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Pallid sturgeon basin-wide contaminants assessment

Pallid sturgeon (Scaphirhynchus albus), listed as endangered in 1990 under the federal Endangered Species Act (United States Fish and Wildlife Service (USFWS), 1990), have declined due to habitat loss, commercial fishing, and hybridization. Pollution in the Missouri and Mississippi Rivers has to-date only received minor attention as a factor in the on-going decline of wild pallid sturgeon populations (Jacobson et al. 2016a; Bergman 2008). Pallid sturgeon experts and contaminant specialists conceived of the Pallid Sturgeon Basin-Wide Contaminants Assessment (Assessment) to identify potentially harmful contaminants (contaminants of concern), their distribution within pallid sturgeon habitat, and their effects on pallid sturgeon at the landscape level. Extant water quality and analytical chemistry data from samples of river water, sediment, and sturgeon tissues from past studies, assessments, or monitoring activities throughout the species’ range were used to establish a list of contaminants. The list includes: metal and non-metal elements, pesticides, organic industrial chemicals, hormones, nutrients, and other potential water quality contaminants. Environmental samples collected from January 1, 2001 through December 31, 2014, when available, were used for all evaluations. This report is effectively a screening level hazard assessment whereby contituents of concern that may pose a potential harm to pallid sturgeon have been identified. These constituents of concern warrant further examination to determine the level of risk they pose to pallid sturgeon. The Assessment process was one of comparing the existing environmental data for individual constituents to reference values for adverse effects on fish specifically or aquatic life generally. The product of the Assessment is a simplified summary that is geographically organized by pallid sturgeon management unit that generally categorizes each individual contaminant or water quality constituent according to operationally defined levels of concern. This hazard assessment identifies potential constituents of concern to pallid sturgeon and may support prioritization for future data collection and research to enable a quantitative risk assessment. Regional data density at spatial and temporal scales notwithstanding, the Assessment points to some generalities in contaminant concerns within and across management units. Metals but not pesticides are the predominant contaminant of concern in the Great Plains Management Unit (GPMU). In the Central Lowlands Management Unit (CLMU), selenium exceeds benchmark levels. Triazine herbicides are potentially of concern in all but the GPMU. Concentrations of legacy contaminants such as PCBs and DDT and its metabolites exceeded benchmarks in samples from the CLMU, Interior Highlands Mangement Unit (IHMU), and Coastal Plains Management Unit (CPMU), but local and national trends indicate environmental levels of these contaminants continue to decline. Observed concentrations of nutrients and indicators of nutrient pollution were above benchmark levels throughout the pallid sturgeon’s range; however, the significance for pallid sturgeon health specifically is unknown. Almost no information exists on contemporary contaminants of concern such as the natural and synthetic estrogens (estradiol, ethinyl estradiol, and estrone) or polybrominated diphenyls (PBDEs). There are considerable informational data gaps for contaminants throughout the species’ range. Water quality measurements were the most frequent data encountered whereas, sediment and tissue data were orders of magnitude less frequent. The paucity of sediment and tissue concentrations, particularly the latter, prevents any meaningful conclusions regarding adverse effects of these contaminants on the growth and reproduction of pallid sturgeon. However, the Assessment could form the basis for regional workshops with subject matter specialists to develop plans to evaluate the contaminants most likely to affect pallid sturgeon health.

Missouri River basin, Mississippi River basin

Advances in solid-phase extraction disks for environmental chemistry

The development of solid-phase extraction (SPE) for environmental chemistry has progressed significantly over the last decade to include a number of new sorbents and new approaches to SPE. One SPE approach in particular, the SPE disk, has greatly reduced or eliminated the use of chlorinated solvents for the analysis of trace organic compounds. This article discusses the use and applicability of various SPE disks, including micro-sized disks, prior to gas chromatography-mass spectrometry for the analysis of trace organic compounds in water.

TrAC - Trends in Analytical Chemistry

Determination of δ 18 O and δ 15 N in Nitrate

The analyses of both O and N isotopic compositions of nitrate have many potential applications in studies of nitrate sources and reactions in hydrology, oceanography, and atmospheric chemistry, but simple and precise methods for these analyses have yet to be developed. Testing of a new method involving reaction of potassium nitrate with catalyzed graphite (C + Pd + Au) at 520 °C resulted in quantitative recovery of N and O from nitrate as free CO 2 , K 2 CO 3 , and N 2 . The δ 18 O values of nitrate reference materials were obtained by analyzing both the CO 2 and K 2 CO 3 from catalyzed graphite combustion. Provisional values of δ 18 O VSMOW for the internationally distributed KNO 3 reference materials IAEA-N3 and USGS-32 were both equal to +22.7 ± 0.5‰. Because the fraction of free CO 2 and the isotopic fractionation factor between CO 2 and K 2 CO 3 were constant in the combustion products, the δ 18 O value of KNO 3 could be calculated from measurements of the δ 18 O of free CO 2 . Thus, δ 18 O KNO 3 = a δ 18 O free CO 2 − b , where a and b were equal to 0.9967 and 3.3, respectively, for the specific conditions of the experiments. The catalyzed graphite combustion method can be used to determine δ 18 O of KNO 3 from measurements of δ 18 O of free CO 2 with reproducibility on the order of ±0.2‰ or better if local reference materials are prepared and analyzed with the samples. Reproducibility of δ 15 N was ±0.1‰ after trace amounts of CO were removed.

