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Characterization of surface-water quality based on real-time monitoring and regression analysis, Quivira National Wildlife Refuge, south-central Kansas, December 1998 through June 2001

Because of the considerable wildlife benefits offered by the Quivira National Wildlife Refuge in south-central Kansas, there is a desire to ensure suitable water quality. To assess the quality of water flowing from Rattlesnake Creek into the refuge, the U.S. Geological Survey collected periodic water samples from December 1998 through June 2001 and analyzed the samples for physical properties, dissolved solids, total suspended solids, suspended sediment, major ions, nutrients, metals, pesticides, and indicator bacteria. Concentrations of 10 of the 125 chemicals analyzed did not meet water-quality criteria to protect aquatic life and drinking water in a least one sample. These were pH, turbidity, dissolved oxygen, dissolved solids, sodium, chloride, phosphorus, total coliform bacteria, E. coli bacteria, and fecal coliform bacteria. No metal or pesticide concentrations exceeded water-quality criteria. Twenty-two of the 43 metals analyzed were not detected, and 36 of the 46 pesticides analyzed were not detected. Because dissolved solids, sodium, chloride, fecal coliform bacteria, and other chemicals that are a concern for the health and habitat of fish and wildlife at the refuge cannot be measured continuously, regression equations were developed from a comparison of the analytical results of periodic samples and in-stream monitor measurements of specific conductance, pH, water temperature, turbidity, and dissolved oxygen. A continuous record of estimated chemical concentrations was developed from continuously recorded in-stream measurements. Annual variation in water quality was evaluated by comparing 1999 and 2000 sample data- the 2 years for which complete data sets were available. Median concentrations of alkalinity, fluoride, nitrate, and fecal coliform bacteria were smaller or did not change from 1999 to 2000. Dissolved solids, total suspended solids, sodium, chloride, sulfate, total organic nitrogen, and total phosphorus had increases in median concentrations from 1999 to 2000. Increases in the median concentrations of the major ions were expected due to decreased rainfall in 2000 and very low streamflow late in the year. Increases for solids and nutrients may have been due to the unusually high streamflow in the early spring of 2000. This was the time of year when fields were tilled, exposing solids and nutrients that were transported with runoff to Rattlesnake Creek. Load estimates indicate the chemical mass transported into the refuge and can be used in the development of total maximum daily loads (as specified by the U.S. Environmental Protection Agency) for water-quality contaminants in Rattlesnake Creek. Load estimates also were used to evaluate seasonal variation in water quality. Seasonal variation was most pronounced in the estimates of nutrient loads, and most of the nutrient load transported to the refuge occurred during just a few periods of surface runoff in the spring and summer. This information may be used by resource managers to determine when water-diversion strategies would be most beneficial. Load estimates also were used to calculate yields, which are useful for site comparisons. The continuous and real-time nature of the record of estimated concentrations, loads, and yields may be important for resource managers, recreationalists, or others for evaluating water-diversion strategies, making water-use decisions, or assessing the environmental effects of chemicals in time to prevent adverse effects on fish or other aquatic life at the refuge.

Kansas↗

Parameterizing an aeolian erosion model for rangelands

Aeolian processes are fundamental to arid and semi-arid ecosystems, but modeling approaches are poorly developed for assessing impacts of management and environmental change on sediment transport rates over meaningful spatial and temporal scales. For model estimates to provide value, estimates of sediment flux that encapsulate intra- and inter-annual and spatial variability are needed. Further, it is important to quantify and communicate transparent estimates of model uncertainty to users. Here, we present a wind erosion and dust emission model parameterized for rangelands using a Generalized Likelihood Uncertainty Estimation framework. Modeled horizontal sediment flux was calibrated using data from five diverse grassland and shrubland sites from the USDA National Wind Erosion Research Network. Observations of wind speed, vegetation height, length of gaps between vegetation, and percent bare ground were used as model inputs. Horizontal sediment flux estimates from 10,000 independently selected parameter sets were compared to flux observations from 44 ∼ month-long collection periods to calculate a likelihood measure for each model. Results show good agreement for individual sampling periods across sites with few observations falling outside prediction bounds and a one-to-one relationship between median predictions and observations. Additionally, combined distributions of sediment flux estimates from all sample periods for a given site closely approximated the probability of observing a given flux at that site. These results suggest AERO effectively represents temporal variability in aeolian transport rates at rangeland sites and provides robust assessments suitable for assessing land health and better predicting changes in air quality and the impacts of land management activities.

Aeolian Research↗

A national reconnaissance for pharmaceuticals and other organic wastewater contaminants in the United States - II) Untreated drinking water sources

Numerous studies have shown that a variety of manufactured and natural organic compounds such as pharmaceuticals, steroids, surfactants, flame retardants, fragrances, plasticizers and other chemicals often associated with wastewaters have been detected in the vicinity of municipal wastewater discharges and livestock agricultural facilities. To provide new data and insights about the environmental presence of some of these chemicals in untreated sources of drinking water in the United States targeted sites were sampled and analyzed for 100 analytes with sub-parts per billion detection capabilities. The sites included 25 ground- and 49 surface-water sources of drinking water serving populations ranging from one family to over 8 million people. Sixty-three of the 100 targeted chemicals were detected in at least one water sample. Interestingly, in spite of the low detection levels 60% of the 36 pharmaceuticals (including prescription drugs and antibiotics) analyzed were not detected in any water sample. The five most frequently detected chemicals targeted in surface water were: cholesterol (59%, natural sterol), metolachlor (53%, herbicide), cotinine (51%, nicotine metabolite), β-sitosterol (37%, natural plant sterol), and 1,7-dimethylxanthine (27%, caffeine metabolite); and in ground water: tetrachloroethylene (24%, solvent), carbamazepine (20%, pharmaceutical), bisphenol-A (20%, plasticizer), 1,7-dimethylxanthine (16%, caffeine metabolite), and tri (2-chloroethyl) phosphate (12%, fire retardant). A median of 4 compounds were detected per site indicating that the targeted chemicals generally occur in mixtures (commonly near detection levels) in the environment and likely originate from a variety of animal and human uses and waste sources. These data will help prioritize and determine the need, if any, for future occurrence, fate and transport, and health-effects research for subsets of these chemicals and their degradates most likely to be found in water resources used for drinking water in the United States.

