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USGS2017

U.S. Geological Survey Karst Interest Group Proceedings, San Antonio, Texas, May 16–18, 2017

Introduction and Acknowledgments Karst aquifer systems are present throughout parts of the United States and some of its territories, and have developed in carbonate rocks (primarily limestone and dolomite) and evaporites (gypsum, anhydrite, and halite) that span an interval of time encompassing more than 550 million years. The depositional environments, diagenetic processes, post-depositional tectonic events, and geochemical weathering processes that form karst aquifers are varied and complex. These factors involve biological, chemical, and physical changes that when combined with the diverse climatic regimes in which karst development has taken place, result in the unique dual- or triple-porosity nature of karst aquifers. These complex hydrogeologic systems typically represent challenging and unique conditions to scientists attempting to study groundwater flow and contaminant transport in these terrains. The dissolution of carbonate rocks and the subsequent development of distinct and beautiful landscapes, caverns, and springs have resulted in the most exceptional karst areas being designated as national or state parks. Tens of thousands of similar areas in the United States have been developed into commercial caverns and known privately owned caves. Both public and private properties provide access for scientists to study the flow of groundwater in situ . Likewise, the range and complexity of landforms and groundwater flow systems associated with karst terrains are enormous, perhaps more than for any other aquifer type. Karst aquifers and landscapes that form in tropical areas, such as the cockpit karst along the north coast of Puerto Rico, differ greatly from karst landforms in more arid climates, such as the Edwards Plateau in west-central Texas or the Guadalupe Mountains near Carlsbad, New Mexico, where hypogenic processes have played a major role in speleogenesis. Many of these public and private lands also contain unique flora and fauna associated with these karst hydrogeologic systems. As a result, numerous federal, state, and local agencies have a strong interest in the study of karst terrains. Many of the major springs and aquifers in the United States have developed in carbonate rocks, such as the Floridan aquifer system in Florida and parts of Alabama, Georgia, and South Carolina; the Ozark Plateaus aquifer system in parts of Arkansas, Kansas, Missouri, and Oklahoma; and the Edwards-Trinity aquifer system in west-central Texas. These aquifers, and the springs that discharge from them, serve as major water-supply sources and form unique ecological habitats. Competition for the water resources of karst aquifers is common, and urban development and the lack of attenuation of contaminants in karst areas due to dissolution features that form direct pathways into karst aquifers can impact the ecosystem and water quality associated with these aquifers. The concept for developing a platform for interaction among scientists within the U.S. Geological Survey (USGS) working on karst-related studies evolved from the November 1999 National Groundwater Meeting of the USGS. As a result, the Karst Interest Group (KIG) was formed in 2000. The KIG is a loose-knit, grass-roots organization of USGS and non-USGS scientists and researchers devoted to fostering better communication among scientists working on, or interested in, karst science. The primary mission of the KIG is to encourage and support interdisciplinary collaboration and technology transfer among scientists working in karst areas. Additionally, the KIG encourages collaborative studies between the different mission areas of the USGS as well as with other federal and state agencies, and with researchers from academia and institutes. To accomplish its mission, the KIG has organized a series of workshops that have been held near nationally important karst areas. To date (2017) seven KIG workshops, including the workshop documented in this report, have been held. The workshops typically include oral and poster sessions on selected karst-related topics and research, as well as field trips to local karst areas. To increase non-USGS participation an effort was made for the workshops to be held at a university or institute beginning with the fourth workshop. Proceedings of the workshops are published by the USGS and are available online at the USGS publications warehouse https://pubs.er.usgs.gov/ by using the search term “karst interest group.” The first KIG workshop was held in St. Petersburg, Florida, in 2001, in the vicinity of the large springs and other karst features of the Floridan aquifer system. The second KIG workshop was held in 2002, in Shepherdstown, West Virginia, in proximity to the carbonate