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USGS2023

Nitrifying microorganisms linked to biotransformation of perfluoroalkyl sulfonamido precursors from legacy aqueous film forming foams

Drinking water supplies across the United States have been contaminated by firefighting and fire-training activities that use aqueous film-forming foams (AFFF) containing per- and polyfluoroalkyl substances (PFAS). Much of the AFFF is manufactured using electrochemical fluorination by 3M. Precursors with six perfluorinated carbons (C6) and non-fluorinated amine substituents make up approximately one-third of the PFAS in 3M AFFF. C6 precursors can be transformed through nitrification (microbial oxidation) of amine moieties into perfluorohexane sulfonate (PFHxS), a compound of regulatory concern. Here, we report biotransformation of the most abundant C6 sulfonamido precursors in 3M AFFF with available commercial standards (FHxSA, PFHxSAm, and PFHxSAmS) in microcosms representative of the groundwater/surface water boundary. Results show rapid (<1 day) biosorption to living cells by precursors but slow biotransformation into PFHxS (1–100 pM day –1 ). The transformation pathway includes one or two nitrification steps and is supported by the detection of key intermediates using high-resolution mass spectrometry. Increasing nitrate concentrations and total abundance of nitrifying taxa occur in parallel with precursor biotransformation. Together, these data provide multiple lines of evidence supporting microbially limited biotransformation of C6 sulfonamido precursors involving ammonia-oxidizing archaea ( Nitrososphaeria ) and nitrite-oxidizing bacteria ( Nitrospina ). Further elucidation of interrelationships between precursor biotransformation and nitrogen cycling in ecosystems would help inform site remediation efforts.

Environmental Science and Technology↗

USGS2002

Effect of ten quaternary ammonium cations on tetrachloromethane sorption to clay from water

The mineral surface of Wyoming bentonite (clay) was modified by replacing inorganic ions by each of 10 quaternary ammonium compounds, and tetrachloromethane sorption to the modified sorbents from water was studied. Tetrachloromethane sorption from solution to clay modified with tetramethyl-, tetraethyl-, benzyltrimethyl-, or benzyltriethylammonium cations generally is characterized by relatively high solute uptake, isotherm nonlinearity, and competitive sorption (with trichloroethene as the competing sorbate). For these sorbents, the ethyl functional groups yield reduced sorptive capacity relative to methyl groups, whereas the benzyl group appears to have a similar effect on sorbent capacity as the methyl group. Sorption of tetrachloromethane to clay modified with dodecyldimethyl(2-phenoxyethyl)-, dodecyltrimethyl-, tetradecyltrimethyl-, hexadecyltrimethyl-, or benzyldimethylhexadecylammonium bromide is characterized by relatively low solute uptake, isotherm linearity, and noncompetitive sorption. For these sorbents, an increase in the size of the nonpolar functional group(s) causes an increase in the organic carbon normalized sorption coefficient (Koc). No measurable uptake of tetrachloromethane sorption by the unmodified clay or clay modified by ammonium bromide was observed.

Environmental Science & Technology↗

USGS2024

The EnMAP spaceborne imaging spectroscopy mission: Initial scientific results two years after launch

Imaging spectroscopy has been a recognized and established remote sensing technology since the 1980s, mainly using airborne and field-based platforms to identify and quantify key bio- and geo-chemical surface and atmospheric compounds, based on characteristic spectral reflectance features in the visible-near infrared (VNIR) and short-wave infrared (SWIR). Spaceborne missions, a leap in technology, were sparse, starting with the CHRIS/PROBA and EO1/Hyperion missions in the early 2000s, and providing spectroscopy data with limited spectral coverage and/or low data quality in the SWIR. Since 2019, several countries and agencies have successfully launched a number of spaceborne imaging spectroscopy systems into orbit or deployed them on the International Space Station (ISS) such as DESIS, PRISMA, HISUI, GF-5, EnMAP and EMIT. Among these recent missions, the German Environmental Mapping and Analysis Program (EnMAP) stands for its long-term development, sophisticated design with on-board calibration, high data quality requirements, and extensive accompanying science program. EnMAP was launched in April 2022 and, following a successful commissioning phase, started its operational activities in November 2022. The EnMAP mission encompasses global coverage from 80° N to 80° S through on-demand data acquisitions. Data are free and open access with 30 m spatial resolution, a high spectral resolution with a spectral sampling distance of 6.5 nm and 10 nm in the VNIR and SWIR regions respectively, and a high signal-to-noise ratio. In this paper, we aim to present the mission's current status, coverage, science capabilities and performance two years after launch. We show the potential of EnMAP for space-based imaging spectroscopy to operate in various environments, including high and low light levels, dense forests, Antarctic glaciers, and arid agricultural areas. EnMAP enables various applications in fields such as agriculture and forestry, soil compositional, raw materials, and methane mapping, as well as water quality assessment, and snow and ice properties. The results show that EnMAP's performance exceeds the mission requirements, and highlights the significant potential for contribution to scientific exploitation in various geo- and biochemical sciences. EnMAP is also expected to serve as a key tool for the development and testing of data processing algorithms for upcoming global operational missions.