Science of the Total Environment↗

Groundwater quality in the Western San Joaquin Valley study unit, 2010: California GAMA Priority Basin Project

Water quality in groundwater resources used for public drinking-water supply in the Western San Joaquin Valley (WSJV) was investigated by the USGS in cooperation with the California State Water Resources Control Board (SWRCB) as part of its Groundwater Ambient Monitoring and Assessment (GAMA) Program Priority Basin Project. The WSJV includes two study areas: the Delta–Mendota and Westside subbasins of the San Joaquin Valley groundwater basin. Study objectives for the WSJV study unit included two assessment types: (1) a status assessment yielding quantitative estimates of the current (2010) status of groundwater quality in the groundwater resources used for public drinking water, and (2) an evaluation of natural and anthropogenic factors that could be affecting the groundwater quality. The assessments characterized the quality of untreated groundwater, not the quality of treated drinking water delivered to consumers by water distributors. The status assessment was based on data collected from 43 wells sampled by the U.S. Geological Survey for the GAMA Priority Basin Project (USGS-GAMA) in 2010 and data compiled in the SWRCB Division of Drinking Water (SWRCB-DDW) database for 74 additional public-supply wells sampled for regulatory compliance purposes between 2007 and 2010. To provide context, concentrations of constituents measured in groundwater were compared to U.S. Environmental Protection Agency (EPA) and SWRCB-DDW regulatory and non-regulatory benchmarks for drinking-water quality. The status assessment used a spatially weighted, grid-based method to estimate the proportion of the groundwater resources used for public drinking water that has concentrations for particular constituents or class of constituents approaching or above benchmark concentrations. This method provides statistically unbiased results at the study-area scale within the WSJV study unit, and permits comparison of the two study areas to other areas assessed by the GAMA Priority Basin Project statewide. Groundwater resources used for public drinking water in the WSJV study unit are among the most saline and most affected by high concentrations of inorganic constituents of all groundwater resources used for public drinking water that have been assessed by the GAMA Priority Basin Project statewide. Among the 82 GAMA Priority Basin Project study areas statewide, the Delta–Mendota study area ranked above the 90th percentile for aquifer-scale proportions of groundwater resources having concentrations of total dissolved solids (TDS), sulfate, chloride, manganese, boron, chromium(VI), selenium, and strontium above benchmarks, and the Westside study area ranked above the 90th percentile for TDS, sulfate, manganese, and boron. In the WSJV study unit as a whole, one or more inorganic constituents with regulatory or non-regulatory, health-based benchmarks were present at concentrations above benchmarks in about 53 percent of the groundwater resources used for public drinking water, and one or more organic constituents with regulatory health-based benchmarks were detected at concentrations above benchmarks in about 3 percent of the resource. Individual constituents present at concentrations greater than health-based benchmarks in greater than 2 percent of groundwater resources used for public drinking water included: boron (51 percent, SWRCB-DDW notification level), chromium(VI) (25 percent, SWRCB-DDW maximum contaminant level (MCL)), arsenic (10 percent, EPA MCL), strontium (5.1 percent, EPA Lifetime health advisory level (HAL)), nitrate (3.9 percent, EPA MCL), molybdenum (3.8 percent, EPA HAL), selenium (2.6 percent, EPA MCL), and benzene (2.6 percent, SWRCB-DDW MCL). In addition, 50 percent of the resource had TDS concentrations greater than non-regulatory, aesthetic-based SWRCB-DDW upper secondary maximum contaminant level (SMCL), and 44 percent had manganese concentrations greater than the SWRCB-DDW SMCL. Natural and anthropogenic factors that could affect the groundwater quality were evaluated by using results from statistical testing of associations between constituent concentrations and values of potential explanatory factors, inferences from geochemical and age-dating tracer results, and by considering the water-quality results in the context of the hydrogeologic setting of the WSJV study unit. Natural factors, particularly the lithologies of the source areas for groundwater recharge and of the aquifers, were the dominant factors affecting groundwater quality in most of the WSJV study unit. However, where groundwater resources used for public supply included groundwater recharged in the modern era, mobilization of constituents by recharge of water used for irrigation also affected groundwater quality. Public-supply wells in the Westside study area had a median depth of 305 m and primarily tapped groundwater recharged hundreds to thousands of years ago, whereas public-supply wells in the Delta–Mendota study area had a median depth of 85 m and primarily tapped either groundwater recharged within the last 60 years or groundwater consisting of mixtures of this modern recharge and older recharge. Public-supply wells in the WSJV study unit are screened in the Tulare Formation and zones above and below the Corcoran Clay Member are used. The Tulare Formation primarily consists of alluvial sediments derived from the Coast Ranges to the west, except along the valley trough at the eastern margin of the WSJV study unit where the Tulare Formation consists of fluvial sands derived from the Sierra Nevada to the east. Groundwater from wells screened in the Sierra Nevada sands had manganese-reducing or manganese- and iron-reducing oxidation-reduction (redox) conditions. These redox conditions commonly were associated with elevated arsenic or molybdenum concentrations, and the dominance of arsenic(III) in the dissolved arsenic supports reductive dissolution of iron and manganese oxyhydroxides as the mechanism. In addition, groundwater from many wells screened in Sierra Nevada sands contained low concentrations of nitrite or ammonium, indicating reduction of nitrate by denitrification or dissimilatory processes, respectively. Geology of the Coast Ranges westward of the study unit strongly affects groundwater quality in the WSJV. Elevated concentrations of TDS, sulfate, boron, selenium and strontium in groundwater were primarily associated with aquifer sediments and recharge derived from areas of the Coast Ranges dominated by Cretaceous-to-Miocene age, organic-rich, reduced marine shales, known as the source of selenium in WSJV soils, surface water, and groundwater. Low sulfur-isotopic values (δ34S) of dissolved sulfate indicate that the sulfate was largely derived from oxidation of biogenic pyrite from the shales, and correlations with trace element concentrations, geologic setting, and groundwater geochemical modeling indicated that distributions of sulfate, strontium, and selenium in groundwater were controlled by dissolution of secondary sulfate minerals in soils and sediments. Elevated concentrations of chromium(VI) were primarily associated with aquifer sediments and recharge derived from areas of the Coast Ranges dominated by the Franciscan Complex and ultramafic rocks. The Franciscan Complex also has boron-rich, sodium-chloride dominated hydrothermal fluids that contribute to elevated concentrations of boron and TDS. Groundwater from wells screened in Coast Ranges alluvium was primarily oxic and relatively alkaline (median pH value of 7.55) in the Delta–Mendota study area, and primarily nitrate-reducing or suboxic and alkaline (median pH value of 8.4) in the Westside study area. Many groundwater samples from those wells have elevated concentrations of arsenic(V), molybdenum, selenium, or chromium(VI), consistent with desorption of metal oxyanions from mineral surfaces under those geochemical conditions. High concentrations of benzene were associated with deep wells located in the vicinity of petroleum deposits at the southern end of the Westside study area. Groundwater from these wells had premodern age and anoxic geochemical conditions, and the ratios among concentrations of hydrocarbon constituents were different from ratios found in fuels and combustion products, which is consistent with a geogenic source for the benzene rather than contamination from anthropogenic sources. Water stable-isotope compositions, groundwater recharge temperatures, and groundwater ages were used to infer four types of groundwater: (1) groundwater derived from natural recharge of water from major rivers draining the Sierra Nevada; (2) groundwater primarily derived from natural recharge of water from Coast Ranges runoff; (3) groundwater derived from recharge of pumped groundwater applied to the land surface for irrigation; and (4) groundwater derived from recharge during a period of much cooler paleoclimate. Water previously used for irrigation was found both above and below the Corcoran Clay, supporting earlier inferences that this clay member is no longer a robust confining unit. Recharge of water used for irrigation has direct and indirect effects on groundwater quality. Elevated nitrate concentrations and detections of herbicides and fumigants in the Delta–Mendota study area generally were associated with greater agricultural land use near the well and with water recharged during the last 60 years. However, the extent of the groundwater resource affected by agricultural sources of nitrate was limited by groundwater redox conditions sufficient to reduce nitrate. The detection frequency of perchlorate in Delta–Mendota groundwater was greater than expected for natural conditions. Perchlorate, nitrate, selenium, and strontium concentrations were correlated with one another and were greater in groundwater inferred to be recharge of previously pumped groundwater used for irrigation. The source of the perchlorate, selenium, and strontium appears to be salts deposited in the soils and sediments of the arid WSJV that are dissolved and flushed into groundwater by the increased amount of recharge caused by irrigation. In the Delta–Mendota study area, the groundwater with elevated concentrations of selenium was found deeper in the aquifer system than it was reported by a previous study 25 years earlier, suggesting that this transient front of groundwater with elevated concentrations of constituents derived from dissolution of soil salts by irrigation recharge is moving down through the aquifer system and is now reaching the depth zone used for public drinking water supply.

