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Assessment of PDMS-water partition coefficients: implications for passive environmental sampling of hydrophobic organic compounds

Solid-phase microextraction (SPME) has shown potential as an in situ passive-sampling technique in aquatic environments. The reliability of this method depends upon accurate determination of the partition coefficient between the fiber coating and water (K f ). For some hydrophobic organic compounds (HOCs), K f values spanning 4 orders of magnitude have been reported for polydimethylsiloxane (PDMS) and water. However, 24% of the published data examined in this review did not pass the criterion for negligible depletion, resulting in questionable K f values. The range in reported K f is reduced to just over 2 orders of magnitude for some polychlorinated biphenyls (PCBs) when these questionable values are removed. Other factors that could account for the range in reported K f , such as fiber-coating thickness and fiber manufacturer, were evaluated and found to be insignificant. In addition to accurate measurement of K f , an understanding of the impact of environmental variables, such as temperature and ionic strength, on partitioning is essential for application of laboratory-measured K f values to field samples. To date, few studies have measured K f for HOCs at conditions other than at 20 degrees or 25 degrees C in distilled water. The available data indicate measurable variations in K f at different temperatures and different ionic strengths. Therefore, if the appropriate environmental variables are not taken into account, significant error will be introduced into calculated aqueous concentrations using this passive sampling technique. A multiparameter linear solvation energy relationship (LSER) was developed to estimate log K f in distilled water at 25 degrees C based on published physicochemical parameters. This method provided a good correlation (R2 = 0.94) between measured and predicted log K f values for several compound classes. Thus, an LSER approach may offer a reliable means of predicting log K f for HOCs whose experimental log K f values are presently unavailable. Future research should focus on understanding the impact of environmental variables on K f . Obtaining the data needed for an LSER approach to estimate K f for all environmentally relevant HOCs would be beneficial to the application of SPME as a passive-sampling technique.

Environmental Science & Technology

Widespread use of the nitrification inhibitor nitrapyrin: Assessing benefits and costs to agriculture, ecosystems, and environmental health

Agricultural production and associated applications of nitrogen (N) fertilizers have increased dramatically in the last century, and current projections to 2050 show that demands will continue to increase as the human population grows. Applied in both organic and inorganic fertilizer forms, N is an essential nutrient in crop productivity. Increased fertilizer applications, however, create the potential for more N loss before plant uptake. One strategy for minimizing N loss is the use of enhanced efficiency fertilizers, fortified with a nitrification inhibitor, such as nitrapyrin. In soils and water, nitrapyrin inhibits the activity of ammonia monooxygenase, a microbial enzyme that catalyzes the first step of nitrification from ammonium to nitrite. Potential benefits of using nitrification inhibitors range from reduced nitrate leaching and nitrous oxide emissions to increased crop yield. The extent of these benefits, however, depends on environmental conditions and management practices. Thus, such benefits are not always realized. Additionally, nitrapyrin has been shown to transport off-field, and it is unknown what effects environmental nitrapyrin could have on nontarget organisms and the ecological nitrogen cycle. Here, we review the agronomic and environmental benefits and costs of nitrapyrin use and present a series of research questions and considerations to be addressed with future nitrification inhibitor research.

Environmental Science and Technology

Bioaccumulation and transfer of per- and polyfluoroalkyl substances (PFAS) in a stream and riparian food web contaminated by food processing wastewater

We evaluated the bioaccumulation and transfer of per- and polyfluoroalkyl substances (PFAS) in a stream food web contaminated by a food processing facility. Abiotic (i.e., water, sediment, and foam) and biotic (i.e., algae, aquatic insect larvae and adults, fish, and riparian spiders) matrices were sampled upstream and downstream of the facility’s wastewater outfall. Compared with upstream, PFAS concentrations were 600-fold higher in downstream water (mean ∑ 40 PFAS 3.67 ng mL –1 ± 0.48 (standard error)) and reflected inputs from the outfall, with 6:2 fluorotelomer sulfonate (6:2 FTS) dominating the PFAS profile. Within the aquatic food web, perfluorooctanesulfonate (PFOS) was the most biomagnified, and 6:2 FTS was the most biodiluted. In contrast, insect-mediated transfer of PFAS to riparian spiders showed trophic enrichment of 6:2 FTS and dilution of PFOS. We observed significant positive associations between phospholipid membrane-water partition coefficient (log K MW ) and perfluoroalkyl carboxylate (PFCA) chain length on bioaccumulation across most biological matrices, demonstrating that these chemical parameters are predictive of PFAS bioaccumulation potential in the field. Our research reveals important differences in aquatic versus terrestrial exposure for certain PFAS and that biological processes (e.g., trophic interactions and metamorphosis) and chemical properties (e.g., chain length, log K MW , and concentration) control PFAS uptake, bioaccumulation, and transfer in linked freshwater and terrestrial ecosystems.

