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Applications of optical sensors for high-frequency water-quality monitoring and research

The recent commercial availability of in-situ optical sensors, together with new techniques for data collection and analysis, provides the opportunity to monitor a wide range of water-quality constituents over time scales during which environmental conditions actually change. Traditional approaches for data collection (daily to monthly discrete samples) are often limited by high sample collection, processing, and analytical costs, difficult site access, and logistical challenges, particularly for long-term sampling at a large number of sites. Optical sensors that continuously measure constituents in the environment by absorbance or fluorescence properties (Figure 1) have had a long history of use in oceanography for measuring highly resolved concentrations and fluxes of organic matter, nutrients, and algal material. However, much of the work using commercially-available optical sensors in rivers and streams has taken place in only the last few years. Figure 1. [NOT SHOWN] Optical sensor technology is now sufficiently developed to warrant broader application for research and monitoring in coastal and freshwater systems, and the United States Geological Survey (a U.S. science agency) is now using these sensors in a variety of research and monitoring programs to better understand water quality in-situ and in real-time. Examples are numerous and range from the applications of nitrate sensors for calculating loads to estuaries susceptible to hypoxia (Pellerin et al., 2014) to the use of fluorometers to estimate methymercury fluxes (Bergamaschi et al., 2011) and disinfection byproduct formation (Carpenter et al., 2013). Transmitting these data in real-time provides information that can be used for early trend detection, help identify monitoring gaps critical for water management, and provide science-based decision support across a range of issues related to water quality, freshwater ecosystems, and human health. Despite the value of these sensors, collecting data that meet high-quality standards requires investment in and adherence to tested and established methods and protocols for sensor operation and data management (Pellerin et al., 2013). For example, optical sensor measurements can be strongly influenced by a variety of matrix effects, including water temperature, inner filtering from highly colored water, and scattering of light by suspended particles (Downing et al., 2012). Characterizing and correcting sensors for these effects – as well as the continued development of common methodologies and protocols for sensor use – will be critical to ensuring comparable measurements across sites and over time. In addition, collaborative efforts such as the Nutrient Sensor Challenge (www.nutrients-challenge.org) will continue to accelerate the development, production and use of affordable, reliable and accurate sensors for a range of environments. REFERENCES Bergamaschi .B.A., Fleck J.A., Downing B.D., Boss E., Pellerin B.A., Ganju N.K., Schoellhamer D.H., Byington A.A., Heim W.A., Stephenson M., Fujii R. (2011), Methyl mercury dynamics in a tidal wetland quantified using in situ optical measurements. Limnology and Oceanography, 56(4): 1355-1371. Carpenter K.D., Kraus T.E.C., Goldman J.H., Saraceno J., Downing B.D., Bergamaschi B.A., McGhee G., Triplett T. (2013), Sources and Characteristics of Organic Matter in the Clackamas River, Oregon, Related to the Formation of Disinfection By-products in Treated Drinking Water: U.S. Geological Survey Scientific Investigations Report 2013–5001, 78 p. Downing .B.D., Pellerin B.A., Bergamaschi B.A., Saraceno J., Kraus T.E.K. (2012), Seeing the light: The effects of particles, temperature and inner filtering on in situ CDOM fluorescence in rivers and streams. Limnology and Oceanography: Methods, 10: 767-775. Pellerin B.A., Bergamaschi B.A., Downing B.D., Saraceno J., Garrett J.D., Olsen L.D. (2013), Optical Techniques for the Determination of Nitrate in En

Conference Paper

Cyanobacterial harmful algal blooms and U.S. Geological Survey science capabilities

Cyanobacterial harmful algal blooms (CyanoHABs) are increasingly a global concern because CyanoHABs pose a threat to human and aquatic ecosystem health and cause economic damages. Despite advances in scientific understanding of cyanobacteria and associated compounds, many unanswered questions remain about occurrence, environmental triggers for toxicity, and the ability to predict the timing, duration, and toxicity of CyanoHABs. U.S. Geological Survey (USGS) scientists are leading a diverse range of studies to address CyanoHAB issues in water bodies throughout the United States, using a combination of traditional methods and emerging technologies, and in collaboration with numerous partners. By providing practical applications of cutting edge CyanoHAB research, USGS studies have advanced scientific understanding, enabling the development of approaches to help protect ecological and human health.

