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Comparison of two estrogen chemically activated luciferase expression cell bioassays to liquid chromatography–mass spectrometry for quantifying estrone in water samples

Chemically activated luciferase expression (CALUX) cell bioassays are popular tools for assessing endocrine activity of chemicals such as certain environmental contaminants. Although activity equivalents can be obtained from CALUX analysis, directly comparing these equivalents to those obtained from analytical chemistry methods can be problematic because of the complexity of endocrine active pathways. We explored the suitability of two estrogen CALUX bioassays (the Organisation for Economic Co-operation and Development–approved VM7Luc4E2 cell bioassay and the VM7LucERβc9 cell bioassay) for quantitation of estrogen. Quadrupole-time of flight ultraperformance liquid chromatography–mass spectrometry (LC/MS) was selected as a comparative method. Regression analysis of measured estrone (E1) calibration samples showed all three methods to be highly predictive of nominal concentrations ( p ≤ 7.5 × 10 –51 ). Extracts of water sampled from laboratory dilutor tanks containing E1 at 0, 20, and 200 ng/L alone and in combination with atrazine were selected to test the quantitative capabilities of the CALUX assays. Process controls (0 and 100 ng E1/L) and a separate E1 standard (10 ng/ml, used to prepare the E1 process control) were also tested. Levels of E1 determined by LC/MS analysis and bioanalytical equivalents (ng E1/L) determined by CALUX analyses were comparable except in certain instances where the samples required dilution prior to CALUX analyses (e.g., the E1 process control and E1 standard). In those instances, measurements by CALUX were slightly but significantly decreased relative to LC/MS. Atrazine had no effect on the ability of either LC/MS or the CALUX bioassays to quantify E1. The present study illustrates the CALUX bioassays as successful in quantifying an estrogen in simple water samples and further characterizes their utility for screening. Environ Toxicol Chem 2023;42:333–339. Published 2022. This article is a U.S. Government work and is in the public domain in the USA.

Environmental Toxicology and Chemistry

Laboratory toxicity and benthic invertebrate field colonization of Upper Columbia River sediments: Finding adverse effects using multiple lines of evidence

From 1930 to 1995, the Upper Columbia River (UCR) of northeast Washington State received approximately 12 million metric tons of smelter slag and associated effluents from a large smelter facility located in Trail, British Columbia, approximately 10 km north of the United States–Canadian border. Studies conducted during the past two decades have demonstrated the presence of toxic concentrations of heavy metals in slag-based sandy sediments, including cadmium, copper, zinc, and lead in the UCR area as well as the downstream reservoir portion of Lake Roosevelt. We conducted standardized whole-sediment toxicity tests with the amphipod Hyalella azteca (28-day) and the midge Chironomus dilutus (10-day) on 11 samples, including both UCR and study-specific reference sediments. Metal concentrations in sediments were modeled for potential toxicity using three approaches: (1) probable effects quotients (PEQs) based on total recoverable metals (TRMs) and simultaneously extracted metals (SEMs); (2) SEMs corrected for acid-volatile sulfides (AVS; i.e., ∑SEM − AVS); and (3) ∑SEM − AVS normalized to the fractional organic carbon (f oc ) (i.e., ∑SEM − AVS/f oc ). The most highly metal-contaminated sample (∑PEQ TRM = 132; ∑PEQ SEM = 54; ∑SEM − AVS = 323; and ∑SEM − AVS/ foc = 64,600 umol/g) from the UCR was dominated by weathered slag sediment particles and resulted in 80% mortality and 94% decrease in biomass of amphipods; in addition, this sample significantly decreased growth of midge by 10%. The traditional ∑AVS – SEM, uncorrected for organic carbon, was the most accurate approach for estimating the effects of metals in the UCR. Treatment of the toxic slag sediment with 20% Resinex SIR-300 metal-chelating resin significantly decreased the toxicity of the sample. Samples ∑SEM − AVS > 244 was not toxic to amphipods or midge in laboratory testing, indicating that this value may be an approximate threshold for effects in the UCR. In situ benthic invertebrate colonization studies in an experimental pond (8-week duration) indicated that two of the most metal-contaminated UCR sediments (dominated by high levels of sand-sized slag particles) exhibited decreased invertebrate colonization compared with sand-based reference sediments. Field-exposed SIR-300 resin samples also exhibited decreased invertebrate colonization numbers compared with reference materials, which may indicate behavioral avoidance of this material under field conditions. Multiple lines of evidence (analytical chemistry, laboratory toxicity, and field colonization results), along with findings from previous studies, indicate that high metal concentrations associated with slag-enriched sediments in the UCR are likely to adversely impact the growth and survival of native benthic invertebrate communities. Additional laboratory toxicity testing, refinement of the applications of sediment benchmarks for metal toxicity, and in situ benthic invertebrate studies will assist in better defining the spatial extent, temporal variations, and ecological impacts of metal-contaminated sediments in the UCR system.

