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Factors affecting temporal variability of arsenic in groundwater used for drinking water supply in the United States

The occurrence of arsenic in groundwater is a recognized environmental hazard with worldwide importance and much effort has been focused on surveying and predicting where arsenic occurs. Temporal variability is one aspect of this environmental hazard that has until recently received less attention than other aspects. For this study, we analyzed 1245 wells with two samples per well. We suggest that temporal variability, often reported as affecting very few wells, is perhaps a larger issue than it appears and has been masked by datasets with large numbers of non-detect data. Although there was only a slight difference in arsenic concentration variability among samples from public and private wells (p = 0.0452), the range of variability was larger for public than for private wells. Further, we relate the variability we see to geochemical factors&mdash;primarily variability in redox&mdash;but also variability in pH and major-ion chemistry. We also show that in New England there is a weak but statistically significant indication that seasonality may have an effect on concentrations, whereby concentrations in the first two quarters of the year (January&ndash;June) are significantly lower than in the second two quarters (July&ndash;December) (p < 0.0001). In the Central Valley of California, though not statistically significant (p = 0.4169), arsenic concentration is lower in the first quarter of the year but increases in subsequent quarters. In both regions, these changes appear to follow groundwater levels. It is possible that this difference in arsenic concentrations is related to groundwater level changes, pumping stresses, evapotranspiration effects, or perhaps mixing of more oxidizing, lower pH recharge water in wetter months. Focusing on the understanding the geochemical conditions in aquifers where arsenic concentrations are concerns and causes of geochemical changes in the groundwater environment may lead to a better understanding of where and by how much arsenic will vary over time.

Science of the Total Environment↗

Environmental magnetic implications of greigite (Fe3S4) formation in a 3 m.y. lake sediment record from Butte Valley, northern California Andrew

Authigenic greigite (Fe 3 S 4 ) has been identified in several horizons of lake beds in a 102-m core from Butte Valley, northern California, using mineral magnetic methods and x-ray diffraction analysis. The presence of greigite has several implications for the paleoenvironmental record from Butte Valley. First, its occurrence in 2.5–3.0 Ma strata confirms that greigite can persist in the geological record for long periods of time. Second, the detrital mineral magnetic record may be partially obscured by the presence of authigenic greigite and care must be taken in interpreting magnetic variations in the greigite-bearing zones as paleoclimate proxies. Third, differences in the timing of remanence acquisition for authigenic and detrital phases may compromise studies of high-frequency geomagnetic field variations. Fourth, greigite may also be significant as a paleoenvironmental indicator of lake and sediment chemistry. The magnetic detection of greigite may therefore provide important information about paleolimnological conditions.

Geophysical Research Letters↗

Response curves for phosphorus plume lengths from reactive-solute-transport simulations of onland disposal of wastewater in noncarbonate sand and gravel aquifers