California↗

Comparative toxicity of aquatic per- and polyfluoroalkyl substance exposure in three species of amphibians

Per- and polyfluoroalkyl substances (PFAS) are contaminants of concern due to their widespread occurrence in the environment, persistence, and potential to elicit a range of negative health effects. Per- and polyfluoroalkyl substances are regularly detected in surface waters, but their effects on many aquatic organisms are still poorly understood. Species with thyroid-dependent development, like amphibians, can be especially susceptible to PFAS effects on thyroid hormone regulation. We examined sublethal effects of aquatic exposure to four commonly detected PFAS on larval northern leopard frogs ( Rana [Lithobates] pipiens ), American toads ( Anaxyrus americanus ), and eastern tiger salamanders ( Ambystoma tigrinum ). Animals were exposed for 30 days (frogs and salamanders) or until metamorphosis (toads) to 10, 100, or 1000 μg/L of perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorohexane sulfonate (PFHxS), or 6:2 fluorotelomer sulfonate (6:2 FTS). We determined that chronic exposure to common PFAS can negatively affect amphibian body condition and development at concentrations as low as 10 µg/L. These effects were highly species dependent, with species having prolonged larval development (frogs and salamanders) being more sensitive to PFAS than more rapidly developing species (toads). Our results demonstrate that some species could experience sublethal effects at sites with surface waters highly affected by PFAS. Our results also indicate that evaluating PFAS toxicity using a single species may not be sufficient for accurate amphibian risk assessment. Future studies are needed to determine whether these differences in susceptibility can be predicted from species' life histories and whether more commonly occurring environmental levels of PFAS could affect amphibians.

