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At least 433 records · Page 24Linked to original sources

Optimizing cryo-focused pyrolysis GC/MS for tracing soil organic matter across diverse ecosystems

The cycling of organic matter in terrestrial soils and sediments is central to a range of biogeochemical processes that regulate nutrient cycling, crop productivity, trace gas emissions, and contaminant transport. Pyrolysis-gas chromatography/mass spectrometry (py-GC/MS) is a powerful tool for characterizing bulk soil organic matter (SOM) at the molecular level. In this study, we used a cryo-focused py-GC/MS system to analyze soil samples from seven diverse ecosystems: vernal pool, prairie pothole, temperate forest, tropical forest, tundra, wildfire-affected boreal forest, and grassland. We addressed a key bottleneck in molecular-level SOM characterization by developing an automated data analysis pipeline to optimize py-GC/MS and complementary evolved gas analysis/mass spectrometry (EGA/MS) methods, incorporating advanced tools for data deconvolution, developing a custom compound class library, and implementing fragmentation spectrum-based molecular networking for the first time. This improved workflow was applied to soil samples from all seven ecosystems, including multiple depths and density fractions. Our findings demonstrate that ecosystem type plays a dominant role in shaping compositional differences in SOM. We also identified trends in the source of SOM compounds (e.g., microbial vs. plant-derived) across soil depth and density fractions, which are critical for understanding persistence and turnover of SOM. Our molecular networking analysis indicated that although many compounds are widespread across ecosystems, others are restricted to specific environments, such as wetlands. This underscores the utility of molecular-level data in elucidating the complexity of SOM composition and the environmental drivers that shape it. Such molecular-level insights can deepen our knowledge of biogeochemical SOM cycles.

Environmental Science and Technology↗

High-frequency data reveal deicing salts drive elevated specific conductance and chloride along with pervasive and frequent exceedances of the U.S. Environmental Protection Agency aquatic life criteria for chloride in urban streams

Increasing specific conductance (SC) and chloride concentrations [Cl] negatively affect many stream ecosystems. We characterized spatial variability in SC, [Cl], and exceedances of Environmental Protection Agency [Cl] criteria using nearly 30 million high-frequency observations (2–15 min intervals) for SC and modeled [Cl] from 93 sites across three regions in the eastern United States: Southeast, Mid-Atlantic, and New England. SC and [Cl] increase substantially from south to north and within regions with impervious surface cover (ISC). In the Southeast, [Cl] weakly correlates with ISC, no [Cl] exceedances occur, and [Cl] concentrations are constant with time. In the Mid-Atlantic and New England, [Cl] and [Cl] exceedances strongly correlate with ISC. [Cl] criteria are frequently exceeded at sites with greater than 9–10% ISC and median [Cl] higher than 30–80 mg/L. Tens to hundreds of [Cl] exceedances observed annually at most of these sites help explain previous research where stream ecosystems showed changes at (primarily nonwinter) [Cl] as low as 30–40 mg/L. Mid-Atlantic chronic [Cl] exceedances occur primarily in December–March. In New England, exceedances are common in nonwinter months. [Cl] is increasing at nearly all Mid-Atlantic and New England sites with the largest increases at sites with higher [Cl].

Environmental Science and Technology↗

Tracing the uptake of Hg(II) in an iron-reducing bacterium using mercury stable isotopes

Anaerobic microorganisms play a key role in the biological mercury (Hg) cycle due to their ability to produce bioaccumulative neurotoxic methylmercury (MeHg). However, despite recent advances, how bacteria accumulate inorganic Hg [Hg(II)] prior to methylation is largely unknown. In this study, we applied Hg stable isotopes to measure changes in cellular compartments of Geobacter sulfurreducens and a nonmethylating mutant strain to investigate intracellular transport of Hg(II). Both strains accumulated intracellular Hg(II) that was lower in δ 202 Hg relative to dissolved extracellular Hg(II), demonstrating mass-dependent fractionation during uptake. Hg reduction by the mutant strain (50% Hg concentration loss in 24 h) resulted in higher δ 202 Hg values of cellular Hg than in wild-type cells. Further observations showed increasing δ 202 Hg values in dissolved extracellular MeHg and Hg(II) but decreasing δ 202 Hg values of intracellular Hg(II) in wild-type G. sulfurreducens suggesting that external Hg pools may be the proximate source of Hg for methylation in this bacterium. This investigation demonstrates that cellular uptake is comprised of multiple processes and transformations that influence Hg(II) prior to methylation, which can impart distinct isotopic signatures to Hg(II) and MeHg pools in the environment.

