i) variable backgrounds, and (ii) exchange between the sample and the local atmosphere during sample introduction. In addition, we will present calibration data, and data demonstrating the effectiveness of the Micro-Combustion Cartridge at removing organics, which can result in spectroscopic interference. Finally, we will compare localized leaf water data against integrated whole leaf water data to demonstrate the added value of being able to sample small (approximately 5 mm diameter) areas of a leaf, and compare the results of measuring samples with high TDS on an IM and a Picarro High Precision Vaporizer.