Trail

De facto water reuse: Bioassay suite approach delivers depth and breadth in endocrine active compound detection

Although endocrine disrupting compounds (EDCs) have been detected in wastewater and surface waters worldwide using a variety of in vitro effects-based screening tools, e.g. bioassays, few have examined potential attenuation of environmental contaminants by both natural (sorption, degradation, etc) and anthropogenic (water treatment practices) processes. This study used several bioassays and quantitative chemical analyses to assess residence-time weighted samples at six sites along a river in the northeastern United States beginning upstream of a waste water treatment plant (WWTP) outfall and proceeding downstream along the stream reach to a drinking water treatment plant (DWTP). Known steroidal estrogens were quantified and changes in signaling pathway molecular initiating events (activation of estrogen, androgen, glucocorticoid, peroxisome proliferator-activated, pregnane X receptor, and aryl hydrocarbon receptor signaling networks) were identified in water extracts. In initial multi-endpoint assays geographic and receptor-specific endocrine activity patterns in transcription factor signatures and nuclear receptor activation were discovered. In subsequent single endpoint receptor-specific bioassays, estrogen (16 of 18 samples; 0.01 to 28 ng estradiol equivalents [E2Eqs]/L) glucocorticoid (3 of 18 samples; 1.8 to 21 ng dexamethasone equivalents [DexEqs]/L), and androgen (2 of 18 samples; 0.95 to 2.1 ng dihydrotestosterone equivalents [DHTEqs]/L) receptor transcriptional activation occurred above respective assay method detection limits (0.04 ng E2Eqs/L, 1.2 ng DexEqs/L, and 0.77 ng DHTEqs/L) in multiple sampling events. Estrogen activity, the most often detected, correlated well with measured concentrations of known steroidal estrogens (R2 = 0.890). Overall, activity indicative of multiple types of endocrine active compounds was highest in wastewater effluent samples, while activity downstream was progressively lower, and negligible in (unfinished) treated water. This multiple bioassay approach, in conjunction with targeted analytical chemistry methods, has gained acceptance among water quality screening programs. Not only was estrogenic and glucocorticoid activity confirmed in the effluent by utilizing multiple methods concurrently, but other activated signaling networks that historically received less attention (i.e. peroxisome proliferator-activated receptor) were also detected.

Science of the Total Environment

In vitro effects-based method and water quality screening model for use in pre- and post-distribution treated waters