Analytical Chemistry

An interlaboratory study to test instrument performance of hydrogen dual-inlet isotope-ratio mass spectrometers

An interlaboratory comparison of forty isotope-ratio mass spectrometers of different ages from several vendors has been performed to test 2 H/ 1 H performance with hydrogen gases of three different isotopic compositions. The isotope-ratio results (unsufficiently corrected for H 3 + contribution to the m/z = 3 collector, uncorrected for valve leakage in the change-over valves, etc.) expressed relative to one of these three gases covered a wide range of values: –630‰ to –790‰ for the second gas and –368‰ to –462‰ for the third gas. After normalizing the isotopic abundances of these test gases (linearly adjusting the δ values so that the gases with the lowest and highest 2 H content were identical for all laboratories), the standard deviation of the 40 measurements of the intermediate gas was a remarkably low 0.85‰. It is concluded that the use of scaling factors is mandatory for providing accurate internationally comparable isotope-abundance values. Linear scaling for the isotope-ratio scales of gaseous hydrogen mass spectrometers is completely adequate.

Fresenius' Journal of Analytical Chemistry

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

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.

TrAC - Trends in Analytical Chemistry

Catalytic determination of vanadium in water

A kinetic determination of V(V) as a catalyst was spectrophotometrically performed by using the indicator reaction of Gallamine blue (GB + ) and bromate at pH 2.0. The reaction was followed by measuring absorbance change for a fixed-time of 3 min at 537 nm. The variables such as reagent concentration, pH, buffer concentration, ionic strength and temperature were optimized to improve the selectivity and sensitivity. Under the optimized conditions, the determination of V(V) was performed in the range 1–100 μg L −1 with limits of detection and quantification of 0.31 and 0.94 μg L −1 . The developed kinetic method is sufficiently sensitive, selective and simple. It was successfully applied to the speciative determination of total V and inorganic dissolved vanadium species, V(V) and V(IV) in environmental water samples. The oxidizing property of permanganate is used to differentiate between V(IV) and V(V) species. The V(IV) content was found by subtracting the V(V) content from those of total V. The recovery is above 95% for V(V) spiked samples. Additionally, the accuracy was validated by analysis of a certified water sample, CRM TMDA-53.3, and the results were in good agreement with the certified value.

Analytical Chemistry

Chapter 8 Tool for monitoring hydrophilic contaminants in water: polar organic chemical integrative sampler (POCIS)

The development of the polar organic chemical integrative sampler (POCIS) provides environmental scientists and policy makers a tool for assessing the presence and potential impacts of the hydrophilic component of these organic contaminants. The POCIS provides a means for determining the time-weighted average (TWA) concentrations of targeted chemicals that can be used in risk assessments to determine the biological impact of hydrophilic organic compounds (HpOCs) on the health of the impacted ecosystem. Field studies have shown that the POCIS has advantages over traditional sampling methods in sequestering and concentrating ultra-trace to trace levels of chemicals over time resulting in increased method sensitivity, ability to detect chemicals with a relatively short residence time or variable concentrations in the water, and simplicity in use. POCIS extracts can be tested using bioassays and can be used in organism dosing experiments for determining toxicological significance of the complex mixture of chemicals sampled. The POCIS has been successfully used worldwide under various field conditions ranging from stagnant ponds to shallow creeks to major river systems in both fresh and brackish water.

Comprehensive Analytical Chemistry

Selective trace enrichment of chlorotriazine pesticides from natural waters and sediment samples using terbuthylazine molecularly imprinted polymers

Two molecularly imprinted polymers were synthesized using either dichloromethane or toluene as the porogen and terbuthylazine as the template and were used as solid-phase extraction cartridges for the enrichment of six chlorotriazines (deisopropylatrazine, deethylatrazine, simazine, atrazine, propazine, and terbuthylazine) in natural water and sediment samples. The extracted samples were analyzed by liquid chromatography/diode array detection (LC/DAD). Several washing solvents, as well as different volumes, were tested for their ability to remove the matrix components nonspecifically adsorbed on the sorbents. This cleanup step was shown to be of prime importance to the successful extraction of the pesticides from the aqueous samples. The optimal analytical conditions were obtained when the MIP imprinted using dichloromethane was the sorbent, 2 mL of dichloromethane was used in the washing step, and the preconcentrated analytes were eluted with 8 mL of methanol. The recoveries were higher than 80% for all the chlorotriazines except for propazine (53%) when 50- or 100-mL groundwater samples, spiked at 1 ??g/L level, were analyzed. The limits of detection varied from 0.05 to 0.2 ??g/L when preconcentrating a 100-mL groundwater sample. Natural sediment samples from the Ebre Delta area (Tarragona, Spain) containing atrazine and deethylatrazine were Soxhlet extracted and analyzed by the methodology developed in this work. No significant interferences from the sample matrix were noticed, thus indicating good selectivity of the MIP sorbents used.