Open-File Report

Development of high surface area organosilicate nanoparticulate thin films for use in sensing hydrophobic compounds in sediment and water

The scope of this study was to apply advances in materials science, specifically the use of organosilicate nanoparticles as a high surface area platform for passive sampling of chemicals or pre-concentration for active sensing in multiple-phase complex environmental media. We have developed a novel nanoporous organosilicate (NPO) film as an extraction phase and proof of concept for application in adsorbing hydrophobic compounds in water and sediment. We characterized the NPO film properties and provided optimization for synthesis and coatings in order to apply the technology in environmental media. NPO films in this study had a very high surface area, up to 1325 m 2 /g due to the high level of mesoporosity in the film. The potential application of the NPO film as a sorbent phase for sensors or passive samplers was evaluated using a model hydrophobic chemical, polychlorinated biphenyls (PCB), in water and sediment. Sorption of PCB to this porous high surface area nanoparticle platform was highly correlated with the bioavailable fraction of PCB measured using whole sediment chemistry, porewater chemistry determined by solid-phase microextraction fiber methods, and the Lumbriculus variegatus bioaccumulation bioassay. The surface-modified NPO films in this study were found to highly sorb chemicals with a log octanol-water partition coefficient (K ow ) greater than four; however, surface modification of these particles would be required for application to other chemicals.

Biosensors

Insights on geochemical, isotopic, and volumetric compositions of produced water from hydraulically fractured Williston Basin oil wells

Tracing produced water origins from wells hydraulically fractured with freshwater-based fluids is sometimes predicated on assumptions that (1) each geological formation contains compositionally unique brine and (2) produced water from recently hydraulically fractured wells resembles fresher meteoric water more so than produced water from older wells. These assumptions are not valid in Williston Basin oil wells sampled in this study. Although distinct average 228 Ra/ 226 Ra ratios were found in water produced from the Bakken and Three Forks Formations, average δ 2 H, δ 18 O, specific gravity, and conductivity were similar but exhibited significant variability across five oil fields within each formation. Furthermore, initial produced water (“flowback”) was operationally defined based on the presence of glycol ether compounds and water from wells that had produced <56% of the amount of fluids injected and sampled within 160 days of fracturing. Flowback unexpectedly exhibited higher temperature, specific gravity, conductivity, δ 2 H, and δ 18 O, but lower oxidation–reduction potential and δ 11 B, relative to the wells thought to be producing formation brines (from wells with a produced-to-injected water ratio [PIWR] > 0.84 and sampled more than 316 days after fracturing). As such, establishing an overall geochemical and isotopic signature of produced water compositions based solely on chemical similarity to meteoric water and formation without the consideration of well treatments, well completion depth, or lateral location across the basin could be misleading if these signatures are assumed to be applicable across the entire basin. These findings have implications for using produced water compositions to understand the interbasin fluid flow and trace sources of hydraulic fracturing fluids.

Montana, North Dakota

Metal reactivity in laboratory burned wood from a watershed affected by wildfires

We investigated interfacial processes affecting metal mobility by wood ash under laboratory-controlled conditions using aqueous chemistry, microscopy, and spectroscopy. The Valles Caldera National Preserve in New Mexico experiences catastrophic wildfires of devastating effects. Wood samples of Ponderosa Pine, Colorado Blue Spruce, and Quaking Aspen collected from this site were exposed to temperatures of 60, 350, and 550 °C. The 350 °C Pine ash had the highest content of Cu (4997 ± 262 mg kg –1 ), Cr (543 ± 124 mg kg –1 ), and labile dissolved organic carbon (DOC, 11.3 ± 0.28 mg L –1 ). Sorption experiments were conducted by reacting 350 °C Pine, Spruce, and Aspen ashes separately with 10 μM Cu(II) and Cr(VI) solutions. Up to a 94% decrease in Cu(II) concentration was observed in solution while Cr(VI) concentration showed a limited decrease (up to 13%) after 180 min of reaction. X-ray photoelectron spectroscopy (XPS) analyses detected increased association of Cu(II) on the near surface region of the reacted 350 °C Pine ash from the sorption experiments compared to the unreacted ash. The results suggest that dissolution and sorption processes should be considered to better understand the potential effects of metals transported by wood ash on water quality that have important implications for postfire recovery and response strategies.