Recent urban public water supply contamination events emphasize the importance of screening treated drinking water quality after distribution. In vitro bioassays, when run concurrently with analytical chemistry methods, are effective tools to evaluating the efficacy of water treatment processes and water quality. We tested 49 water samples representing the Chicago Department of Water Management service areas for estrogen, (anti)androgen, glucocorticoid receptor-activating contaminants and cytotoxicity. We present a tiered screening approach suitable to samples with anticipated low-level activity and initially tested all extracts for statistically identifiable endocrine activity; performing a secondary dilution-response analysis to determine sample EC 50 and biological equivalency values (BioEq). Estrogenic activity was detected in untreated Lake Michigan intake water samples using mammalian (5/49; median: 0.21 ng E2Eq/L) and yeast cell (5/49; 1.78 ng E2Eq/L) bioassays. A highly sensitive (anti)androgenic activity bioassay was applied for the first time to water quality screening and androgenic activity was detected in untreated intake and treated pre-distribution samples (4/49; 0.93 ng DHTEq/L). No activity was identified above method detection limits in the yeast androgenic, mammalian anti-androgenic, and both glucocorticoid bioassays. Known estrogen receptor agonists were detected using HPLC/MS-MS (estrone: 0.72-1.4 ng/L; 17α-estradiol: 1.3-1.5 ng/L; 17β-estradiol: 1.4 ng/L; equol: 8.8 ng/L), however occurrence did not correlate with estrogenic bioassay results. Many studies have applied bioassays to water quality monitoring using only relatively small samples sets often collected from surface and/or wastewater effluent. However, to realistically adapt these tools to treated water quality monitoring, water quality managers must have the capacity to screen potentially hundreds of samples in short timeframes. Therefore, we provided a tiered screening model that increased sample screening speed, without sacrificing statistical stringency, and detected estrogenic and androgenic activity only in pre-distribution Chicago area samples.

Illinois, Indiana

De facto water reuse: Investigating the fate and transport of chemicals of emerging concern from wastewater discharge through drinking water treatment using non-targeted analysis and suspect screening

Wastewater is a source for many contaminants of emerging concern (CECs), and surface waters receiving wastewater discharge often serve as source water for downstream drinking water treatment plants. Nontargeted analysis and suspect screening methods were used to characterize chemicals in residence-time-weighted grab samples and companion polar organic chemical integrative samplers (POCIS) collected on three separate hydrologic sampling events along a surface water flow path representative of de facto water reuse. The goal of this work was to examine the fate of CECs along the study flow path as water is transported from wastewater effluent through drinking water treatment. Grab and POCIS samples provided a comparison between residence-time-weighted single-point and integrative sample results. This unique and rigorous study design, coupled with advanced analytical chemistry tools, provided important insights into chemicals found in drinking water and their potential sources, which can be used to help prioritize chemicals for further study. K -means clustering analysis was used to identify patterns in chemical occurrences across both sampling sites and sampling events. Chemical features that occurred frequently or survived drinking water treatment were prioritized for identification, resulting in the probable identification of over 100 CECs in the watershed and 28 CECs in treated drinking water.

Environmental Science & Technology

Evaluation of 6PPD-quinone lethal toxicity and sublethal effects on disease resistance and swimming fitness in coastal cutthroat trout (Oncorhynchus clarkii clarkii)

6PPD-quinone (6PPDQ), derived from the tire-protectant 6PPD reacting with ozone, is an emerging contaminant of concern owing to its role in coho salmon ( Oncorhynchus kisutch ) deaths via urban runoff mortality syndrome (URMS). Given the impact of 6PPDQ on aquatic life in urban streams, we addressed the acute toxicity of 6PPDQ exposure on coastal cutthroat trout (CCT) ( Oncorhynchus clarkii clarkii ), a species sympatric with coho salmon in natal watersheds. Using static exposures coupled with analytical chemistry, we determined the 24-h LC 50 values for alevin (297.2 ng/L), swim-up fry (39.6 ng/L), 5-month parr (103.3 ng/L), and 13-month juveniles (185.9 ng/L)─values similar to toxicity observed in coho salmon. Additionally, the 96-h LC 50 (77.6 ng/L) was 2.4 times more lethal for juvenile CCT. We assessed potential effects of sublethal 6PPDQ exposure on disease resistance to infectious hematopoietic necrosis (IHN), an endemic viral disease of Pacific salmon, and to swimming performance. Sublethal 6PPDQ (53.6 ng/L) did not affect survival of parr exposed to IHN virus compared to virus alone. Conversely, 6PPDQ exposure as low as 72.2 ng/L significantly reduced 15- and 24-month juvenile swimming performance, and 120.5 ng/L 6PPDQ increased blood hematocrit. Overall, CCT are the second most sensitive species tested to date for 6PPDQ sensitivity which further emphasizes the need for identifying alternatives to 6PPD.

