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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

The role of the Everglades Mangrove Ecotone Region (EMER) in regulating nutrient cycling and wetland productivity in South Florida

The authors summarize the main findings of the Florida Coastal Everglades Long-Term Ecological Research (FCE-LTER) program in the EMER, within the context of the Comprehensive Everglades Restoration Plan (CERP), to understand how regional processes, mediated by water flow, control population and ecosystem dynamics across the EMER landscape. Tree canopies with maximum height <3 m cover 49% of the EMER, particularly in the SE region. These scrub/dwarf mangroves are the result of a combination of low soil phosphorus (P < 59 μg P g dw −1 ) in the calcareous marl substrate and long hydroperiod. Phosphorus limits the EMER and its freshwater watersheds due to the lack of terrigenous sediment input and the phosphorus-limited nature of the freshwater Everglades. Reduced freshwater delivery over the past 50 years, combined with Everglades compartmentalization and a 10 cm rise in coastal sea level, has led to the landward transgression (∼1.5 km in 54 years) of the mangrove ecotone. Seasonal variation in freshwater input strongly controls the temporal variation of nitrogen and P exports (99%) from the Everglades to Florida Bay. Rapid changes in nutrient availability and vegetation distribution during the last 50 years show that future ecosystem restoration actions and land use decisions can exert a major influence, similar to sea level rise over the short term, on nutrient cycling and wetland productivity in the EMER.

Florida

Occurrence of cyanazine compounds in groundwater: Degradates more prevalent than the parent compound

A recently developed analytical method using liquid chromatography/mass spectrometry was used to investigate the occurrence of cyanazine and its degradates cyanazine acid (CAC), cyanazine amide (CAM), deethylcyanazine (DEC), and deethylcyanazine acid (DCAC) in groundwater. This research represents some of the earliest data on the occurrence of cyanazine degradates in groundwater. Although cyanazine was infrequently detected in the 64 wells across Iowa sampled in 1999, cyanazine degradates were commonly found during this study. The most frequently detected cyanazine compound was DCAC (32.8%) followed by CAC (29.7%), CAM (17.2%), DEC (3.1%), and cyanazine (3.1%). The frequency of detection for cyanazine or one or more of its degradates (CYTOT) was more than 12-fold over that of cyanazine alone (39.1% for CYTOT versus 3.1% for cyanazine). Of the total measured concentration of cyanazine, only 0.2% was derived from its parent compound - with DCAC (74.1%) and CAC (18.4%) comprising 92.5% of this total. Thus, although DCAC and CAC had similar frequencies of detection, DCAC was generally present in higher concentrations. No concentrations of cyanazine compounds for this study exceeded water-quality criteria for the protection of human health. Only cyanazine, however, has such a criteria established. Nevertheless, because these cyanazine degradates are still chlorinated, they may have similar toxicity as their parent compound - similar to what has been found with the chlorinated degradates of atrazine. Thus, the results of this study documented that data on the degradates for cyanazine are critical for understanding its fate and transport in the hydrologic system. Furthermore, the prevalence of the chlorinated degradates of cyanazine found in groundwater suggests that to accurately determine the overall effect on human health and the environment from cyanazine its degradates should also be considered. In addition, because CYTOT was found in 57.6% of the samples collected from alluvial aquifers, about 2-5 times more frequently than the other major aquifer types (glacial drift, bedrock/karst, bedrock/nonkarst) under investigation, this finding has long-term implications for the occurrence of CYTOT in streams. It is anticipated that low-level concentrations of CYTOT will continue to be detected in streams for years after the use of cyanazine has terminated (scheduled for the year 2000 in the United States), primarily through its movement from groundwater into streams during base-flow conditions.

