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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↗

Comparative evaluation of statistical and mechanistic models of Escherichia coli at beaches in southern Lake Michigan

Statistical and mechanistic models are popular tools for predicting the levels of indicator bacteria at recreational beaches. Researchers tend to use one class of model or the other, and it is difficult to generalize statements about their relative performance due to differences in how the models are developed, tested, and used. We describe a cooperative modeling approach for freshwater beaches impacted by point sources in which insights derived from mechanistic modeling were used to further improve the statistical models and vice versa. The statistical models provided a basis for assessing the mechanistic models which were further improved using probability distributions to generate high-resolution time series data at the source, long-term “tracer” transport modeling based on observed electrical conductivity, better assimilation of meteorological data, and the use of unstructured-grids to better resolve nearshore features. This approach resulted in improved models of comparable performance for both classes including a parsimonious statistical model suitable for real-time predictions based on an easily measurable environmental variable (turbidity). The modeling approach outlined here can be used at other sites impacted by point sources and has the potential to improve water quality predictions resulting in more accurate estimates of beach closures.

Lake Michigan, Ogden Dunes↗

Chlorinated byproducts of neonicotinoids and their metabolites: An unrecognized human exposure potential?

We recently reported the initial discovery of neonicotinoid pesticides in drinking water and their potential for transformation through chlorination and alkaline hydrolysis during water treatment. The objectives of this research were: (1) to determine if neonicotinoid metabolites are relevant to drinking water exposure and (2) to identify the products formed from chlorination of neonicotinoids and their metabolites. Desnitro-imidacloprid and imidacloprid-urea, two known metabolites of imidacloprid, are documented for the first time in drinking water. Desnitro-imidacloprid was present above the lower level of detection (0.03 ng/L) in 67% of samples (six of nine) from drinking water systems but detectable in all samples (up to 0.6 ng/L). Although concentrations of desnitro-imidacloprid were lower than concentrations of the parent neonicotinoids, desnitro-imidacloprid exhibits significantly greater mammalian toxicity than imidacloprid. Using LC-HR-ToF-MS/MS analysis of results from laboratory experiments, we propose structures for novel transformation products resulting from the chlorination of clothianidin, imidacloprid, desnitro-imidacloprid, imidacloprid-urea, and hydrolysis products of thiamethoxam. Formation of chlorinated neonicotinoid byproducts occurs at time scales relevant to water treatment and/or distribution for the imidacloprid metabolites ( t 1/2 values from 2.4 min to 1.0 h) and thiamethoxam hydrolysis products (4.8 h). Neonicotinoid metabolites in finished drinking water and potential formation of novel disinfection byproducts during treatment and/or distribution are relevant to evaluating the exposure and potential impacts of neonicotinoids on human health.

Environmental Science & Technology Letters↗

Assessing pesticide application contributions of per- and polyfluoroalkyl substances (PFAS) in agricultural streams

Research has documented per-and polyfluoroalkyl substances (PFAS) to be prevalent in streams impacted by urban sources; less is known regarding PFAS contributions via pesticide applications: PFAS coming from pesticide containers and “inert” ingredients not listed on pesticide formulation labels. To better understand co-occurrence of pesticides and PFAS in agricultural streams, 10 streams were sampled in two agricultural valleys in northern California, USA during two periods of pesticide application (May and July of 2024). Water samples were analyzed for 183 pesticides and 57 PFAS. Sixty pesticides were detected: 23 herbicides, 18 insecticides, 18 fungicides, and 1 synergist. Overall detection frequencies (DF) ranged from 0 to 100%, and concentrations ranged from non-detect (ND) to 782 ng/L (fluxapyroxad). Fourteen PFAS were detected: 6 perfluoroalkyl carboxylates, 5 perfluoroalkyl sulfonates, 2 perfluoroalkyl acid precursors, and 1 perfluoroalkyl phosphinic acid with DFs ranging from 0 to 60% (PFOA) and concentrations ranging from ND to 20 ng/L (PFBA). Co-occurrence of PFAS and pesticides was observed in 80% of samples. Adopting the global definition of PFAS (includes fluorinated pesticides), pesticide applications are a likely source of instream PFAS. Examination of total organic fluorine and transformations to terminal and ultra-short PFAS could further elucidate pesticide contributions to environmental PFAS.