Environmental Science and Technology

Mapping the distribution of materials in hyperspectral data using the USGS Material Identification and Characterization Algorithm (MICA)

Identifying materials by measuring and analyzing their reflectance spectra has been an important method in analytical chemistry for decades. Airborne and space-based imaging spectrometers allow scientists to detect materials and map their distributions across the landscape. With new satellite-borne hyperspectral sensors planned for the future, for example, HYSPIRI (HYPerspectral InfraRed Imager), robust methods are needed to fully exploit the information content of hyperspectral remote sensing data. A method of identifying and mapping materials using spectral feature based analysis of reflectance data in an expert-system framework called MICA (Material Identification and Characterization Algorithm) is described in this paper. The core concepts and calculations of MICA are presented. A MICA command file has been developed and applied to map minerals in the full-country coverage of the 2007 Afghanistan HyMap hyperspectral data.

Conference Paper

Detection limits of quantitative and digital PCR assays and their influence in presence-absence surveys of environmental DNA

A set of universal guidelines is needed to determine the limit of detection (LOD) in PCR-based analyses of low concentration DNA. In particular, environmental DNA (eDNA) studies require sensitive and reliable methods to detect rare and cryptic species through shed genetic material in environmental samples. Current strategies for assessing detection limits of eDNA are either too stringent or subjective, possibly resulting in biased estimates of species’ presence. Here, a conservative LOD analysis grounded in analytical chemistry is proposed to correct for overestimated DNA concentrations predominantly caused by the concentration plateau, a nonlinear relationship between expected and measured DNA concentrations. We have used statistical criteria to establish formal mathematical models for both quantitative and droplet digital PCR. To assess the method, a new Grass Carp ( Ctenopharyngodon idella ) TaqMan assay was developed and tested on both PCR platforms using eDNA in water samples. The LOD adjustment reduced Grass Carp occupancy and detection estimates while increasing uncertainty – indicating that caution needs to be applied to eDNA data without LOD correction. Compared to quantitative PCR, digital PCR had higher occurrence estimates due to increased sensitivity and dilution of inhibitors at low concentrations. Without accurate LOD correction, species occurrence and detection probabilities based on eDNA estimates are prone to a source of bias that cannot be reduced by an increase in sample size or PCR replicates. Other applications also could benefit from a standardized LOD such as GMO food analysis, and forensic and clinical diagnostics.

Molecular Ecology Resources

Spectroscopic remote sensing for material identification, vegetation characterization, and mapping

Identifying materials by measuring and analyzing their reflectance spectra has been an important procedure in analytical chemistry for decades. Airborne and space-based imaging spectrometers allow materials to be mapped across the landscape. With many existing airborne sensors and new satellite-borne sensors planned for the future, robust methods are needed to fully exploit the information content of hyperspectral remote sensing data. A method of identifying and mapping materials using spectral feature analyses of reflectance data in an expert-system framework called MICA (Material Identification and Characterization Algorithm) is described. MICA is a module of the PRISM (Processing Routines in IDL for Spectroscopic Measurements) software, available to the public from the U.S. Geological Survey (USGS) at http://pubs.usgs.gov/of/2011/1155/. The core concepts of MICA include continuum removal and linear regression to compare key diagnostic absorption features in reference laboratory/field spectra and the spectra being analyzed. The reference spectra, diagnostic features, and threshold constraints are defined within a user-developed MICA command file (MCF). Building on several decades of experience in mineral mapping, a broadly-applicable MCF was developed to detect a set of minerals frequently occurring on the Earth's surface and applied to map minerals in the country-wide coverage of the 2007 Afghanistan HyMap data set. MICA has also been applied to detect sub-pixel oil contamination in marshes impacted by the Deepwater Horizon incident by discriminating the C-H absorption features in oil residues from background vegetation. These two recent examples demonstrate the utility of a spectroscopic approach to remote sensing for identifying and mapping the distributions of materials in imaging spectrometer data.