Environmental Toxicology and Chemistry↗

Investigating hydrologic alteration in the Pearl and Pascagoula River basins using rule-based model trees

Anthropogenic hydrologic alteration threatens the health of riverine ecosystems. Machine learning algorithms that employ the use of model trees to predict hydrologic alteration are underrepresented in related literature. This study assesses hydrologic alteration in the Pearl and Pascagoula River basins using modeled daily streamflow . Hydrologic alteration was determined by hypothesis testing and the computation of the net change across 60 years. Cubist models were developed for both basins to predict hydrologic alteration and to identify important basin characteristics. Results from net change and the hypothesis test indicated the basins were essentially identical with respect to the amount of hydrologic alteration. Cubist models for the basins successfully made accurate predictions of hydrologic alteration and demonstrated that the importance of basin geomorphology and land cover on alteration differed in both basins. The results of the study demonstrate the feasibility of model trees in assessing hydrologic alteration.

Mississippi↗

Riverine pesticide trends in the United States: Assessing a decade of national-scale monitoring

Pesticides in freshwater systems can compromise water availability by degrading water quality, with implications for human health and aquatic life. Despite recognition of the need for national-scale monitoring and analysis, few studies have documented long-term trends in surface water pesticide contamination across the US. This study addresses that need by analyzing temporal trends and acute and chronic benchmark exceedances for aquatic life and human health from 81 river sites sampled from 2013 to 2022 using an analytical method targeting 80 pesticides. The majority (79%) of single site and pesticide combinations had too few pesticide detections to estimate trends. When detections were more frequent, increasing trends in concentration were twice as common as decreasing trends. Increasing pesticide concentrations were common in primary drainages of the Mississippi River Basin. Aquatic life benchmarks were exceeded by 19 pesticides, and exceedances were geographically widespread, with both acute and chronic aquatic life benchmark exceedances at 62% of sites. The herbicides atrazine and metolachlor and the insecticide imidacloprid were identified as the greatest threats to surface water availability based on their trends and aquatic life benchmark exceedances. These findings demonstrate the need for continued monitoring and trend analysis, driver investigation, and management strategies to protect freshwater resources.

conterminous United States↗

Predicted climate-induced reductions in scavenging in eastern North America

Scavenging is an important function within ecosystems where scavengers remove organic matter, reduce disease, stabilize food webs, and generally make ecosystems more resilient to environmental changes. Global change (i.e., changing climate and increasing human impact) is currently influencing scavenger communities. Thus, understanding what promotes species richness in scavenger communities can help prioritize management actions. Using a long-term dataset from camera traps deployed with animal carcasses as bait along a 1881 km latitudinal gradient in the Appalachian Mountains of eastern USA, we investigated the relative impact of climate and humans on the species richness and diversity of vertebrate scavengers. Our most supported models for both mammalian and avian scavengers included climatic, but not human, variables. The richness of mammalian and avian scavengers detected was highest during relatively warm (5–10°C) and dry (100–150 mm precipitation) winters, when food was likely limited and both reliance on and detection of carrion was high. The diversity of mammalian and avian scavengers detected was highest under drier conditions. We then used these results to project the future species richness of scavengers that would be detected within our sampling area and under the climate scenario of 2070 (emissions level RCP8.5). Our predictions suggest up to 80% and 67% reductions, respectively, in the richness of avian and mammalian scavengers that would be detected at baited sites. Climate-induced shifts in behavior (i.e., reduction in scavenging, even if present) at this scale could have cascading implications for ecosystem function, resilience, and human health. Further, our study highlights the importance of conducting studies of scavenger community dynamics within ecosystems across wide spatial gradients within temperate environments. More broadly, these findings build upon our understanding of the impacts of climate-induced adjustments in behavior that can likely have negative impacts on systems at a large scale.

Appalachian Mountains↗

Factors affecting water quality in selected carbonate aquifers in the United States, 1993-2005