California↗

A fresh look at road salt: Aquatic toxicity and water-quality impacts on local, regional, and national scales

A new perspective on the severity of aquatic toxicity impact of road salt was gained by a focused research effort directed at winter runoff periods. Dramatic impacts were observed on local, regional, and national scales. Locally, samples from 7 of 13 Milwaukee, Wisconsin area streams exhibited toxicity in Ceriodaphnia dubia and Pimephales promelas bioassays during road-salt runoff. Another Milwaukee stream was sampled from 1996 to 2008 with 72% of 37 samples exhibiting toxicity in chronic bioassays and 43% in acute bioassays. The maximum chloride concentration was 7730 mg/L. Regionally, in southeast Wisconsin, continuous specific conductance was monitored as a chloride surrogate in 11 watersheds with urban land use from 6.0 to 100%. Elevated specific conductance was observed between November and April at all sites, with continuing effects between May and October at sites with the highest specific conductance. Specific conductance was measured as high as 30 800 ??S/cm (Cl = 11 200 mg/L). Chloride concentrations exceeded U.S. Environmental Protection Agency (USEPA) acute (860 mg/L) and chronic (230 mg/L) water-quality criteria at 55 and 100% of monitored sites, respectively. Nationally, U.S. Geological Survey historical data were examined for 13 northern and 4 southern metropolitan areas. Chloride concentrations exceeded USEPA water-quality criteria at 55% (chronic) and 25% (acute) of the 168 monitoring locations in northern metropolitan areas from November to April. Only 16% (chronic) and 1% (acute) of sites exceeded criteria from May to October. At southern sites, very few samples exceeded chronic water-quality criteria, and no samples exceeded acute criteria. ?? 2010 American Chemical Society.

Environmental Science & Technology↗

Fate of 4-nonylphenol and 17β-estradiol in the Redwood River of Minnesota

The majority of previous research investigating the fate of endocrine-disrupting compounds has focused on single processes generally in controlled laboratory experiments, and limited studies have directly evaluated their fate and transport in rivers. This study evaluated the fate and transport of 4-nonylphenol, 17β-estradiol, and estrone in a 10-km reach of the Redwood River in southwestern Minnesota. The same parcel of water was sampled as it moved downstream, integrating chemical transformation and hydrologic processes. The conservative tracer bromide was used to track the parcel of water being sampled, and the change in mass of the target compounds relative to bromide was determined at two locations downstream from a wastewater treatment plant effluent outfall. In-stream attenuation coefficients ( k stream ) were calculated by assuming first-order kinetics (negative values correspond to attenuation, whereas positive values indicate production). Attenuation of 17β-estradiol ( k stream = −3.2 ± 1.0 day –1 ) was attributed primarily due to sorption and biodegradation by the stream biofilm and bed sediments. Estrone ( k stream = 0.6 ± 0.8 day –1 ) and 4-nonylphenol ( k stream = 1.4 ± 1.9 day –1 ) were produced in the evaluated 10-km reach, likely due to biochemical transformation from parent compounds (17β-estradiol, 4-nonylphenolpolyethoxylates, and 4-nonyphenolpolyethoxycarboxylates). Despite attenuation, these compounds were transported kilometers downstream, and thus additive concentrations from multiple sources and transformation of parent compounds into degradates having estrogenic activity can explain their environmental persistence and widespread observations of biological disruption in surface waters.

Minnesota↗

Exposure and transport of alkaloids and phytoestrogens from soybeans to agricultural soils and streams in the Midwestern United States

Phytotoxins are naturally produced toxins with potencies similar/higher than many anthropogenic micropollutants. Nevertheless, little is known regarding their environmental fate and off-field transport to streams. To fill this research gap, a network of six basins in the Midwestern United States with substantial soybean production was selected for the study. Stream water ( n = 110), soybean plant tissues ( n = 8), and soil samples ( n = 16) were analyzed for 12 phytotoxins (5 alkaloids and 7 phytoestrogens) and 2 widely used herbicides (atrazine and metolachlor). Overall, at least 1 phytotoxin was detected in 82% of the samples, with as many as 11 phytotoxins detected in a single sample (median = 5), with a concentration range from below detection to 37 and 68 ng/L for alkaloids and phytoestrogens, respectively. In contrast, the herbicides were ubiquitously detected at substantially higher concentrations (atrazine: 99% and metolachlor: 83%; the concentrations range from below detection to 150 and 410 ng/L, respectively). There was an apparent seasonal pattern for phytotoxins, where occurrence prior to and during harvest season (September to November) and during the snow melt season (March) was higher than that in December–January. Runoff events increased phytotoxin and herbicide concentrations compared to those in base-flow conditions. Phytotoxin plant concentrations were orders of magnitude higher compared to those measured in soil and streams. These results demonstrate the potential exposure of aquatic and terrestrial organisms to soybean-derived phytotoxins.