Surface-water resources in Massachusetts often are affected by eutrophication, excessive plant growth, which has resulted in impaired use for a majority of the freshwater ponds and lakes and a substantial number of river-miles in the State. Because supply of phosphorus usually is limiting to plant growth in freshwater systems, control of phosphorus input to surface waters is critical to solving the impairment problem. Wastewater is a substantial source of phosphorus for surface water, and removal of phosphorus before disposal may be necessary. Wastewater disposed onland by infiltration loses phosphorus from the dissolved phase during transport through the subsurface and may be an effective disposal method; quantification of the phosphorus loss can be simulated to determine disposal feasibility. In 2003, the U.S. Geological Survey, in cooperation with the Massachusetts Department of Environmental Protection, initiated a project to simulate distance of phosphorus transport in the subsurface for plausible conditions of onland wastewater disposal and subsurface properties. A coupled one-dimensional unsaturated-zone and three-dimensional saturated-zone reactive-solute-transport model (PHAST) was used to simulate lengths of phosphorus plumes. Knowledge of phosphorus plume length could facilitate estimates of setback distances for wastewater-infiltration sites from surface water that would be sufficient to protect the surface water from eutrophication caused by phosphorus transport through the subsurface and ultimate discharge to surface water. The reactive-solute-transport model PHAST was used to simulate ground-water flow, solute transport, equilibrium chemistry for dissolved and sorbed species, and kinetic regulation of organic carbon decomposition and phosphate mineral formation. The phosphorus plume length was defined for the simulations as the maximum extent of the contour for the 0.015 milligram-per-liter concentration of dissolved phosphorus downgradient from the infiltration bed after disposal cessation. Duration of disposal before cessation was assumed to be 50 years into an infiltration bed of 20,000 square feet at the rate of 3 gallons per square foot per day. Time for the maximum extent of the phosphorus plume to develop is on the order of 100 years after disposal cessation. Simulations indicated that phosphorus transport beyond the extent of the 0.015 milligram-per-liter concentration contour was never more than 0.18 kilogram per year, an amount that would likely not alter the ecology of most surface water. Simulations of phosphorus plume lengths were summarized in a series of response curves. Simulated plume lengths ranged from 200 feet for low phosphorus-concentration effluents (0.25 milligram per liter) and thick (50 feet) unsaturated zones to 3,400 feet for high phosphorus-concentration effluents (14 milligrams per liter) discharged directly into the aquifer (unsaturated-zone thickness of 0 feet). Plume length was nearly independent of unsaturated-zone thickness at phosphorus concentrations in the wastewater that were less than 2 milligrams per liter because little or no phosphorus mineral formed at low phosphorus concentrations. For effluents of high phosphorus concentration, plume length varied from 3,400 feet for unsaturated-zone thickness of 0 to 2,550 feet for unsaturated-zone thickness of 50 feet. Model treatments of flow and equilibrium-controlled chemistry likely were more accurate than rates of kinetically controlled reactions, notably precipitation of iron-phosphate minerals; the kinetics of such reactions are less well known and thus less well defined in the model. Sensitivity analysis indicated that many chemical and physical aquifer properties, such as hydraulic gradient and model width, did not affect the simulated plume length appreciably, but duration of discharge, size of infiltration bed, amount of dispersion, and number of sorption sites on the aquifer sediments did affect plume length appreciably. Because simulation of plume length in carbonate-mineral sediments indicated that the plume would be substantially longer than in noncarbonate-mineral sediments, the application of the response curves in locations with carbonate-mineral sediments would be inappropriate. The effect of carbonate minerals in sediments is to increase pH, which causes decreased sorption of phosphorus on aquifer sediments. Phosphorus removal from solution by precipitation onto aquifer sediments is more efficient at high concentrations of disposed phosphorus than at low concentrations. At very low phosphorus concentrations, the solubility product of phosphorus minerals is not exceeded and no phosphorus mineral forms. An important consequence is that removal of dissolved phosphorus from the plume by processes in the subsurface is decreased the more that removal efforts are applied in treatment before wastewater is disposed. Model simulations indicate that removal of phosphorus from wastewater disposed through septic systems would have the advantage of efficient phosphorus removal in the subsurface because phosphorus concentrations are high in septic-system effluent. Short plume lengths result from wastewater disposal through septic systems because of the efficient phosphorus removal and because of the low volume of wastewater involved. The simulation results for small-volume systems are not quantitative, however, because wastewater-infiltration rates are much lower than those of the higher-volume system that was used to calibrate the model and to create the plume-length response curves. The response curves for phosphorus plume lengths, as defined by the maximum extent of the 0.015 milligram-per-liter concentration contour, is clearly defined in the model simulations, although the relation between simulated plume length and protective setback distance is subject to interpretation. Phosphorus does move beyond the point at which the simulated 0.015 milligram-per-liter concentration contour has stopped, so that a determination of protective setback distance must include a consideration of whether that continued flux, or some other flux amount, is appropriate. Also, simulations indicate that phosphorus plumes do not reach their full extent until 50 to 200 years after disposal cessation, depending on concentration of phosphorus disposed. No phosphorus plume has been monitored for that long after cessation, so there is no way to verify the long-term simulation results.