Iowa

Fishway Entrance Palisade

This technical report summarizes the work that was conducted by the University of Massachusetts Amherst and the United States Geological Survey (USGS), along with other project partners, on the Fishway Entrance Palisade (EP), a projected funded through the Department of Energy’s (DOE) funding opportunity titled ‘Innovative Solutions for Fish Passage at Hydropower Dams’ (DE‐FOA‐0001662). The period of performance ranged from September 1, 2018 through September 30, 2021. The EP is a novel fish passage engineering technology designed to provide more favorable entry conditions for fish and to reduce costs relative to conventional fishway auxiliary water systems (AWS). The EP project has four primary components. First, the Northeast United States Auxiliary Water Systems Database was created (Northeast Fishway Auxiliary Water Systems Database Section). The database, developed with material provided by the U.S. Fish and Wildlife Service, contains information on fishway type (e.g., lift, Denil, pool and weir) and Auxiliary Water System (AWS) details (e.g., water conveyance method, diffuser type) for 60 hydroelectric sites in the region. Findings indicate that nearly 4 out of every 10 fishway in the region is a fish lift and approximately 1 out of every 4 is a Denil ladder. The remainder are a mix of vertical slot fishways, pool and weirs, and Ice Harbor fishways. Furthermore, over half of all AWS systems use floor diffusers to discharge the auxiliary (or attraction) water into the entrance of a fishway, whereas only 14% use wall diffusers. Second, limited experiments on a conventional AWS with live, actively migrating fish were conducted at the USGS Easter Ecological Science Center (EESC) S.O. Conte Research Laboratory (Conventional Auxiliary Water System Experiments Section). This study determined how water velocity through a wall diffuser, without turning vanes or timber baffles to distribute the flow, affects the behavior and passage of adult American shad, a conservative surrogate species for migratory fish on the East Coast. Two gross diffuser velocity treatments were examined, 0.5 ft/s and 1.0 ft/s. These wall diffuser velocities represented current (0.5 ft/s) and past (1.0 ft/s) design criteria guidelines set forth by the USFWS North Atlantic-Appalachian Region (Rojas 2020; USFWS 2019). Six trials with a total of 151 American Shad were conducted in June of 2019 for the two treatments. No differences in American shad passage efficiency were discovered between the two treatments, while approximately 3 in every 4 attempts were successful at passing the diffuser. While these results may appear to indicate that the generally accepted gross wall diffuser velocity criteria for American shad of 0.5 ft/s could be safely increased to 1.0 ft/s, further analysis is warranted. Furthermore, it is unknown how other migratory and resident fish species that traverse these structures would be impacted by such a change. Studying the wall diffuser hydraulics led to an important AWS observation. Without turning vanes or timber baffles in this study, doubling the diffuser area was insufficient at producing the type of flow field change one may expect by halving the gross diffuser velocity. Instead, the flow fields throughout each treatments study area were similar, which led to similar results in shad performance. This not only highlights the importance of installing flow guidance devices like turning vanes, but also to the importance of properly maintaining them, which can be costly. Third, more expansive experiments on the novel EP were conducted in the spring of 2019 and 2021 (Fishway Entrance Palisade Experiments). The goal of this study was to determine how adult American shad responded to a variety of conditions at a full-scale EP. A total of six treatments were examined by changing the average auxiliary channel velocity between 1.0 and 5.0 ft/s in intervals of 1.0 ft/s and by inserting/removing an entrance gate at the opening of the fishway. Thirty trials with a total of 1,273 shad were conducted over the two years. In all treatments, at least ~7 out of every 10 fish successfully passed the EP diffuser and swam into the entrance channel within the 3.5-hour long trial, highlighting the general effectiveness of the novel AWS technology. In both study years, lower velocities through the EP diffuser led to increased shad performance, though performance peaked for the 2 ft/s velocity treatment. This treatment condition represents an approximate six-fold increase in gross diffuser velocity relative to conventional auxiliary water systems, which in turn presents opportunities for cost savings (e.g., reduction in diffuser size). Shad performance, in general, was worse in 2019 than in 2021, potentially due to the different run timing when our trials were conducted (2019 trials occurred near the end of the migration season, unlike in 2021). Treatments in 2019 had approximately a 20% reduction in entrance efficiency by the trial end, including a 16.7% drop for the 3 ft/s velocity treatment in 2019 relative to 2021 (the only carryover treatment between years). Lastly, adding an entrance gate caused a significant delay to entry. The time to 25% entry raised ~20 minutes from the near instantaneous 25% entry that was reported for the other treatments conducted in the same year (2021). Though by the end of the 3.5-hour trial, the overall entrance efficiency nearly matched those of the other 2021 treatments. The fourth and final component of the EP project was an economic analysis that focused on the cost of attraction and environmental flows (Modeling Power Generation Losses Due to Environmental and Fish Passage Attraction Flows at a Run-Of-River Hydroelectric Operation in the Northeast). The study assessed the economic impact of meeting environmental flow requirements at a representative hydroelectric facility and fish lift in the Northeast. An initial finding of the study was that there is a paucity of published data on the costs of meeting attraction and environmental flows. This is due, in part, to the proprietary nature of this data. To explore the costs associated with these flows, three types of environmental flows were assessed: upstream fishway attraction flows, downstream fishway attraction flows, and habitat maintenance minimum flows. A physics-based model was developed and calibrated with three years of hourly generation and flow data as inputs. Gage flow inputs were adjusted and used to calculate power generated. To address hydrologic variability, the model was executed to simulate 30 years of historical flows. Results indicate that both interannual and seasonal climatic factors impact the costs of meeting environmental flow requirements. Generation potential is most strongly curtailed during dry years in terms of maximizing the capacity factor (the percent of time a plant generates at capacity). Dry years, and especially dry summers, have the most significant costs associated with mitigation flows. Of the three types of flows, habitat flows are most costly in terms of power production, followed by upstream attraction flows. Downstream attraction flows are least costly. This finding is the likely result of differences in both flow rates and duration of the seasonal requirement for each flow. Overall, environmental flows represented a 2-12% loss in annual generation, but losses during a dry summer can reach over 20%.

