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At least 343 records · Page 19Linked to original sources
USGS1997

Analysis of environmental data with censored observations

The potential threats to humans and to terrestrial and aquatic ecosystems from environmental contamination could depend on the sum of the concentrations of different chemicals. However, direct summation of environmental data is not generally feasible because it is common for some chemical concentrations to be recorded as being below the analytical reporting limit. This creates special problems in the analysis of the data. A new model selection procedure, named forward censored regression, is introduced for selecting an appropriate model for environmental data with censored observations. The procedure is demonstrated using concentrations of atrazine (2-chloro-4-ethylamino-6-isopropylamino- s -triazine), deethylatrazine (DEA, 2-amino-4-chloro-6-isopropylamino- s -triazine), and deisopropylatrazine (DIA, 2-amino-4-chloro-6-ethylamino- s -triazine) in groundwater in the midwestern United States by using the data derived from a previous study conducted by the U.S. Geological Survey. More than 80% of the observations for each compound for this study were left censored at 0.05 μg/L. The values for censored observations of atrazine, DEA, and DIA are imputed with the selected models. The summation of atrazine residue (atrazine + DEA + DIA) can then be calculated using the combination of observed and imputed values to generate a pseudo-complete data set. The all-subsets regression procedure is applied to the pseudo-complete data to select the final model for atrazine residue. The methodology presented can be used to analyze similar cases of environmental contamination involving censored data.

Environmental Science & Technology↗
USGS2018

Concentrations of lead and other inorganic constituents in samples of raw intake and treated drinking water from the municipal water filtration plant and residential tapwater in Chicago, Illinois, and East Chicago, Indiana, July–December 2017

The U.S. Geological Survey (USGS) Environmental Health Mission Area (EHMA) is providing comprehensive science on sources, movement, and transformation of contaminants and pathogens in watershed and aquifer drinking-water supplies and in built water and wastewater infrastructure (referred to as the USGS Water and Wastewater Infrastructure project) in the Greater Chicago Area and elsewhere in the United States, to fill data gaps identified by stakeholders and collaborators in drinking water and public health. EHMA Water and Wastewater Infrastructure research specifically provides insight into natural factors in the environment as well as those water-infrastructure components and processes (such as source-water corrosivity, treatment, plumbing, and so forth) that might influence human exposure to chemical and microbial contaminants at the residential tap. This infrastructure-exposure research role is fulfilled uniquely by the USGS and not by the U.S. Environmental Protection Agency (EPA), other agencies, or municipalities that focus on regulatory and policy activities and related compliance. The USGS approach to assessing the possible links between human health and chemical contaminant and pathogen exposure in drinking water is conducted in collaboration with public health experts and includes comprehensive characterization of the presence/absence and concentrations of more than 500 organic and 27 inorganic chemical constituents at the point of use (tap). Laboratory results for lead and other inorganic contaminants in Chicago, Illinois, and East Chicago, Indiana, residential tapwater are being released to ensure the timely release of quality-assured data to participants in the study. Concentrations of lead and other inorganic constituents were assessed in drinking water at the point of use (kitchen tap or filter) in 45 residential locations and in two locations within each of the two Chicago water purification plants and the two East Chicago water filtration plants during July–December 2017. Three methods were used for analyzing lead. The most sensitive method had a reporting limit of 0.020 micrograms per liter (µg/L). When using the most sensitive analytical method, lead was detected in 39 of 45 residential tapwater samples, with concentrations ranging from less than 0.020 µg/L to 5.31 µg/L (median of the detected values = 0.481 µg/L). Concentrations of lead also were detected in Lake Michigan intake water at all water purification/filtration plant facilities at concentrations ranging from 0.083 to 0.330 µg/L, but were not detected above the reporting limit in any samples of treated, pre-distribution drinking water at any of the water purification/filtration plant facilities. Because the USGS Water and Wastewater Infrastructure project in the Greater Chicago Area is focused on the potential human exposure to a broad suite of organic and inorganic contaminants in drinking water and is not focused specifically on lead, the sampling protocol did not include “first-draw,” stagnant sampling and samples were collected with point-of-use treatment in place, if present. Thus, the lead results reported herein are not appropriate for assessment of compliance with the EPA 1991 Lead and Copper Rule. Information resources for lead mitigation and water filtration are provided.

