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Evaluation of legacy and emerging organic chemicals using passive sampling devices on the North Branch Au Sable River near Lovells, Michigan, June 2018

The North Branch Au Sable River, located in the northern lower peninsula of Michigan near Lovells, Michigan, has historically been known for its brook trout ( Salvelinus fontinalis ) and its status as a blue ribbon trout stream; however, within the past few decades, there has been a decline in fish population. The objectives of this study were to assess if concentrations of organic chemicals were present in quantities in the North Branch Au Sable River that may potentially harm aquatic species and to establish current baseline concentrations of organic chemicals against which future data can be compared. Passive sampling technology was used to collect information on the concentration, occurrence, transport, and fate of organic chemicals; these samplers absorb dissolved organic chemicals in the river over several weeks, as the timing and intensity of pesticide applications and the frequency of storm events and irrigation can cause fluctuations in organic chemical loading to surface waters. The chemical classes investigated as part of this study included pesticides (both legacy [organochlorine] and current use), polychlorinated biphenyls, polybrominated diphenyl ethers (PBDEs), and polycyclic aromatic hydrocarbons (PAHs). Passive samplers, including semipermeable membrane devices and polar organic chemical integrative samplers, were deployed at four locations along the North Branch Au Sable River, near Lovells, Mich., in June 2018 for a total of 28 days. Several organic chemicals were detected in the North Branch Au Sable River at low concentrations. Organic chemicals were detected at every sampling location on the North Branch Au Sable River; however, not all chemicals were detected at every location. The highest number of organic chemicals were detected at the most downstream sampling site (North Branch Au Sable River at Kellogg's Bridge), and the lowest number of organic chemicals were detected at the next site upstream (North Branch Au Sable River at Twin Bridge Road). The organic contaminants most frequently detected at all sampling locations include the legacy pesticides pentachloroanisole, trans -chlordane, p,p'-dichlorodiphenyldichloroethylene, and p,p'-dichlorodiphenyltrichloroethane; the PBDE PBDE-28; and the PAHs 2-methylphenanthrene and perylene. Organic chemical concentrations detected on the North Branch Au Sable River were below almost all water-quality benchmarks included in this report. However, low concentrations of organic chemicals may still pose a risk to aquatic organisms and throughout the trophic hierarchy because of low-dose additive and synergistic mixture effects, transgenerational effects, and a lack of established water-quality benchmarks for many organic chemicals. This report provides data on the current (2018) state of the North Branch Au Sable River and provided a baseline of organic contaminant data against which future data on the North Branch Au Sable River can be evaluated.

Michigan

Brine migration from a flooded salt mine in the Genesee Valley, Livingston County, New York: Geochemical modeling and simulation of variable-density flow

The Retsof salt mine in upstate New York was flooded from 1994 to 1996 after two roof collapses created rubble chimneys in overlying bedrock that intersected a confined aquifer in glacial sediments. The mine now contains about 60 billion liters of saturated halite brine that is slowly being displaced as the weight of overlying sediments causes the mine cavity to close, a process that could last several hundred years. Saline water was detected in the confined aquifer in 2002, and a brine-mitigation project that includes pumping followed by onsite desalination was implemented in 2006 to prevent further migration of saline water from the collapse area. A study was conducted by the U.S. Geological Survey using geochemical and variable-density flow modeling to determine sources of salinity in the confined aquifer and to assess (1) processes that control movement and mixing of waters in the collapse area, (2) the effect of pumping on salinity, and (3) the potential for anhydrite dissolution and subsequent land subsidence resulting from mixing of waters induced by pumping. The primary source of salinity in the collapse area is halite brine that was displaced from the flooded mine and transported upward by advection and dispersion through the rubble chimneys and surrounding deformation zone. Geochemical and variable-density modeling indicate that salinity in the upper part of the collapse area is partly derived from inflow of saline water from bedrock fracture zones during water-level recovery (January 1996 through August 2006). The lateral diversion of brine into bedrock fracture zones promoted the upward migration of mine water through mixing with lower density waters. The relative contributions of mine water, bedrock water, and aquifer water to the observed salinity profile within the collapse area are controlled by the rates of flow to and from bedrock fracture zones. Variable-density simulations of water-level recovery indicate that saline water has probably not migrated beyond the collapse area, while simulations of pumping indicate that further upward migration of brine and saline water is now prevented by groundwater withdrawals under the brine-mitigation project. Geochemical modeling indicates that additional land subsidence as a result of anhydrite dissolution in the collapse area is not a concern, as long as the rate of brine pumping is less than the rate of upward flow of brine from the flooded mine. The collapse area above the flooded salt mine is within a glacially scoured bedrock valley that is filled with more than 150 meters of glacial drift. A confined aquifer at the bottom of the glacial sediments (referred to as the lower confined aquifer, or LCA) was the source of most of the water that flooded the mine. Two rubble chimneys that formed above the roof collapses in 1994 hydraulically connect the flooded mine to the LCA through 180 meters of sedimentary rock. From 1996 through 2006, water levels in the aquifer system recovered and the brine-displacement rate ranged from 4.4 to 1.6 liters per second, as estimated from land-surface subsidence above the mine. A zone of fracturing within the bedrock (the deformation zone) formed around the rubble chimneys as rock layers sagged toward the mine cavity after the roof collapses. Borehole geophysical surveys have identified three saline-water-bearing fracture zones in the bedrock: at stratigraphic contacts between the Onondaga and Bertie Limestones (O/B-FZ) and the Bertie Limestone and the Camillus Shale (B/C-FZ), and in the Syracuse Formation (Syr-FZ). The only outlets for brine displaced from the mine are through the rubble chimneys, but some of the brine could be diverted laterally into fracture zones in the rocks that lie between the mine and the LCA. Inverse geochemical models developed using PHREEQC indicate that halite brine in the flooded mine is derived from a mixture of freshwater from the LCA (81 percent), saline water from bedrock fracture zones (16 percent), and an hypothesized bromide-rich brine (3 percent) assumed to originate from salt-bearing rocks above the flooded mine. Geochemical modeling results also indicate that halite brine entering the rubble chimneys is diluted by both bedrock water and aquifer water, and that water from the mine has not reached the bedrock surface. Forward geochemical models indicate that additional land subsidence could occur if pumping from the brine-mitigation project were to introduce either freshwater or bedrock water that is undersaturated with respect to anhydrite into the lower part of the rubble chimneys. In this unlikely scenario, the maximum subsidence rates are predicted to range from 0.6 to 1.1 centimeters per year—subsidence rates would be lower (0.1 to 0.6 centimeters per year) if ion-exchange reactions affect the water chemistry. Variable-density, transient groundwater-flow models were constructed using SEAWAT to simulate the movement of saline water, aquifer water, bedrock water, and brine within the rubble chimneys and surrounding deformation zone during the 10.7-year period following flooding of the salt mine. Two three-dimensional models reproduced the profile of halite saturation with depth measured in September 2006 reasonably well, and neither model indicated that saline water had migrated beyond the collapse area. The models differed in the number of fracture zones represented: one zone in model A (O/B-FZ) and three zones in model B (O/B-FZ, B/C-FZ, and Syr-FZ). It is unknown whether model A or model B better represents current conditions because the lateral extents of the B/C-FZ and Syr-FZ have not been delineated beyond the collapse area. In model A, the salinity of water in the upper part of the rubble chimneys is derived mainly from the inflow of bedrock water from the O/B-FZ, as indicated by geochemical models. Bedrock water that was pushed upward by brine during the 10.7-year simulation period formed a diffuse front above a nearly horizontal brine level in both chimneys. In model B, some of the salinity in the upper part of the rubble chimneys is derived from mine water. The rate of bedrock-water inflow from the O/B-FZ was lower in model B than in model A, and mixing with waters from the Syr-FZ and B/C-FZ transported mine water higher in the water column than in model A. Simulated brine levels in both chimneys sloped northward, reflecting lateral diversion of brine into the B/C-FZ, and less aquifer water was displaced from the collapse area than in model A. Models A and B were used to simulate changes in water levels and salinity produced by pumping for the brine-mitigation project from September 2006 through February 2008. Both simulations indicated that current pumping rates are sufficient to offset upward migration of brine and saline water through the collapse area and, therefore, to further prevent contamination of the LCA. A greater decrease in salinity was simulated in model B, however, because the porosity of the rubble chimneys was lower (6 percent compared to 10 percent in model A), and some brine and saline waters were diverted through the B/C-FZ. Model B better simulates the influent saturation to the desalination plant, the amount of halite produced, and the observed declines in saturations than model A, which is more consistent with results of geochemical modeling. Sensitivity analyses indicate that the actual brine-displacement rate could be lower than estimated because simulated declines in saturations underpredict the observed decline from September 2006 through February 2008. Although halite saturations within the upper part of the collapse area are predicted to decrease with continued pumping, brine displacement from the flooded mine is expected to continue for hundreds of years. Simulations of a shutdown of the brine-mitigation project indicate southward migration of saline water through the LCA, extending 700 meters to the model boundary within 10 years. Continued migration of saline water would eventually form a pool in the LCA in a bedrock depression 8 kilometers south of the collapse area near Sonyea, but the large relative density of the saline water would likely prevent it from reaching overlying aquifers. Simulations also indicate that brine will migrate through bedrock fracture zones—some brine could possibly emerge updip to the north where the subcrop area of the Bertie Limestone intersects the bedrock surface near Avon, but the projected time of travel is unknown.