Environmental Science and Technology Letters↗

Tracking fish lifetime exposure to mercury using eye lenses

Mercury (Hg) uptake in fish is affected by diet, growth, and environmental factors such as primary productivity or oxygen regimes. Traditionally, fish Hg exposure is assessed using muscle tissue or whole fish, reflecting both loss and uptake processes that result in Hg bioaccumulation over entire lifetimes. Tracking changes in Hg exposure of an individual fish chronologically throughout its lifetime can provide novel insights into the processes that affect Hg bioaccumulation. Here we use eye lenses to determine Hg uptake at an annual scale for individual fish. We assess the widely distributed benthic round goby ( Neogobius melanostomus ) from the Baltic Sea, Lake Erie, and the St. Lawrence River. We aged layers of the eye lens using proportional relationships between otolith length at age and eye lens radius for each individual fish. Mercury concentrations were quantified using laser ablation inductively coupled plasma mass spectrometry. The eye lens Hg content revealed that Hg exposure increased with age in Lake Erie and the Baltic Sea but decreased with age in the St. Lawrence River, a trend not detected using muscle tissues. This novel methodology for measuring Hg concentration over time with eye lens chronology holds promise for quantifying how global change processes like increasing hypoxia affect the exposure of fish to Hg.

Environmental Science and Technology↗

Establishing an in vitro model to assess the toxicity of 6PPD-quinone and other tire wear transformation products

The tire wear transformation product 6PPD-quinone (6PPDQ) has been implicated as the causative factor for broad scale mortality events for coho salmon in the Pacific Northwest. Highly variable sensitivity to 6PPDQ in closely related salmonids complicates efforts to evaluate the broader toxicological impacts to aquatic ecosystems. Our goals were to (1) validate the large range of in vivo species sensitivities reported for coho, Chinook, and sockeye salmon and (2) develop an in vitro platform for assessing 6PPDQ toxicity. In vivo studies confirmed the acute sensitivity of juvenile coho (12 h LC 50 = 80.4 ng/L) and demonstrated that sockeye salmon were not vulnerable to mortality. Chinook salmon were sensitive to 6PPDQ mortality at initial concentrations >25 μg/L, ∼10-fold greater than reported environmental measurements. In vitro , the coho salmon cell line CSE-119 was acutely sensitive to 6PPDQ (metabolic EC 50 = 7.9 μg/L, cytotoxicity EC 50 = 6.1 μg/L). Analogous Chinook (CHSE-214) and sockeye salmon (SSE-5) cell lines were nonresponsive in both assays, and rainbow trout RTG-2 cells began showing metabolic effects at 68 μg/L (EC 5 ). Recreation of species-specific 6PPDQ sensitivity in vitro implicates conserved modes of action in CSE-119 that could be utilized for mechanistic studies of 6PPDQ toxicity and screening of other PPD transformation products.

Environmental Science and Technology Letters↗

Mercury isotope values in shoreline spiders reveal transfer of aquatic mercury sources to terrestrial food webs

The transfer of aquatic contaminants, including mercury (Hg), to terrestrial food webs is an often-overlooked exposure pathway to terrestrial animals. While research has implemented the use of shoreline spiders to assess aquatic to terrestrial Hg transfer, it is unclear whether Hg sources, estimated from isotope ratios, can be successfully resolved to inform site assessments and remedy effectiveness. To examine aquatic to terrestrial Hg transfer, we collected shoreline spiders ( Tetragnatha spp.) and aquatic insect larvae (suborder Anisoptera) across a mosaic of aquatic and shoreline habitats in the St. Louis River and Bad River, tributaries to Lake Superior. The fraction of industrial Hg in sediments was reflected in the δ 202 Hg values of aquatic dragonfly larvae and predatory fish, connecting benthic Hg sources to the aquatic food web. Shoreline spiders mirrored these aquatic Hg source signatures with highly positive correlations in δ 202 Hg between tetragnathids and dragonfly larvae ( r 2 = 0.90). Further assessment of different spider taxa (i.e., araneids and pisaurids) revealed that differences in prey consumption and foraging strategies resulted in isotope differences, highlighting the importance of spider taxa selection for Hg monitoring efforts.

Minnesota, Wisconsin↗

Evidence of long-range transport of selenium downstream of coal mining operations in the Elk River Valley, Canada

Expanding coal-mining operations in the Elk River Valley (British Columbia, Canada) have increased total selenium (Se) concentrations in the transboundary Lake Koocanusa (Canada and United States), but the spatial extent of Se transport from the Elk River Mines is unknown. We evaluated multiple lines of evidence of long-range transport of Se at five sites downstream of the mines relative to a site unaffected by the mines. First, all mine-affected sites had increasing trends in flow-normalized Se concentrations between 2005 and 2021 (35–89%), while no trend was observed at the unaffected site between 2005 and 2017. Second, all mine-affected sites had elevated annual mean Se concentrations and 5-year mean annual loads (2013–2017) by up to an order of magnitude relative to the unaffected site. Third, Se concentrations and the magnitude of the concentration trend generally decreased with distance downstream from the mines while loads increased, which is consistent with the downstream transport of the bulk of the Se load from the mines with smaller contributions from other sources. These results provide multiple lines of evidence that Se from the Elk River Mines is transported over 575 river kilometers and may pose risks to aquatic life in the transboundary Columbia River.