Final Technical Report

Sources and characteristics of organic matter in the Clackamas River, Oregon, related to the formation of disinfection by-products in treated drinking water

This study characterized the amount and quality of organic matter in the Clackamas River, Oregon, to gain an understanding of sources that contribute to the formation of chlorinated and brominated disinfection by-products (DBPs), focusing on regulated DBPs in treated drinking water from two direct-filtration treatment plants that together serve approximately 100,000 customers. The central hypothesis guiding this study was that natural organic matter leaching out of the forested watershed, in-stream growth of benthic algae, and phytoplankton blooms in the reservoirs contribute different and varying proportions of organic carbon to the river. Differences in the amount and composition of carbon derived from each source affects the types and concentrations of DBP precursors entering the treatment plants and, as a result, yield varying DBP concentrations and species in finished water. The two classes of DBPs analyzed in this study-trihalomethanes (THMs) and haloacetic acids (HAAs)-form from precursors within the dissolved and particulate pools of organic matter present in source water. The five principal objectives of the study were to (1) describe the seasonal quantity and character of organic matter in the Clackamas River; (2) relate the amount and composition of organic matter to the formation of DBPs; (3) evaluate sources of DBP precursors in the watershed; (4) assess the use of optical measurements, including in-situ fluorescence, for estimating dissolved organic carbon (DOC) concentrations and DBP formation; and (5) assess the removal of DBP precursors during treatment by conducting treatability "jar-test" experiments at one of the treatment plants. Data collection consisted of (1) monthly sampling of source and finished water at two drinking-water treatment plants; (2) event-based sampling in the mainstem, tributaries, and North Fork Reservoir; and (3) in-situ continuous monitoring of fluorescent dissolved organic matter (FDOM), turbidity, chlorophyll- a , and other constituents to continuously track source-water conditions in near real-time. Treatability tests were conducted during the four event-based surveys to determine the effectiveness of coagulant and powdered activated carbon (PAC) on the removal of DBP precursors. Sample analyses included DOC, total particulate carbon (TPC), total and dissolved nutrients, absorbance and fluorescence spectroscopy, and, for regulated DBPs, concentrations of THMs and HAAs in finished water and laboratory-based THM and HAA formation potentials (THMFP and HAAFP, respectively) for source water and selected locations throughout the watershed. The results of this study may not be typical given the record and near record amounts of precipitation that occurred during spring that produced streamflow much higher than average in 2010-11. Although there were algal blooms, lower concentrations of chlorophyll- a were observed in the water column during the study period compared to historical data. Concentrations of DBPs in finished (treated) water averaged 0.024 milligrams per liter (mg/L) for THMs and 0.022 mg/L for HAAs; maximum values were about 0.040 mg/L for both classes of DBPs. Although DBP concentrations were somewhat higher within the distribution system, none of the samples collected for this study or for the quarterly compliance monitoring by the water utilities exceeded levels permissible under existing U.S. Environmental Protection Agency (USEPA) regulations: 0.080 mg/L for THMs and 0.060 mg/L for HAAs. DOC concentrations were generally low in the Clackamas River, typically about 1.0-1.5 mg/L. Concentrations in the mainstem occasionally increased to nearly 2.5 mg/L during storms; DOC concentrations in tributaries were sometimes much higher (up to 7.8 mg/L). The continuous in-situ FDOM measurements indicated sharp rises in DOC concentrations in the mainstem following rainfall events; concentrations were relatively stable during summer base flow. Even though the first autumn storm mobilized appreciable quantities of carbon, higher concentrations of DBPs in finished water were observed 3-weeks later, after the ground was saturated from additional rainfall. The majority of the DOC in the lower Clackamas River appears to originate from the upper basin, suggesting terrestrial carbon was commonly the dominant source. Lower-basin tributaries typically contained the highest concentrations of DOC and DBP precursors and contributed substantially to the overall loads in the mainstem during storms. During low-flow periods, tributaries were not major sources of DOC or DBP precursors to the Clackamas River. Although the dissolved fraction of organic carbon contributed the majority of DBP precursors, at times the particulate fraction (inorganic sediment and organic particles including detritus and algal material) contributed a substantial fraction of DBP