Environmental Science & Technology

Exposure to human-associated chemical markers of fecal contamination and self-reported illness among swimmers at recreational beaches

Anthropogenic chemicals have been proposed as potential markers of human fecal contamination in recreational water. However, to date, there are no published studies describing their relationships with illness risks. Using a cohort of swimmers at seven U.S. beaches, we examined potential associations between the presence of chemical markers of human fecal pollution and self-reported gastrointestinal (GI) illness, diarrhea, and respiratory illness. Swimmers were surveyed about their beach activities, water exposure, and baseline symptoms on the day of their beach visit, and about any illness experienced 10–12 days later. Risk differences were estimated using model-based standardization and adjusted for the swimmer’s age, beach site, sand contact, rainfall, and water temperature. Sixty-two chemical markers were analyzed from daily water samples at freshwater and marine beaches. Of those, 20 were found consistently. With the possible exception of bisphenol A and cholesterol, no chemicals were consistently associated with increased risks of illness. These two chemicals were suggestively associated with 2% and 1% increased risks of GI illness and diarrhea in both freshwater and marine beaches. Additional research using the more sensitive analytic methods currently available for a wider suite of analytes is needed to support the use of chemical biomarkers to quantify illness risk and identify fecal pollution sources.

Alabama, Indiana, Michigan, Mississippi, Ohio, Rho

Agencies collaborate, develop a cyanobacteria assessment network

Cyanobacteria are a genetically diverse group of photosynthetic microorganisms that occupy a broad range of habitats on land and water all over the world. They release toxins that can cause lung and skin irritation, alter the taste and odor of potable water, and cause human and animal illness. Cyanobacteria blooms occur worldwide, and climate change may increase the frequency, duration, and extent of these bloom events. Rapid detection of potentially harmful blooms is essential to protect humans and animals from exposure. Information about potential for exposure, such as bloom duration, frequency, and extent, is especially critical for developing environmental management decisions during periods of limited resources and funding. The National Research Council (NRC) report Exposure Science in the 21st Century suggested that effectively assessing and mitigating exposures requires techniques for rapid measurement of a stressor, such as an algal bloom, across diverse geographic, temporal, and biologic scales (e.g., various bloom concentrations) and an enhanced infrastructure to address threats [ NRC , 2012]. The report specifically calls for approaches that use diverse information, such as satellite remote sensing, to identify and understand exposures that may pose a threat to ecosystems or human health. A collaborative effort integrates the work of the U.S. Environmental Protection Agency (EPA), NASA, the National Oceanic and Atmospheric Administration (NOAA), and the U.S. Geological Survey (USGS) to provide an approach for using satellite ocean color capabilities in U.S. fresh and brackish water quality management decisions. The overarching goal of this collaborative project is to detect and quantify cyanobacteria blooms using satellite data records in order to support the environmental management and public use of U.S. lakes and reservoirs. Satellite remote sensing tools may enable policy makers and environmental managers to assess the sustainability of watershed ecosystems and the services they provide, now and in the future. Satellite technology allows us to develop early-warning indicators of cyanobacteria blooms at the local scale while maintaining continuous national coverage.

Eos, Earth and Space Science News

The U.S. Geological Survey Ecosystem Science Strategy, 2012-2022 - Advancing discovery and application through collaboration