Illinois, Indiana, Iowa, Minnesota, Missouri, Sout↗

Transport of chemical and microbial compounds from known wastewater discharges: Potential for use as indicators of human fecal contamination

The quality of drinking and recreational water is currently (2005) determined using indicator bacteria. However, the culture tests used to analyze for these bacteria require a long time to complete and do not discriminate between human and animal fecal material sources. One complementary approach is to use chemicals found in human wastewater, which would have the advantages of (1) potentially shorter analysis times than the bacterial culture tests and (2) being selected for human-source specificity. At 10 locations, water samples were collected upstream and at two successive points downstream from a wastewaster treatment plant (WWTP); a treated effluent sample was also collected at each WWTP. This sampling plan was used to determine the persistence of a chemically diverse suite of emerging contaminants in streams. Samples were also collected at two reference locations assumed to have minimal human impacts. Of the 110 chemical analytes investigated in this project, 78 were detected at least once. The number of compounds in a given sample ranged from 3 at a reference location to 50 in a WWTP effluent sample. The total analyte load at each location varied from 0.018 μg/L at the reference location to 97.7 μg/L in a separate WWTP effluent sample. Although most of the compound concentrations were in the range of 0.01−1.0 μg/L, in some samples, individual concentrations were in the range of 5−38 μg/L. The concentrations of the majority of the chemicals present in the samples generally followed the expected trend:  they were either nonexistent or at trace levels in the upstream samples, had their maximum concentrations in the WWTP effluent samples, and then declined in the two downstream samples. This research suggests that selected chemicals are useful as tracers of human wastewater discharge.

Environmental Science & Technology↗

Linear solvation energy relationship of the limiting partition coefficient of organic solutes between water and activated carbon

A linear solvation energy relationship has been found for 353 values of the limiting adsorption coefficients of diverse chemicals: log K = −0.37 + 0.0341 V i − 1.07β + D + 0.65 P with R = 0.951, s = 0.51, n = 353, and F = 818.0, where V i is the intrinsic molar volume; β is a measure of the hydrogen bond acceptor strength of the solute; D is an index parameter for the research group which includes the effects of the different types of carbon used, the temperature, and the length of time allowed for the adsorption equilibrium to be established; and P is an index parameter for the flatness of the molecule. P is defined to be unity if there is an aromatic system in the molecule or if there is a double bond or series of conjugated double bonds with no more that one non-hydrogen atom beyond the double bond and zero otherwise. A slightly better fit is obtained if the two-thirds power of V i is used as a measure of the surface area in place of the volume term: log K = −1.75 + 0.227 V 2/3 − 1.10β + D + 0.60 P with R = 0.954, s = 0.49, n = 353, and F = 895.39. This is the first quantitative measure of the effect of the shape of the molecule on its tendency to be adsorbed on activated carbon.

Environmental Science & Technology↗

U.S. Geological Survey Karst Interest Group Proceedings, Carlsbad, New Mexico, April 29-May 2, 2014