Environmental Science & Technology

Air pollutant intrusion into the Wieliczka Salt Mine

The Wieliczka Salt Mine World Cultural Heritage Site contains many rock salt sculptures that are threatened by water vapor condensation from the mine ventilation air. Gaseous and particulate air pollutant concentrations have been measured both outdoors and within the Wieliczka Salt Mine, along with pollutant deposition fluxes to surfaces within the mine. One purpose of these measurements was to determine whether or not low deliquescence point ionic materials (e.g., NH4NO3) are accumulating on surfaces to an extent that would exacerbate the water vapor condensation problems in the mine. It was found that pollutant gases including SO2 and HNO3 present in outdoor air are removed rapidly and almost completely from the air within the mine by deposition to surfaces. Sulfur isotope analyses confirm the accumulation of air pollutant-derived sulfur in liquid dripping from surfaces within the mine. Particle deposition onto interior surfaces in the mine is apparent, with resulting soiling of some of those sculptures that have been carved from translucent rock salt. Water accumulation by salt sculpture surfaces was studied both experimentally and by approximate thermodynamic calculations. Both approaches suggest that the pollutant deposits on the sculpture surfaces lower the relative humidity (RH) at which a substantial amount of liquid water will accumulate by 1% to several percent. The extraordinarily low SO2 concentrations within the mine may explain the apparent success of a respiratory sanatorium located deep within the mine.

Environmental Science & Technology

Molecular identification of water-extractable organic carbon from thermally heated soils: C-13 NMR and accurate mass analyses find benzene and pyridine carboxylic acids

To simulate the effects of wildfire on the combustion process in soils and their potential to leach organic compounds into streams and groundwater, mineral soil samples were heated at temperatures of 150–550 °C. Then, the soils were leached with deionized water, filtered, and analyzed for dissolved organic carbon. The water extract was concentrated by both XAD-8 and XAD-4 resins and analyzed by C-13 nuclear magnetic resonance and liquid chromatography time-of-flight mass spectrometry. Approximately 15–20% of the water-extractable organic carbon was identified as benzene dicarboxylic acids, tricarboxylic acids, and tetracarboxylic acid isomers, commonly called BPCAs. Also identified were isomers of pyridine dicarboxylic acids and tricarboxylic acids (PCAs). The conversion of soil organic carbon to BPCAs occurs at 250 °C and reaches a maximum between 350 and 450 °C. At higher temperatures (>450 °C), the BPCA concentrations decrease, suggesting decarboxylation and conversion to carbon dioxide and water. This is the first report of BPCAs and PCAs in water-extractable organic carbon from thermally altered soil and suggest that these compounds are possible candidates for further water-quality studies in watersheds affected by wildfire. Finally, BPCAs and PCAs could contribute to the black carbon and nitrogen in seawater and are worthy of future investigation.

Environmental Science and Technology

Role of biofilms in sorptive removal of steroidal hormones and 4-nonylphenol compounds from streams