Remote Sensing of Environment↗

USGS2013

Optimizing stream water mercury sampling for calculation of fish bioaccumulation factors

Mercury (Hg) bioaccumulation factors (BAFs) for game fishes are widely employed for monitoring, assessment, and regulatory purposes. Mercury BAFs are calculated as the fish Hg concentration (Hg fish ) divided by the water Hg concentration (Hg water ) and, consequently, are sensitive to sampling and analysis artifacts for fish and water. We evaluated the influence of water sample timing, filtration, and mercury species on the modeled relation between game fish and water mercury concentrations across 11 streams and rivers in five states in order to identify optimum Hg water sampling approaches. Each model included fish trophic position, to account for a wide range of species collected among sites, and flow-weighted Hg water estimates. Models were evaluated for parsimony, using Akaike’s Information Criterion. Better models included filtered water methylmercury (FMeHg) or unfiltered water methylmercury (UMeHg), whereas filtered total mercury did not meet parsimony requirements. Models including mean annual FMeHg were superior to those with mean FMeHg calculated over shorter time periods throughout the year. FMeHg models including metrics of high concentrations (80th percentile and above) observed during the year performed better, in general. These higher concentrations occurred most often during the growing season at all sites. Streamflow was significantly related to the probability of achieving higher concentrations during the growing season at six sites, but the direction of influence varied among sites. These findings indicate that streamwater Hg collection can be optimized by evaluating site-specific FMeHg - UMeHg relations, intra-annual temporal variation in their concentrations, and streamflow-Hg dynamics.

Environmental Science & Technology↗

USGS2002

Determination of phosphate in natural waters by activation analysis of tungstophosphoric acid

Activation analysis may be used to determine quantitatively traces of phosphate in natural waters. Methods based on the reaction 31 P( n,γ ) 32 P are subject to interference by sulfur and chlorine which give rise to 32 P through n,p and n,α reactions. If the ratio of phosphorus to sulfur or chlorine is small, as it is in most natural waters, accurate analyses by these methods are difficult to achieve. In the activation analysis method, molybdate and tungstate ions are added to samples containing phosphate ion to form tungstomolybdophosphoric acid. The complex is extracted with 2,6-dimethyl-4-heptanone. After activation of an aliquot of the organic phase for 1 hour at a flux of 10 13 neutrons per cm 2 , per second, the gamma spectrum is essentially that of tungsten-187. The induced activity is proportional to the concentration of phosphate in the sample. A test of the method showed it to give accurate results at concentrations of 4 to at least 200 p.p.b. of phosphorus when an aliquot of 100 μl. was activated. By suitable reagent purification, counting for longer times, and activation of larger aliquots, the detection limit could be lowered several hundredfold.

Environmental Science & Technology↗

USGS2009

Removal of organic wastewater contaminants in septic systems using advanced treatment technologies

The detection of pharmaceuticals and other organic wastewater contaminants (OWCs) in ground water and surface-water bodies has raised concerns about the possible ecological impacts of these compounds on nontarget organisms. On-site wastewater treatment systems represent a potentially significant route of entry for organic contaminants to the environment. In this study, effluent samples were collected and analyzed from conventional septic systems and from systems using advanced treatment technologies. Six of 13 target compounds were detected in effluent from at least one septic system. Caffeine, paraxanthine, and acetaminophen were the most frequently detected compounds, and estrogenic activity was detected in 14 of 15 systems. The OWC concentrations were significantly lower in effluent after sand filtration (p < 0.01) or aerobic treatment (p < 0.05) as compared with effluent that had not undergone advanced treatment. In general, concentrations in conventional systems were comparable to those measured in previous studies of municipal wastewater treatment plant (WWTP) influent, and concentrations in systems after advanced treatment were comparable to previously measured concentrations in WWTP effluent. These data indicate that septic systems using advanced treatment can reduce OWCs in treated effluent to similar concentrations as municipal WWTPs. Copyright ?? 2009 by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. All rights reserved.