New York

Anthropogenic organic compounds in source water of selected community water systems that use groundwater, 2002-05

Source water, defined as groundwater collected from a community water system well prior to water treatment, was sampled from 221 wells during October 2002 to July 2005 and analyzed for 258 anthropogenic organic compounds. Most of these compounds are unregulated in drinking water and include pesticides and pesticide degradates, gasoline hydrocarbons, personal-care and domestic-use products, and solvents. The laboratory analytical methods used in the study have detection levels that commonly are 100 to 1,000 times lower than State and Federal standards and guidelines for protecting water quality. Detections of anthropogenic organic compounds do not necessarily indicate a concern to human health but rather help to identify emerging issues and track changes in occurrence and concentrations over time. Less than one-half (120) of the 258 compounds were detected in at least one source-water sample. Chloroform, in 36 percent of samples, was the most commonly detected of the 12 compounds that were in about 10 percent or more of source-water samples. The herbicides atrazine, metolachlor, prometon, and simazine also were among the commonly detected compounds. The commonly detected degradates of atrazine - deethylatrazine and deisopropylatrazine - as well as degradates of acetochlor and alachlor, generally were detected at concentrations similar to or greater than concentrations of the parent herbicide. The compounds perchloroethene, trichloroethene, 1,1,1-trichloroethane, methyl tert-butyl ether, and cis-1,2-dichloroethene also were detected commonly. The most commonly detected compounds in source-water samples generally were among those detected commonly across the country and reported in previous studies by the U.S. Geological Survey's National Water-Quality Assessment Program. Relatively few compounds were detected at concentrations greater than human-health benchmarks, and 84 percent of the concentrations were two or more orders of magnitude less than benchmarks. Five compounds (perchloroethene, trichloroethene, 1,2-dibromoethane, acrylonitrile, and dieldrin) were detected at concentrations greater than their human-health benchmark. The human-health benchmarks used for comparison were U.S. Environmental Protection Agency Maximum Contaminant Levels (MCLs) for regulated compounds and Health-Based Screening Levels developed by the U.S. Geological Survey in collaboration with the U.S. Environmental Protection Agency and other agencies for unregulated compounds. About one-half of all detected compounds do not have human-health benchmarks or adequate toxicity information to evaluate results in a human-health context. Ninety-four source-water and finished-water (water that has passed through all the treatment processes but prior to distribution) sites were sampled at selected community water systems during June 2004 to September 2005. Most of the samples were analyzed for compounds that were detected commonly or at relatively high concentrations during the initial source-water sampling. The majority of the finished-water samples represented water blended with water from one or more other wells. Thirty-four samples were from water systems that did not blend water from sampled wells with water from other wells prior to distribution. The comparison of source- and finished-water samples represents an initial assessment of whether compounds present in source water also are present in finished water and is not intended as an evaluation of water-treatment efficacy. The treatment used at the majority of the community water systems sampled is disinfection, which, in general, is not designed to remove the compounds monitored in this study. Concentrations of all compounds detected in finished water were less than their human-health benchmarks. Two detections of perchloroethene and one detection of trichloroethene in finished water had concentrations within an order of magnitude of the MCL. Concentrations of disinfection by-products were

Scientific Investigations Report

Effects of wetland vs. landscape variables on parasite communities of Rana pipiens: Links to anthropogenic factors

The emergence of several diseases affecting amphibian populations worldwide has prompted investigations into determinants of the occurrence and abundance of parasites in frogs. To understand the spatial scales and identify specific environmental factors that determine risks of parasitism in frogs, helminth communities in metamorphic frogs of the northern leopard frog ( Rana pipiens ) were examined in relation to wetland and landscape factors at local (1 km) and regional (10 km) spatial extents in an agricultural region of Minnesota (USA) using regression analyses, ordination, and variance partitioning techniques. Greater amounts of forested and woody wetland habitats, shorter distances between woody wetlands, and smaller-sized open water patches in surrounding landscapes were the most consistently positive correlates with the abundances, richness, and diversity of helminths found in the frogs. Wetland and local landscape variables were suggested as most important for larval trematode abundances, whereas local and regional landscape variables appeared most important for adult helminths. As previously reported, the sum concentration of atrazine and its metabolite desethylatrazine, was the strongest predictor of larval trematode communities. In this report, we highlight the additional influences of landscape factors. In particular, our data suggest that anthropogenic activities that have resulted in the loss of the availability and connectivity of suitable habitats in the surrounding landscapes of wetlands are associated with declines in helminth richness and abundance, but that alteration of wetland water quality through eutrophication or pesticide contamination may facilitate the transmission of certain parasite taxa when they are present at wetlands. Although additional research is needed to quantify the negative effects of parasitism on frog populations, efforts to reduce inputs of agrochemicals into wetlands to limit larval trematode infections may be warranted, given the current high rates of amphibian declines and extinction events.