Stream biofilms play an important role in geochemical processing of organic matter and nutrients, however, the significance of this matrix in sorbing trace organic contaminants is less understood. This study focused on the role of stream biofilms in sorbing steroidal hormones and 4-nonylphenol compounds from surface waters using biofilms colonized in situ on artificial substrata and subsequently transferred to the laboratory for controlled batch sorption experiments. Steroidal hormones and 4-nonylphenol compounds readily sorb to stream biofilms as indicated by organic matter partition coefficients ( K om , L kg –1 ) for 17β-estradiol (10 2.5–2.8 L kg –1 ), 17α-ethynylestradiol (10 2.5–2.9 L kg –1 ), 4-nonylphenol (10 3.4–4.6 L kg –1 ), 4-nonylphenolmonoethoxylate (10 3.5–4.0 L kg –1 ), and 4-nonylphenoldiethoxylate (10 3.9–4.3 L kg –1 ). Experiments using water quality differences to induce changes in the relative composition of periphyton and heterotrophic bacteria in the stream biofilm did not significantly affect the sorptive properties of the stream biofilm, providing additional evidence that stream biofilms will sorb trace organic compounds under of variety of environmental conditions. Because sorption of the target compounds to stream biofilms was linearly correlated with organic matter content, hydrophobic partition into organic matter appears to be the dominant mechanism. An analysis of 17β-estradiol and 4-nonylphenol hydrophobic partition into water, biofilm, sediment, and dissolved organic matter matrices at mass/volume ratios typical of smaller rivers showed that the relative importance of the stream biofilm as a sorptive matrix was comparable to bed sediments. Therefore, stream biofilms play a primary role in attenuating these compounds in surface waters. Because the stream biofilm represents the base of the stream ecosystem, accumulation of steroidal hormones and 4-nonylphenol compounds in the stream biofilm may be an exposure pathway for organisms in higher trophic levels.

Environmental Science & Technology

Beach monitoring criteria: reading the fine print

Beach monitoring programs aim to decrease swimming-related illnesses resulting from exposure to harmful microbes in recreational waters, while providing maximum beach access. Managers are advised by the U.S. EPA to estimate microbiological water quality based on a 5-day geometric mean of fecal indicator bacteria (FIB) concentrations or on a jurisdiction-specific single-sample maximum; however, most opt instead to apply a default single-sample maximum to ease application. We examined whether re-evaluation of the U.S. EPA ambient water quality criteria (AWQC) and the epidemiological studies on which they are based could increase public beach access without affecting presumed health risk. Single-sample maxima were calculated using historic monitoring data for 50 beaches along coastal Lake Michigan on various temporal and spatial groupings to assess flexibility in the application of the AWQC. No calculation on either scale was as low as the default maximum (235 CFU/100 mL) that managers typically use, indicating that current applications may be more conservative than the outlined AWQC. It was notable that beaches subject to point source FIB contamination had lower variation, highlighting the bias in the standards for these beaches. Until new water quality standards are promulgated, more site-specific application of the AWQC may benefit beach managers by allowing swimmers greater access to beaches. This issue will be an important consideration in addressing the forthcoming beach monitoring standards.

Environmental Science & Technology

Processes affecting the fate of monoaromatic hydrocarbons in an aquifer contaminated by crude oil

Crude oil spilled from a subsurface pipeline in north-central Minnesota has dissolved in the groundwater, resulting in the formation of a plume of aliphatic, aromatic, and alicyclic hydrocarbons. Comparison of paired oil and groundwater samples collected along the central axis of the residual oil body shows that the trailing edge of the oil is depleted in the more soluble aromatic hydrocarbons (e.g., benzene, toluene, etc.) when compared with the leading edge. At the same time, concentrations of monoaromatic hydrocarbons in groundwater beneath the oil increase as the water moves toward the leading edge of the oil. Immediately downgradient from the leading edge of the oil body, certain aromatic hydrocarbons (e.g., benzene) are found at concentrations near those expected of a system at equilibrium, and the concentrations exhibit little variation over time (???8-20%). Other compounds (e.g., toluene) appear to be undersaturated, and their concentrations show considerably more temporal variation (???20-130%). The former are persistent within the anoxic zone downgradient from the oil, whereas concentrations of the latter decrease rapidly. Together, these observations suggest that the volatile hydrocarbon composition of the anoxic groundwater near the oil body is controlled by a balance between dissolution and removal rates with only the most persistent compounds reaching saturation. Examination of the distributions of homologous series and isomeric assemblages of alkylbenzenes reveals that microbial degradation is the dominant process controlling the fate of these compounds once groundwater moves away from the oil. For all but the most persistent compounds, the distal boundary of the plume at the water table extends no more than 10-15 m down-gradient from the oxic/anoxic transition zone. Thus, transport of the monoaromatic hydrocarbons is limited by redox conditions that are tightly coupled to biological degradation processes.