Illinois, Indiana↗
USGS2024

A multi-marker assessment of sewage contamination in streams using human-associated indicator bacteria, human-specific viruses, and pharmaceuticals

Human sewage contaminates waterways, delivering excess nutrients, pathogens, chemicals, and other toxic contaminants. Contaminants and various sewage indicators are measured to monitor and assess water quality, but these analytes vary in their representation of sewage contamination and the inferences about water quality they support. We measured the occurrence and concentration of multiple microbiological ( n = 21) and chemical ( n = 106) markers at two urban stream locations in Milwaukee, Wisconsin, USA over two years. Five-day composite water samples ( n = 98) were collected biweekly, and sewage influent samples ( n = 25) were collected monthly at a Milwaukee, WI water reclamation facility. We found the vast majority of markers were not sensitive enough to detect sewage contamination. To compare analytes for monitoring applications, five consistently detected human sewage indicators were used to evaluate temporal patterns of sewage contamination, including microbiological (pepper mild mottle virus, human Bacteroides , human Lachnospiraceae ) and chemical (acetaminophen, metformin) markers. The proportion of human sewage in each stream was estimated using the mean influent concentration from the water reclamation facility and the mean concentration of all stream samples for each sewage indicator marker. Estimates of instream sewage pollution varied by marker, differing by up to two orders of magnitude, but four of the five sewage markers characterized Underwood Creek (mean proportions of human sewage ranged 0.0025 % - 0.075 %) as less polluted than Menomonee River (proportions ranged 0.013 % - 0.14 %) by an order of magnitude more. Chemical markers correlated with each other and yielded higher estimates of sewage pollution than microbial markers, which exhibited greater temporal variability. Transport, attenuation, and degradation processes can influence chemical and microbial markers differently and cause variation in human sewage estimates. Given the range of potential human and ecological health effects of human sewage contamination, robust characterization of sewage contamination that uses multiple lines of evidence supports monitoring and research applications.

Wisconsin↗
USGS2019

Accuracy of methods for reporting inorganic element concentrations and radioactivity in oil and gas wastewaters from the Appalachian Basin, U.S. based on an inter-laboratory comparison.

Accurate and precise analyses of oil and gas (O&G) wastewaters and solids ( e.g. , sediments and sludge) are important for the regulatory monitoring of O&G development and tracing potential O&G contamination in the environment. In this study, 15 laboratories participated in an inter-laboratory comparison on the chemical characterization of three O&G wastewaters from the Appalachian Basin and four solids impacted by O&G development, with the goal of evaluating the quality of data and the accuracy of measurements for various analytes of concern. Using a variety of different methods, analytes in the wastewaters with high concentrations ( i.e. , >5 mg L −1 ) were easily detectable with relatively high accuracy, often within ±10% of the most probable value (MPV). In contrast, often less than 7 of the 15 labs were able to report detectable trace metal(loid) concentrations ( i.e. , Cr, Ni, Cu, Zn, As, and Pb) with accuracies of approximately ±40%. Despite most labs using inductively coupled plasma mass spectrometry (ICP-MS) with low instrument detection capabilities for trace metal analyses, large dilution factors during sample preparation and low trace metal concentrations in the wastewaters limited the number of quantifiable determinations and likely influenced analytical accuracy. In contrast, all the labs measuring Ra in the wastewaters were able to report detectable concentrations using a variety of methods including gamma spectroscopy and wet chemical approaches following Environmental Protection Agency (EPA) standard methods. However, the reported radium activities were often greater than ±30% different to the MPV possibly due to calibration inconsistencies among labs, radon leakage, or failing to correct for self-attenuation. Reported radium activities in solid materials had less variability (±20% from MPV) but accuracy could likely be improved by using certified radium standards and accounting for self-attenuation that results from matrix interferences or a density difference between the calibration standard and the unknown sample. This inter-laboratory comparison illustrates that numerous methods can be used to measure major cation, minor cation, and anion concentrations in O&G wastewaters with relatively high accuracy while trace metal(loid) and radioactivity analyses in liquids may often be over ±20% different from the MPV.