Minnesota

Fomites could determine severity of SARS-CoV-2 outbreaks in low-density white-tailed deer (Odocoileus virginianus) populations

The establishment of a reservoir species for zoonotic diseases is concerning for both animal and human health. Severe acute respiratory syndrome coronavirus (SARS-CoV)-2, the coronavirus responsible for the COVID-19 pandemic, has been detected in white-tailed deer ( Odocoileus virginianus ) in the United States. Since its initial detection, various studies have documented circulation and evolution of SARS-CoV-2 in deer, with human cases suspected of spill-back from infectious deer. A priority for mitigating SARS-CoV-2 outbreaks in deer populations is determining the contribution of direct (via aerosols and physical contact) and indirect (via contaminated objects and media) transmission pathways. We expanded existing epidemiological models founded on direct transmission pathways to include three indirect transmission pathways of infection for simulated deer populations, including contaminated water, food waste, and feed piles. Despite lower infection probabilities and transmission hazards (measured by force-of-infection (FOI)) posed solely by these indirect pathways compared to direct transmission pathways, the addition of indirect transmission pathways increased FOI, which had ramifications for the severity of SARS-CoV-2 outbreaks in simulated deer populations, particularly in populations with low degrees of spread between deer (measured by basic reproductive number; R 0 ). We used contact rate models to estimate SARS-CoV-2 spread across deer range in the United States and identified widespread potential for indirect transmission to increase the severity of outbreaks in low-density deer populations. These results indicate that indirect transmission pathways need to be considered in the management of white-tailed deer as a reservoir species for SARS-CoV-2.

Transboundary and Emerging Diseases

Anthropogenic organic compounds in source water of nine community water systems that withdraw from streams, 2002-05

Source water, herein defined as stream water collected at a water-system intake prior to water treatment, was sampled at nine community water systems, ranging in size from a system serving about 3,000 people to one that serves about 2 million people. As many as 17 source-water samples were collected at each site over about a 12-month period between 2002 and 2004 for analysis of 258 anthropogenic organic compounds. Most of these compounds are unregulated in drinking water, and the compounds analyzed include pesticides and selected pesticide degradates, gasoline hydrocarbons, personal-care and domestic-use compounds, and solvents. The laboratory analytical methods used in this study have relatively low detection levels - commonly 100 to 1,000 times lower than State and Federal standards and guidelines for protecting water quality. Detections, therefore, do not necessarily indicate a concern to human health but rather help to identify emerging issues and to track changes in occurrence and concentrations over time. About one-half (134) of the compounds were detected at least once in source-water samples. Forty-seven compounds were detected commonly (in 10 percent or more of the samples), and six compounds (chloroform, atrazine, simazine, metolachlor, deethylatrazine, and hexahydrohexamethylcyclopentabenzopyran (HHCB) were detected in more than one-half of the samples. Chloroform was the most commonly detected compound - in every sample (year round) at five sites. Findings for chloroform and the fragrances HHCB and acetyl hexamethyl tetrahydronaphthalene (AHTN) indicate an association between occurrence and the presence of large upstream wastewater discharges in the watersheds. The herbicides atrazine, simazine, and metolachlor also were among the most commonly detected compounds. Degradates of these herbicides, as well as those of a few other commonly occurring herbicides, generally were detected at concentrations similar to or greater than concentrations of the parent compound. Samples typically contained mixtures of two or more compounds. The total number of compounds and their total concentration in samples generally increased with the amount of urban and agricultural land use in a watershed. Annual mean concentrations of all compounds were less than human-health benchmarks. Single-sample concentrations of anthropogenic organic compounds in source water generally were less than 0.1 microgram per liter and less than established human-health benchmarks. Human-health benchmarks used for comparison were U.S. Environmental Protection Agency (USEPA) Maximum Contaminant Levels (MCLs) for regulated compounds and U.S. Geological Survey Health-Based Screening Levels for unregulated compounds. About one-half of all detected compounds do not have human-health benchmarks or adequate toxicity information for evaluating results in a human-health context. During a second sampling phase (2004-05), source water and finished water (water that has passed through all the treatment processes but prior to distribution) were sampled at eight of the nine community water systems. Water-treatment processes differ among the systems. Specifically, treatment at five of the systems is conventional, typically including steps of coagulation, flocculation, sedimentation, filtration, and disinfection. One water system uses slow sand filtration and disinfection, a second system uses ozone as a preliminary treatment step to conventional treatment, and a third system is a direct filtration treatment plant that uses many of the steps employed in conventional treatment. Most of these treatment steps are not designed specifically to remove the compounds monitored in this study. About two-thirds of the compounds detected commonly in source water were detected at similar frequencies in finished water. Although the water-treatment steps differ somewhat among the eight water systems, the amount of change in concentration of the compounds from source- to finish

Scientific Investigations Report

Variation in metal concentrations across a large contamination gradient is reflected in stream but not linked riparian food webs

Aquatic insects link food web dynamics across freshwater-terrestrial boundaries and subsidize terrestrial consumer populations. Contaminants that accumulate in larval aquatic insects and are retained across metamorphosis can increase dietary exposure for riparian insectivores. To better understand potential exposure of terrestrial insectivores to aquatically-derived trace metals, metal concentrations in water and tissues were analyzed from different components of streams and riparian food webs across a large (2–3 orders of magnitude) metal gradient (e.g., Zn, Cu, Cd, Pb) in the Rocky Mountains (USA). Our research indicates that the trace metal concentration gradient present among streams was lost during metamorphosis of aquatic larval insects into terrestrially flying adults, decoupling terrestrial exposures from aquatic concentrations. This pattern was caused by declines in 1) among-stream variation in trace metal concentrations, 2) relationships between metal concentrations in paired water and food web components, and 3) mean metal concentrations within aquatic food webs and across the aquatic-terrestrial boundary. Specifically, among-stream variation in trace metal concentrations was highest for water and aquatic vegetation, intermediate for aquatic insect larvae (~30% lower than water) and lowest for adult aquatic insects and riparian spiders (~65% lower). Metal concentrations in paired water and food web components ranged from highly related across the stream-metal gradient (slopes ~1) for water and aquatic vegetation, to less related (slopes closer to 0) for aquatic vegetation and aquatic insect larvae, to unrelated (slopes ~0) for aquatic larval and adult insects. Finally, mean metal concentrations were highest in aquatic vegetation and lowest in adult aquatic insects emerging from streams (~50% lower than aquatic vegetation). Our results indicate less efficient trophic transfer and higher metamorphic loss of trace metals from high metal streams (i.e., exposure-dependent transfer). For many trace metals, aquatic-terrestrial dietary transfer is unlikely to be an important source of exposure for terrestrial insectivores of adult aquatic insects.

Science of the Total Environment

Per- and polyfluoroalkyl substances in surface water and sediment in Great Lakes tributaries and relations with watershed attributes

Per- and polyfluoroalkyl substances (PFAS) are chemicals of emerging concern that potentially pose risks to human and environmental health. In May–Oct 2018, sediment and passively collected surface water samples were collected from 62 tributary sites of the Laurentian Great Lakes with site catchments spanning various land cover types. Discrete samples of sediment collected manually and time-integrated surface water samples collected with polar organic chemical integrative samplers (POCIS) were analyzed for 23 and 34 PFAS, respectively. Concentrations of individual PFAS in sediment and surface water varied immensely among sites from below detection to 20,800 ng kg −1 and 247 ng L −1 , respectively. Of all target compounds, PFOS was the most frequently detected in sediment (56 of 62 sites) and had the highest median concentration (132 ng kg −1 ). PFOA, PFHxS, PFOS, PFHpA, and PFNA (full chemical names are listed in online supplementary material Table S2) were detected in all 60 surface water sites, with median estimated concentrations of 5.9, 5.2, 4.6, 3.7, and 1.3 ng L −1 , respectively. Compounds with 8–13 fluorinated carbons comprised a larger proportion of sediment PFAS than compounds with 4–7 fluorinated carbons, whereas compounds with 4–7 fluorinated carbons comprised a greater proportion of PFAS in surface waters. Watershed attributes, including urban land cover, airports per catchment area, and wastewater treatment plants flow percentage were significantly ( p < 0.05) and positively related with PFAS sum concentrations in sediment and (or) surface water. Collectively, these results, albeit with some uncertainty in the estimated concentrations, highlight the relation PFAS occurrence has with human activities and documents widespread low-level PFAS contamination across the Great Lakes basin.