Environmental Science & Technology

Determination of uptake kinetics (sampling rates) by lipid-containing semipermeable membrane devices (SPMDs) for polycyclic aromatic hydrocarbons (PAHs) in water

The use of lipid-containing semipermeable membrane devices (SPMDs) is becoming commonplace, but very little sampling rate data are available for the estimation of ambient contaminant concentrations from analyte levels in exposed SPMDs. We determined the aqueous sampling rates (R(s)s; expressed as effective volumes of water extracted daily) of the standard (commercially available design) 1-g triolein SPMD for 15 of the priority pollutant (PP) polycyclic aromatic hydrocarbons (PAHs) at multiple temperatures and concentrations. Under the experimental conditions of this study, recovery- corrected R(s) values for PP PAHs ranged from ???1.0 to 8.0 L/d. These values would be expected to be influenced by significant changes (relative to this study) in water temperature, degree of biofouling, and current velocity- turbulence. Included in this paper is a discussion of the effects of temperature and octanol-water partition coefficient (K(ow)); the impacts of biofouling and hydrodynamics are reported separately. Overall, SPMDs responded proportionally to aqueous PAH concentrations; i.e., SPMD R(s) values and SPMD-water concentration factors were independent of aqueous concentrations. Temperature effects (10, 18, and 26 ??C) on Rs values appeared to be complex but were relatively small.The use of lipid-containing semipermeable membrane devices (SPMDs) is becoming commonplace, but very little sampling rate data are available for the estimation of ambient contaminant concentrations from analyte levels in exposed SPMDs. We determined the aqueous sampling rates (Rss; expressed as effective volumes of water extracted daily) of the standard (commercially available design) 1-g triolein SPMD for 15 of the priority pollutant (PP) polycyclic aromatic hydrocarbons (PAHs) at multiple temperatures and concentrations. Under the experimental conditions of this study, recovery-corrected Rs values for PP PAHs ranged from ???1.0 to 8.0 L/d. These values would be expected to be influenced by significant changes (relative to this study) in water temperature, degree of biofouling, and current velocity-turbulence. Included in this paper is a discussion of the effects of temperature and octanol-water partition coefficient (KOW); the impacts of biofouling and hydrodynamics are reported separately. Overall, SPMDs responded proportionally to aqueous PAH concentrations; i.e., SPMD RS values and SPMD-water concentration factors were independent of aqueous concentrations. Temperature effects (10, 18, and 26??C) on RS values appeared to be complex but were relatively small.

Environmental Science & Technology

Biological responses of Pacific herring embryos to crude oil are quantifiable at exposure levels below conventional limits of quantitation for PAHs in water and tissues

Pacific herring ( Clupea pallasii ), a cornerstone of marine food webs, generally spawn on marine macroalgae in shallow nearshore areas that are disproportionately at risk from oil spills. Herring embryos are also highly susceptible to toxicity from chemicals leaching from oil stranded in intertidal and subtidal zones. The water-soluble components of crude oil trigger an adverse outcome pathway that involves disruption of the physiological functions of cardiomyocytes in the embryonic herring heart. In previous studies, impaired ionoregulation (calcium and potassium cycling) in response to specific polycyclic aromatic hydrocarbons (PAHs) corresponds to lethal embryolarval heart failure or subtle chamber malformations at the high and low ends of the PAH exposure range, respectively. Sublethal cardiotoxicity, which involves an abnormal outgrowth (ballooning) of the cardiac ventricular chamber soon after hatching, subsequently compromises juvenile heart structure and function, leading to pathological hypertrophy of the ventricle and reduced individual fitness, measured as cardiorespiratory performance. Previous studies have not established a threshold for these sublethal and delayed-in-time effects, even with total (∑)PAH exposures as low as 29 ng/g of wet weight (tissue dose). Here, we extend these earlier findings showing that (1) cyp1a gene expression provides an oil exposure metric that is more sensitive than typical quantitation of PAHs via GC–MS and (2) heart morphometrics in herring embryos provide a similarly sensitive measure of toxic response. Early life stage injury to herring (impaired heart development) thus occurs below the quantitation limits for PAHs in both water and embryonic tissues as a conventional basis for assessing oil-induced losses to coastal marine ecosystems.