Conference Paper

Glass electrodes sensitive to divalent cations

Glass electrodes suitable for measurement of divalent cations have been made and tested. Empirical and theoretical electrode equations have been presented to describe electrode behavior in a variety of aqueous solutions. Most electrodes show response interpretable as showing nearly ideal solid-solution behavior of the cations in the glass surface. The electrodes should be useful in the measurement of divalent-cation activities in natural waters and biological fluids, and useful in general analytical chemistry.

Science

Technological innovations in aquaculture

Technology in aquaculture has expanded at a phenomenal rate during the last 50 to 100 years. Based on both this past progress and the present technological advances being made in our society, it is reasonable to expect aquaculturists to profit from the rapid technological advances being made in both hardware and biological systems. These advances will result as spinoffs from medicine, from analytical chemistry, and most importantly, from the evolution of new consumer products such as auto-focus cameras, electronic watches, and microprocessor-monitored automobiles. We can expect to use economical, reliable instrumentation capable of environmental monitoring for predictive purposes and instrumentation that will contain alarm and control circuits. Genetic engineering will result in biological organisms that produce hormones, drugs, and other biological materials as well as detoxify pollutants on demand. When we as aquaculturists identify the need for a product, that product will be developed.

Fisheries

Chain of custody; recommendations for acceptance and analysis of evidentiary geochemical samples

Personnel from the Analytical Chemistry Services Group (ACSG), Mineral Resource Survey Program, formed a team to determine the policies for acceptance and analysis of geochemical samples. This team contacted law enforcement agencies that handle litigious samples, laboratories that work with samples of special nature, and the Solicitor General, Department of the Interior. Using the knowledge from these agencies as well as the expertise of ACSG personnel, sample control routine procedures, sample control evidentiary procedures, personnel policy governing chain-of-custody samples, and the general polices governing physical security of chain-of custody samples have been enacted.

Circular

Developing integrated methods to address complex resource and environmental issues

Introduction This circular provides an overview of selected activities that were conducted within the U.S. Geological Survey (USGS) Integrated Methods Development Project, an interdisciplinary project designed to develop new tools and conduct innovative research requiring integration of geologic, geophysical, geochemical, and remote-sensing expertise. The project was supported by the USGS Mineral Resources Program, and its products and acquired capabilities have broad applications to missions throughout the USGS and beyond. In addressing challenges associated with understanding the location, quantity, and quality of mineral resources, and in investigating the potential environmental consequences of resource development, a number of field and laboratory capabilities and interpretative methodologies evolved from the project that have applications to traditional resource studies as well as to studies related to ecosystem health, human health, disaster and hazard assessment, and planetary science. New or improved tools and research findings developed within the project have been applied to other projects and activities. Specifically, geophysical equipment and techniques have been applied to a variety of traditional and nontraditional mineral- and energy-resource studies, military applications, environmental investigations, and applied research activities that involve climate change, mapping techniques, and monitoring capabilities. Diverse applied geochemistry activities provide a process-level understanding of the mobility, chemical speciation, and bioavailability of elements, particularly metals and metalloids, in a variety of environmental settings. Imaging spectroscopy capabilities maintained and developed within the project have been applied to traditional resource studies as well as to studies related to ecosystem health, human health, disaster assessment, and planetary science. Brief descriptions of capabilities and laboratory facilities and summaries of some applications of project products and research findings are included in this circular. The work helped support the USGS mission to “provide reliable scientific information to describe and understand the Earth; minimize loss of life and property from natural disasters; manage water, biological, energy, and mineral resources; and enhance and protect our quality of life.” Activities within the project include the following: Spanned scales from microscopic to planetary; Demonstrated broad applications across disciplines; Included life-cycle studies of mineral resources; Incorporated specialized areas of expertise in applied geochemistry including mineralogy, hydrogeology, analytical chemistry, aqueous geochemistry, biogeochemistry, microbiology, aquatic toxicology, and public health; and Incorporated specialized areas of expertise in geophysics including magnetics, gravity, radiometrics, electromagnetics, seismic, ground-penetrating radar, borehole radar, and imaging spectroscopy. This circular consists of eight sections that contain summaries of various activities under the project. The eight sections are listed below: Laboratory Facilities and Capabilities, which includes brief descriptions of the various types of laboratories and capabilities used for the project; Method and Software Development, which includes summaries of remote-sensing, geophysical, and mineralogical methods developed or enhanced by the project; Instrument Development, which includes descriptions of geophysical instruments developed under the project; Minerals, Energy, and Climate, which includes summaries of research that applies to mineral or energy resources, environmental processes and monitoring, and carbon sequestration by earth materials; Element Cycling, Toxicity, and Health, which includes summaries of several process-oriented geochemical and biogeochemical studies and health-related research activities; Hydrogeology and Water Quality, which includes descriptions of innovative geophysical, remote-sensing, and geochemical research pertaining to hydrogeology and water-quality applications; Hazards and Disaster Assessment, which includes summaries of research and method development that were applied to natural hazards, human-caused hazards, and disaster assessments; and Databases and Framework Studies, which includes descriptions of fundamental applications of geophysical studies and of the importance of archived data.