Carbonate aquifers are an important source of water in the United States; however, these aquifers can be particularly susceptible to contamination from the land surface. The U.S. Geological Survey National Water-Quality Assessment (NAWQA) Program collected samples from wells and springs in 12 carbonate aquifers across the country during 1993–2005; water-quality results for 1,042 samples were available to assess the factors affecting ground-water quality. These aquifers represent a wide range of climate, land-use types, degrees of confinement, and other characteristics that were compared and evaluated to assess the effect of those factors on water quality. Differences and similarities among the aquifers were also identified. Samples were analyzed for major ions, radon, nutrients, 47 pesticides, and 54 volatile organic compounds (VOCs). Geochemical analysis helped to identify dominant processes that may contribute to the differences in aquifer susceptibility to anthropogenic contamination. Differences in concentrations of dissolved oxygen and dissolved organic carbon and in ground-water age were directly related to the occurrence of anthropogenic contaminants. Other geochemical indicators, such as mineral saturation indexes and calcium-magnesium molar ratio, were used to infer residence time, an indirect indicator of potential for anthropogenic contamination. Radon exceeded the U.S. Environmental Protection Agency proposed Maximum Contaminant Level (MCL) of 300 picocuries per liter in 423 of 735 wells sampled, of which 309 were drinking-water wells. In general, land use, oxidation-reduction (redox) status, and degree of aquifer confinement were the most important factors affecting the occurrence of anthropogenic contaminants. Although none of these factors individually accounts for all the variation in water quality among the aquifers, a combination of these characteristics accounts for the majority of the variation. Unconfined carbonate aquifers that had high percentages of urban or agricultural land, or a combination of both, had higher concentrations and higher frequency of detections for most of the anthropogenic contaminants than areas with other combinations of land use and degree of aquifer confinement. Redox status is an indicator of more recently recharged water and affects the fate of some contaminants. Median concentrations of nitrate were highest in the Valley and Ridge and Piedmont aquifers and lowest in the Biscayne and Silurian-Devonian/Upper carbonate aquifers. Nitrate concentrations were significantly higher in unconfined aquifers than in confined aquifers and semiconfined/mixed confined aquifers (wells in aquifers with breached confining layers or wells open to both a confined and an unconfined aquifer). Water recharged after 1953 had significantly higher concentrations of nitrate than water recharged prior to 1953. Redox status was also a key factor affecting nitrate concentrations; in recently recharged waters, samples in oxic waters had significantly higher concentrations of nitrate than anoxic waters, regardless of land use in the area around the well. Samples from 54 wells (5 percent) exceeded the U.S. Environmental Protection Agency MCL of 10 mg/L for nitrate in drinking water. Most of the samples exceeding the drinking-water standard (52 samples, or 5 percent) were in domestic supply wells in agricultural areas. The Piedmont and Valley and Ridge aquifers had the largest number of samples (45) exceeding the MCL; in the remaining aquifers only 9 samples had concentrations of nitrate that exceeded the MCL (about 1 percent). None of the water recharged prior to 1953 and only a single sample from a confined aquifer had nitrate concentrations that exceeded 10 mg/L as N. Wells were sampled for a minimum of 47 pesticides. Detection frequencies and comparisons varied depending on the assessment level used. At least 1 of the 47 pesticides was detected at 510 (50 percent) of the 1,027 sites where pesticide data were available using the ‘all detections’ assessment level—that is, including any quantified detection as well as any estimated values where the compound was definitively detected. Multiple pesticides were frequently detected in a sample of water from a site; 34 percent of the samples had two to five pesticides detected in the same sample, and 4 percent of the samples had six or more pesticides detected. Dieldrin was detected at 20 sites, 9 of which were from either domestic or public supply wells, at a concentration above the Health-Based Screening Level (HBSL) of 0.002 µg/L. Diazinon was detected at a concentration greater than the HBSL of 1 µg/L at a single site, which was also a domestic supply well. These are the only samples where a pesticide exceeded a human-health benchmark. The most frequently occurring pesticide compounds were four herbicides—atrazine, simazine, metolachlor, and prometon—and deethylatrazine, a degradate of atrazine. These pesticides typically were detected at concentrations that were less than 10 percent of a human-health benchmark. Of the four frequently occurring pesticides, only samples for atrazine (3 percent) and simazine (0.1 percent) had concentrations that exceeded 10 percent of the human-health benchmark; most of these cases were in agricultural areas. It is important to note, however, that the most frequently occurring pesticide degradate compound—deethylatrazine—has no human-health benchmark. Using a common assessment level of 0.01 µg/L, four of the aquifers—Biscayne, Mississippian, Piedmont, and Valley and Ridge—had at least one of these five compounds detected in more than 30 percent of the wells sampled. These four aquifers, along with the Ordovician, Ozark Plateaus, and Prairie du Chien aquifers were the aquifers or aquifer systems that had concentrations of pesticides that exceeded 10 percent of a human-health benchmark. Water recharged after 1953 had a significantly higher percentage of detections of pesticides than water recharged before 1953, and water from unconfined aquifers had a significantly higher percentage of detections of pesticides than water from confined or semiconfined/mixed confined aquifers. Water from sites in unconfined aquifers, where land use was agricultural or urban, accounted for the vast majority of detections of pesticides. Dissolved oxygen concentration was positively related to pesticide occurrence, which likely reflects the positive association between dissolved oxygen concentration and recently recharged water. Water samples were collected for analysis of VOCs at 793 sites—154 samples were analyzed for 54 VOCs from 1993 through 1995 and 639 samples were analyzed for 86 VOCs from 1996 through 2005. Twenty percent of samples contained one or more VOCs at concentrations greater than or equal to 0.2 µg/L (159 of 793 samples). The aquifers with the highest percentage of samples containing one or more VOCs were the Castle Hayne (about 41 percent of samples) and Biscayne aquifers (34 percent). The most frequently detected VOCs were chloroform, tetrahydrofuran, tetrachloroethene (PCE), toluene, acetone, ethylmethylketone, methyl tert-butyl ether (MTBE), and trichloroethene (TCE). Low-level concentrations of VOCs occurred in a much larger percentage of a subset of the data (the 639 samples analyzed using a low-level analytical method). In these samples, 69 percent of the 639 samples contained 1 or more VOCs, indicating the vulnerability of the carbonate aquifers to low-level VOC contamination. Four VOCs were detected at concentrations exceeding their respective MCLs in five samples, all of which were from drinking-water wells. Vinyl chloride concentrations exceeded the MCL of 2 µg/L in two samples from urban areas in the unconfined Biscayne aquifer. PCE, TCE, and 1,2-dichloropropane each had one sample with a concentration greater than their MCLs of 5 µg/L; these samples were from agricultural and urban areas in the unconfined Mississippian aquifer. Water quality in the 12 carbonate aquifers was highly variable. Most of the samples met drinking-water standards. The occurrence of anthropogenic contaminants was related to contaminant sources but also was affected by degree of aquifer confinement, ground-water age, and redox status. Areas with higher amounts of agricultural or urban land in unconfined aquifers were the most likely to have elevated concentrations of anthropogenic contaminants.

Scientific Investigations Report↗

Metrics for assessing the quality of groundwater used for public supply, CA, USA: Equivalent-population and area

Data from 11 000 public supply wells in 87 study areas were used to assess the quality of nearly all of the groundwater used for public supply in California. Two metrics were developed for quantifying groundwater quality: area with high concentrations (km2 or proportion) and equivalent-population relying upon groundwater with high concentrations (number of people or proportion). Concentrations are considered high if they are above a human-health benchmark. When expressed as proportions, the metrics are area-weighted and population-weighted detection frequencies. On a statewide-scale, about 20% of the groundwater used for public supply has high concentrations for one or more constituents (23% by area and 18% by equivalent-population). On the basis of both area and equivalent-population, trace elements are more prevalent at high concentrations than either nitrate or organic compounds at the statewide-scale, in eight of nine hydrogeologic provinces, and in about three-quarters of the study areas. At a statewide-scale, nitrate is more prevalent than organic compounds based on area, but not on the basis of equivalent-population. The approach developed for this paper, unlike many studies, recognizes the importance of appropriately weighting information when changing scales, and is broadly applicable to other areas.