Ecosystem science is critical to making informed decisions about natural resources that can sustain our Nation’s economic and environmental well-being. Resource managers and policy-makers are faced with countless decisions each year at local, state, tribal, territorial, and national levels on issues as diverse as renewable and non-renewable energy development, agriculture, forestry, water supply, and resource allocations at the urban-rural interface. The urgency for sound decision-making is increasing dramatically as the world is being transformed at an unprecedented pace and in uncertain directions. Environmental changes are associated with natural hazards, greenhouse gas emissions, and increasing demands for water, land, food, energy, mineral, and living resources. At risk is the Nation’s environmental capital, the goods and services provided by resilient ecosystems that are vital to the health and well-being of human societies. Ecosystem science—the study of systems of organisms interacting with their environment and the consequences of natural and human-induced change on these systems—is necessary to inform decision-makers as they develop policies to adapt to these changes. This Ecosystems Science Strategy is built on a framework that includes basic and applied science. It highlights the critical roles that USGS scientists and partners can play in building scientific understanding and providing timely information to decision-makers. The strategy underscores the connection between scientific discoveries and the application of new knowledge. The strategy integrates ecosystem science and decision-making, producing new scientific outcomes to assist resource managers and providing public benefits. The USGS is uniquely positioned to play an important role in ecosystem science. With its wide range of expertise, the agency can bring holistic, cross-scale, interdisciplinary capabilities to the design and conduct of monitoring, research, and modeling and to new technologies for data collection, management, and visualization. Collectively, these capabilities can be used to reveal ecological patterns and processes, explain how and why ecosystems change, and forecast change over different spatial and temporal scales. USGS science can provide managers with options and decision-support tools to use resources sustainably. The USGS has long-standing, collaborative relationships with the DOI and other partners in the natural sciences, in both conducting science and its application. The USGS engages these partners in cooperative investigations that otherwise would lack the necessary support or be too expensive for a single bureau to conduct. The heart of this strategy is a framework and vision for USGS ecosystems science that focuses on five long-term goals, which are seen as interconnected and reinforcing components: • Improve understanding of ecosystem structure, function, and processes. The focus for this goal is an understanding of how ecosystems work, including the dynamics of species, their populations, interactions, and genetics, and how they change across spatial and temporal scales. • Advance understanding of how drivers influence ecosystem change. The challenges here are explaining the drivers of ecosystem change, their spatio-temporal patterns, their uncertainties and interactions, and their influence on ecosystem processes and dynamics. • Improve understanding of the services that ecosystems provide to society. Here the emphasis is on the measurement of environmental capital and ecosystem services, and the identification of sources and patterns of change in space and time. • Develop tools, technologies, and capacities to inform decision-making about ecosystems. This includes developing new technologies and approaches for conducting applications-oriented ecosystem science. A principal challenge will be how to quantify uncertainty and incorporate it in decision analysis. • Apply science to enhance strategies for management, conservation, and restoration of ecosystems. These challenges include development of novel approaches to monitoring, assessment, and restoration of ecosystems; new methods to address species of concern and communities at risk; and innovations in decision analysis and support to address imminent ecosystem changes or those that are underway. Closely integrated with the five goals are four strategic approaches that provide the path forward for the USGS Ecosystems Mission Area. These approaches cross-cut all of the goals and are seen as essential to the implementation of this strategy: • Assess information needs for ecosystem science through enhanced partnerships. Work with the DOI and other agencies and institutions to identify, design, and implement priority decision-driven ecological research. • Promote the use of interdisciplinary ecosystem science. Design and conduct interdisciplinary process-oriented research in ecosystem science. • Enhance modeling and forecasting. Build models to forecast ecosystem change, assess future management scenarios, and reduce uncertainties through an adaptive learning process. • Support decision-making. Use quantitative approaches to assess the vulnerabilities of ecosystems, habitats, and species, and evaluate strategies for adaptation, restoration, and sustainable management. Following the strategic approaches are a set of proposed actions that represent a sampling of specific activities that align with this strategy and that address the Nation’s most pressing environmental needs. The strategy emphasizes coordination of activities across the USGS mission areas pursuant to these goals. Ecosystem science is inherently interdisciplinary and requires a broad perspective that incorporates the biological and physical sciences, climate science, information technology, and scientific capacity in mission areas across the Bureau. With its emphasis on coordination, this strategy can provide a critical underpinning for integrated science efforts with scientists from multiple mission areas of the USGS working together. Of course, the USGS will continue to conduct both discipline-specific and interdisciplinary investigations, and both will continue to be vital parts of the ecosystem science portfolio. Finally, the strategy stresses the importance of coordination with other Federal agencies and organizations in the natural resources community. The USGS collaborates with resource agencies in the DOI and other organizations throughout the world to meet societal needs for species and ecosystem management. Working with these agencies and organizations, the USGS will play a key role over the next decade in advancing the scientific foundation for sustaining the natural resources that diverse, productive, resilient ecosystems provide.