Elk River Valley↗

An interpretation of differences between field and laboratory pH values reported by the National Atmospheric Deposition Program/National Trends Network monitoring program

Differences between field and laboratory pH values reported by the National Atmospheric Deposition Program/National Trends Network (NADP/NTN) monitoring program from 1984 through 1986 are investigated. Median differences in hydrogen ion concentration between laboratory and field pH determinations at sites averaged -4.6 μ equiv/L in natural precipitation samples on an annual basis. The median difference found in external quality assurance samples analyzed during the same time period was -11 μ equiv/L. The results suggest a systematic bias in pH values reported by the NADP/NTN network. The bias appears to have a fixed component of approximately -7 μ equiv/L, which can be attributed to the sampling bucket and lid, and a seasonal and regional component that ranges from +4 to -22 μ equiv/L at the 10th and 90th percentiles. Differences were found to be independent of sample pH and sample volume. The magnitude of the bias has implications for the interpretation of previously published pH and hydrogen ion concentration and deposition values in the western United States.

Environmental Science and Technology↗

Accumulation and diagenesis of chlorinated hydrocarbons in lacustrine sediments

Two sediment cores were taken from the Rochester Basin of eastern Lake Ontario and analyzed for the radionuclides 210Pb and 137Cs and several high molecular weight chlorinated hydrocarbons (CHs). The two sites are geographically proximate but differ in sedimentation rate, permitting sedimentation-dependent processes to be factored out. The 210Pb chronology showed a mixed depth of 3-5 cm and an intrinsic time resolution of 11-14 years. Vertically integrated numbers of deposit-feeding oligochaete worms and burrowing organisms are insufficient to homogenize the sediment on the time scale of CH inputs, which are non steady state. U.S. production and sales of polychlorinated biphenyls (PCBs), DDT, Mirex, and hexachlorobenzene (HCB), as determinants of the shape of the input function, adequately predict the overall shape and, in many cases, details in the sedimentary profile. Sediment focusing factors (FF) inferred from 137Cs and 210Pb inventories averaged 1.17 and 1.74 for cores E-30 and G-32, respectively. This permitted CH accumulation rates to be corrected for focusing. Apparent molecular diffusion coefficients modeled for many of the CHs were about (1-3) ?? 10-9 cm2/s.

Environmental Science and Technology↗

Variations in suspended sediment and associated trace element concentrations in selected riverine cross sections

Detailed sampling and subsequent analyses of riverine suspended sediment obtained from six rivers in the United States indicate substantial differences in suspended sediment concentrations and possibly in some associated trace elements, depending on whether depth- and width-integrated, point, or pumping samples are used. In addition, the data from time-series, depth-integrated sampling indicate that there can be substantial short-term (on the order of 20-30 min) spatial and/or temporal variations in suspended-sediment concentrations. Despite this, major element concentrations are remarkably stable both spatially and temporally. Trace element concentrations are generally stable; however, some spatial and temporal variations may occur.

Environmental Science and Technology↗

Zinc isotopic signatures in eight lake sediment cores from across the United States

Zinc is an important trace element pollutant in urban environments; however, the extent of Zn contamination and the sources of urban Zn pollution are often unclear. We measured Zn concentrations and isotopes in sediment cores collected from eight lakes or reservoirs across the United States. We paired these data with historical records of land use within each watershed to calculate a mean Zn concentration and δ 66 Zn for natural (less than 5% urban land use; 123 ± 21.7 mg/kg; +0.33 ± 0.08‰, n = 6 lakes) and urban (greater than 70% urban land use; 389 ± 200 mg/kg; +0.14 ± 0.07‰, n = 3 lakes) lake sediments. The relation between Zn concentration data and Zn isotope data allows us to create a mixing model between two end members: natural and urban. The δ 66 Zn of the urban end-member is consistent with Zn pollution from vehicle-related sources (tire wear and emissions). Application of this model to samples collected from lakes recording periods ranging from 5 to 70% urban land use in their surrounding watersheds indicates that the lakes and reservoirs were affected by large amounts of Zn from urban sources.

conterminous United States↗

Relating carbon monoxide photoproduction to dissolved organic matter functionality