Massachusetts↗

Effects of contaminants in dredge material from the Lower Savannah River

Contaminants entering aquatic systems from agricultural, industrial, and municipal activities are generally sequestered in bottom sediments. The environmental significance of contaminants associated with sediments dredged from Savannah Harbor, Georgia, USA, are unknown. To evaluate potential effects of contaminants in river sediments and sediments dredged and stored in upland disposal areas on fish and wildlife species, solid-phase sediment and sediment pore water from Front River, Back River, an unnamed Tidal Creek on Back River, and Middle River of the distributary system of the lower Savannah River were tested for toxicity using the freshwater amphipod Hyalella azteca . In addition, bioaccumulation of metals from sediments collected from two dredge-disposal areas was determined using the freshwater oligochaete Lumbriculus variegatus . Livers from green-winged teals ( Anas crecca ) and lesser yellowlegs ( Tringa flavipes ) foraging in the dredge-spoil areas and raccoons ( Procyon lotor ) from the dredge-disposal/river area and an upland site were collected for metal analyses. Survival of H. azteca was not reduced in solid-phase sediment exposures, but was reduced in pore water from several locations receiving drainage from dredge-disposal areas. Basic water chemistry (ammonia, alkalinity, salinity) was responsible for the reduced survival at several sites, but PAHs, metals, and other unidentified factors were responsible at other sites. Metal residues in sediments from the Tidal Creek and Middle River reflected drainage or seepage from adjacent dredge-disposal areas, which could potentially reduce habitat quality in these areas. Trace metals increased in L. variegatus exposed in the laboratory to dredge-disposal sediments; As, Cu, Hg, Se, and Zn bioaccumulated to concentrations higher than those in the sediments. Certain metals (Cd, Hg, Mo, Se) were higher in livers of birds and raccoons than those in dredge-spoil sediments suggesting bioavailability. Cadmium, Ct, Hg, Pb, and Se in livers from raccoons collected near the river and dredge-disposal areas were significantly higher than those of raccoons from the upland control site. Evidence of bioaccumulation from laboratory and field evaluations and concentrations in sediments from dredge-disposal areas and river channels demonstrated that some metals in the dredge-disposal areas are mobile and biologically available. Drainage from dredge-disposal areas may be impacting habitat quality in the river, and fish and wildlife that feed and nest in the disposal area pm the lower Savannah River may be at risk from metal contamination.

Georgia, South Carolina↗

Regional target loads of atmospheric nitrogen and sulfur deposition for the protection of stream and watershed soil resources of the Adirondack Mountains, USA

Acidic deposition contributes to a range of environmental impacts across forested landscapes, including acidification of soil and drainage water, toxic aluminum mobilization, depletion of available soil nutrient cations, and impacts to forest and aquatic species health and biodiversity. In response to decreasing levels of acidic deposition, soils and drainage waters in some regions of North America have become gradually less acidic. Thresholds of atmospheric deposition at which adverse ecological effects are manifested are called critical loads (CLs) and/or target loads (TLs). Target loads are developed based on approaches that account for spatial and temporal aspects of acidification and recovery. Exceedance represents the extent to which current or projected future levels of acidic deposition exceed the level expected to cause ecological harm. We report TLs of sulfur (S) and nitrogen (N) deposition and the potential for ecosystem recovery of watershed soils and streams in the Adirondack region of New York State, resources that have been less thoroughly investigated than lakes. Regional TLs were calculated by statistical extrapolation of hindcast and forecast simulations of 25 watersheds using the process-based model PnET-BGC coupled with empirical observations of stream hydrology and established sensitivity of sugar maple ( Acer saccharum ) to soil base saturation and brook trout ( Salvelinus fontinalis ) to stream acid neutralizing capacity (ANC). Historical impacts and the expected recovery timeline of regional soil and stream chemistry and fish community condition within the Adirondack Park were evaluated. Analysis suggests that many low-order Adirondack streams and associated watershed soils have low TLs (<40 meq/m 2 /yr of N+S deposition) to achieve specified benchmarks for recovery of soil base saturation or stream ANC. Acid-sensitive headwater and low-order streams and watershed soils in the region are expected to experience continued adverse effects from N and S deposition well into the future even under aggressive emissions reductions. Watershed soils and streams in the western Adirondack Park are particularly vulnerable to acidic deposition and currently in exceedance of TLs. The methods used for linking statistical and process-based models to consider chemical and biological response under varying flow conditions at the regional scale in this study can be applied to other areas of concern.

New York↗

Prioritizing US Geological Survey science on salinization and salinity in candidate and selected priority river basins

The US Geological Survey (USGS) is selecting and prioritizing basins, known as Integrated Water Science basins, for monitoring and intensive study. Previous efforts to aid in this selection process include a scientifically defensible and quantitative assessment of basins facing human-caused water resource challenges (Van Metre et al. in Environmental Monitoring and Assessment , 192(7), 458 2020). In the present work, we explore this ranking process based on water quality considerations, specifically salinity and salinization. We selected top candidate basins to study salinity and salinization issues in 18 hydrologic regions that include 163 candidate basins. Our prioritization is based on quantitative assessment of sources of salinity, drivers of change, and receptors that must respond to those sources and drivers. Source terms represented in the prioritization include geology, depth to brackish groundwater, stream conductivity, chloride in precipitation, urban and agricultural land use, application of road salt as a deicer, and irrigation. Drivers represented in prioritization include changes in chemical weathering as a result of changes in rainwater chemistry. Receptors include measures of water stress, measurements of stream ecological health, and socioeconomic factors. In addition, we present research activities for the USGS on salinity and salinization that can be pursued in these basins including assessment of sources, pathways, and loadings; predicting and understanding changes in sources, peaks, and trends; understanding the components of salinity and mobilization of contaminants; understanding the relationship between salinization and changing ecosystems; and developing knowledge on the causes and distribution of groundwater salinity, brackish water resources, and challenges related to desalination.