Journal of Environmental Quality↗

USGS2011

Influence of changing water sources and mineral chemistry on the everglades ecosystem

Human influences during the previous century increased mineral inputs to the Florida Everglades by changing the sources and chemistry of surface inflows. Biogeochemical responses to this enrichment include changes in the availability of key limiting nutrients such as P, the potential for increased turnover of nutrient pools due to accelerated plant decomposition, and increased rates of mercury methylation associated with sulfate enrichment. Mineral enrichment has also been linked to the loss of sensitive macrophyte species, although dominant Everglades species appear tolerant of a broad range of mineral chemistry. Shifts in periphyton community composition and function provide an especially sensitive indicator of mineral enrichment. Understanding the influence of mineral chemistry on Everglades processes and biota may improve predictions of ecosystem responses to ongoing hydrologic restoration efforts and provide guidelines for protecting remaining mineral-poor areas of this peatland.

Florida↗

USGS2010

Tapping environmental history to recreate America's colonial hydrology

Throughout American history water resources have played integral roles in shaping patterns of human settlement and networks of biological and economic exchange. In turn, humans have altered hydrologic systems to meet their needs. A paucity of climate and water discharge data for the seventeenth and eighteenth centuries, however, has left America's preindustrial hydrology largely unstudied. As a result, there have been few detailed, quantifiable, regional assessments of hydrologic change between the time of first European settlement and the dawn of industrial expansion. As scientists labor to understand present-day hydrologic systems and make predictions about the future, the value of expanding the geographic (1, 2) and temporal scopes (3, 4) of their studies has become increasingly evident. Pollen and tree-ring analyses have helped shed light on past climate and land-use patterns. But other nonscientific sources and methods can be equally revealing and in some cases complement empirical studies (5). This paper argues that environmental science, particularly that concerned with the human dimensions of water resources, stands to profit from using historical literature and archival sources. By considering work in environmental history, forging closer working relationships between the geophysical and social sciences, and seriously entertaining narratives as a form of evidence, environmental scientists can not only look farther into the past and across broader geographic areas, but they can also more accurately describe the nuances and complexities that define the ways humans have changed the world around them. In this paper, we present the recommendations of a multidisciplinary summer institute that developed 1) a conceptual and methodological framework for conducting historical hydrology, and 2) suggestions for ways that historical information can be used to inform the hydrologic sciences. Our intent here is to encourage further work along these or similar lines. We believe that future efforts that build on our famework and draw and expand upon the sources referenced below will produce scholarship of great utility to both environmental and social sciences.

Environmental Science & Technology↗

USGS2024

Chemical composition of leachates from hydraulic fracturing proppants from surficial releases in southeastern New Mexico

Resin-coated proppants (RCPs) are used in hydraulic fracturing of oil and gas wells to improve well performance; however, these proppants could be a cause for environmental concern if they are disposed of improperly. In this study, we investigate the water-leachable organic and inorganic constituents from proppants collected from surficial releases of RCPs in southeastern New Mexico. Significant concentrations of nonvolatile dissolved organic matter (>100 mg C/L) and phenolic compounds (>50 mg phenol/L) were identified in one of the proppant leachates, with further gas chromatography–mass spectrometry analysis identifying isomers of bisphenol F, a known endocrine disruptor analogous to bisphenol A, as the main organic constituents within this leachate. Fluorescence excitation–emission matrices analyses of proppant leachates identified several peaks associated with phenolic compounds, similar to previously studied oilfield wastewaters. Precursors of polyurethane production, including the inhalation sensitizer methylene diphenyl diisocyanate, were identified in the leachate from another proppant sample. An understanding of leachable compounds from RCPs is vital to management of environmental contamination from surficial releases, protecting the public and industry workers from associated hazards, and identifying the sources of organic compounds in oilfield wastewaters.

New Mexico↗

USGS2013

Source and transport of human enteric viruses in deep municipal water supply wells

Until recently, few water utilities or researchers were aware of possible virus presence in deep aquifers and wells. During 2008 and 2009 we collected a time series of virus samples from six deep municipal water-supply wells. The wells range in depth from approximately 220 to 300 m and draw water from a sandstone aquifer. Three of these wells draw water from beneath a regional aquitard, and three draw water from both above and below the aquitard. We also sampled a local lake and untreated sewage as potential virus sources. Viruses were detected up to 61% of the time in each well sampled, and many groundwater samples were positive for virus infectivity. Lake samples contained viruses over 75% of the time. Virus concentrations and serotypes observed varied markedly with time in all samples. Sewage samples were all extremely high in virus concentration. Virus serotypes detected in sewage and groundwater were temporally correlated, suggesting very rapid virus transport, on the order of weeks, from the source(s) to wells. Adenovirus and enterovirus levels in the wells were associated with precipitation events. The most likely source of the viruses in the wells was leakage of untreated sewage from sanitary sewer pipes.