aquifers of the northern Shenandoah Valley, and highlighted an invited presentation on karst literature by the late Barry F. Beck of P.E. LaMoreaux and Associates. The third KIG workshop was held in 2005, in Rapid City, South Dakota, near evaporite karst features in limestones of the Madison Group in the Black Hills of South Dakota. The Rapid City KIG workshop included field trips to Wind Cave National Park and Jewel Cave National Monument, and featured a presentation by Thomas Casadevall, then USGS Central Region Director, on the status of Earth science at the USGS. The fourth KIG workshop in 2008 was hosted by the Hoffman Environmental Research Institute and Center for Cave and Karst Studies at Western Kentucky University in Bowling Green, Kentucky, near Mammoth Cave National Park and karst features of the Chester Upland and Pennyroyal Plateau. The workshop featured a late-night field trip into Mammoth Cave led by Rickard Toomey and Rick Olsen, National Park Service. The fifth KIG workshop in 2011 was a joint meeting of the USGS KIG and University of Arkansas HydroDays, hosted by the Department of Geosciences at the University of Arkansas in Fayetteville. The workshop featured an outstanding field trip to the unique karst terrain along the Buffalo National River in the southern Ozarks, and a keynote presentation on paleokarst in the United States was delivered by Art and Peggy Palmer. The sixth KIG workshop was hosted by the National Cave and Karst Research Institute (NCKRI) in 2014, in Carlsbad, New Mexico. George Veni, Director of the NCKRI, served as a co-chair of the workshop with Eve Kuniansky of the USGS. The workshop featured speaker Dr. Penelope Boston, Director of Cave and Karst Studies at New Mexico Tech, Socorro, and Academic Director at the NCKRI, who addressed the future of karst research. The field trip on evaporite karst of the lower Pecos Valley was led by Lewis Land (NCKRI karst hydrologist), and the field trip on the geology of Carlsbad Caverns National Park was led by George Veni. This current seventh KIG workshop is being held in San Antonio at the University of Texas at San Antonio (UTSA). This 2017 workshop is being hosted by the Department of Geological Sciences’ Student Geological Society (SGS), and student chapters of the American Association of Petroleum Geologists (AAPG) and Association of Engineering Geologists (AEG), with support by the UTSA Department of Geological Sciences and Center for Water Research. The UTSA student chapter presidents, Jose Silvestre (SGS), John Cooper (AAPG), and Tyler Mead (AEG) serve as co-chairs of the 2017 workshop with Eve Kuniansky of the USGS. The technical session committee is chaired by Eve Kuniansky, USGS, and includes Michael Bradley, Tom Byl, Rebecca Lambert, John Lane, and James Kaufmann, all USGS, and Patrick Tucci, retired USGS. The logistics committee includes Amy Clark, Yongli Gao, and Lance Lambert (Department Chair), UTSA Department of Geological Sciences; and Ryan Banta and Allan Clark, USGS, San Antonio, Texas. The field trip committee is chaired by Allan Clark and includes Amy Clark, Yongli Gao, and Keith Muehlestein, UTSA; Marcus Gary, Edwards Aquifer Authority and University of Texas at Austin; Ron Green, Southwest Research Institute; Geary Schindel, Edwards Aquifer Authority; and George Veni, NCKRI. Additionally, two organizations have assisted the UTSA student chapters in hosting the meeting by donating funds to the chapters: the Edwards Aquifer Authority, San Antonio, Texas, and the Barton Springs Edwards Aquifer Authority, Austin, Texas. Additionally, Yongli Gao, Center for Water Research and Department of Geological Sciences, UTSA, helped develop sessions on cave and karst research in China for this workshop. These proceedings could not have been accomplished without the assistance of Lawrence E. Spangler as co-editor who not only has subject matter expertise, but also serves as an editor with the USGS Science Publishing Network. We sincerely hope that this workshop continues to promote future collaboration among scientists of varied and diverse backgrounds, and improves our understanding of karst aquifer systems in the United States and its territories. The extended abstracts of USGS authors were peer reviewed and approved for publication by the USGS. Articles submitted by university researchers and other federal and state agencies did not go through the formal USGS peer review and approval process, and therefore may not adhere to USGS editorial standards or stratigraphic nomenclature. However, all articles had a minimum of two peer reviews and were edited for consistency of appearance in the proceedings. The use of trade, firm or product names is for descriptive purposes only and does not imply endorsement by the U.S. Government. The USGS Water Availability and Use Science Program funded the publication costs of the proceedings.