Open-File Report

Science needs for determining the effects of climate change on harmful algal blooms in the southeastern United States

The Southeastern United States has many lakes, streams, and reservoirs that serve as important drinking water sources with recreational, agricultural, and ecological uses. However, harmful algal blooms (HABs) are becoming more common in these waters, causing health issues for humans and animals. HABs have been listed as a contaminant of emerging concern, and the magnitude, frequency, and duration of HABs appear to be increasing at the global scale. While it is well known that nutrients stimulate algae growth, it is not clear how climate change and other parameters stimulate the development of toxin production by HABs. The scientific literature describes parameters, such as storm occurrence, temperature, dissolved metals, erosion of soils, increasing length of growing season, discharge, and hydroperiod, that may affect algae growth and toxin production. Climate and hydrologic models address many of the physical and environmental parameters that influence HABs, but no climate models directly address HABs. This report compiles information from the existing literature pertaining to HABs and the modeling and forecasting of HABS. This compilation is done through the incorporation of climate change models. HAB research that involves climate change will require multiple disciplines that bring together ecologists, hydrologists, climatologists, engineers, economists, and new technology. Resource managers could use geographic data about the occurrence and distribution of HABs to develop models that identify waterbodies more vulnerable to HAB events. Development of such models will require teams capable of integrating biological, chemical, and physical factors. Model development will require additional research that can resolve anthropogenic and climate-related environmental factors to identify trends in freshwater HABs. The complexity and interconnectedness of the parameters that influence HAB occurrences will make model development challenging and require rigorous regional calibration.

Open-File Report

U.S. Geological Survey ecosystems science strategy—Advancing discovery and application through collaboration

Executive Summary Ecosystem science is critical to making informed decisions about natural resources that can sustain our Nation’s economic and environmental well-being. Resource managers and policymakers are faced with countless decisions each year at local, regional, and national levels on issues as diverse as renewable and nonrenewable energy development, agriculture, forestry, water supply, and resource allocations at the urban-rural interface. The urgency for sound decisionmaking is increasing dramatically as the world is being transformed at an unprecedented pace and in uncertain directions. Environmental changes are associated with natural hazards, greenhouse gas emissions, and increasing demands for water, land, food, energy, mineral, and living resources. At risk is the Nation’s environmental capital, the goods and services provided by resilient ecosystems that are vital to the health and wellbeing of human societies. Ecosystem science—the study of systems of organisms interacting with their environment and the consequences of natural and human-induced change on these systems—is necessary to inform decisionmakers as they develop policies to adapt to these changes. This Ecosystems Science Strategy is built on a framework that includes basic and applied science. It highlights the critical roles that U.S. Geological Survey (USGS) scientists and partners can play in building scientific understanding and providing timely information to decisionmakers. The strategy underscores the connection between scientific discoveries and the application of new knowledge, and it integrates ecosystem science and decisionmaking, producing new scientific outcomes to assist resource managers and providing public benefits. We envision the USGS as a leader in integrating scientific information into decisionmaking processes that affect the Nation’s natural resources and human well-being. The USGS is uniquely positioned to play a pivotal role in ecosystem science. With its wide range of expertise, the Bureau can bring holistic, cross-scale, interdisciplinary capabilities to the design and conduct of monitoring, research, and modeling and to new technologies for data collection, management, and visualization. Collectively, these capabilities can be used to reveal ecological patterns and processes, explain how and why ecosystems change, and forecast change over different spatial and temporal scales. USGS science can provide managers with options and decision-support tools to use resources sustainably. The USGS has long-standing, collaborative relationships with the Department of the Interior (DOI) and other partners in the natural sciences, in both conducting science and applying the results. The USGS engages these partners in cooperative investigations that otherwise would lack the necessary support or be too expensive for a single bureau to conduct. The heart of this strategy is a framework for USGS ecosystems science that focuses on five long-term goals, which are seen as interconnected components that reinforce our vision of the USGS providing science that is at the forefront of decisionmaking: Improve understanding of ecosystem structure, function, and processes. The focus for this goal is an understanding of how ecosystems work, including the dynamics of species, their populations, interactions, and genetics, and how they change across spatial and temporal scales. Advance understanding of how drivers influence ecosystem change. The challenges here are explaining the drivers of ecosystem change, their spatio-temporal patterns, their uncertainties and interactions, and their influence on ecosystem processes and dynamics. Improve understanding of the services that ecosystems provide to society. Here the emphasis is on the measurement of environmental capital and ecosystem services, and the identification of sources and patterns of change in space and time. Develop tools, technologies, and capacities to inform decisionmaking about ecosystems. This includes developing new technologies and approaches for conducting applications-oriented ecosystem science. A principal challenge will be how to quantify uncertainty and incorporate it in decision analysis. Apply science to enhance strategies for management, conservation, and restoration of ecosystems. These challenges include development of novel approaches to monitoring, assessment, and restoration of ecosystems; new methods to address species of concern and communities at risk; and innovations in decision analysis and support to address imminent ecosystem changes or those that are underway. Closely integrated with the five goals are four strategic approaches that provide the path forward for the USGS Ecosystems Mission Area. These approaches cross-cut all of the goals and are seen as essential to the implementation of this strategy: Assess information needs for ecosystem science through enhanced partnerships. Work with the DOI and other agencies and institutions to identify, design, and implement priority decision-driven ecological research. Promote the use of interdisciplinary ecosystem science. Design and conduct interdisciplinary process-oriented research in ecosystem science. Enhance modeling and forecasting. Build models to forecast ecosystem change, assess future management scenarios, and reduce uncertainties through an adaptive learning process. Support decisionmaking. Use quantitative approaches to assess the vulnerabilities of ecosystems, habitats, and species, and evaluate strategies for adaptation, restoration, and sustainable management. Following the four strategic approaches are a set of proposed actions that represent a sampling of specific USGS activities that align with this strategy and that address the Nation’s most pressing environmental needs. The strategy emphasizes coordination of activities across the USGS mission areas pursuant to these goals. Ecosystem science is inherently interdisciplinary and requires a broad perspective that incorporates the biological and physical sciences, climate science, information technology, and scientific capacity in mission areas across the Bureau. With its emphasis on coordination, this strategy can provide a critical underpinning for integrated science efforts with scientists from multiple mission areas of the USGS working together. Of course, the USGS will continue to conduct discipline-specific and interdisciplinary investigations, and both will continue to be vital parts of the ecosystem science portfolio. Finally, the strategy stresses the importance of coordination with other Federal agencies and organizations in the natural resources community. The USGS collaborates with resource agencies in the DOI and other organizations throughout the world to meet societal needs for species and ecosystem management. Working with these agencies and organizations, the USGS will play a key role in guiding sound decisionmaking during the next decade by advancing the scientific foundation for sustaining the natural resources that diverse, productive, resilient ecosystems provide.