precursors. Considering just the main-stem sites, on average, 10 percent of THMFP and 32 percent of HAAFP were attributed to particulate carbon. This finding suggests water-treatment methods that remove particles prior to chlorination would reduce finished-water DBP concentrations to some degree. Overall, concentrations of THM and HAA precursors were closely linked to DOC concentrations; laboratory DBP formation potentials (DBPFPs) clearly showed that THMFP and HAAFP were greatest in the downstream tributaries that contained elevated carbon concentrations. However, carbon-normalized "specific" formation potentials for THMs and HAAs (STHMFP and SHAAFP, respectively) revealed changes in carbon character over time that affected the two types of DBP classes differently. HAA precursors were elevated in waters containing aromatic-rich soil-derived material arising from forested areas. In contrast, THM precursors were associated with carbon having a lower aromatic content; highest STHMFP occurred in autumn 2011 in the mainstem from North Fork Reservoir downstream to LO DWTP. This pattern suggests the potential for a link between THM precursors and algal-derived carbon. The highest STHMFP value was measured within North Fork Reservoir, indicating reservoir derived carbon may be important for this class of DBPs. Weak correlations between STHMFP and SHAAFP emphasize that precursor sources for these types of DBPs may be different. This highlights not only that different locations within the watershed produce carbon with different reactivity (specific DBPFP), but also that different management approaches for each class of DBP precursors could be required for control. Treatability tests conducted on source water during four basin-wide surveys demonstrated that an average of about 40 percent of DOC can be removed by coagulation. While the decrease in THMFP following coagulation was similar to DOC, the decrease in HAAFP was much greater (approximately 70 percent), indicating coagulation is particularly effective at removing HAA precursors'likely because of the aromatic nature of the carbon associated with HAA precursors. Several findings from this study have direct implications for managing drinking-water resources and for providing useful information that may help improve treatment-plant operations. For example, the use of in-situ fluorometers that measure FDOM provided an excellent proxy for DOC concentration in this system and revealed short-term, rapid changes in DOC concentration during storm events. In addition, the strong correlation between FDOM values measured in-situ and HAA5 concentrations in finished water may permit estimation of continuous HAA concentrations, as was done here. As part of this study, multiple in-situ FDOM sensors were deployed continuously and in real-time to characterize the composition of dissolved organic matter. Although the initial results were promising, additional research and engineering developments will be needed to demonstrate the full utility of these sensors for this purpose. In conclusion, although DBPFPs were strongly correlated to DOC concentration, some DBPs formed from particulate carbon, including terrestrial leaf material and algal material such as planktonic species of blue-green algae and sloughed filaments, stalks, and cells of benthic algae. Different precursor sources in the watershed were evident from the data, suggesting specific actions may be available to address some of these sources. In-situ measurements of FDOM proved to be an excellent proxy for DOC concentration as well as HAA formation during treatment, which suggests further development and refinement of these sensors have the potential to provide real-time information about complex watershed processes to operators at the drinking-water treatment plants. Follow-up studies could examine the relative roles that terrestrial and algal sources have on the DBP precursor pool to better understand how watershed-management activities may be affecting the transport of these compounds to Clackamas River drinking-water intakes. Given the low concentrations of algae in the water column during this study, additional surveys during more typical river conditions could provide a more complete understanding of how algae contribute DBP precursors. Further development of FDOM-sensor technology can improve our understanding of carbon dynamics in the river and how concentrations may be trending over time. This study was conducted in collaboration with Clackamas River Water and the City of Lake Oswego water utilities. Other research partners included Oregon Health and Science University in Hillsboro, Oregon, Alexin Laboratory in Tigard, Oregon, U.S. Geological Survey National Research Program Laboratory in Denver, Colorado, and the U.S. Geological Survey Water Science Centers in Portland, Oregon, and Sacramento, California. This project was supported with funding from Clackamas River Water, City of Lake Oswego, the U.S. Geological Survey, and the Water Research Foundation.

Oregon