Scientific Investigations Report↗
USGS2020

Critical shifts in trace metal transport and remediation performance under future low river flows

Exceptionally low river flows are predicted to become more frequent and more severe across many global regions as a consequence of climate change. Investigations of trace metal transport dynamics across streamflows reveal stark changes in water chemistry, metal transformation processes, and remediation effectiveness under exceptionally low-flow conditions. High spatial resolution hydrological and water quality datasets indicate that metal-rich groundwater will exert a greater control on stream water chemistry and metal concentrations because of climate change. This is because the proportion of stream water sourced from mined areas and mineralized strata will increase under predicted future low-flow scenarios (from 25% under Q45 flow to 66% under Q99 flow in this study). However, mineral speciation modelling indicates that changes in stream pH and hydraulic conditions at low flow will decrease aqueous metal transport and increase sediment metal concentrations by enhancing metal sorption directly to streambed sediments. Solute transport modelling further demonstrates how increases in the importance of metal-rich diffuse groundwater sources at low flow could minimize the benefits of point source metal contamination treatment. Understanding metal transport dynamics under exceptionally low flows, as well as under high flows, is crucial to evaluate ecosystem service provision and remediation effectiveness in watersheds under future climate change scenarios.

Environmental Science & Technology↗
USGS1996

Pesticides in streams draining agricultural and urban areas in Colorado

A study was conducted from April 1993 through April 1994 to describe and compare the occurrence and distribution of pesticides in streams in a small agricultural and a small urban area in Colorado. Twenty-five water samples collected at least monthly at the mouths of two tributary streams of the South Plate River were analyzed for 47 pesticides. The results indicate that both agricultural and urban areas are probable sources for pesticides in streams. In the agricultural area, 30 pesticides were detected, and in the urban area, 22 pesticides were detected in one or more samples. Most often, the more frequently detected pesticides in both areas also were some of the more commonly used pesticides. In both areas, pesticide concentrations were higher during the summer (application period) with maximum concentrations generally occurring in storm runoff. The year-round detection of some pesticides in both areas at consistently low concentrations, regardless of season or streamflow volume, could indicate that these compounds persist in the shallow alluvial aquifer year-round.

Environmental Science & Technology↗
USGS2000

Effect of a constructed wetland on disinfection byproducts: Removal processes and production of precursors

The fate of halogenated disinfection byproducts (DBPs) in treatment wetlands and the changes in the DBP formation potential as wastewater treatment plant (WWTP)-derived water moves through the wetlands were investigated. Wetland inlet and outlet samples were analyzed for total organic halide (TOX), trihalomethanes (TH M), haloacetic acids (HAA), dissolved organic carbon (DOC), and UV absorbance. Removal of DBPs by the wetland ranged from 13 to 55% for TOX, from 78 to 97% for THM, and from 67 to 96% for HAA. The 24-h and 7-day nonpurgeable total organic halide (NPTOX), THM, and HAA formation potential yields were determined at the inlet and outlet of these wetlands. The effect of wetlands on the production of DBP precursors and their DBP-formation potential yield from wastewater was dramatic. The wetlands increased DBP yield up to a factor of almost 30. Specific changes in the DOC precursors were identified using 13C NMR spectroscopy.The fate of halogenated disinfection byproducts (DBPs) in treatment wetlands and the changes in the DBP formation potential as wastewater treatment plant (WWTP)-derived water moves through the wetlands were investigated. Wetland inlet and outlet samples were analyzed for total organic halide (TOX), trihalomethanes (THM), haloacetic acids (HAA), dissolved organic carbon (DOC), and UV absorbance. Removal of DBPs by the wetland ranged from 13 to 55% for TOX, from 78 to 97% for THM, and from 67 to 96% for HAA. The 24-h and 7-day nonpurgeable total organic halide (NPTOX), THM, and HAA formation potential yields were determined at the inlet and outlet of these wetlands. The effect of wetlands on the production of DBP precursors and their DBP-formation potential yield from wastewater was dramatic. The wetlands increased DBP yield up to a factor of almost 30. Specific changes in the DOC precursors were identified using 13C NMR spectroscopy.

Environmental Science & Technology↗
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,&gamma; ) 32 P are subject to interference by sulfur and chlorine which give rise to 32 P through n,p and n,&alpha; 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 &mu;l. 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↗