Appalachian Basin↗
USGS2000

Analysis of selected herbicide metabolites in surface and ground water of the United States

One of the primary goals of the US Geological Survey (USGS) Laboratory in Lawrence, Kansas, is to develop analytical methods for the analysis of herbicide metabolites in surface and ground water that are vital to the study of herbicide fate and degradation pathways in the environment. Methods to measure metabolite concentrations from three major classes of herbicides — triazine, chloroacetanilide and phenyl-urea — have been developed. Methods for triazine metabolite detection cover nine compounds: six compounds are detected by gas chromatography/mass spectrometry; one is detected by high-performance liquid chromatography with diode-array detection; and eight are detected by liquid chromatography/mass spectrometry. Two metabolites of the chloroacetanilide herbicides — ethane sulfonic acid and oxanilic acid — are detected by high-performance liquid chromatography with diode-array detection and liquid chromatography/mass spectrometry. Alachlor ethane sulfonic acid also has been detected by solid-phase extraction and enzyme-linked immunosorbent assay. Six phenylurea metabolites are all detected by liquid chromatography/mass spectrometry; four of the six metabolites also are detected by gas chromatography/mass spectrometry. Additionally, surveys of herbicides and their metabolites in surface water, ground water, lakes, reservoirs, and rainfall have been conducted through the USGS laboratory in Lawrence. These surveys have been useful in determining herbicide and metabolite occurrence and temporal distribution and have shown that metabolites may be useful in evaluation of non-point-source contamination.

Science of the Total Environment↗
USGS2010

Detecting temporal trends in species assemblages with bootstrapping procedures and hierarchical models

Quantifying patterns of temporal trends in species assemblages is an important analytical challenge in community ecology. We describe methods of analysis that can be applied to a matrix of counts of individuals that is organized by species (rows) and time-ordered sampling periods (columns). We first developed a bootstrapping procedure to test the null hypothesis of random sampling from a stationary species abundance distribution with temporally varying sampling probabilities. This procedure can be modified to account for undetected species. We next developed a hierarchical model to estimate species-specific trends in abundance while accounting for species-specific probabilities of detection. We analysed two long-term datasets on stream fishes and grassland insects to demonstrate these methods. For both assemblages, the bootstrap test indicated that temporal trends in abundance were more heterogeneous than expected under the null model. We used the hierarchical model to estimate trends in abundance and identified sets of species in each assemblage that were steadily increasing, decreasing or remaining constant in abundance over more than a decade of standardized annual surveys. Our methods of analysis are broadly applicable to other ecological datasets, and they represent an advance over most existing procedures, which do not incorporate effects of incomplete sampling and imperfect detection.

Philosophical Transactions of the Royal Society B:↗
USGS2004

Floodtide pulses after low tides in shallow subembayments adjacent to deep channels

In shallow waters surface gravity waves (tides) propagate with a speed proportional to the square root of water depth (c=g(h+η)). As the ratio of free surface displacement to mean depth (η/h) approaches unity the wave will travel noticeably faster at high tide than at low tide, creating asymmetries in the tidal form. This physical process is explained analytically by the increased significance of friction and the nonlinear terms in the continuity and momentum equations. In a tidal system comprising a shallow bay adjacent to a deeper channel, tidal asymmetries will be more prevalent in the shallow bay. Thus strong barotropic gradients can be generated between the two, producing rapid accelerations of currents into the bay (relative to other bay tidal processes) and create a maximum peak in the flood tide that we describe as a floodtide pulse. These floodtide pulses can promote a landward flux of suspended-sediment into the bay. In Grizzly Bay (part of northern San Francisco Bay, USA), field observations verify the occurrence of floodtide pulses during the lowest low tides of the year. No pulses were observed in neighboring Honker Bay, which has an average depth ~30 cm greater than Grizzly Bay. Numerical simulations of northern San Francisco Bay using realistic bathymetry demonstrated that floodtide pulses occurred in Grizzly Bay but not in Honker Bay, consistent with the observations. Both observations and numerical simulations show that floodtide pulses promote a landward flux of sediment into Grizzly Bay. Numerical simulations of an idealized bay-channel system quantify the importance of mean depth and friction in creating these floodtide pulses.