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) 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, and involve biological, chemical, and physical changes. These factors, combined with the diverse climatic regimes under which karst development in these rocks 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 has resulted in the most exceptional karst areas of the United States being designated as national or state parks; commercial caverns and known privately owned caves number in the tens of thousands. 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 as 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 can impact the ecosystem and water quality of 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 Ground-Water 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 other federal and state agencies, and with researchers from academia and institutes. The KIG also encourages younger scientists by participation of students in the poster and oral sessions. To accomplish its mission, the KIG has organized a series of workshops that are held near nationally important karst areas. To date (2014) six 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 features. Proceedings of the workshops are published by the USGS and are available online at http://water.usgs.gov/ogw/karst/kig . The first KIG workshop was held in St. Petersburg, Florida, February 13–16, 2001, in the vicinity of the large springs and other karst features of the Floridan aquifer system. The second KIG workshop was held August 20–22, 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 September 12–15, 2005, in Rapid City, South Dakota, nearby to karst features in evaporites and limestones of the Madison Group in the Black Hills of South Dakota, including Wind Cave National Park and Jewel Cave National Monument. The workshop also included a featured presentation by Thomas Casadevall, Central Region Director, USGS, on the status of earth science at the USGS and evening trips to Jewel Cave led by Mike Wiles, National Park Service (NPS) and Wind Cave led by Rod Horrocks, NPS. The fourth KIG workshop was held May 27–29, 2008, and 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 with Rickard Toomey and Rick Olsen, NPS. The fifth workshop was held April 26–29, 2011, and 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 of the southern Ozarks and a keynote presentation on paleokarst in the United States by Art and Peggy Palmer. This sixth and current 2014 KIG workshop is hosted by the National Cave and Karst Research Institute (NCKRI) in Carlsbad, New Mexico, with Director of NCKRI, George Veni, serving as co-chair of the workshop with Eve Kuniansky, USGS. The session planning committee for this sixth workshop includes Van Brahana, USGS retired and University of Arkansas Professor Emeritus; Tom Byl, USGS and Tennessee State University; Zelda Bailey, former Director of NCKRI and retired Director, National Institute of Standards and Technology, Boulder Laboratory, Colorado; Patrick Tucci, USGS retired; and Mike Bradley, Allan Clark, Geoff Delin, Daniel Doctor, James Kaufmann, Eve Kuniansky, Randy Orndorff, Larry Spangler, and Dave Weary of the USGS. The karst hydrology field trip on Thursday will be led by Lewis Land (NCKRI karst hydrologist) and the optional Friday field trip on the geology of Carlsbad Caverns National Park will be led by George Veni. The keynote speaker is Dr. Penelope Boston, Director of Cave and Karst Studies at New Mexico Tech, Socorro, and Academic Director at NCKRI, who will address the future of karst research. Additionally, there is a featured presentation “Irish karst and its management,” by Caoimhe Hickey, The Geological Survey of Ireland, preceding a panel discussion on “Collaboration During Times of Limited Resources.” The extended abstracts of USGS authors were peer reviewed and approved for publication by the U.S. Geological Survey. 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 our editorial standards or stratigraphic nomenclature and is not research conducted or data collected by the USGS. However, all articles had at a minimum of two peer reviews, and all articles were edited for consistency of appearance in the published Proceedings. The use of trade, firm or product names in any article is for descriptive purposes only and does not imply endorsement by the U.S. Government. The USGS, Office of Groundwater, provides technical support for the Karst Interest Group website and public availability of the Proceedings from these workshops, and the USGS Groundwater Resources Program funds the publication costs. Finally, the cover illustration is the work of Ann Tihansky, USGS, used since the first KIG workshop in 2000.

Scientific Investigations Report↗

Tracking nonpoint source nitrogen pollution in human-impacted watersheds

Nonpoint source nitrogen (N) pollution is a leading contributor to U.S. water quality impairments. We combined watershed N mass balances and stable isotopes to investigate fate and transport of nonpoint N in forest, agricultural, and urbanized watersheds at the Baltimore Long-Term Ecological Research site. Annual N retention was 55%, 68%, and 82% for agricultural, suburban, and forest watersheds, respectively. Analysis of δ 15 N-NO 3 – , and δ 18 O-NO 3 – indicated wastewater was an important nitrate source in urbanized streams during baseflow. Negative correlations between δ 15 N-NO 3 – and δ 18 O-NO 3 – in urban watersheds indicated mixing between atmospheric deposition and wastewater, and N source contributions changed with storm magnitude (atmospheric sources contributed ∼50% at peak storm N loads). Positive correlations between δ 15 N-NO 3 – and δ 18 O-NO 3 – in watersheds suggested denitrification was removing septic system and agriculturally derived N, but N from belowground leaking sewers was less susceptible to denitrification. N transformations were also observed in a storm drain (no natural drainage network) potentially due to organic carbon inputs. Overall, nonpoint sources such as atmospheric deposition, wastewater, and fertilizer showed different susceptibility to watershed N export. There were large changes in nitrate sources as a function of runoff, and anticipating source changes in response to climate and storms will be critical for managing nonpoint N pollution.