Analytical Chemistry

Improvements in the gaseous hydrogen-water equilibration technique for hydrogen isotope ratio analysis

Improved precision in the H 2 -H 2 O equilibration method for δD analysis has been achieved in an automated system. Reduction in 1- σ standard deviation of a single mass-spectrometer analysis to 1.3 ‰ is achieved by (1) bonding catalyst to glass rods and assigning use to specific equilibration chambers to monitor performance of catalyst, (2) improving the apparatus design, and (3) reducing the H 3 + contribution of the mass-spectrometer ion source. For replicate analysis of a water sample, the standard deviation improved to 0.8 ‰ . H 2 S-bearing samples and samples as small as 0.1 mL can be analyzed routinely with this method.

Analytical Chemistry

Sources and magnitude of bias associated with determination of polychlorinated biphenyls in environmental samples

Recently compiled data on the composition of commercial Aroclor mixtures and ECD (electron capture detector) response factors for all 209 PCB congeners are used to develop estimates of the bias associated with determination of polychlorinated blphenyis. During quantitation of multlcomponent peaks by congener-specific procedures error is introduced because of variable ECD response to isomeric PCBs. Under worst case conditions, the magnitude of this bias can range from less than 2% to as much as 600%. Multicomponent peaks containing the more highly and the lower chlorinated congeners experience the most bias. For this reason, quantitation of Σ PCB in Aroclor mixtures dominated by these species (e.g. 1016) are potentially subject to the greatest error. Comparison of response factor data for ECDs from two laboratories shows that the sign and magnitude of calibration bias for a given multicomponent peak is variable and depends, in part, on the response characteristics of individual detectors. By using the most abundant congener (of each multicomponent peak) for purposes of calibration, one can reduce the maximum bias to less than 55%. Moreover, due to cancellation of errors, the bias resulting from summation of all peak concentrations (i.e. Σ PCB) becomes vanishingly small (<1.2%). In contrast, bias associated with determination of Σ PCB as Aroclor equivalents by the traditional Aroclor method is potentially large (>200%) and highly variable in sign and magnitude. In this case, bias originates not only from the incomplete chromatographic resolution of PCB congeners but also the overlapping patterns of the Aroclor mixtures. Together these results illustrate the advantages of the congener-specific method of PCB quantitation over the traditional Aroclor Method and the extreme difficulty of estimating bias incurred by the latter procedure on a post hoc basis.

Analytical Chemistry

Inductively coupled plasma-mass spectrometry as an element-specific detector for field-flow fractionation particle separation

An inductively coupled plasma-mass spectrometer was used for the quantitative measurement of trace elements In specific,submicrometer size-fraction particulates, separated by sedimentation field-flow fractionation. Fractions were collected from the eluent of the field-flow fractionation centrifuge and nebulized, with a Babington-type pneumatic nebulizer, into an argon inductively coupled plasma-mass spectrometer. Measured Ion currents were used to quantify the major, minor, and trace element composition of the size-separated colloidal (< 1-microm diameter) particulates. The composition of surface-water suspended matter collected from the Yarra and Darling rivers in Australia is presented to illustrate the usefulness of this tool for characterizing environmental materials. An adsorption experiment was performed using cadmium lon to demonstrate the utility for studying the processes of trace metal-suspended sediment interactions and contaminant transport in natural aquatic systems.

Analytical Chemistry

Determination of selected azaarenes in water by bonded-phase extraction and liquid chromatography

A method for the rapid and simple quantitative determination of quinoline, isoquinoline, and five selected three-ring azaarenes in water has been developed. The azaarene fraction is separated from its carbon analogues on n-octadecyl packing material by edition with acidified water/acetonitrile. Concentration as great as 1000-fold is achieved readily. Instrumental analysis involves high-speed liquid chromatography on flexible-walled, wide-bore columns with fluorescence and ultraviolet detection at several wavelengths employing filter photometers in series. Method-validation data is provided as azaarene recovery efficiency from fortified samples. Distilled water, river water, contaminated ground water, and secondary-treatment effluent have been tested. Recoveries at part-per-billion levels are nearly quantitative for the three-ring compounds, but they decrease for quinoline and isoquinoline.

Analytical Chemistry