Great Lakes

Insights and strategic opportunities from the USGS 2024 Per- and Polyfluoroalkyl Substances (PFAS) Interagency Workshop

Introduction In 2021, the U.S. Geological Survey (USGS) published Circular 1490 titled, “Integrated Science for the Study of Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) in the Environment: A Strategic Science Vision for the U.S. Geological Survey” (Tokranov and others, 2021). Circular 1490 was created to be a resource for USGS scientists prioritizing and planning research related to per- and polyfluoroalkyl substances (PFAS) and to be a guide for developing partnerships with other scientists, State and Federal agencies, and stakeholders engaged in PFAS research and management and mitigation of the environmental and human-health effects of PFAS. This USGS PFAS Strategic Science Vision document was intended to be the foundation for a “living strategic vision,” periodically providing updates on the state of USGS PFAS research, emerging PFAS data gaps and needs, and progress on interagency and stakeholder PFAS partnerships and priorities. To meet this objective, the USGS planned to host an Interagency and Stakeholder PFAS Workshop every 2–3 years. During September 10–12, 2024, the USGS hosted the first Interagency and Stakeholder PFAS Workshop in Reston, Virginia. The Workshop brought together experts from other Federal agencies (U.S. Environmental Protection Agency, National Institute of Environmental Health Sciences, Food and Drug Administration, Department of Defense [Air Force, Army]), State agencies (Washington Fish and Wildlife, Virginia Department of Transportation), and academia (Harvard University, University of Maryland) to address key challenges relating to the measurement and modeling of PFAS and the implications for environmental health. Participants engaged in in-depth discussions centered around six pivotal topics related to PFAS: (1) sampling protocols, methods and interpretation; (2) environmental sources, source apportionment, and occurrence; (3) environmental fate and transport; (4) human and wildlife exposure routes and risk; (5) bioconcentration, bioaccumulation, and biomagnification; and (6) ecotoxicology and effects. Each topic had three breakout sessions. A recurrent theme of workshop discussions was how data on a nationwide scale for PFAS occurrence in various environmental matrices, including air, water, food crops, biota, soil, and streambed sediment could help to advance scientific understanding. Participants noted significant geospatial data gaps, particularly in the midwestern and southern United States and the Pacific Northwest. PFAS data collection tends to be more robust along the eastern seaboard and in California. Participants stressed how enhancing the integration of large and small datasets across various agencies could help to support national scale understanding of PFAS. To address these gaps, attendees suggested leveraging datasets from Federal entities like the USGS and the U.S. Department of Defense, State agencies, and municipal utility services to develop predictive contaminant detection and transport models. Improved coordination between water quality programs and USGS research could help to facilitate access to valuable data, leading to comprehensive databases that inform PFAS point (wastewater treatment plants and landfills) and nonpoint (runoff from land, atmospheric deposition, food packaging) sources, environmental transport mechanisms, environmental detection and concentrations, potential exposure routes, and health effects on different biota, including humans. A specific request was made to develop a map demarking the depth of modern (1953 or later) groundwater, which is susceptible to surface-derived anthropogenic (that is, human-made) contamination, based on tritium-age dating. Emphasis was placed on incorporation of hydrology, groundwater flow paths, groundwater–surface water interactions, and landscape factors in predictive statistical models as a step to improve contaminant source identification and tracking. Molecular fingerprinting approaches garnered attention as techniques to link specific PFAS mixtures detected in a sample to environmental sources and levels in biota (Dávila-Santiago and others, 2022). Integrating data from abiotic (that is, water, soil, and air) and biotic (that is, living organisms) systems identified as a research opportunity. For example, understanding the composition of soils and sediments, which include a mixture of mineral, plant, and animal components, could advance understanding of exposure pathways. The discussions highlighted opportunities to explore and understand the potential redistribution and biotic exposures of PFAS from biosolid and wastewater treatment plant effluent land application practices, in addition to atmospheric releases and discharges from landfill and wastewater treatment plants. Participants identified research gaps surrounding how these sources may contribute to contamination and may affect surrounding ecosystems, including a better definition of anthropogenic background concentrations. Moving forward, the collection of co-occurrence data was noted as a means to improve understanding of complex mixtures and to leverage companion modeling efforts focused on areas with high and low contamination levels to identify areas of concern and unaffected resources. Participants emphasized how centralized USGS databases and the establishment of sample-metadata archives can help to ensure that samples are preserved and accessible for future research. In conclusion, the workshop participants identified opportunities to bridge data gaps and improve measurement techniques, modeling frameworks, databases, and communication, to enhance the understanding of PFAS and their effects on environmental and human health. Upon completion of the workshop, participants indicated an interest in developing strategic data collection, modeling, and analytical approaches to address these challenges.

Open-File Report

Evaluation of toxicity to the amphipod, Hyalella azteca , and to the midge, Chironomus dilutus ; and bioaccumulation by the oligochaete, Lumbriculus variegatus , with exposure to PCB-contaminated sediments from Anniston, Alabama