Circular

When synthetic chemicals degrade in the environment: What are the absolute fate, effects, and potential risks to humans and the ecosystem?

Various processes degrade synthetic chemicals—pesticides, pharmaceuticals, biocides, and industrials—in the environment ( 1 , 2 ). Consequently, the environment may be exposed to a mixture of the parent compounds and any resulting degradation products (degradates). Recent advances in analytical methodology and greater access to analytical standards have advanced degradates research ( 3 , 4 ). Specifically, research on pesticides has found degradates in surface water ( 5 – 10 ), groundwater ( 11 – 13 ), precipitation ( 14 – 16 ), air ( 17 , 18 ), and sediment ( 19 , 20 ). Pharmaceuticals and detergent degradates also exist in the environment ( 21 – 23 ). Figure 1 shows that degradates were detected as often as or more frequently than the parent compound. Although some regulatory schemes require information about the impacts of degradates on human and environmental health, that information does not exist for many compounds ( 25 , 26 ). Pesticides are the exception. In this article, we bring together the available data to address the environmental behavior of degradates and their effects on organisms and discuss how to identify substances of potential concern. In addition, we cite gaps in the current knowledge and make recommendations for future research requirements. While the article focuses on pesticides, we believe these observations can be extended to biologically active compounds and some industrial substances.

Environmental Science & Technology

Interim report on the scientific investigations in the Animas River watershed, Colorado to facilitate remediation decisions by the U.S. Bureau of Land Management and the U.S. Forest Service, March 29, 2000 meeting, Denver, Colo.