Enviornmental Monitoring and Assessment↗

Design and methods of the Southeast Stream Quality Assessment (SESQA), 2014

During 2014, the U.S. Geological Survey (USGS) National Water-Quality Assessment Program (NAWQA) assessed stream quality across the Piedmont and southern Appalachian Mountain regions of the southeastern United States. This Southeast Stream Quality Assessment (SESQA) simultaneously characterized watershed and stream-reach water-quality stressors along with instream biological conditions, in order to better understand regional stressor-effects relations. The goal of SESQA is to provide communities and policymakers with information about those human and environmental factors that have the greatest impact on stream quality across the region. The SESQA design focused on hydrologic alteration and urbanization because of their importance as ecological stressors of particular concern to Southeast region resource managers. Streamflow and land-use data were used to identify and select sites representing gradients in urbanization and streamflow alteration across the region. One hundred fifteen sites were selected and sampled for as many as 10 weeks during April, May, and June 2014 for contaminants, nutrients, and sediment. This water-quality &ldquo;index&rdquo; period culminated with an ecological survey of habitat, periphyton, benthic macroinvertebrates, and fish at all sites. Sediment was collected during the ecological survey for analysis of sediment chemistry and toxicity testing. Of the 115 sites, 59 were on streams in watersheds with varying degrees of urban land use, 5 were on streams with multiple confined animal feeding operations, and 13 were reference sites with little or no development in their watersheds. The remaining 38 &ldquo;hydro&rdquo; sites were on streams in watersheds with relatively little agricultural or urban development but with hydrologic alteration, such as a dam or reservoir. This report provides a detailed description of the SESQA study components, including surveys of ecological conditions, routine water sampling, deployment of passive polar organic compound integrative samplers for pesticides and contaminants of emerging concern, and synoptic sediment sampling and toxicity testing at all urban, confined animal feeding operation, and reference sites. Continuous water-quality monitoring and daily pesticide sampling efforts conducted at a subset of urban sites are also described.

Alabama, Georgia, North Carolina, South Carolina, ↗

Trend analysis of weekly acid rain data, 1978-83

There are 19 stations in the National Atmospheric Deposition Program which operated over the period 1978-83 and were subsequently incorporated into the National Trends Network in 1983. The precipitation chemistry data for these stations for this period were analyzed for trend, spatial correlation, seasonality, and relationship to precipitation volume. The intent of the analysis was to provide insights on the sources of variation in precipitation chemistry and to attempt to ascertain what statistical procedures may be most useful for ongoing analysis of the National Trends Network data. The Seasonal Kendall test was used for detection of trends in raw concentrations of dissolved constituents, pH and specific conductance, and residuals of these parameters from regression analysis. Forty-one percent of the trends detected in the raw concentrations were downtrends, 4 percent were uptrends, and 55 percent showed no trends at a = 0.2. At a more restrictive significance level of a = 0.05, 24 percent of the trends detected were downtrends, 2 percent were uptrends, and 74 percent showed no trends. The two constituents of greatest interest in terms of human generated emissions and environmental effects, sulfate and nitrate, showed only downtrends, and sulfate showed the largest decreases in concentration per year of all the ions tested.

Water-Resources Investigations Report↗

Synoptic sampling and principal components analysis to identify sources of water and metals to an acid mine drainage stream