The U.S. Environmental Protection Agency (USEPA) requested that as part of the remedial investigation for the Anniston, Alabama Polychlorinated Biphenyl (PCB) Site (Anniston PCB Site), that Pharmacia Corporation and Solutia Inc. (P/S) perform long-term reproduction toxicity tests with the amphipod, Hyalella azteca , and the midge, Chironomus dilutus , and bioaccumulation tests with the oligochaete, Lumbriculus variegatus , using sediment samples collected from reference locations and from Operable Unit 4 of the Anniston PCB Site. The sediment toxicity testing and sediment bioaccumulation results will be used by ARCADIS U.S., Inc. (ARCADIS) as part of a weight-of-evidence assessment to evaluate risks and establish sediment remediation goals for contaminants to sediment-dwelling organisms inhabiting the Anniston PCB Site. The goal of this study was to characterize relations between sediment chemistry and sediment toxicity and relations between sediment chemistry and sediment bioaccumulation in samples of sediments collected from the Anniston PCB Site. A total of 32 samples were evaluated from six test sites and one reference site to provide a wide range in concentrations of chemicals of potential concern (COPCs) including PCBs in samples of whole sediment. The goal of this study was not to determine the extent of sediment contamination across the Anniston PCB Site. Hence, the test sites or samples collected from within a test site were not selected to represent the spatial extent of sediment contamination across the Anniston PCB Site. Sediment chemistry, pore-water chemistry, and sediment toxicity data were generated for 26 sediment samples from the Anniston PCB Site. All of the samples were evaluated to determine if they qualified as reference sediment samples. Those samples that met the chemical selection criteria and biological selection criteria were identified as reference samples and used to develop the reference envelope for each toxicity test endpoint. Physical characterization of samples of whole sediment included analyses of grain size, TOC, and nutrients. Organic chemical characterization of samples of whole sediment included PCB homologs and select (13) PCB congeners, parent and alkylated polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides, and polychlorinated dibenzo-p-dioxins; and dibenzofurans. The PCB aroclors analyzed included 1016, 1221, 1232, 1242, 1248, 1254, 1260, 1262 and 1268. Analyses of whole sediment also included total metals, simultaneously extracted metals, and acid volatile sulfide. Chemical characterization of samples of pore water isolated from samples of whole sediment at the start of the sediment toxicity exposures or at the start of the sediment bioaccumulation exposures included metals, major cations, major anions, dissolved organic carbon, and additional water-quality characteristics. Concentrations of metals or PCBs in pore water during the sediment toxicity exposures or during sediment bioaccumulation exposures also were determined using peeper samples (for metals) or solid-phase microextraction (SPME) samplers (for PCBs). The bioavailability and bioaccumulation of PCBs in 14 sediment samples were investigated using SPME passive samplers and the 28-d L. variegatus whole-sediment bioaccumulation exposures In general the accumulation of PCBs consistently was predicted through the use of organic carbon normalization and equilibrium partitioning. In these sediments, PCB homologs were accumulated differently based on bioavailability and potential to accumulate in oligochaetes. As part of this assessment homolog specific biota sediment accumulation factor values were developed that could be applied across the larger site to predict tissue levels of PCBs. The whole-sediment toxicity tests done with H. azteca and C. dilutus met the established ASTM and USEPA test acceptability criteria. The most responsive H. azteca endpoints were day 42 survival normalized young per female and day 28 biomass and that the most responsive C. dilutus endpoints were adult biomass and percent adult emergence. Overall, between the two species, the most responsive endpoint assessed for these two species was H. azteca survival-normalized young per female (67 percent of the samples classified as toxic). Concentration-response models (CRMs) and site-specific sediment toxicity thresholds (TTs) were generated with matching sediment chemistry and sediment toxicity data. Sediment chemistry, pore-water chemistry, and sediment toxicity data were evaluated for as many as 26 sediment samples from the Anniston PCB Site. The reference-envelope approach was used to identify the sediment samples that were toxic to benthic invertebrates. This procedure involved identification of reference sediment samples, normalizing the toxicity data to reflect control responses, developing a reference envelope for each toxicity test endpoint, and designating each sediment sample as toxic or not toxic for each toxicity test endpoint, for each species, and for all species combined. These results demonstrated percent emergence of adult C. dilutus , biomass of adult C. dilutus , and reproduction of H. azteca normalized to percent survival were among the most responsive endpoints that were evaluated. Therefore, these endpoints were selected for CRM development. The site-specific TTs for whole sediment provide a reliable basis for identifying toxic and not toxic sediment samples in the Anniston PCB Site (that is, for correctly classifying the sediment samples used to derive the TTs as toxic or not toxic, for the endpoint used to derive the TTs). Among the 69 TTs for sediment, the TT LRs for total PCB homologs [499 to 1,870 micrograms per kilogram dry weight (μg/kg DW)] and for lead [(9.48 to 10.3 milligrams per kilogram (mg/kg) DW] based on reproduction of H. azteca or based on emergence or biomass of adult C. dilutus , were the most reliable. Such TTs had low rates of false negative errors (that is, only 0 to 11 percent of the samples below the TT were toxic to benthic invertebrates), low rates of false positive errors (only 0 to 6 percent of the samples greater than the TT were not toxic to benthic invertebrates), and high rates of correct classification (that is, 92 to 96 percent). The site-specific TTs for PCBs and other COPCs derived in this study also were compared to empirically based sediment quality guidelines (SQGs), to equilibrium-partitioning based SQGs, and to the results of spiked-sediment toxicity tests. The results of this evaluation indicated that the site-specific sediment TTs for PCBs were comparable to the consensus-based SQGs that were derived for PCBs. In addition, the site-specific sediment TTs for PCBs are well within the range of SQGs derived using the equilibrium partitioning approach. The site-specific sediment TTs for PCBs also are consistent with the results of chronic TTs that have been estimated for benthic invertebrates using the results of spiked-sediment toxicity tests. As the site-specific sediment TTs for PCBs are consistent with empirically based SQGs, equilibrium-partitioning based SQGs, and results of sediment-spiking studies, these site- specific sediment TTs likely represent the concentrations of PCBs that are sufficient to cause toxicity to benthic invertebrates (as opposed to simply being correlated with adverse effects on the survival, weight, or reproduction of benthic invertebrates). Importantly, such site-specific sediment TTs have been demonstrated to accurately classify sediment samples as toxic or not toxic to benthic invertebrates at the Anniston PCB Site. In contrast, the TTs for metals, PAHs, and organochlorine pesticides were generally lower than consensus-based SQGs (that is, probable effect concentrations), and LC 50s (median lethal effect concentrations) generated in spiked-sediment toxicity tests, indicating that these COPCs are likely not the main contributors to the observed toxicity of the site sediments evaluated in this study. The reproduction endpoint for H. azteca provided lower TTs compared to the day 28 biomass endpoint for H. azteca and the emergence or biomass endpoints for adult C. dilutus provided lower TTs compared to the day 13 biomass endpoint for C. dilutus .

Alabama

Making ‘chemical cocktails’ – Evolution of urban geochemical processes across the periodic table of elements

Urbanization contributes to the formation of novel elemental combinations and signatures in terrestrial and aquatic watersheds, also known as ‘chemical cocktails.’ The composition of chemical cocktails evolves across space and time due to: (1) elevated concentrations from anthropogenic sources, (2) accelerated weathering and corrosion of the built environment, (3) increased drainage density and intensification of urban water conveyance systems, and (4) enhanced rates of geochemical transformations due to changes in temperature, ionic strength, pH, and redox potentials. Characterizing chemical cocktails and underlying geochemical processes is necessary for: (1) tracking pollution sources using complex chemical mixtures instead of individual elements or compounds; (2) developing new strategies for co-managing groups of contaminants; (3) identifying proxies for predicting transport of chemical mixtures using continuous sensor data; and (4) determining whether interactive effects of chemical cocktails produce ecosystem-scale impacts greater than the sum of individual chemical stressors. First, we discuss some unique urban geochemical processes which form chemical cocktails, such as urban soil formation, human-accelerated weathering, urban acidification-alkalinization, and Freshwater Salinization Syndrome. Second, we review and synthesize global patterns in concentrations of major ions, carbon and nutrients, and trace elements in urban streams across different world regions and make comparisons with reference conditions. In addition to our global analysis, we highlight examples from watersheds in the Baltimore-Washington DC area, USA, which show increased transport of major ions, trace metals, and nutrients across streams draining a well-defined land-use gradient. Urbanization increased the concentrations of multiple major and trace elements in streams draining human-dominated watersheds compared to reference conditions. Chemical cocktails of major and trace elements were formed over diurnal cycles coinciding with changes in streamflow, dissolved oxygen, pH, and other variables measured by high-frequency sensors. Some chemical cocktails of major and trace elements were also significantly related to specific conductance (p < 0.05), which can be measured by sensors. Concentrations of major and trace elements increased, peaked, or decreased longitudinally along streams as watershed urbanization increased, which is consistent with distinct shifts in chemical mixtures upstream and downstream of other major cities in the world. Our global analysis of urban streams shows that concentrations of multiple elements along the periodic table significantly increase when compared with reference conditions. Furthermore, similar biogeochemical patterns and processes can be grouped among distinct mixtures of elements of major ions, dissolved organic matter, nutrients, and trace elements as chemical cocktails. Chemical cocktails form in urban waters over diurnal cycles, decades, and throughout drainage basins. We conclude our global review and synthesis by proposing strategies for monitoring and managing chemical cocktails using source control, ecosystem restoration, and green infrastructure. We discuss future research directions applying the watershed chemical cocktail approach to diagnose and manage environmental problems. Ultimately, a chemical cocktail approach targeting sources, transport, and transformations of different and distinct elemental combinations is beneficial to more holistically monitor and manage the emerging impacts of chemical mixtures in the world's fresh waters.