INTRODUCTION The joint U.S. Department of the Interior and U.S. Department of Agriculture Abandoned Mine Lands Initiative (AMLI) was developed as a collaborative effort between the Federal land management agencies (FLMA, that is the U.S. Bureau of Land Management and the U.S. Forest Service) and the U.S. Geological Survey (USGS) in 1996. The stated goal of the AML Initiative was to develop a strategy for gathering and communicating the scientific information needed to develop effective and cost-efficient remediation of abandoned mines within the framework of a watershed. Four primary objectives of the AMLI are to: 1. Provide the scientific information needed (in the short-term) by the FLMAs to make decisions related to the design and implementation of cleanup actions, 2. Develop a multi-disciplined, multi-division approach that integrates geologic, hydrologic, geochemical and ecological information into a knowledge base for sound decision making, 3. Transfer technologies developed within the scientific programs of the USGS to the field and demonstrate their suitability to solve real, practical problems, and 4. Establish working relationships among involved members of land management and regulatory agencies within the framework of a watershed approach to the cleanup of abandoned mines. Long-term process-based research, including development of analytical tools, is recognized as being critical to the long-term success in remediating watersheds impacted by historical mining activities (AML 5-year plan, http://amli.usgs.gov/amli). In a meeting of Federal agencies (U.S. Bureau of Land Management [BLM], U.S. Bureau of Reclamation [BOR], U.S. National Park Service [NPS], U.S. Forest Service [USFS], the U.S. Environmental Protection Agency [EPA], the U.S. Fish and Wildlife Service [F&WS]), and State agencies (Colorado Division of Public Health and Environment, Colorado Division of Mines and Geology), several watersheds were examined within the state whose water quality was presumed to be impacted by historical mining activities. The Animas River watershed (fig. 1) was selected by the State and Federal agencies as one of two watersheds in the U.S. to be studied in detail by the USGS in the AML Initiative. Beginning in October 1997, each of the four Divisions of the USGS (Water Resources, Geologic, Biological Resources, and National Mapping) initiated a collaborative integrated science study of the watershed. Funds were provided from USGS base funding to each of the four Divisions in response to the priorities set by Congressional action and within the flexibility provided by the budgetary framework funding individual research programs. The AML Initiative provides for a five-year focused scientific effort in the two watersheds with final synthesis of the scientific results from each to be published in 2001. Publications are released on the AML web site on a regular basis (http://amli.usgs.gov/amli). On March 29, 2000, the USGS hosted a meeting for the BLM and USFS to discuss remediation options that were under consideration for the summer of 2000. The purpose of this report is to provide an overview of the scientific rational provided by the USGS to meet objective one above, and to summarize our preliminary interpretations of our data. Additional information from sites on private lands have been collected by the State of Colorado, EPA, and the ARSG. Unfortunately, these data have not been fully supplied to the USGS so our conclusions are based only upon our data. These interpretations provide science-based constraints on possible remediation options to be considered by the FLMA, the State, and local property owners in the Animas River watershed. The report is presented in outline format to facilitate discussion of remediation options at the March 29, 2000 meeting. Not all historical mining sites within the watershed are on public lands. This should not be construed to be a final report of the USGS

Denver

Limitations in the use of commercial humic acids in water and soil research

Seven samples of commercial "humic acids", purchased from five different suppliers, were studied, and their characteristics were compared with humic and fulvic acids isolated from streams, soils, peat, leonardite, and a dopplerite sample. Cross-polarization and magic-angle spinning 13C NMR spectroscopy clearly shows pronounced differences between the commercial materials and all other samples. Elemental and infrared spectroscopic data do not show such clear-cut differences but can be used as supportive evidence, with the 13C NMR data, to substantiate the above distinctions. As a result of these differences and due to the general lack of information relating to the source, method of isolation, or other pretreatment of the commercial materials, these commercial products are not considered to be appropriate for use as analogues of true soil and water humic substances, in experiments designed to evaluate the nature and reactivity of humic substances in natural waters and soils.

Environmental Science & Technology

Recent and historic drivers of landscape change in the Everglades ridge, slough, and Tree Island mosaic

More than half of the original Everglades extent formed a patterned peat mosaic of elevated ridges, lower and more open sloughs, and tree islands aligned parallel to the dominant flow direction. This ecologically important landscape structure remained in a dynamic equilibrium for millennia prior to rapid degradation over the past century in response to human manipulation of the hydrologic system. Restoration of the patterned landscape structure is one of the primary objectives of the Everglades restoration effort. Recent research has revealed that three main drivers regulated feedbacks that initiated and maintained landscape structure: the spatial and temporal distribution of surface water depths, surface and subsurface flow, and phosphorus supply. Causes of recent degradation include but are not limited to perturbations to these historically important controls; shifts in mineral and sulfate supply may have also contributed to degradation. Restoring predrainage hydrologic conditions will likely preserve remaining landscape pattern structure, provided a sufficient supply of surface water with low nutrient and low total dissolved solids content exists to maintain a rainfall-driven water chemistry. However, because of hysteresis in landscape evolution trajectories, restoration of areas with a fully degraded landscape could require additional human intervention.