Circular

Chemical analyses of coal, coal-associated rocks and coal combustion products collected for the National Coal Quality Inventory

In 1999, the USGS initiated the National Coal Quality Inventory (NaCQI) project to address a need for quality information on coals that will be mined during the next 20-30 years. At the time this project was initiated, the publicly available USGS coal quality data was based on samples primarily collected and analyzed between 1973 and 1985. The primary objective of NaCQI was to create a database containing comprehensive, accurate and accessible chemical information on the quality of mined and prepared United States coals and their combustion byproducts. This objective was to be accomplished through maintaining the existing publicly available coal quality database, expanding the database through the acquisition of new samples from priority areas, and analysis of the samples using updated coal analytical chemistry procedures. Priorities for sampling include those areas where future sources of compliance coal are federally owned. This project was a cooperative effort between the U.S. Geological Survey (USGS), State geological surveys, universities, coal burning utilities, and the coal mining industry. Funding support came from the Electric Power Research Institute (EPRI) and the U.S. Department of Energy (DOE).

Open-File Report

Biomonitoring our streams

Testing for chemical pollution in our nation's streams has traditionally meant using analytical chemistry. In recent years, environmental agencies have endorsed biological monitoring to enhance or replace chemical monitoring. The theory behind biological monitoring (biomonitoring) is to use the organisms living in the aquatic system as a measure of water quality. This concept was applied to air quality and used by miners who took canaries into deep mines with them. If the canary died, the miners knew the air was bad, and they had to leave the mine. Biomonitoring an aquatic system uses the same theoretical approach . Aquatic organisms are subject to pollutants in the stream as it flows by, day or night. Consequently, the health of the organisms reflects the quality of the water they live in. If the pollution levels reach a critical concentration, certain organisms will die, migrate away, or fail to reproduce, eventually leading to the disappearance of those species at the polluted site. Normally, these organisms will return if conditions improve in the system. The three general components of an aquatic ecosystem that influence the biological community are: water chemistry, geomorphology, and hydrology. Each component influences the health of the biological community individually and together . Toxic chemicals are only a single factor within the water-chemistry component. The relation of these three components to each other can be shown on a triangle (figure 1). The relative importance of one component may change with time and location . At certain times of the year or in different geographical settings, a single factor may exert primary control on the well-being of the biological community. For example, straightening a stream and removing all woody debris drastically alters a stream's geomorphology. This results in loss of natural habitat and shelter for certain organisms. The organisms that require this shelter will disappear from the modified system. Separating the influence of one component from the others is difficult. Consideration of all three components and their interactions is critical when interpreting biomonitormg data.