Applied Geochemistry

Identification of metrics to monitor salt marsh integrity on National Wildlife Refuges in relation to conservation and management objectives

Executive Summary Most salt marshes in the US have been degraded by human activities, and threats from physical alterations, surrounding land-use, species invasions, and global climate change persist. Salt marshes are unique and highly productive ecosystems with high intrinsic value to wildlife, and many National Wildlife Refuges (NWRs) have been established in coastal areas to protect large tracts of salt marsh and wetland-dependent species. Various management practices are employed routinely on coastal NWRs to restore and enhance marsh integrity and ensure ecosystem sustainability. Prioritizing NWR salt marshes for application of management actions and choosing among multiple management options requires scientifically-based methods for assessing marsh condition. Monitoring is integral to structured decision-making (SDM), a formal process for decomposing a decision into its essential elements. Within a natural resource context, SDM involves identifying management objectives, alternative management actions, and expected management outcomes. The core of SDM is a set of criteria for measuring system performance and evaluating management responses. Therefore, use of SDM to frame natural resource decisions leads to logical selection of monitoring attributes that are linked explicitly to management needs. We used SDM to guide selection of variables for monitoring the ecological integrity of salt marshes within the National Wildlife Refuge System (NWRS). Our objectives were to identify indicators of salt marsh integrity that are effective across large geographic regions, responsive to a wide range of threats, and feasible to implement within funding and staffing constraints of the NWRS. In April, 2008, we engaged interdisciplinary experts in a week-long rapid prototyping SDM workshop to define the essential elements of salt marsh management decisions on refuges throughout the northeastern, southwestern, and northwestern US, corresponding to respective Regions 5, 2, and 1 of the US Fish and Wildlife Service (FWS). Through this process we identified measurable attributes for monitoring salt marsh ecosystems that are integrated into conservation practice and target management objectives. The following salt marsh attributes were identified through the SDM process either for describing state condition to determine management needs or for evaluating the achievement of management objectives: historical condition and geomorphic setting; ditch density; surrounding land use; ratio of open water area to vegetation area; rate of pesticide application; environmental contaminant concentration; change in marsh surface elevation relative to sea level rise; tidal range and groundwater level; surface topography; salinity; and species composition and abundance of vegetation, invasive species, invertebrates, nekton, and breeding and wintering birds. The identified attributes were too broadly defined to serve as operational monitoring variables. Therefore, we tested specific metrics for quantifying most of these attributes in summers of 2008 and 2009. The first four attributes in the above list can be characterized by office-based analysis of existing GIS data layers. The remaining attributes require field-based methods for assessment. We were forced to exclude a small number of attributes from field tests due to inconsistent data (pesticide application rate, environmental contaminant concentrations) or requirements that exceeded the scope of this project (change in marsh surface elevation; surface topography; benthic invertebrates; wintering birds). We evaluated potential metrics for evaluating all remaining field attributes. In partnership with NWRS biologists, we tested rapid versus intensive metrics for monitoring field attributes (tidal range and groundwater level; marsh surface elevation; salinity; and species composition and abundance of vegetation, invasive species, nekton, and breeding birds) at coastal refuges throughout FWS Region 5. Seven refuges participated in metric testing in 2008: Rachel Carson (ME), Parker River (MA), Wertheim (NY), E. B. Forsythe (NJ), Bombay Hook (DE), Prime Hook (DE), and Eastern Shore of Virginia Complex (VA). These seven and two additional refuges participated in metric testing in 2009: Rhode Island Complex (RI) and Stewart B. McKinney (CT). We based all field metrics on existing protocols for salt marsh assessment. Sampling locations were determined randomly within delineated marsh study units (MSUs) at each refuge. Detailed field methods are provided in appendices to this report. Measurements for individual metrics were averaged across samples within MSUs during each year of sampling. Each year, correlation or regression analysis was conducted on average measurements across MSUs within each attribute set to identify redundant metrics. Statistical redundancy between a pair of metrics within an attribute set (i.e., correlation or regression slopes with p-values < 0.05) was considered justification for eliminating one of the pair from the regional set of monitoring metrics. Decisions regarding metric elimination versus retention were based on feasibility of monitoring, considering such factors as sampling time, resources required, and potential for regional standardization in implementation. The result of these tests is a reduced suite of monitoring metrics that targets NWRS management decisions and is practicable for implementing on a regional scale. Based on these tests, we recommend the following list of metrics for monitoring integrity of NWRS salt marshes (marsh attribute category is in parentheses): (historical condition and geomorphic setting) position of marsh in the landscape, marsh shape, degree of fill and/or fragmentation, degree of tidal flushing, amount of aquatic edge; (ditch density) ranking of ditch density from none to severe; (surrounding land use) relative proportion of agricultural land in a 150-m buffer around the marsh, relative proportion of natural land in a 150-m buffer around the marsh, relative proportion of natural land in a 1-km buffer around the marsh; (ratio of open water area to vegetation area) ratio of open water to emergent herbaceous wetlands within the marsh; (marsh surface elevation) elevation referenced to NAVD88 in a representative area of the marsh; (tidal range and groundwater level) percent of time the marsh surface is flooded during deployment of a continuous water-level monitor at a representative marsh location, mean depth of surface flooding as measured by a continuous water-level monitor at a representative location; (salinity) salinity measured in surface water; (vegetation community) vegetation species richness using the point-intercept method in 100-m diameter survey plots, percent cover of various marsh community types within 100-m diameter survey plots; (invasive species abundance) percent cover of invasive plant species measured using the point-intercept method in 100-m diameter survey plots; (nekton community) nekton density, nekton species richness, length of Fundulus heteroclitus ; (breeding bird community) abundance of Willets counted per point during standard call-broadcast surveys, summed abundance of tidal marsh obligate species (Clapper Rail, Willet, Saltmarsh Sparrow, Seaside Sparrow) counted per point during standard call-broadcast surveys. Metrics describing the historical condition, geomorphic setting, and broad landscape features can be assessed using existing GIS databases. Our results support use of rapid methods to assess the majority of field metrics; only those used to describe the nekton community must be measured using intensive methods (throw traps or ditch nets, dependant on habitat configuration). Implementation of these metrics for quantitative assessment of NWRS salt marsh integrity in FWS Region 5 requires developing sampling designs for each refuge. Additionally, it is important to determine how the monitoring information will be used within a management context. SDM should be used to complete the analysis of salt marsh management decisions. The next steps would involve 1) prioritizing and weighting the management objectives; 2) predicting responses to individual management actions in terms of objectives and metrics; 3) using multiattribute utility theory to convert all measurable attributes to a common utility scale; 4) determining the total management benefit of each action by summing utilities across objectives; and 5) maximizing the total management benefits within cost constraints for each refuge. This process would allow the optimum management decisions for NWRS salt marshes to be selected and implemented based directly on monitoring data and current understanding of marsh responses to management actions. Monitoring the outcome of management actions would then allow new monitoring data to be incorporated into subsequent decisions.