Wisconsin↗

USGS2019

Fungicides: An overlooked pesticide class?

Fungicides are indispensable to global food security and their use is forecasted to intensify. Fungicides can reach aquatic ecosystems and occur in surface water bodies in agricultural catchments throughout the whole growing season due to their frequent, prophylactic application. However, in comparison to herbicides and insecticides, the exposure to and effects of fungicides have received less attention. We provide an overview of the risk of fungicides to aquatic ecosystems covering fungicide exposure (i.e., environmental fate, exposure modelling, and mitigation measures) as well as direct and indirect effects of fungicides on microorganisms, macrophytes, invertebrates, and vertebrates. We show that fungicides occur widely in aquatic systems, that the accuracy of predicted environmental concentrations is debatable, and that fungicide exposure can be effectively mitigated. We additionally demonstrate that fungicides can be highly toxic to a broad range of organisms and can pose a risk to aquatic biota. Finally, we outline central research gaps that currently challenge our ability to predict fungicide exposure and effects, promising research avenues, and shortcomings of the current environmental risk assessment for fungicides.

Environmental Science & Technology↗

USGS2011

Influence of dissolved organic matter on the environmental fate of metals, nanoparticles, and colloids

We have known for decades that dissolved organic matter (DOM) plays a critical role in the biogeochemical cycling of trace metals and the mobility of colloidal particles in aquatic environments. In recent years, concerns about the ecological and human health effects of metal-based engineered nanoparticles released into natural waters have increased efforts to better define the nature of DOM interactions with metals and surfaces. Nanomaterials exhibit unique properties and enhanced reactivities that are not apparent in larger materials of the same composition 1,2 or dissolved ions of metals that comprise the nanoparticles. These nanoparticle-specific properties generally result from the relatively large proportion of the atoms located at the surface, which leads to very high specific surface areas and a high proportion of crystal lattice imperfections relative to exposed surface area. Nanoscale colloids are ubiquitous in nature,2 and many engineered nanomaterials have analogs in the natural world. The properties of these materials, whether natural or manmade, are poorly understood, and new challenges have been presented in assessing their environmental fate. These challenges are particularly relevant in aquatic environments where interactions with DOM are key, albeit often overlooked, moderators of reactivity at the molecular and nanocolloidal scales.

Environmental Science & Technology↗

USGS2003

Evaluation of specific ultraviolet absorbance as an indicator of the chemical composition and reactivity of dissolved organic carbon

Specific UV absorbance (SUVA) is defined as the UV absorbance of a water sample at a given wavelength normalized for dissolved organic carbon (DOC) concentration. Our data indicate that SUVA, determined at 254 nm, is strongly correlated with percent aromaticity as determined by 13C NMR for 13 organic matter isolates obtained from a variety of aquatic environments. SUVA, therefore, is shown to be a useful parameter for estimating the dissolved aromatic carbon content in aquatic systems. Experiments involving the reactivity of DOC with chlorine and tetramethylammonium hydroxide (TMAH), however, show a wide range of reactivity for samples with similar SUVA values. These results indicate that, while SUVA measurements are good predictors of general chemical characteristics of DOC, they do not provide information about reactivity of DOC derived from different types of source materials. Sample pH, nitrate, and iron were found to influence SUVA measurements.

Environmental Science & Technology↗

USGS2021

Optical properties of water for prediction of wastewater contamination, human-associated bacteria, and fecal indicator bacteria in surface water at three watershed scales

Relations between spectral absorbance and fluorescence properties of water and human-associated and fecal indicator bacteria were developed for facilitating field sensor applications to estimate wastewater contamination in waterways. Leaking wastewater conveyance infrastructure commonly contaminates receiving waters. Methods to quantify such contamination can be time consuming, expensive, and often nonspecific. Human-associated bacteria are wastewater specific but require discrete sampling and laboratory analyses, introducing latency. Human sewage has fluorescence and absorbance properties different than those of natural waters. To assist real-time field sensor development, this study investigated optical properties for use as surrogates for human-associated bacteria to estimate wastewater prevalence in environmental waters. Three spatial scales were studied: Eight watershed-scale sites, five subwatershed-scale sites, and 213 storm sewers and open channels within three small watersheds (small-scale sites) were sampled (996 total samples) for optical properties, human-associated bacteria, fecal indicator bacteria, and, for selected samples, human viruses. Regression analysis indicated that bacteria concentrations could be estimated by optical properties used in existing field sensors for watershed and subwatershed scales. Human virus occurrence increased with modeled human-associated bacteria concentration, providing confidence in these regressions as surrogates for wastewater contamination. Adequate regressions were not found for small-scale sites to reliably estimate bacteria concentrations likely due to inconsistent local sanitary sewer inputs.