California↗
USGS2009

Approaches to modeling weathered regolith

Sustainable soils are a requirement for maintaining human civilizations ( Carter and Dale 1974 ; Lal 1989 ). However, as the “most complicated biomaterial on the planet” ( Young and Crawford 2004 ), soils represent one of the most difficult systems to understand and model with respect to chemical, physical, and biological coupling over time (Fig. 1 ). Despite the complexity of these interactions, certain patterns in soil properties and development are universally observed and have been used in soil science as a means for classification. Elemental, mineralogical, or isotopic concentrations in soils plotted versus depth beneath the land surface comprise such patterns. Soil depth profiles are often reported for solid soil materials, and, less frequently, for solutes in soil pore waters. These profiles cross a large range in spatial scales that traditionally have been studied by different disciplines. For example, shallow, biologically active horizons are commonly defined as the soil zone in agronomic studies whereas the mobile layer of the regolith is referred to as soil in geomorphological studies. In contrast, many geochemical studies target chemical weathering to tens or even hundreds of meters in depth, sometimes extending the definition of “soils” to include the entire regolith down to parent bedrock or alluvium. Soil profiles also exhibit a large range in temporal scales ( Amundson 2004 ; Brantley 2008b ). Solid-state profiles document chemical and mineralogical changes integrated over the time scales of evolution of regolith from protolith. This “geologic time” can vary from tens to hundreds of years for weathered material developed on moraines deposited by active glaciers ( Anderson et al. 1997 ), to millions or possibly hundreds of millions of years of regolith evolution as documented in laterites and bauxites on stable cratons ( Nahon 1986 ). In contrast, solute profiles reflect much shorter time scales corresponding to the residence time of the soil water which commonly ranges from days to decades ( Stonestrom et al. 1998 ). Factors impacting soil minerals can therefore be related to geologically old processes while those impacting pore waters are related to contemporary processes. We first discuss a geochemical frame work for modeling soil profiles, including a simple scheme that depends on the extent of enrichment or depletion. Such profiles are comprised of reaction fronts affected by chemical, hydrologic, geologic and biologic processes that control soil evolution. We then present a hierarchy of models that have been used to interpret both solid state and solute compositions in regolith. The more simple approaches to model depletion in soils, using analytical models, are first described. The most elementary of these is a linear model that calculates rate constants from the slopes of either solid or solute weathering gradients: these rate constants represent lumped parameters that describe weathering in terms of an integrated reaction rate. Two other analytical models are then presented that have been used to fit solid state elemental profiles with exponential and sigmoidal functions. All of these analytical approaches are derived for models of soils as containing a limited number of components, phases, and species. At a more complex level, numerical models are then presented to elucidate how kinetic and transport parameters as well as chemical, hydrologic, and physical soil data can be incorporated. We consider two forms of these models, first relatively simple spreadsheet calculators and then more sophisticated multi-component, multi-phase reactive-transport numerical codes. Our treatment of reactive transport modeling is relatively cursory, in recognition of the treatment in the chapter by Steefel and Maher (2009 , this volume). Because these models incorporate more phases, components, and species than the other approaches and explicitly model the more fundamental reaction mechanisms involved, they generally have a greater need for parameterization. In our conclusion section, we discuss how this hierarchy of approaches can yield generalizations about soils that are often complementary.