California↗

The potential influence of changing climate on the persistence of salmonids of the inland west

The Earth's climate warmed steadily during the 20th century, and mean annual air temperatures are estimated to have increased by 0.6°C (Intergovernmental Panel on Climate Change, 2007). Although many cycles of warming and cooling have occurred in the past, the most recent warming period is unique in its rate and magnitude of change (Siegenthaler and others, 2005) and in its association with anthropogenic emissions of greenhouse gases (Intergovernmental Panel on Climate Change , 2007). The climate in the western United States warmed in concert with the global trend but at an accelerated rate (+0.8°C during the 20th century; Saunders and others, 2008). The region could also prove especially sensitive to future changes because the relatively small human population is growing rapidly, as are demands on limited water supplies. Regional hydrological patterns are dominated by seasonal snow accumulation at upper elevations. Most of the region is relatively dry, and both terrestrial and aquatic ecosystems are strongly constrained b y water availability (Barnett and others, 2008; Brown and others, 2008). Stream environments are dynamic and climatically extreme, and salmonid fishes are the dominant elements of the native biodiversity (McPhail and Lindsey, 1986; Waples and others, 2008). Salmonids have broad economic and ecologic importance, but a century of intensive water resource development, nonnative fish stocking, and land use has significantly reduced many populations and several taxa are now protected under the Endangered Species Act (Thurow and others, 1997; Trotter, 2008). Because salmonids require relatively pristine, cold water environments and are often isolated in headwater habitats, members of this group may be especially vulnerable to the effects of a warming climate (Keleher and Rahel, 1996; Rieman and others, 2007; Williams and others, 2009). Warming during the 20th century drove a series of environmental trends that have profound implications for many aspects of salmonid habitat, including disturbance regimes such as wildfire, and unfavorable changes to thermal and hydrologic properties of aquatic systems. Warmer air temperatures have been associated with decreased winter snow accumulations, have accelerated snowmelt, and have advanced the timing of peak runoff by several days to weeks across most of western North America (Stewart and others, 2005; Barnett and others, 2008). Less snow and earlier runoff decrease aquifer recharge, make less water available for groundwater inputs to streams, and are contributing to widespread decreases in summer low flows (Stewart and others, 2005; Rood and others, 2008; Luce and Holden 2009). Interannual variability in stream flow is increasing, as is the persistence of multi-year extreme conditions (McCabe and others, 2004; Pagano and Garen 2005). In many areas of western North America, flood risks have increased in association with warmer temperatures during the 20th century (Hamlet and Lettenmaier, 2005). Streams where midwinter temperatures are near freezing have proven especially sensitive to increased flooding because of associated transitional hydrological patterns (mixtures of rainfall and snowmelt) and propensity for occasional rain-on-snow events to rapidly melt winter snowpack and generate large floods (Hamlet and Lettenmaier, 2005). Stream temperatures in many areas are increasing (Peterson and Kitchell, 2001; Morrison and others, 2002; Bartholow, 2005; Kaushal and others, 2010), due to both air temperature increases and reduced summer flows that make streams more sensitive to warmer air temperatures (Isaak and others, 2010). In recent decades, wildfires have become more common across much of the western United States during periods of more frequent droughts (Westerling and others, 2006; Hoerling and Eischeid, 2007), and local stream temperature can increase in postfire environments (Gresswell, 1999; Dunham and others, 2007). Fire-related temperature increase within streams is commonly a transient phenomenon, lasting only until riparian vegetation has recovered (Gresswell, 1999); however, ongoing climate change could preclude recovery to higher stature, prefire vegetation types in some areas (McKenzie and others, 2004; van Mantgem and Stephenson, 2007), resulting in a loss of critical riparian shading. Additionally, when wildfires occur in steep mountain topographies, the vegetation that stabilize s soils on hillslopes is often killed and landslides become more prevalent (Gresswell, 1999). Landslides int o stream channels form debris flows composed of sediment slurries and dead trees that can scour channels to bedrock and further exacerbate stream heating, delay recovery of riparian areas, or extirpate fish populations (Gresswell, 1999; May and Gresswell, 2003; Dunham and others, 2007). Changes in stream environments will shift habitat distributions, sometimes unpredictably, in both time and space for many salmonid fishes. Water temperature fundamentally influences aquatic ecosystem health because distribution, reproduction, fitness, and survival of ectothermic organisms are inextricably linked to the thermal regime of the environment. Historically, research has focused on defining lethal thermal limits of salmonids (Eaton and others, 1995; Selong and others, 2001; Todd and others, 2008); however, water temperature is known to be important in biological processes at a variety of spatial scales and levels of biological organization (Rahel and Olden, 2008; McCullough and others, 2009). For instance, trout are affected directly by water temperature through feeding, metabolism, and growth rates, and indirectly by factors such as prey availability and species interactions (Wehrly and others, 2007; Rahel and Olden, 2008). Where cold water temperatures currently limit habitat suitability and distributions of some species (for example, at the highest and most northerly distributional extents; Nakano and others, 1996; Coleman and Fausch, 2007), a warming climate may gradually increase the quality and extent of suitable habitat. Over time, previously constrained populations are expected to expand into these new habitats and increase in number. Some evidence suggests this may already be happening in Alaska, where streams in recently deglaciated areas are being colonized by emigrants from nearby salmon and char populations (Milner and others, 2000). Unfortunately, many of the sensitive salmonid species that are often the focus of western managers are unlikely to benefit from future water temperature increases. Warmer stream temperatures will facilitate invasion by nonnative species that are broadly established in downstream areas into upstream areas where they will compete with native species (Rieman and others, 2006; Rahel and Olden, 2008; Fausch and others, 2009). In other cases, warmer stream temperatures will render thermally suitable habitats unsuitable in downstream areas and effect net losses of habitat because upstream distributions are often constrained by streams that are too small or steep (Hari and others, 2006; Isaak and others, 2010). Both scenarios are realistic for fish species like bull trout ( Salvelinus confluentus ) (Rieman and others, 2006; Rieman and others, 2007), the various subspecies of cutthroat trout ( Oncorhynchus clarkii ) (Williams and others, 2009), Gila trout ( Oncorhynchus gilae gilae ) (Kennedy and others, 2008), and Apache trout ( Oncorhynchus gilae apache ) (Rinne and Minckley, 1985; Carmichael and others, 1993). As native species are increasingly confined to smaller and more isolated habitats by a gradually warming climate, the effects of wildfires (whether related to lethal changes in water quality during a fire, channel debris flows, or chronic postfire warming ) could have greater proportional effects on remaining habitats (for example, Brown and others, 2001; Rieman and others, 2007). If these changes were accompanied by additional hydrologic alterations associated with changes to the magnitude, frequency, duration, timing, and rate of change of discharge patterns (Jager and others, 1999; Henderson and others, 2000), populations may begin to lose some of their historic resilience and become ever more susceptible to local extirpations. As dramatic and extensive as climatic and environmental trends are for salmonid habitats, global climate models (GCMs) project that many of these trends will continue and even accelerate until at least the middle of the 21st century (Intergovernmental Panel on Climate Change, 2007). Current projections suggest mean annual air temperatures will increase by an additional 1–3°C, and early indications are that climate trajectory is at the higher end of this range (Pittock, 2006; Raupach and others, 2007). Although predicted changes vary considerably, even the most conservative estimates suggest a warming rate that will be twice that observed during the 20th century. Projections for the midcentury are most certainly due to the effects of greenhouse gases already emitted or predicted in the short term, uncertainties of the effects of longer-term greenhouse gas emissions, short-term climate cycles, and process errors associated with climate models (Cox and Stephenson, 2007). Projections of changes in total precipitation are less certain than those for air temperatures, but most GCMs project relatively small changes in the Northwest, with the exception of slightly drier summer periods (Mote and others, 2008; Karl and others, 2009). In the Southwest, however, significant decreases (such as 15–30 percent ) are projected during most periods of the year, and this area is one of the few for which Intergovernmental Panel on Climate Change (2007) precipitation projections have a high level of certainty (Hoerling and Eischeid, 2007; Karl and others, 2009). Clearly, managers of native salmonids in the wester n United States should consider adjusting management strategies to accommodate a warmer and possibly drier future (Williams and others, 2009). Tools are needed to forecast where important changes may occur and how conservation efforts should be prioritized. In this Open-File Report, we document our initial efforts in this regard for 10 species and subspecies of inland trout and Montana Arctic grayling ( Thymallus arcticus ) across the western United States.