Aqueous solutions of humic substances (HSs) and pure monomeric aromatics were irradiated to investigate the chemical controls upon carbon monoxide (CO) photoproduction from dissolved organic matter (DOM). HSs were isolated from lakes, rivers, marsh, and ocean. Inclusion of humic, fulvic, hydrophobic organic, and hydrophilic organic acid fractions from these environments provided samples diverse in source and isolation protocol. In spite of these major differences, HS absorption coefficients (a) and photoreactivities (a bleaching and CO production) were strongly dependent upon HS aromaticity ( r 2 >0.90; n = 11), implying aromatic moieties are the principal chromophores and photoreactants within HSs, and by extension, DOM. Carbonyl carbon and CO photoproduction were not correlated, implying that carbonyl moieties are not quantitatively important in CO photoproduction. CO photoproduction efficiency of aqueous solutions of monomeric aromatic compounds that are common constituents of organic matter varied with the nature of ring substituents. Specifically, electron donating groups increased, while electron withdrawing groups decreased CO photoproductivity, supporting our conclusion that carbonyl substituents are not quantitatively important in CO photoproduction. Significantly, aromatic CO photoproduction efficiency spanned 3 orders of magnitude, indicating that variations in the CO apparent quantum yields of natural DOM may be related to variations in aromatic DOM substituent group chemistry.

Environmental Science and Technology↗

The Western Airborne Contaminant Assessment Project (WACAP): An interdisciplinary evaluation of the impacts of airborne contaminants in Western U.S. National Parks

The concept of a nature reserve such as a National Park is to maintain a location for the enjoyment and study of a pristine environment. However, many pollutants are now known to spread far and wide from their (point[s] of) origin. To grasp the extent of pervasive and boundary-less pollution, the ambitious WACAP study evaluated contaminant data collected from Western U.S. National Parks in various media. In this Feature, Landers et al. summarize the report and speak to its utility moving forward.

Environmental Science and Technology↗

Critical review of mercury methylation and methylmercury demethylation rate constants in aquatic sediments for biogeochemical modeling

Mercury is a toxin that causes neurological impairments in adults, is particularly harmful for fetuses and children, and is deadly in severe cases, making it a worldwide health concern. Methylmercury (MeHg) is the environmentally relevant form of mercury (Hg) because it biomagnifies along the food chain. Methylmercury is mainly produced in aquatic sediments via methylation of inorganic Hg (Hg(II)) and transformed back via demethylation. Because transformation rates determine MeHg concentrations, quantification of methylation and demethylation rates is needed to inform management of MeHg. Published rate constants for Hg(II) methylation ( 𝑘 𝑚 ) and MeHg demethylation ( 𝑘 𝑑 ) vary greatly, stemming partly from differences in experimental methods. We conducted a comprehensive review of rate laws, evaluated published rate constants, and performed biogeochemical simulations to assess variability in reported 𝑘 𝑚 and 𝑘 𝑑 . Based on selected studies employing the same pseudo-first-order rate law and similar experimental methods, we found that 𝑘 𝑚 = 0.04 ± 0.03 d −1 is a reasonable range for wetland sediments. Over a number of environments, maximum 𝑘 𝑑 was smaller at sites without Hg source ( 𝑘 𝑑 = 0.5 d −1 ) than at sites with identified Hg source ( 𝑘 𝑑 = 1.8 d −1 ). Larger variability and higher uncertainty in 𝑘 𝑑 compared to 𝑘 𝑚 highlight the need for more research on MeHg demethylation rates. This critical review: (a) aids the design of future experimental studies of 𝑘 𝑚 and 𝑘 𝑑 ; (b) provides guidance for comparing rate constants from different studies; (c) presents a biogeochemical reaction model to assess rate constants; and (d) informs selection of 𝑘 𝑚 and 𝑘 𝑑 values from the literature for use in model simulations.

Critical Reviews in Environmental Science and Tech↗

Coastal Prairie Restoration Information System: Version 1 (Louisiana)

The Coastal Prairie Restoration Information System (CPR) is a Microsoft Access database that allows users to query and view data about Louisiana coastal prairie species. Less than 0.1% of Louisiana's coastal prairie vegetation remains in a relatively undisturbed condition. Encompassing as much as 1 million hectares of land, coastal prairie is a hybrid of coastal wetlands and tall grass prairie. Over 550 plant species have been identified in Louisiana's coastal prairies to date. Efforts to conserve and restore this endangered ecosystem are limited by the ability of workers to identify and access knowledge about this diverse group of plants. In this database, a variety of data are provided for each of 650 coastal prairie species in Louisiana. The database was developed at the U.S. Geological Survey National Wetlands Research Center by Larry Allain, with software development by Myra Silva. Additional funding was provided by the biology department of the University of Louisiana at Lafayette (ULL), the ULL Center for Environmental and Ecological Technology, and the National Science Foundation.

Data Series↗