Reviews in Mineralogy and Geochemistry↗
USGS2008

PFReports: A program for systematic checking of annual peaks in NWISWeb

The accuracy, characterization, and completeness of the U.S. Geological Survey (USGS) peak-flow data drive the determination of flood-frequency estimates that are used daily to design water and transportation infrastructure, delineate flood-plain boundaries, and regulate development and utilization of lands throughout the Nation and are essential to understanding the implications of climate change on flooding. Indeed, this high-profile database reflects and highlights the quality of USGS water-data collection programs. Its extension and improvement are essential to efforts to strengthen USGS networks and science leadership and is worthy of the attention of Water Science Center (WSC) hydrographers. This document describes a computer program, PFReports, and its output that facilitates efficient and robust review and correction of data in the USGS Peak Flow File (PFF) hosted as part of NWISWeb (the USGS public Web interface to much of the data stored and managed within the National Water Information System or NWIS). Checks embedded in the program are recommended as part of a more comprehensive assessment of peak flow data that will eventually include examination of possible regional changes, seasonal changes, and decadal variations in magnitude, timing, and frequency. Just as important as the comprehensive assessment, cleaning up the database will increase the likelihood of improved WSC regional flood-frequency equations. As an example of the value of cleaning up the PFF, data for 26,921 sites in the PFF were obtained. Of those sites, 17,542 sites had peak streamflow values and daily values. For the 17,542 sites, 1,097 peaks were identified that were less than the daily value for the day on which the peak occurred. Of the 26,921 sites, 11,643 had peak streamflow values, concurrent daily values, and at least 10 peaks. At the 11,643 sites, 2,205 peaks were identified as potential outliers in a regression of peak streamflows on daily values. Previous efforts to identify problems with the PFF were time consuming, laborious, and often ineffective. This new suite of checks represents an effort to automate identification of specific problems without plotting or printing large amounts of data that may not have problems. In addition, the results of the checks of the peak flow files are delivered through the World Wide Web with links to individual reports so that WSCs can focus on specific problems in an organized and standardized fashion. Over the years, technical reviews, regional-flood studies, and user inquiries have identified many minor and some major problems in the PFF. However, the cumbersome nature of the PFF editor and a lack of analytical tools have hampered efforts at quality assurance/quality control (QA/QC) and subsequently to make needed revisions to the database. This document is organized to provide information regarding PFReports, especially those tests involving regression and to provide an overview of the review procedures for utilizing the output. It also may be used as a reference for the data qualification codes and abbreviations for the tests. Results of the checks for all peak flow files (March 2008) are available at http://nd.water.usgs.gov/internal/pfreports/.

Open-File Report↗
USGS2021

Inclusion of pesticide transformation products is key to estimating pesticide exposures and effects in small U.S. streams

Improved analytical methods can quantify hundreds of pesticide transformation products (TPs), but understanding of TP occurrence and potential toxicity in aquatic ecosystems remains limited. We quantified 108 parent pesticides and 116 TPs in more than 3 700 samples from 442 small streams in mostly urban basins across five major regions of the United States. TPs were detected nearly as frequently as parents (90 and 95% of streams, respectively); 102 TPs were detected at least once and 28 were detected in >20% samples in at least one region—TPs of 9 herbicides, 2 fungicides (chlorothalonil and thiophanate-methyl), and 1 insecticide (fipronil) were the most frequently detected. TPs occurred commonly during baseflow conditions, indicating chronic environmental TP exposures to aquatic organisms and the likely importance of groundwater as a TP source. Hazard quotients based on acute aquatic-life benchmarks for invertebrates and nonvascular plants and vertebrate-centric molecular endpoints (sublethal effects) quantify the range of the potential contribution of TPs to environmental risk and highlight several TP exposure–response data gaps. A precautionary approach using equimolar substitution of parent benchmarks or endpoints for missing TP benchmarks indicates that potential aquatic effects of pesticide TPs could be underestimated by an order of magnitude or more.

Environmental Science and Technology↗
USGS1997

Method for determination of methyl tert-butyl ether and its degradation products in water

An analytical method is described that can detect the major alkyl ether compounds that are used as gasoline oxygenates (methyl tert-butyl ether, MTBE; ethyl tert-butyl ether, ETBE; and tert-amyl methyl ether, TAME) and their most characteristic degradation products (tert-butyl alcohol, TBA; tert-butyl formate, TBF; and tert-amyl alcohol, TAA) in water at sub-ppb concentrations. The new method involves gas chromatography (GC) with direct aqueous injection (DAI) onto a polar column via a splitless injector, coupled with detection by mass spectrometry (MS). DAI-GC/MS gives excellent agreement with conventional purge-and-trap methods for MTBE over a wide range of environmentally relevant concentrations. The new method can also give simultaneous identification of polar compounds that might occur as degradation products of gasoline oxygenates, such as TBA, TBF, TAA, methyl acetate, and acetone. When the method was applied to effluent from a column microcosm prepared with core material from an urban site in New Jersey, conversion of MTBE to TBA was observed after a lag period of 35 days. However, to date, analyses of water samples from six field sites using the DAI-GC/MS method have not produced evidence for the expected products of in situ degradation of MTBE.An analytical method is described that can detect the major alkyl ether compounds that are used as gasoline oxygenates (methyl tert-butyl ether, MTBE; ethyl tert-butyl ether, ETBE; and tert-amyl methyl ether, TAME) and their most characteristic degradation products (tert-butyl alcohol, TBA; tert-butyl formate, TBF; and tert-amyl alcohol, TAA) in water at sub-ppb concentrations. The new method involves gas chromatography (GC) with direct aqueous injection (DAI) onto a polar column via a splitless injector, coupled with detection by mass spectrometry (MS). DAI-GC/MS gives excellent agreement with conventional purge-and-trap methods for MTBE over a wide range of environmentally relevant concentrations. The new method can also give simultaneous identification of polar compounds that might occur as degradation products of gasoline oxygenates, such as TBA, TBF, TAA, methyl acetate, and acetone. When the method was applied to effluent from a column microcosm prepared with core material from an urban site in New Jersey, conversion of MTBE to TBA was observed after a lag period of 35 days. However, to date, analyses of water samples from six field sites using the DAI-GC/MS method have not produced evidence for the expected products of in situ degradation of MTBE.