Connecticut, Delaware, Maine, Massachusetts, New J

Selenium loading through the Blackfoot River watershed--linking sources to ecosystem

The upper Blackfoot River watershed in southeast Idaho receives drainage from 11 of 16 phosphate mines that have extracted ore from the Phosphoria Formation, three of which are presently active. Toxic effects from selenium (Se), including death of livestock and deformity in aquatic birds, were documented locally in areas where phosphatic shales are exposed ( Piper et al., 2000 ; Presser et al., Chapter 11). Current drainage conditions are leading to Se bioaccumulation at concentrations that pose a risk to fish in the Blackfoot River and its tributaries (Hamilton et al., Chapter 18). A gaging station on the Blackfoot River was re-activated in April 2001 to assess hydrologic conditions and concentration, load, and speciation for Se discharges on a watershed scale. The gaging-station data are considered to represent regional drainage conditions in the upper Blackfoot River water- shed because of its location near the outlet of the watershed and directly upstream of the Blackfoot Reservoir. Watershed discharges for 2001 and 2002 were below minimum hydrologic conditions for the gage as documented by the historical record. Drought emergencies were declared in the area in both 2001 and 2002. Unmonitored diversions for irrigation that routinely take place during the snowmelt season also affected conditions downstream. Annual cycles in Se concentration, load, and selenate (Se 6+ ) reached maxima in the spring during the period of maximum flow at the gaging station. Thirty-seven to 44% of annual flow occurred dur- ing the three-month high-flow season (April through June) in 2001 and 56% of annual flow occurred during that time period in 2002. Extrapolation from historical hydrographs for average and wet years and a limited data set of regional Se concentrations for 2001 and 2002 indicated potential for a 3.6- to 7.4-fold increase in Se loading because of increased seasonal flows in the Blackfoot River watershed. Supplementation data indicate that: (a) the difference between total Se and dissolved Se, as a measure of the contribution of particulate Se, was < 10% except at the peak of con- centration when total Se was 18% more than dissolved Se; (b) selenite (Se 4+ ) represented less than 10% of the dissolved species during all months of 2001; and (c) dissolved Se was approximately a 50:50 mixture of selenate and organic selenide (operationally defined Se 2- ) during summer 2001 (June through August). Ecological risk based on regional Se drainage occurred during both the high- and low-flow seasons. Seventy to 83% of the Se load occurred during the high-flow season. During early May of both years, dissolved-Se concentrations exceeded the criterion for the protection of aquatic life and the ecological threshold of 5 gL 1 Se at which sub- stantive risk occurs. During the majority of the three-month high-flow season, dissolved- Se concentrations exceeded the 2 gL 1 Se concern level for aquatic biota. The Se concentration in suspended material during high flow in 2002 was within the range of marginal risk to aquatic life (2-4 gg 1 Se, dry weight). Selenate was the major species during peak flows, with both selenate and organic selenide being major species during relatively low-flow periods in summer. A change in speciation to reduced Se may indicate elevated biotic productivity during summer months and could result in enhanced Se uptake in food webs. In addition to the magnitude of regional Se release in the Blackfoot River watershed, Se concentrations in individual source drains and waste-rock seeps, and those predicted by experimental column leaching of proposed mining overburden materials, also indicate that drainage options that currently meet existing demands for phosphate mining cause eco- logical risk thresholds to be exceeded. At times, the drinking-water Se standard (50 g L 1 Se) and the criterion for hazardous Se waste (1000 L -1 Se) ( US Department of the Interior, 1998 ; US Environmental Protection Agency, 1987 ) are also exceeded. For water-years 2001 and 2002, seasonal increased input of water in the mining area resulted in increased Se transport, suggesting a mechanism of contamination that involves a significant Se reservoir. Hence, recognition and monitoring of Se loading to the envi- ronment on a mass balance basis (i.e. inputs, fluxes and storage within environmental media, and outputs) are essential to evaluating how to control Se concentrations within environmentally protective ranges ( Presser and Piper, 1998 ). In areas where release of Se to aquatic systems is anticipated as a product of future expansion of phosphate mining, continuous monitoring of flow and development of seasonal Se loading patterns would help to model watersheds in terms of sources, flow periods, and environmental-Se con- centrations that most influence bioavailability. These data, in turn, could be linked to Se- bioaccumulation models specific to food webs and vulnerable species of the impacted areas to accurately project ecological effects. Gaging at this site on the Blackfoot River is planned to continue in order to establish a long-term (>10 year) record of hydrologic conditions.

Idaho

Water resources inventory of Connecticut Part 10: Lower Connecticut River basin

The lower Connecticut River basin study area in south-central Connecticut includes 639 square miles and is drained principally by the Connecticut River and by seven smaller streams that flow directly to Long Island Sound between the West River on the west and the Connecticut River on the east. The population in 1979 was estimated to be 210,380. Much of the industrial development and population centers are in the Mattabesset River basin in the northwestern part, and the largest water use is also in the Mattabesset River basin. Precipitation averages 47 inches per year and provides an abundant supply of water. About 20 inches returns to the atmosphere as evapotranspiration, and the remainder either flows directly to streams or percolates to the water table, eventually discharging to Long Island Sound. Small quantities of water are exported from the basin by the New Haven and Meridan Water Departments, and small quantities are imported by the New Britain Water Department and Metropolitan Direct Commission. Precipitation during 1931-60 resulted in an average annual runoff of 302 billion gallons. In inflow from the Connecticut River is added to the average annual runoff, the 4,370 billion gallon s per year is potentially available for water ue. The domestic, institutional, commercial, and industrial (other than cooling water) water use for 1970 was 7 billion gallons, which is only 3 percent of the total water used, whereas 97 percent of the total is cooling water for power plants. Approximately 60 percent of the 7 billion gallons is treated before being discharged back to the streams. The total amount of fresh water used during 1970 was estimated to be 256,000 million gallons (Mgal), of which 247,000 Mgal was used for cooling water at stream electric-generating plants. The quantity for domestic, commercial, industrial, and agricultural used was 9,000 Mgal, which was approximately 120 gallons a day per person. Public water systems providing 70 percent of these requirement and all the systems supplying water met the drinking water standards of the Connecticut General Assembly (1975). Till is widespread and generally provides only small amounts of water. Wells in till normally yield only a few hundred gallons of water daily and may be inadequate during dry periods. The thickness of of till ranges from 0 to 15 feet; a median thickness of 26 feet is estimated from information provided in drillers' logs of 467 wells penetrating underlying bedrock. The till is generally used only as an emergency or secondary source of water. Bedrock aquifers underlie the entire area and include sedimentary and crystalline (igneous and metamorphic) rock types. These aquifers supply small and usually reliable quantities of water to wells and are the chief source of water for many rural homes and farms., About 90 percent of the wells tapping bedrock yield at least 2 gal/min. The median yields from wells tapping aquifers in sedimentary, igneous, and metamorphic rocks are 11, 8, and 6.5 gal/min, respectively. The quantity of water potentially available from stratified drift was estimated on the basis of hydraulic characteristics of the aquifers, mathematical modeling of the aquifer system, and evaluation of natural and induced recharge. Long-term yields estimated or ten areas underlain by significant thickness of stratified drift range from 0.4 to 4.4 million gallons per day (Mgal/d). A change in well spacing or numbering could increase the long-term yields, but detailed modeling verification studies are needed to confirm optimal well locations. The chemical and physical (turbidity, color, taste, and sediment load) quality of water is good. The water if generally low in dissolved solids and is classified as soft to hard. Surface water is less mineralized than ground water, especially during high flow, when it is primarily derived from surface runoff rather than groundwater runoff. A median dissolved-solids concentration of 42 milligrams per liter (mg/L) and median hardness of 18 mg/L were determined from water samples collected from 26 streams during the high-flow period. During the low-flow period, median dissolved-solids concentration of 61 mg/L and median hardness of 27 mg/L were determined from sample from the same streams. The quality of water in stratified-drift and crystalline-rock aquifers is generally better than that in the sedimentary-rock aquifers. Water from 32 wells tapping stratified drift had median dissolved-solids concentrations of 116 mg/L; and 33 wells tapping stratified drift and 42 tapping crystalline rock had median hardness of 73 mg/L and 68 mg/L, respectively. Water from 32 wells tapping sedimentary rock had median dissolved concentrations of 231 and 156 mg/L, respectively. Sedimentary rock generally yields the hardest water. Iron and manganese occur objectionable concentrations in places, particularly in water from streams draining swamps and in water from aquifers either rich in iron and manganese-nearing minerals or where the reducing environment for solution of these minerals is favorable. Concentrations of iron in excess of 0.3 mg/L were found in 35 percent of the high streamflow samples, and in 45 percent of the ground-water samples. Most of the high iron and manganese concentration in streams and aquifers are found east of the Connecticut River. Human activities and tidal influence along the coast have modified the quality of water in much f the study area. The greatest influence from human activities has been in the northwestern part, in the Mattabesset River basin. There, the quality of water has been affected by domestic and animal wastes, which cause high dissolved-solids concentrations, high nitrate and phosphate loads and high bacterial counts. In the entire area, high nitrate in groundwater occur only locally, and its presence in an individual water supply is chiefly a function of its proximity to sources of contamination, of well construction, and of thickness of overburden. Thirty public-supply wells did have water that had high sodium concentrations or objectionable iron and manganese concentrations, but these are not considered health hazards in the concentrations found in the water samples. Streams, wetlands, and some aquifers along the sough boundary of the basin contain salty water because of tidal movement or extensive ground-water withdrawals. High sediment concentrations also occur as a result of tidal influence in this area.