Environmental Science & Technology↗

Incidence of the enterococcal surface protein ( esp ) gene in human and animal fecal sources

The occurrence of the enterococcal surface protein ( esp ) gene in the opportunistic pathogens Enterococcus faecalis and E. faecium is well-documented in clinical research. Recently, the esp gene has been proposed as a marker of human pollution in environmental waters; however, information on its relative incidence in various human and animal fecal sources is limited. We have determined the occurrence of the esp gene in enterococci from human ( n = 64) and animal ( n = 233) fecal samples by polymerase chain reaction using two primer sets: one presumably specific for E. faecium ( esp fm ) and the other for both E. faecalis and E. faecium ( esp fs/fm ). We believe that this research is the first to explore the use of esp fs/fm for the detection of human waste in natural environmental settings. The incidence in human sources was 93.1% esp fm and 100% esp fs/fm in raw sewage influent; 30% for both esp fm and esp fs/fm in septic waste; and 0% esp fm and 80% esp fs/fm in active pit toilets. The overall occurrence of the gene in animal feces was 7.7% ( esp fs/fm ) and 4.7% ( esp fm ); animal types with positive results included dogs (9/43, all esp fm ), gulls (10/34, esp fs/fm ; 2/34, esp fm ), mice (3/22, all esp fs/fm ), and songbirds (5/55, all esp fs/fm ). The esp gene was not detected in cat (0/34), deer (0/4), goose (0/18), or raccoon (0/23) feces. The inconsistent occurrence, especially in septic and pit toilet sewage, suggests a low statistical power of discrimination between animal and human sources, which means a large number of replicates should be collected. Both esp fm and esp fs/fm were common in raw sewage, but neither one efficiently differentiated between animal and other human sources.

Environmental Science & Technology↗

Relationship and variation of qPCR and culturable enterococci estimates in ambient surface waters are predictable

The quantitative polymerase chain reaction (qPCR) method provides rapid estimates of fecal indicator bacteria densities that have been indicated to be useful in the assessment of water quality. Primarily because this method provides faster results than standard culture-based methods, the U.S. Environmental Protection Agency is currently considering its use as a basis for revised ambient water quality criteria. In anticipation of this possibility, we sought to examine the relationship between qPCR-based and culture-based estimates of enterococci in surface waters. Using data from several research groups, we compared enterococci estimates by the two methods in water samples collected from 37 sites across the United States. A consistent linear pattern in the relationship between cell equivalents (CCE), based on the qPCR method, and colony-forming units (CFU), based on the traditional culturable method, was significant (P < 0.05) at most sites. A linearly decreasing variance of CCE with increasing CFU levels was significant (P < 0.05) or evident for all sites. Both marine and freshwater sites under continuous influence of point-source contamination tended to reveal a relatively constant proportion of CCE to CFU. The consistency in the mean and variance patterns of CCE versus CFU indicates that the relationship of results based on these two methods is more predictable at high CFU levels (e.g., log 10 CFU > 2.0/100 mL) while uncertainty increases at lower CFU values. It was further noted that the relative error in replicated qPCR estimates was generally higher than that in replicated culture counts even at relatively high target levels, suggesting a greater need for replicated analyses in the qPCR method to reduce relative error. Further studies evaluating the relationship between culture and qPCR should take into account analytical uncertainty as well as potential differences in results of these methods that may arise from sample variability, different sources of pollution, and environmental factors.

Environmental Science & Technology↗

Aquatic invasive species in the Chesapeake Bay drainage—Research-based needs and priorities of U.S. Geological Survey partners and collaborators