Environmental Science & Technology↗
USGS2002

Characterization and copper binding of humic and nonhumic organic matter isolated from the South Platte River: Evidence for the presence of nitrogenous binding site

Humic substances typically constitute 40−60% of the dissolved organic matter (DOM) in surface waters. However, little information is available regarding the metal binding properties of the nonhumic hydrophilic portion of the DOM. In this study, humic and nonhumic DOM samples were isolated from the South Platte River (Colorado, DOC = 2.6 mg·L - 1 , SUVA 254 = 2.4 L/mg·m) using a two-column array of XAD-8 and XAD-4 resins. The three major isolated fractions of DOM, which accounted for 57% of the bulk DOM, were characterized using a variety of analytical tools. Proton and copper binding properties were studied for each fraction. The main objective of this work was to compare the structural and chemical characteristics of the isolated fractions and test models describing DOM reactivity toward metal ions. The characterization work showed significant structural differences between the three isolated fractions of DOM. The hydrophobic acid fraction (i.e., humic substances isolated from the XAD-8 resin) gave the largest C/H, C/O, and C/N ratios and aromatic carbon content among the three isolated fractions. The transphilic acid (TPHA) fraction (“transphilic” meaning fraction of intermediate polarity isolated from the XAD-4 resin) was found to incorporate the highest proportion of polysaccharides, whereas the transphilic neutral (TPHN) fraction was almost entirely proteinaceous. The gradual increase of the charge with pH for the three DOM fractions is most likely caused by a large distribution of proton affinity constants for the carboxylic groups, as well as a second type of group more generally considered to be phenolic. In the case of the DOM fraction enriched in proteinaceous material (i.e., TPHN fraction), the results showed that the amino groups are responsible for the charge reversal. For low copper concentrations, nitrogen-containing functional groups similar to those of amino acids are likely to be involved in complexation, in agreement with previously published data.

Colorado↗
USGS2025

Revealing organofluorine contamination in effluents and surface waters with complementary analytical approaches: Fluorine-19 nuclear magnetic resonance spectroscopy (19F-NMR) and liquid chromatography-tandem mass spectrometry (LC-MS/MS)

Fluorinated organic contaminants, including per- and polyfluoroalkyl substances (PFASs) and fluorinated pesticides and pharmaceuticals (FPPs), pose a persistent threat to environmental health. Widely used liquid chromatography-tandem mass spectrometry (LC-MS/MS) methods fail to capture large fractions of total organofluorine in environmental samples, confounding the assessment of fluorinated contamination. Fluorine-19 nuclear magnetic resonance spectroscopy ( 19 F-NMR) is an inclusive method for total and class-based organofluorine analysis. Here, we apply 19 F-NMR to 31 effluent, surface water, and foam samples collected at 13 potential organofluorine point sources or source regions and compare the results to targeted LC-MS/MS for 34 or 64 PFASs. LC-MS/MS detected a median of 11.4% of total organofluorine detected by 19 F-NMR (range: nondetect to 8190 nM F 19 F-NMR; nondetect to 8010 nM F LC-MS/MS). The highest 19 F-NMR total organofluorine concentrations, detected in wastewater treatment plant (WWTP)-associated foam and at a soy oil production facility, arose from resonances characteristic of per- and polyfluorinated alkyl chains. 19 F-NMR resonances from aryl CF 3 moieties were abundant in the WWTP-associated samples, consistent with prior reports of substantial contributions from pharmaceuticals to WWTP effluents. 19 F-NMR enables the quantitative assessment of total organofluorine and qualitative insight into fluorinated structures, providing complementary analysis of organofluorine compounds missed by targeted mass spectrometry-based protocols.