Arizona, California, Colorado, Idaho, Montana, Nev↗

Mercury burdens in Chinese mitten crabs (Eriocheir sinensis) in three tributaries of southern San Francisco Bay, California, USA

Chinese mitten crabs (Eriocheir sinensis), endemic to Asia, were first reported in the San Francisco Bay in 1992. They are now established in nearly all San Francisco Bay tributaries. These crabs accumulate more metals, such as mercury, than crustaceans living in the water column. Because their predators include fish, birds, mammals and humans, their mercury burdens have an exceptional potential to impact the ecosystem and public health. We sought to elucidate the potential threat of mitten crab mercury burdens in three adjacent streams in southern San Francisco Bay, one of which is known to be contaminated with mercury. Mitten crabs had hepatopancreas concentrations of total mercury and methylmercury that did not differ among streams. The maximum burden we measured was below the action level of 1 ppm recommended by the USEPA. Hepatopancreas concentrations of methylmercury declined with increasing crab size, suggesting a mechanism for mercury excretion and that predators might reduce mercury exposure if they select larger crabs. Because mercury may be heterogeneously distributed among tissues, estimation of the impacts of crab mercury burdens on the environment requires more data on the feeding preferences of predators. Hepatopancreas concentrations of mercury decline with crab size, which may have important consequences for bio-magnification in food webs. ?? 2004 Elsevier Ltd. All rights reserved.

Environmental Pollution↗

A review on cylindrospermopsin: the global occurrence, detection, toxicity and degradation of a potent cyanotoxin

Cylindrospermopsin is an important cyanobacterial toxin found in water bodies worldwide. The ever-increasing and global occurrence of massive and prolonged blooms of cylindrospermopsin-producing cyanobacteria poses a potential threat to both human and ecosystem health. Its toxicity is associated with metabolic activation and may involve mechanisms that adversely affect a wide variety of targets in an organism. Cylindrospermopsin has been shown to be cytotoxic, dermatotoxic, genotoxic, hepatotoxic in vivo, developmentally toxic, and may be carcinogenic. Human exposure may occur through drinking water, during recreational activities and by consuming foods in which the toxin may have bioaccumulated. Drinking water shortages of sufficient quality coupled with growing human pressures and climate variability and change necessitate an integrated and sustainable water management program. This review presents an overview of the importance of cylindrospermopsin, its detection, toxicity, worldwide distribution, and lastly, its chemical and biological degradation and removal by natural processes and drinking water treatment processes.