Critical Reviews in Environmental Science and Tech

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

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

Biogeochemical controls on diel cycling of stable isotopes of dissolved 02 and dissolved inorganic carbon in the Big Hole River, Montana

Rivers with high biological productivity typically show substantial increases in pH and dissolved oxygen (DO) concentration during the day and decreases at night, in response to changes in the relative rates of aquatic photosynthesis and respiration. These changes, coupled with temperature variations, may impart diel (24-h) fluctuations in the concentration of trace metals, nutrients, and other chemical species. A better understanding of diel processes in rivers is needed and will lead to improved methods of data collection for both monitoring and research purposes. Previous studies have used stable isotopes of dissolved oxygen (DO) and dissolved inorganic carbon (DIC) as tracers of geochemical and biological processes in streams, lakes, and marine systems. Although seasonal variation in δ 18 O of DO in rivers and lakes has been documented, no study has investigated diel changes in this parameter. Here, we demonstrate large (up to 13‰) cycles in δ 18 O-DO for two late summer sampling periods in the Big Hole River of southwest Montana and illustrate that these changes are correlated to variations in the DO concentration, the C-isotopic composition of DIC, and the primary productivity of the system. The magnitude of the diel cycle in δ 18 O-DO was greater in August versus September because of the longer photoperiod and warmer water temperatures. This study provides another biogeochemical tool for investigating the O 2 and C budgets in rivers and may also be applicable to lake and groundwater systems.

Montana

Fate and behavior tools related to inland spill response—Workshop on the U.S. Geological Survey’s role in Federal science support