Connecticut

Ecological requirements for pallid sturgeon reproduction and recruitment in the Missouri River—A synthesis of science, 2005 to 2012

This report is intended to synthesize the state of the scientific understanding of pallid sturgeon ecological requirements to provide recommendations for future science directions and context for Missouri River restoration and management decisions. Recruitment of pallid sturgeon has been low to non-existent throughout its range. Emerging understanding of the genetic structure of pallid sturgeon populations sets a broad framework for species and river management decisions, including decisions about managing the future genetic diversity of the species, but also decisions about where and what type of river restoration actions will be effective for subpopulations of this highly migratory species. Adult pallid sturgeon may migrate hundreds of kilometers (km) to spawn and their progeny may disperse even greater distances downstream as drifting free embryos. As a result of their complex life history pallid sturgeon naturally exploit a wide range of habitats during their life cycles. The construction of dams and reservoirs has fragmented habitats and may have shifted Missouri River subpopulations downstream. Research has not identified one primary biological or ecological constraint that appears to limit populations of the pallid sturgeon. With the present (2013) state of knowledge many life stages and life-stage transitions cannot be ruled out as contributing to recruitment failure. Biological opinions in 2000 (and amended in 2003) presented the dominant hypotheses for recruitment failure that existed at that time. Emphasis was on the role of the flow regime, specifically spring flow pulses (&ldquo;spring rises&rdquo;), to condition spawning substrate and cue reproductive aggregations and migrations, and on low flows and additional slow, shallow-water area to serve as rearing habitat for age-0 to juvenile pallid sturgeon. Studies on spawning habitat dynamics have documented that habitat patches selected for spawning by fish in the Lower Missouri River (Missouri River downstream from Gavins Point Dam to the confluence with the Mississippi River) are dominantly on outside, revetted bends in the deepest, fastest, and most turbulent water. Studies in more natural habitat on the Yellowstone River have documented spawning in convergent flow in the middle of the channel on discrete patches of gravel within a sand-dominated channel, an arrangement that may be more effective in attracting aggregations of reproductive fish compared to the nearly continuous revetment on the Lower Missouri River. Pallid sturgeon spawn in the spring and early summer during periods of increasing day length. Water temperature consistently exerts a threshold effect for spawning at 16&ndash;18 &deg;C. In addition, the role of water temperature is indicated by pauses and reversals in upstream migrations that have been associated with cold weather fronts that create a transient decrease in water temperature. From 2005 to 2012 on the Lower Missouri River, no obvious relations between flow pulses and fish movements and spawning behaviors have been apparent. However, pallid sturgeon tracking at the Upper Missouri&ndash;Yellowstone confluence indicates that in most years, most telemetered pallid sturgeon migrate out of the Missouri River and into the Yellowstone River in the June&ndash;July timeframe in association with the spring pulse. This pattern was disrupted in 2011 when a high flow pulse with warm temperatures and high turbidity emanated from the Milk River, followed by record releases from Fort Peck Dam, and 36&ndash;39 percent of the telemetered population migrated up the Upper Missouri. This result supports the hypothesis that sufficiently large flow pulses may trigger migration and aggregation but it is not clear that functional pulses are within reservoir management authorities. Notably, a pallid sturgeon free embryo was captured on the Upper Missouri River in 2011 and another single, genetically confirmed embryo was captured on the Yellowstone River in 2012. Research on free-embryo drift has indicated the potential for hundreds of miles of downstream dispersal. Lack of distance to accommodate the extended downstream dispersal period of free embryos on the Upper Missouri and Yellowstone Rivers is the predominant hypothesis for recruitment failure in the upper basin. Long drift distances in the Lower Missouri River may be responsible for shifting Lower Missouri River sub-populations further into the Middle Mississippi River. Physical understanding of drift processes indicates that mean velocities could be slowed through decreased discharges or increased channel hydraulic radius (width and topographic diversity) to reduce free-embryo dispersal distances. In addition, the probability that free embryos are transported into and retained in channel-margin habitats is theoretically amenable to channel re-engineering that would increase cross-channel secondary currents in bends or channel expansions. Considerable uncertainty persists, however, about whether extended drift of Lower Missouri River larvae is responsible for recruitment failure. If drift distance is limiting, it is important to discern whether it would be advisable to retain larvae within the Missouri River, and where along the river restoration projects should be placed to optimize survival and growth of age-0 and juvenile sturgeon. Longitudinal differences in female pallid sturgeon fecundity lend support to the hypothesis that recruitment failure may be due, in part, to fish having insufficient nutrition to produce the numbers of gametes needed for the population to grow, perhaps because of simultaneous declines in prey-fish populations and their habitats. Establishing a chain of causality from habitat decline, to prey-fish populations, to sturgeon diets, to sturgeon fecundity, and to pallid sturgeon population growth presents a considerable scientific challenge. In addition to the dominant hypotheses relating pallid sturgeon populations to changes in flow regime and channel morphology, other factors have been identified that might be sources of stress and contribute to recruitment failure. Among these are water quality and contaminants. Ambient water-quality monitoring on the Missouri River has demonstrated summer episodes when dissolved oxygen dips below 5 milligrams per liter, a threshold that may be stressful especially to age-0 and juvenile sturgeon. Documented cases of intersex in shovelnose and pallid sturgeon indicate that agricultural and municipal sources of endocrine disrupting chemicals also may have a role in pallid sturgeon recruitment failure. Scientific understanding of the ecological requirements of pallid sturgeon has increased almost exponentially in the last two decades, and efforts are now turning from understanding fundamental biology of the species to quantifying how population dynamics relate to potential management actions. Progress in developing the science needed to inform management actions on the Missouri River may benefit from continuation of monitoring of reproductive cycles, reproductive movements, growth, and survival of telemetry tagged adults, increased emphasis on focused, complementary field and laboratory studies of factors influencing early life history, implementation of studies to resolve the role of food limitations in growth, survival, and reproductive condition, and implementation of studies designed specifically to parameterize models linking management to populations.

Missouri River