Open-File Report

Detailed study of selenium and selected constituents in water, bottom sediment, soil, and biota associated with irrigation drainage in the San Juan River area, New Mexico, 1991-95

In response to increasing concern about the quality of irrigation drainage and its potential effects on fish, wildlife, and human health, the U.S. Department of the Interior began the National Irrigation Water Quality Program (NIWQP) to investigate these concerns at irrigation projects sponsored by the Department. The San Juan River area in northwestern New Mexico was one of the areas designated for study. Study teams composed of scientists from the U.S. Geological Survey, the U.S. Fish and Wildlife Service, the Bureau of Reclamation, and the Bureau of Indian Affairs collected water, bottom-sediment, soil, and biological samples at 61 sites in the San Juan River area during 1993-94. Supplemental data collection conducted during 1991-95 by the Bureau of Indian Affairs and its contractor extended the time period and sampling sites available for analysis. Analytical chemistry performed on samples indicated that most potentially toxic elements other than selenium generally were not high enough to be of concern to fish, wildlife, and human health. Element concentrations in some water, bottom-sediment, soil, and biological samples exceeded applicable standards and criteria suggested by researchers in current literature. Selenium concentrations in water samples from 28 sites in the study area exceeded the 2-microgramper-liter (lg/L) wildlife-habitat standard. Vanadium concentrations in water exceeded the 100-Kg/L standard for livestock-drinking water at one site. In biota, selenium and aluminum concentrations regularly equaled or exceeded avian dietary threshold concentrations. In bottom sediment and soil, element concentrations above the upper limit of the baseline range for western soils were: selenium, 24 exceedances; lead, 2 exceedances; molybdenum, 2 exceedances;strontium, 4 exceedances; and zinc, 4 exceedances. Concentrations of total selenium in bottom-sediment and soil samples were significantly greater for Cretaceous than for non-Cretaceous soil types in the study area and were generally similar for habitats within and outside irrigation-affected areas. Mean and median total-selenium concentrations in samples from areas with Cretaceous soil types were 4.6 and 2.2 micrograms per gram (ps/g), respectively. Mean and median total-selenium concentrations in samples from areas with non-Cretaceous soil types were 0.6 and 0.15 pg/g, respectively. Samples from the study area had low concentrations of organic constituents. Organochlorine pesticides and polychlorinated biphenyls were detected in a few biological samples at low concentrations. Polycyclic aromatic hydrocarbon (PAH) compounds were not detected in whole-water samples collected using conventional water-sampling techniques. In tests involving the use of semipermeable-membrane devices to supplement conventional water assays for PAH's, low concentrations of PAH's were found at several locations in the Hammond Irrigation Supply Canal, but were not detected in the Hammond ponds at the downstream reach of the Hammond irrigation service area. PAH compounds do not appear to reach the San Juan River through the Hammond Canal. Data indicate that water samples from irrigation-drainage-affected habitats had increased mean selenium concentrations compared with samples from irrigation-delivery habitat. The mean selenium concentration in water was greatest at seeps and tributaries draining irrigated land (17 μg/L); less in irrigation drains and in ponds on irrigated land (61.tg/L); and least in backwater, the San Juan River, and irrigation-supply water (0.5 - 0.6 μg/L). Statistical tests imply that irrigation significantly increases selenium concentrations in water samples when a Department of the Interior irrigation project is developed on selenium-rich sediments. Water samples from sites with Cretaceous soils had significantly greater selenium concentrations than water samples from sites with non-Cretaceous soils. Water samples from Department of the Interior project irrigation-drainage sites developed on Cretaceous soils contained a mean selenium concentration about 10 times greater than those in samples from Department of the Interior project sites developed on non-Cretaceous soils. Selenium was much less concentrated in water than in bottom sediment, soil, or biota in the study area. The range in concentrations of dissolved selenium in water was less than 1 ptg/L to 37 1.1g/L (less than 1 to 37 parts per billion). The range in concentrations of total selenium in bottom sediment and soil was less than 0.1 to 23lig/g (less than 100 to 23,000 parts per billion). The range in concentration of selenium in biota was less than 0.1 to 24.0 fig/g (less than 100 to 24,000 parts per billion). Data indicated that bioaccumulation and leaching from soil were the important processes at the study area that lead to elevated levels of selenium. Other processes examined included: (1) evapoconcentration of selenium; (2) atmospheric deposition of aerosols containing selenium; and (3) contamination of surface water by point-source or non-point-source discharges. Selenium concentrations in biological samples were evaluated by a number of variables including: (1) media sampled (emergent and submergent plants, nektonic and benthic invertebrates, omnivore/herbivore and carnivore fish, and terrestrial and aquatic amphibians); (2) habitat (San Juan River main-stem reaches, backwaters, tributary reaches, irrigation delivery or drainage canals, and ponds); (3) irrigation project area and reference sites; and (4) soil type (non-Cretaceous or Cretaceous soils). Graphical techniques and nonparametric statistical tests were applied to determine the influence of selected physiographic variables on selenium concentrations in biological samples collected in the San Juan River area. Species of sucker and of smaller fish contained significantly higher selenium concentrations in the upstream portion of the river where a productive community of plants and animals is found that is associated with warming, nutrient-rich waters discharged from an upstream reservoir. Selenium concentrations in algae, odonates, and mosquitofish collected from both irrigation-drain and pond habitats underlain by Cretaceous soils were significantly greater than in those collected from similar habitats underlain by non-Cretaceous soils. Investigators conclude that the major factor affecting the variability of selenium accumulation in biota at aquatic habitats was the presence of underlying Cretaceous soils. Median selenium concentrations were less than 2 lAg/g for plant samples, less than 7 μg/g for invertebrate samples, and less than 6 lAg/g for whole-fish samples collected from aquatic habitats underlain by non-Cretaceous soils. Similar samples collected from aquatic habitats underlain by Cretaceous soils contained median selenium concentrations two to five times greater. Leaching of selenium from Cretaceous soils in the San Juan River area increases the accumulation of selenium concentrations in the biota and thereby increases the exposure and potential health risks associated with selenium to migratory birds, fish, and other wildlife that use these aquatic habitats extensively. Aquatic habitats presenting the greatest average exposure to excess selenium concentrations in the diets of resident wildlife are from consumption of plants, invertebrates, and fish at irrigation-drain habitats underlain by Cretaceous soils. Of the irrigation projects evaluated in the San Juan River area, the highest median selenium concentrations in algae, cattail leaves, odonate nymphs, mosquitofish, and leopard frog samples from the study area were collected from the east hogback irrigation drain.