Environmental Science & Technology↗
USGS2010

A role for analytical chemistry in advancing our understanding of the occurrence, fate, and effects of Corexit Oil Dispersants

On April 24, 2010, the sinking of the Deepwater Horizon oil rig resulted in the release of oil into the Gulf of Mexico. As of July 19, 2010, the federal government's Deepwater Horizon Incident Joint Information Center estimates the cumulative range of oil released is 3,067,000 to 5,258,000 barrels, with a relief well to be completed in early August. By comparison, the Exxon Valdez oil spill released a total of 260,000 barrels of crude oil into the environment. As of June 9, BP has used over 1 million gallons of Corexit oil dispersants to solubilize oil and help prevent the development of a surface oil slick. Oil dispersants are mixtures containing solvents and surfactants that can exhibit toxicity toward aquatic life and may enhance the toxicity of components of weathered crude oil. Detailed knowledge of the composition of both Corexit formulations and other dispersants applied in the Gulf will facilitate comprehensive monitoring programs for determining the occurrence, fate, and biological effects of the dispersant chemicals. The lack of information on the potential impacts of oil dispersants has caught industry, federal, and state officials off guard. Until compositions of Corexit 9500 and 9527 were released by the U.S. Environmental Protection Agency online, the only information available consisted of Material Safety Data Sheets (MSDS), patent documentation, and a National Research Council report on oil dispersants. Several trade and common names are used for the components of the Corexits. For example, Tween 80 and Tween 85 are oligomeric mixtures.

Environmental Science & Technology↗
USGS2024

Atlas of microscopic images of biochar using reflected light microscopy in biochar characterization

Derived through the thermochemical conversion of biomass, biochar is a carbon-rich substance recognized for its significance in environmental applications and sustainable agriculture. As interest in its utilization continues to rise, it becomes crucial to comprehend how the source material and pyrolysis parameters influence the properties of biochar and, consequently, to research the suitability of various analytical methods for characterizing it. Despite the current utilization of numerous physical and chemical methods, the untapped potential of reflected light microscopy warrants further exploration. While a few recent studies suggest a correlation between certain microscopic characteristics and selected physical and chemical properties of biochar, the data are limited and difficult to compare. This is primarily due to variations in the types of original biomass used and lack of information about pyrolysis conditions. Moreover, because only a limited number of photographs taken under a reflected light microscope are publicly available to-date, it is difficult to evaluate morphological differences between various biochars and other organic materials such as inertinites from coal, charcoal, etc. To address limited availability of publicly available data, this “Atlas of Microscopic Images of Biochar” presents a collection of more than 300 images contributed by researchers from Poland, the United States, Canada, Australia, Brazil, and Denmark. These photomicrographs capture optical characteristics of a diverse array of biochar, demonstrating its unique morphological and structural features. This visual documentation can serve as a valuable resource for researchers, industry professionals, educators, and enthusiasts interested in investigating the complexities of biochar forms.

Indiana Journal of Earth Sciences↗
USGS2017

Influence of sediment chemistry and sediment toxicity on macroinvertebrate communities across 99 wadable streams of the Midwestern USA

Simultaneous assessment of sediment chemistry, sediment toxicity, and macroinvertebrate communities can provide multiple lines of evidence when investigating relations between sediment contaminants and ecological degradation. These three measures were evaluated at 99 wadable stream sites across 11 states in the Midwestern United States during the summer of 2013 to assess sediment pollution across a large agricultural landscape. This evaluation considers an extensive suite of sediment chemistry totaling 274 analytes (polycyclic aromatic hydrocarbons, organochlorine compounds, polychlorinated biphenyls, polybrominated diphenyl ethers, trace elements, and current-use pesticides) and a mixture assessment based on the ratios of detected compounds to available effects-based benchmarks. The sediments were tested for toxicity with the amphipod Hyalella azteca (28-d exposure), the midge Chironomus dilutus (10-d), and, at a few sites, with the freshwater mussel Lampsilis siliquoidea (28-d). Sediment concentrations, normalized to organic carbon content, infrequently exceeded benchmarks for aquatic health, which was generally consistent with low rates of observed toxicity. However, the benchmark-based mixture score and the pyrethroid insecticide bifenthrin were significantly related to observed sediment toxicity. The sediment mixture score and bifenthrin were also significant predictors of the upper limits of several univariate measures of the macroinvertebrate community (EPT percent, MMI (Macroinvertebrate Multimetric Index) Score, Ephemeroptera and Trichoptera richness) using quantile regression. Multivariate pattern matching (Mantel-like tests) of macroinvertebrate species per site to identified contaminant metrics and sediment toxicity also indicate that the sediment mixture score and bifenthrin have weak, albeit significant, influence on the observed invertebrate community composition. Together, these three lines of evidence (toxicity tests, univariate metrics, and multivariate community analysis) suggest that elevated contaminant concentrations in sediments, in particular bifenthrin, is limiting macroinvertebrate communities in several of these Midwest streams.