Executive Summary There is a growing body of tools available for science support for determining the fate and behavior of industrial and agricultural chemicals that are rapidly injected (“spilled”) into aquatic environments. A 2-day roundtable-style workshop was held by the U.S. Geological Survey (USGS) in Middleton, Wisconsin, in December 2017 to describe and explore existing Federal science support for spill fate and behavior tools used for inland spills, ongoing and new fate and behavior studies, and science gaps in planning and response tools as part of the USGS Midcontinent Region’s efforts to include spill response as part of its strategic plans. A total of 28 attendees representing a variety of Federal, State, and regional entities presented on programs and tools used in various aspects of spill response. Most programs and tools discussed were for spills in riverine environments but tools and applications for spills in lakes, on land surfaces, in urban storm sewer networks, and groundwater also were discussed. A primary workshop focus was to facilitate communication and increase potential for future collaboration among agencies for inland spill science support. The role and need for more USGS science support within the inland spill community was discussed. Enhanced communication is needed within the USGS and the U.S. Department of the Interior science programs, as well as within and among other agencies that do emergency planning and response. A main conclusion of the workshop was that there are untapped resources of the USGS outlined in the agency’s science strategy that could strengthen science support for fate and behavior tools in inland areas, especially in the Upper Mississippi River, Ohio River, and Great Lakes Basins where large freshwater resources overlap with dense corridors of oil and hazardous substances, with transportation networks, and with large populations centers. Fate and behavior tools are being developed quickly for inland spill response by multiple Federal agencies in partnership with local and regional entities. Applicability of these tools ranges from planning and preparedness, to the early stages of spill response for protection of human life and property, and to the application of monitoring and models to assess the long-term consequences of spills. Key findings from the workshop, with an emphasis on potential further development of USGS science support, include the following: •The national and regional response to spills occurs within an established system that must be respected by all parties involved in spill response. The USGS’s role is to support spill responders who are physically working at a spill scene, deploying booms and using other efforts to contain and recover spilled materials. •The USGS has tools that have been used throughout spill response operations, from early response to recovery and restoration. Developing a more formal role for the USGS to participate in science support for inland spills on a consistent basis is a desired outcome. This will require the USGS to improve internal and external communication and would be best accomplished by assigning one or more coordinator positions within the agency to plan and oversee USGS spill-response efforts. More involvement of the USGS on National and Regional Response Teams, especially in the realm of the Science and Technology Subcommittees, will gofar in increasing external communication and integration of fate and behavior tools. •Rapid response to spills requires modeling and mapping of plumes and associated time-of-travel estimation for a range of stream sizes across the United States. Many existing models use USGS streamgage data and the USGS National Hydrography Dataset. Nearly all existing models would benefit from updated linkages to USGS StreamStats and its soon-to-be released time-of-travel estimates,real-time velocity, stream morphology, and slope data. Integrating USGS tools with those from other agencies could be done to better serve the larger spill response community. • A problem is that existing models to rapidly predict plume extent, as well as more followup/longer-term fate and transport models, can be unknown or unavailable to spill responders. Thus, creating and strengthening linkages among USGS scientists skilled at using these tools is needed to support spill response with the on-scene responders. • Research for inland spill fate and behavior done outside of an immediate spill response can assist with spill planning and preparedness by (1) revealing sites likely to experience spills in the future (high-risk sites) and (2) understanding how a spilled substance might behave under a range of environmental conditions. However, USGS research on this topic has been scarce and subject to funding availability. Examples include the 2010 Line 6B Spill release into the Kalamazoo River in Michigan, where the USGS provided science support for a variety of fate and behavior tools for stream and impoundment environments. A long-term research site in Bemidji, Minnesota, provides important insights into transformations and longevity of spilled oil in groundwater and groundwater-surface water interactions. • Linking stream models to other components of this inland environment, including groundwater, overland flow, and karst, is needed. Stream network data can be linked to underground conduits such as storm sewers and karst groundwater systems. Stream models can also be linked with geospatial data such as that contained in U.S. Environmental Protection Agency’s interactive mapping tools. • The USGS is uniquely qualified to collect water-quality data during spills in the United States because of its many geographically dispersed water science centers, its knowledge and preparedness for flood measurement and documentation, and its cadre of skilled water-quality employees. Rapid-deployment gages, used for floods, could also be used for spills if they included spill-specific sensors. Coordinated expertise at USGS water and environmental science centers can be used for monitoring spill effects and for assessing risk to water quality and ecological communities. • Scientists at the USGS have proven capable of providing science coordination and technical assistance within the Incident Command Structure at the request of the lead on-scene coordinator. This external coordination, as well as internal communication within USGS Water, Hazards, and Ecosystems Mission Areas, could be improved by establishing and naming a USGS spills coordinator. Scott Morlock, Jo Ellen Hinck, and Faith Fitzpatrick are currently (2017) serving in informal coordination roles in addition to their traditional duties.

Open-File Report

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

Deep-sea coral research and technology program: Alaska deep-sea coral and sponge initiative final report

Deep-sea coral and sponge ecosystems are widespread throughout most of Alaska’s marine waters. In some places, such as the central and western Aleutian Islands, deep-sea coral and sponge resources can be extremely diverse and may rank among the most abundant deep-sea coral and sponge communities in the world. Many different species of fishes and invertebrates are associated with deep-sea coral and sponge communities in Alaska. Because of their biology, these benthic invertebrates are potentially impacted by climate change and ocean acidification. Deepsea coral and sponge ecosystems are also vulnerable to the effects of commercial fishing activities. Because of the size and scope of Alaska’s continental shelf and slope, the vast majority of the area has not been visually surveyed for deep-sea corals and sponges. NOAA’s Deep Sea Coral Research and Technology Program (DSCRTP) sponsored a field research program in the Alaska region between 2012–2015, referred to hereafter as the Alaska Initiative. The priorities for Alaska were derived from ongoing data needs and objectives identified by the DSCRTP, the North Pacific Fishery Management Council (NPFMC), and Essential Fish Habitat-Environmental Impact Statement (EFH-EIS) process. This report presents the results of 15 projects conducted using DSCRTP funds from 2012-2015. Three of the projects conducted as part of the Alaska deep-sea coral and sponge initiative included dedicated at-sea cruises and fieldwork spread across multiple years. These projects were the eastern Gulf of Alaska Primnoa pacifica study, the Aleutian Islands mapping study, and the Gulf of Alaska fish productivity study. In all, there were nine separate research cruises carried out with a total of 109 at-sea days conducting research. The remaining projects either used data and samples collected by the three major fieldwork projects or were piggy-backed onto existing research programs at the Alaska Fisheries Science Center (AFSC).

NOAA Technical Memorandum