New Mexico

Assessing environmental oil spill based on fluorescence images of water samples and deep learning

Measuring oil concentration in the aquatic environment is essential for determining the potential exposure, risk, or injury for oil spill response and natural resource damage assessment. Conventional analytical chemistry methods require samples to be collected in the field, shipped, and processed in the laboratory, which is also rather time-consuming, laborious, and costly. For rapid field response immediately after a spill, there is a need to estimate oil concentration in near real time. To make the oil analysis more portable, fast, and cost effective, we developed a plug-and-play device and a deep learning model to assess oil levels in water using fluorescent images of water samples. We constructed a 3D-printed device to collect fluorescent images of solvent-extracted water samples using an iPhone. We prepared approximately 1,300 samples of oil at different concentrations to train and test the deep learning model. The model comprises a convolutional neural network and a novel module of histogram bottleneck block with an attention mechanism to exploit the spectral features found in low-contrast images. This model predicts the oil concentration in weight per volume based on fluorescence image. We devised a confidence interval estimator by combining gradient boosting and polymodal regressor to provide a confidence assessment of our results. Our model achieved sufficient accuracy to predict oil levels for most environmental applications. We plan to improve the device and iPhone application as a near-real-time tool for oil spill responders to measure oil in water.

Journal of Environmental Informatics

Fate of estrogenic compounds during municipal sludge stabilization and dewatering

This project brought together a team of experts in the fields of environmental engineering, analytical chemistry and hydrogeology, and biological assay analysis to evaluate the occurrence and fate of estrogenic compounds and the estrogenicity of biosolids derived from wastewater treatment. The primary objective of the study was to provide key baseline information concerning the estrogenicity (measured with in vitro bioassays) and concentrations of individual estrogenic compounds and other trace organic chemicals through common wastewater treatment processes. This research is important for developing information critical to the assessment of the potential risks associated with biosolids land application. Published by WERF. 178 pages. Soft cover and online PDF. (2010)

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