Science of the Total Environment↗
USGS2019

A stratigraphic approach to inferring depositional ages from detrital geochronology data

With the increasing use of detrital geochronology data for provenance analyses, we have also developed new constraints on the age of otherwise undateable sedimentary deposits. Because a deposit can be no older than its youngest mineral constituent, the youngest defensible detrital mineral age defines the maximum depositional age of the sampled bed. Defining the youngest `defensible' age in the face of uncertainty (e.g., analytical and geological uncertainty, or sample contamination) is challenging. The current standard practice of finding multiple detrital minerals with indistinguishable ages provides confidence that a given age is not an artifact; however, we show how requiring this overlap reduces the probability of identifying the true youngest component age. Barring unusual complications, the principle of superposition dictates that sedimentary deposits must get younger upsection. This fundamental constraint can be incoporated into the analysis of depositional ages in sedimentary sections through the use of Bayesian statistics, allowing for the inference of bounded estimates of true depositional ages and uncertainties from detrital geochronology so long as some minimum age constraints are present. We present two approaches for constructing a Bayesian model of deposit ages, first solving directly for the ages of deposits with the prior constraint that the ages of units must obey stratigraphic ordering, and second describing the evolution of ages with a curve that represents the sediment accumulation rate. Using synthetic examples we highlight how this method preforms in less-than-ideal circumstances. In an example from the Magallanes Basin of Patagonia, we demonstrate how introducing other age information from the stratigraphic section (e.g., fossil assemblages or radiometric dates) and formalizing the stratigraphic context of samples provides additional constraints on and information regarding depositional ages or derived quantities (e.g., sediment accumulation rates) compared to isolated analysis of individual samples.

Frontiers in Earth Science↗
USGS2008

A national reconnaissance for pharmaceuticals and other organic wastewater contaminants in the United States - II) Untreated drinking water sources

Numerous studies have shown that a variety of manufactured and natural organic compounds such as pharmaceuticals, steroids, surfactants, flame retardants, fragrances, plasticizers and other chemicals often associated with wastewaters have been detected in the vicinity of municipal wastewater discharges and livestock agricultural facilities. To provide new data and insights about the environmental presence of some of these chemicals in untreated sources of drinking water in the United States targeted sites were sampled and analyzed for 100 analytes with sub-parts per billion detection capabilities. The sites included 25 ground- and 49 surface-water sources of drinking water serving populations ranging from one family to over 8 million people. Sixty-three of the 100 targeted chemicals were detected in at least one water sample. Interestingly, in spite of the low detection levels 60% of the 36 pharmaceuticals (including prescription drugs and antibiotics) analyzed were not detected in any water sample. The five most frequently detected chemicals targeted in surface water were: cholesterol (59%, natural sterol), metolachlor (53%, herbicide), cotinine (51%, nicotine metabolite), β-sitosterol (37%, natural plant sterol), and 1,7-dimethylxanthine (27%, caffeine metabolite); and in ground water: tetrachloroethylene (24%, solvent), carbamazepine (20%, pharmaceutical), bisphenol-A (20%, plasticizer), 1,7-dimethylxanthine (16%, caffeine metabolite), and tri (2-chloroethyl) phosphate (12%, fire retardant). A median of 4 compounds were detected per site indicating that the targeted chemicals generally occur in mixtures (commonly near detection levels) in the environment and likely originate from a variety of animal and human uses and waste sources. These data will help prioritize and determine the need, if any, for future occurrence, fate and transport, and health-effects research for subsets of these chemicals and their degradates most likely to be found in water resources used for drinking water in the United States.

Science of the Total Environment↗