Environmental Science: Processes and Impacts↗

Evaluation of daily stream temperature predictions (1979-2021) across the contiguous United States using a spatiotemporal aware machine learning algorithm

Stream temperature controls a variety of physical and biological processes that affect ecosystems, human health, and economic activities. We used 42 years (1979–2021) of data to predict daily summary statistics of stream temperature across >50,000 stream reaches in the contiguous United States using a recurrent graph convolution network. We comprehensively documented the performance – both across all reaches and by stream type (e.g., reservoir or groundwater influence) – as a baseline for future improvement. The model showed reach-level RMSE of <2 °C with 90 % prediction intervals that contain 90.7 % of observations. We also assessed how the model captured variability in ecologically relevant metrics (e.g., R 2 for annual 7-day maximum = 0.76; R 2 for days exceeding 25 °C = 0.75). This model does not outperform state-of-the-art machine learning efforts (e.g., RMSE ≤1.5 °C) due to a limited input set but does provide the most spatially complete modeling to date to support water availability assessments.

contiguous United States↗

Removal of inorganic mercury and methylmercury from surface waters following coagulation of dissolved organic matter with metal-based salts

The presence of inorganic mercury (IHg) and methylmercury (MeHg) in surface waters is a health concern worldwide. This study assessed the removal potential use of metal-based coagulants as a means to remove both dissolved IHg and MeHg from natural waters and provides information regarding the importance of Hg associations with the dissolved organic matter (DOM) fraction and metal hydroxides. Previous research indicated coagulants were not effective at removing Hg from solution; however these studies used high concentrations of Hg and did not reflect naturally occurring concentrations of Hg. In this study, water collected from an agricultural drain in the Sacramento-San Joaquin Delta was filtered to isolate the dissolved organic matter (DOM) fraction. The DOM was then treated with a range of coagulant doses to determine the efficacy of removing all forms of Hg from solution. Three industrial-grade coagulants were tested: ferric chloride, ferric sulfate, and polyaluminum chloride. Coagulation removed up to 85% of DOM from solution. In the absence of DOM, all three coagulants released IHg into solution, however in the presence of DOM the coagulants removed up to 97% of IHg and 80% of MeHg. Results suggest that the removal of Hg is mediated by DOM-coagulant interactions. There was a preferential association of IHg with the more aromatic, higher molecular weight fraction of DOM but no such relationship was found for MeHg. This study offers new fundamental insights regarding large-scale removal of Hg at environmentally relevant regarding large-scale removal of Hg at environmentally relevant concentrations.

Science of the Total Environment↗

Hydrological controls on methylmercury distribution and flux in a tidal marsh

The San Francisco Estuary, California, contains mercury (Hg) contamination originating from historical regional gold and Hg mining operations. We measured hydrological and geochemical variables in a tidal marsh of the Palo Alto Baylands Nature Preserve to determine the sources, location, and magnitude of hydrological fluxes of methylmercury (MeHg), a bioavailable Hg species of ecological and health concern. Based on measured concentrations and detailed finite-element simulation of coupled surface water and saturated-unsaturated groundwater flow, we found pore water MeHg was concentrated in unsaturated pockets that persisted over tidal cycles. These pockets, occurring over 16% of the marsh plain area, corresponded to the marsh root zone. Groundwater discharge (e.g., exfiltration) to the tidal channel represented a significant source of MeHg during low tide. We found that nonchannelized flow accounted for up to 20% of the MeHg flux to the estuary. The estimated net flux of filter-passing (0.45 μm) MeHg toward estuary was 10 ± 5 ng m –2 day –1 during a single 12-h tidal cycle, suggesting an annual MeHg load of 1.17 ± 0.58 kg when the estimated flux was applied to present tidal marshes and planned marsh restorations throughout the San Francisco Estuary.

Environmental Science & Technology↗

What goes up must come down: Integrating air and water quality monitoring for nutrients

Excess nitrogen and phosphorus (“nutrients”) loadings continue to affect ecosystem function and human health across the U.S. Our ability to connect atmospheric inputs of nutrients to aquatic end points remains limited due to uncoupled air and water quality monitoring. Where connections exist, the information provides insights about source apportionment, trends, risk to sensitive ecosystems, and efficacy of pollution reduction efforts. We examine several issues driving the need for better integrated monitoring, including: coastal eutrophication, urban hotspots of deposition, a shift from oxidized to reduced nitrogen deposition, and the disappearance of pristine lakes. Successful coordination requires consistent data reporting; collocating deposition and water quality monitoring; improving phosphorus deposition measurements; and filling coverage gaps in urban corridors, agricultural areas, undeveloped watersheds, and coastal zones.

Environmental Science and Technology↗

Joint spatial modeling bridges the gap between disparate disease surveillance and population monitoring efforts informing conservation of at-risk bat species

White-Nose Syndrome (WNS) is a wildlife disease that has decimated hibernating bats since its introduction in North America in 2006. As the disease spreads westward, assessing the potentially differential impact of the disease on western bat species is an urgent conservation need. The statistical challenge is that the disease surveillance and species response monitoring data are not co-located, available at different spatial resolutions, non-Gaussian, and subject to observation error requiring a novel extension to spatially misaligned regression models for analysis. Previous work motivated by epidemiology applications has proposed two-step approaches that overcome the spatial misalignment while intentionally preventing the human health outcome from informing estimation of exposure. In our application, the impacted animals contribute to spreading the fungus that causes WNS, motivating development of a joint framework that exploits the known biological relationship. We introduce a Bayesian, joint spatial modeling framework that provides inferences about the impact of WNS on measures of relative bat activity and accounts for the uncertainty in estimation of WNS presence at non-surveyed locations. Our simulations demonstrate that the joint model produced more precise estimates of disease occurrence and unbiased estimates of the association between disease presence and the count response relative to competing two-step approaches. Our statistical framework provides a solution that leverages disparate monitoring activities and informs species conservation across large landscapes. Stan code and documentation are provided to facilitate access and adaptation for other wildlife disease applications.

Journal of Agricultural, Biological and Environmen↗