Environmental Science and Technology

Bacterial oxidation of methyl bromide in Mono Lake, California

The oxidation of methyl bromide (MeBr) in the water column of Mono Lake, CA, was studied by measuring the formation of H14CO3 from [14C]MeBr. Potential oxidation was detected throughout the water column, with highest rates occurring in the epilimnion (5-12 m depth). The oxidation of MeBr was eliminated by filter-sterilization, thereby demonstrating the involvement of bacteria. Vertical profiles of MeBr activity differed from those obtained for nitrification and methane oxidation, indicating that MeBr oxidation is not simply a co-oxidation process by either nitrifiers or methanotrophs. Furthermore, specific inhibitors of methane oxidation and/or nitrification (e.g., methyl fluoride, acetylene, allyl sulfide) had no effect upon the rate of MeBr oxidation in live samples. Of a variety of potential electron donors added to Mono Lake water, only trimethylamine resulted in the stimulation of MeBr oxidation. Cumulatively, these results suggest that the oxidation of MeBr in Mono Lake waters is attributable to trimethylamine-degrading methylotrophs. Neither methyl chloride nor methanol inhibited the oxidation of [14C]MeBr in live samples, indicating that these bacteria directly oxidized MeBr rather than the products of MeBr nucleophilic substitution reactions.

Environmental Science & Technology

Spatial and seasonal variability of dissolved methylmercury in two stream basins in the Eastern United States

We assessed methylmercury (MeHg) concentrations across multiple ecological scales in the Edisto (South Carolina) and Upper Hudson (New York) River basins. Out-of-channel wetland/floodplain environments were primary sources of filtered MeHg (F-MeHg) to the stream habitat in both systems. Shallow, open-water areas in both basins exhibited low F-MeHg concentrations and decreasing F-MeHg mass flux. Downstream increases in out-of-channel wetlands/floodplains and the absence of impoundments result in high MeHg throughout the Edisto. Despite substantial wetlands coverage and elevated F-MeHg concentrations at the headwater margins, numerous impoundments on primary stream channels favor spatial variability and lower F-MeHg concentrations in the Upper Hudson. The results indicated that, even in geographically, climatically, and ecologically diverse streams, production in wetland/floodplain areas, hydrologic transport to the stream aquatic environment, and conservative/nonconservative attenuation processes in open water areas are fundamental controls on dissolved MeHg concentrations and, by extension, MeHg availability for potential biotic uptake.

New York, South Carolina

Mercury speciation and transport via submarine groundwater discharge at a southern California coastal lagoon system

We measured total mercury (HgT) and monomethylmercury (MMHg) concentrations in coastal groundwater and seawater over a range of tidal conditions near Malibu Lagoon, California, and used 222Rn-derived estimates of submarine groundwater discharge (SGD) to assess the flux of mercury species to nearshore seawater. We infer a groundwater-seawater mixing scenario based on salinity and temperature trends and suggest that increased groundwater discharge to the ocean during low tide transported mercury offshore. Unfiltered HgT (U-HgT) concentrations in groundwater (2.2–5.9 pM) and seawater (3.3–5.2 pM) decreased during a falling tide, with groundwater U-HgT concentrations typically lower than seawater concentrations. Despite the low HgT in groundwater, bioaccumulative MMHg was produced in onshore sediment as evidenced by elevated MMHg concentrations in groundwater (0.2–1 pM) relative to seawater (∼0.1 pM) throughout most of the tidal cycle. During low tide, groundwater appeared to transport MMHg to the coast, resulting in a 5-fold increase in seawater MMHg (from 0.1 to 0.5 pM). Similarly, filtered HgT (F-HgT) concentrations in seawater increased approximately 7-fold during low tide (from 0.5 to 3.6 pM). These elevated seawater F-HgT concentrations exceeded those in filtered and unfiltered groundwater during low tide, but were similar to seawater U-HgT concentrations, suggesting that enhanced SGD altered mercury partitioning and/or solubilization dynamics in coastal waters. Finally, we estimate that the SGD HgT and MMHg fluxes to seawater were 0.41 and 0.15 nmol m–2 d–1, respectively – comparable in magnitude to atmospheric and benthic fluxes in similar environments.