Michigan, New York, Ohio, Wisconsin↗

USGS2021

Nutrient improvements in Chesapeake Bay: Direct effect of load reductions and implications for coastal management

In Chesapeake Bay in the United States, decades of management efforts have resulted in modest reductions of nutrient loads from the watershed, but corresponding improvements in estuarine water quality have not clearly materialized. Generalized additive models were used to directly link river flows and nutrient loads from the watershed to nutrient trends in the estuary on a station-by-station basis, which allowed for identification of exactly when and where responses are happening. Results show that Chesapeake Bay total nitrogen and total phosphorus conditions are mostly improving after accounting for variation in freshwater flow. Almost all of these improving nutrient concentrations in the estuary can be explained by reductions in watershed loads entering through 16 rivers and 145 nearby point sources. These two major types of loads from multiple locations across the watershed are together necessary and responsible for improving estuarine nutrient conditions, a finding that is highly relevant to managing valuable estuarine resources worldwide.

Maryland, Virginia↗

USGS2009

A shallow subsurface controlled release facility in Bozeman, Montana, USA, for testing near surface CO2 detection techniques and transport models

A controlled field pilot has been developed in Bozeman, Montana, USA, to study near surface CO2 transport and detection technologies. A slotted horizontal well divided into six zones was installed in the shallow subsurface. The scale and CO2 release rates were chosen to be relevant to developing monitoring strategies for geological carbon storage. The field site was characterized before injection, and CO2 transport and concentrations in saturated soil and the vadose zone were modeled. Controlled releases of CO2 from the horizontal well were performed in the summers of 2007 and 2008, and collaborators from six national labs, three universities, and the U.S. Geological Survey investigated movement of CO2 through the soil, water, plants, and air with a wide range of near surface detection techniques. An overview of these results will be presented.

Montana↗

USGS2016

The estimated six-year mercury dry deposition across North America

Dry deposition of atmospheric mercury (Hg) to various land covers surrounding 24 sites in North America was estimated for the years 2009 to 2014. Depending on location, multiyear mean annual Hg dry deposition was estimated to range from 5.1 to 23.8 μg m –2 yr –1 to forested canopies, 2.6 to 20.8 μg m –2 yr –1 to nonforest vegetated canopies, 2.4 to 11.2 μg m –2 yr –1 to urban and built up land covers, and 1.0 to 3.2 μg m –2 yr –1 to water surfaces. In the rural or remote environment in North America, annual Hg dry deposition to vegetated surfaces is dominated by leaf uptake of gaseous elemental mercury (GEM), contrary to what was commonly assumed in earlier studies which frequently omitted GEM dry deposition as an important process. Dry deposition exceeded wet deposition by a large margin in all of the seasons except in the summer at the majority of the sites. GEM dry deposition over vegetated surfaces will not decrease at the same pace, and sometimes may even increase with decreasing anthropogenic emissions, suggesting that Hg emission reductions should be a long-term policy sustained by global cooperation.

Environmental Science & Technology↗

USGS2013

Understanding water column and streambed thermal refugia for endangered mussels in the Delaware River

Groundwater discharge locations along the upper Delaware River, both discrete bank seeps and diffuse streambed upwelling, may create thermal niche environments that benefit the endangered dwarf wedgemussel (Alasmidonta heterodon). We seek to identify whether discrete or diffuse groundwater inflow is the dominant control on refugia. Numerous springs and seeps were identified at all locations where dwarf wedgemussels still can be found. Infrared imagery and custom high spatial resolution fiber-optic distributed temperature sensors reveal complex thermal dynamics at one of the seeps with a relatively stable, cold groundwater plume extending along the streambed/water-column interface during mid-summer. This plume, primarily fed by a discrete bank seep, was shown through analytical and numerical heat-transport modeling to dominate temperature dynamics in the region of potential habitation by the adult dwarf wedgemussel.

Pennsylvania↗