Executive Summary The U.S. Geological Survey (USGS) is revising the Chesapeake Bay-based science plan to align it with recent U.S. Department of Interior and USGS science priorities that include, as stated in the plan, providing “an integrated understanding of the factors affecting fish habitat, fish health, and landscape conditions” in Chesapeake Bay and its watershed. A report of partner agencies’ needs and priorities related to aquatic invasive species (AIS) science was identified as an informational gap; a report would help to further development of the science program related to aquatic animal health and habitat. This objective was addressed through review of pertinent documentation and conversations with representatives of State, Federal, and regional agencies with vested interests in AIS management in Chesapeake Bay and the Chesapeake Bay drainage area, and this document was produced to summarize the related findings. All agencies and organizations (13) reported that AIS are of general concern, with most stakeholder groups reporting AIS-related issues to be of high priority, including invasive fishes and invertebrates, invasive plants, and microbes including aquatic animal pathogens. Invasive fishes are of great concern to all partner agencies. Channa argus (northern snakehead) and Ictalurus furcatus (blue catfish) are high priority and represent the two most named AIS of concern for these agencies. Nine of 10 stakeholder groups listed northern snakehead as a high priority species, and 6 listed blue catfish as a high priority species as well. Pylodictis olivaris (flathead catfish), invasive crayfish species , and dressenid mussels were also prioritized by multiple partner groups, each receiving specific mention by at least 3 of the 10 stakeholder groups in discussions or documents. Invasive carp, such as Hypophthalmichthys molatrix (silver carp), also received mention by multiple agencies (3 of the 10 stakeholder groups) because these fish represent priority AIS in nearby watersheds and a threat for introduction and dissemination within the Chesapeake Bay watershed from these neighboring regions. Invasive plants are among priority species, and Hydrilla verticillata (hydrilla) topped the list. Hydrilla was reported as a priority species by 5 of the stakeholder groups queried. Trapa natans and T. bispinosa (water chestnut), Phragmites australis (common reed), and Lythrum salicaria (purple loosestrife) were also among the aquatic invasive plants that were prioritized by multiple partner agencies. Multiple stakeholder groups (5 of the 10 groups) also considered Didymosphenia geminata (didymo) and various aquatic animal pathogens among their priority AIS for management considerations. Science needs that were recurrently indicated by stakeholders to support management of invasive species include Technology to enhance biosurveillance capability, such as reliable environmental DNA based detection methodology; Risk assessment modeling to forewarn of and prioritize AIS-related threats; Increased information and intervention methods related to vectors and pathways of AIS introductions; Increased information about the biology and life history of AIS, including information related to trophic interactions, health and disease, and distribution and abundance; and Potential applications of mitigation strategies, including genetically based biocontrol mechanisms. Potential next steps to address the science needs include Development of biosurveillance and risk assessment tools for identification of AIS in proactive management; Development of proactive management techniques to prevent AIS introductions through recognized vectors and pathways; Development of interagency biosurveillance programs to best utilize personnel, funds, and other resources among interested agencies and organizations; Investigations to address life history, consequences, and movement/dissemination of top priority invasive species in the region; Investigations to determine the potential for novel mitigation technologies, such as the application of synthetic biological (genetic) control methods; and Investigations with focus on emerging and high priority AIS in the region, including fishes (blue catfish, flathead catfish, northern snakehead), invertebrates (invasive crayfish and mollusks) and plants (hydrilla, water chestnut, phragmites).

Virginia, Maryland, Delaware, West Virginia, Penns↗

Uptake and disposition of select pharmaceuticals by bluegill exposed at constant concentrations in a flow-through aquatic exposure system

The increasing use of pharmaceuticals has led to their subsequent input into and release from wastewater treatment plants, with corresponding discharge into surface waters that may subsequently exert adverse effects upon aquatic organisms. Although the distribution of pharmaceuticals in surface water has been extensively studied, the details of uptake, internal distribution, and kinetic processing of pharmaceuticals in exposed fish have received less attention. For this research, we investigated the uptake, disposition, and toxicokinetics of five pharmaceuticals (diclofenac, methocarbamol, rosuvastatin, sulfamethoxazole, and temazepam) in bluegill sunfish ( Lepomis macrochirus ) exposed to environmentally relevant concentrations (1000–4000 ng L –1 ) in a flow-through exposure system. Temazepam and methocarbamol were consistently detected in bluegill biological samples with the highest concentrations in bile of 4, 940, and 180 ng g –1 , respectively, while sulfamethoxazole, diclofenac, and rosuvastatin were only infrequently detected. Over 30-day exposures, the relative magnitude of mean concentrations of temazepam and methocarbamol in biological samples generally followed the order: bile ≫ gut > liver and brain > muscle, plasma, and gill. Ranges of bioconcentration factors (BCFs) in different biological samples were 0.71–3960 and 0.13–48.6 for temazepam and methocarbamol, respectively. Log BCFs were statistically positively correlated to pH adjusted log K ow (that is, log D ow ), with the strongest relations for liver and brain ( r 2 = 0.92 and 0.99, respectively), implying that bioconcentration patterns of ionizable pharmaceuticals depend on molecular status, that is, whether a pharmaceutical is un-ionized or ionized at ambient tissue pH. Methocarbamol and temazepam underwent rapid uptake and elimination in bluegill biological compartments with uptake rate constants ( K u ) and elimination rate constants ( K e ) at 0.0066–0.0330 h –1 and 0.0075–0.0384 h –1 , respectively, and half-lives at 18.1–92.4 h. Exposure to mixtures of diclofenac, methocarbamol, sulfamethoxazole, and temazepam had little or no influence on the uptake and elimination rates, suggesting independent multiple uptake and disposition behaviors of pharmaceuticals by fish would occur when exposed to effluent-influenced surface waters.

Environmental Science & Technology↗