California

Potential toxicity of complex mixtures in surface waters from a nationwide survey of United States streams: Identifying in vitro bioactivities and causative chemicals

While chemical analysis of contaminant mixtures remains an essential component of environmental monitoring, bioactivity-based assessments using in vitro systems increasingly play a role in the detection of biological effects. Historically, in vitro assessments focused on a few biological pathways, e.g., aryl hydrocarbon receptor (AhR) or estrogen receptor (ER) activities. High-throughput screening (HTS) technologies have greatly increased the number of biological targets and processes that can be rapidly assessed. Here we screened extracts of surface waters from nationwide survey of United States (US) streams for bioactivities associated with 69 different endpoints using two multiplexed HTS assays. Bioactivity of extracts from 38streams was evaluated and compared with concentrations of over 700 analytes to identify chemicals contributing to observed effects. Eleven primary biological endpoints were detected. Pregnane X receptor and AhR-mediated activities were the most commonly detected. Measured chemicals did not completely account for AhR and PXR responses. Surface waters with AhR and PXR effects were associated with low intensity, developed land-cover. Likewise, elevated bioactivities frequently associated with wastewater discharges included endocrine related endpoints— ER and glucocorticoid receptor (GR). These results underscore the value of bioassay-based monitoring of environmental mixtures for detecting biological effects that could not be ascertained solely through chemical analyses.

Environmental Science & Technology

Peer reviewed: Characterizing aquatic dissolved organic matter

Whether it causes aesthetic concerns such as color, taste, and odor; leads to the binding and transport of organic and inorganic contaminants; produces undesirable disinfection byproducts; provides sources and sinks for carbon; or mediates photochemical processes, the nature and properties of dissolved organic matter (DOM) in water are topics of significant environmental interest. DOM is also a major reactant in and product of biogeochemical processes in which the material serves as a carbon and energy source for biota and controls levels of dissolved oxygen, nitrogen, phosphorus, sulfur, numerous trace metals, and acidity.

Environmental Science & Technology

Estimating lithium concentrations in groundwater used as drinking water for the conterminous United States

Lithium (Li) concentrations in drinking-water supplies are not regulated in the United States; however, Li is included in the 2022 U.S. Environmental Protection Agency list of unregulated contaminants for monitoring by public water systems. Li is used pharmaceutically to treat bipolar disorder, and studies have linked its occurrence in drinking water to human-health outcomes. An extreme gradient boosting model was developed to estimate geogenic Li in drinking-water supply wells throughout the conterminous United States. The model was trained using Li measurements from ∼13,500 wells and predictor variables related to its natural occurrence in groundwater. The model predicts the probability of Li in four concentration classifications, ≤4 μg/L, >4 to ≤10 μg/L, >10 to ≤30 μg/L, and >30 μg/L. Model predictions were evaluated using wells held out from model training and with new data and have an accuracy of 47–65%. Important predictor variables include average annual precipitation, well depth, and soil geochemistry. Model predictions were mapped at a spatial resolution of 1 km 2 and represent well depths associated with public- and private-supply wells. This model was developed by hydrologists and public-health researchers to estimate Li exposure from drinking water and compare to national-scale human-health data for a better understanding of dose–response to low (<30 μg/L) concentrations of Li.

conterminous United States