Combining the synoptic mass balance approach with principal components analysis (PCA) can be an effective method for discretising the chemistry of inflows and source areas in watersheds where contamination is diffuse in nature and/or complicated by groundwater interactions. This paper presents a field-scale study in which synoptic sampling and PCA are employed in a mineralized watershed (Lion Creek, Colorado, USA) under low flow conditions to (i) quantify the impacts of mining activity on stream water quality; (ii) quantify the spatial pattern of constituent loading; and (iii) identify inflow sources most responsible for observed changes in stream chemistry and constituent loading. Several of the constituents investigated (Al, Cd, Cu, Fe, Mn, Zn) fail to meet chronic aquatic life standards along most of the study reach. The spatial pattern of constituent loading suggests four primary sources of contamination under low flow conditions. Three of these sources are associated with acidic (pH <3.1) seeps that enter along the left bank of Lion Creek. Investigation of inflow water (trace metal and major ion) chemistry using PCA suggests a hydraulic connection between many of the left bank inflows and mine water in the Minnesota Mine shaft located to the north-east of the river channel. In addition, water chemistry data during a rainfall-runoff event suggests the spatial pattern of constituent loading may be modified during rainfall due to dissolution of efflorescent salts or erosion of streamside tailings. These data point to the complexity of contaminant mobilisation processes and constituent loading in mining-affected watersheds but the combined synoptic sampling and PCA approach enables a conceptual model of contaminant dynamics to be developed to inform remediation.

Environmental Science and Pollution Research↗

Catalytic determination of vanadium in water

A kinetic determination of V(V) as a catalyst was spectrophotometrically performed by using the indicator reaction of Gallamine blue (GB + ) and bromate at pH 2.0. The reaction was followed by measuring absorbance change for a fixed-time of 3 min at 537 nm. The variables such as reagent concentration, pH, buffer concentration, ionic strength and temperature were optimized to improve the selectivity and sensitivity. Under the optimized conditions, the determination of V(V) was performed in the range 1–100 μg L −1 with limits of detection and quantification of 0.31 and 0.94 μg L −1 . The developed kinetic method is sufficiently sensitive, selective and simple. It was successfully applied to the speciative determination of total V and inorganic dissolved vanadium species, V(V) and V(IV) in environmental water samples. The oxidizing property of permanganate is used to differentiate between V(IV) and V(V) species. The V(IV) content was found by subtracting the V(V) content from those of total V. The recovery is above 95% for V(V) spiked samples. Additionally, the accuracy was validated by analysis of a certified water sample, CRM TMDA-53.3, and the results were in good agreement with the certified value.

Analytical Chemistry↗

Spatial and temporal changes in microbial community structure associated with recharge-influenced chemical gradients in a contaminated aquifer

In a contaminated water‐table aquifer, we related microbial community structure on aquifer sediments to gradients in 24 geochemical and contaminant variables at five depths, under three recharge conditions. Community amplified ribsosomal DNA restriction analysis (ARDRA) using universal 16S rDNA primers and denaturing gradient gel electrophoresis (DGGE) using bacterial 16S rDNA primers indicated: (i) communities in the anoxic, contaminated central zone were similar regardless of recharge; (ii) after recharge, communities at greatest depth were similar to those in uncontaminated zones; and (iii) after extended lack of recharge, communities at upper and lower aquifer margins differed from communities at the same depths on other dates. General aquifer geochemistry was as important as contaminant or terminal electron accepting process (TEAP) chemistry in discriminant analysis of community groups. The Shannon index of diversity ( H ) and the evenness index ( E ), based on DGGE operational taxonomic units (OTUs), were statistically different across community groups and aquifer depths. Archaea or sulphate‐reducing bacteria 16S rRNA abundance was not clearly correlated with TEAP chemistry indicative of methanogenesis or sulphate reduction. Eukarya rRNA abundance varied by depth and date from 0 to 13% of the microbial community. This contaminated aquifer is a dynamic ecosystem, with complex interactions between physical, chemical and biotic components, which should be considered in the interpretation of aquifer geochemistry and in the development of conceptual or predictive models for natural attenuation or remediation.

Environmental Microbiology↗

Causes of acidification of four streams on Laurel Hilld in southwestern Pennsylvania

Atmospheric deposition, soils developed from bedrock, a natural bog, gas wells, and a ski area were all investigated as possible sources of water quality degradation for four streams on Laurel Hill in southwestern Pennsylvania where fish kills have been reported since 1960. An intensive study of the chemistry of atmospheric deposition, soil leachate, and stream water and fish populations was conducted on these basins during 1980&ndash;1981 with emphasis on dormant season periods with runoff from snowmelt and rain. Although bedrock geology was found to control the natural buffering capacity of these streams, only acid precipitation could be linked to sharp drops in pH and increases in total Al concentrations observed during stormflows in the poorly buffered streams. Three poorly buffered streams exhibited drops to pH 4.4 to 4.5 and increases in total Al concentrations up to 1.5 mg/L during observed peak flows. Mineral soil leachate from the three major soil series on the basins during this time exhibited a low pH of 4.3 and mean total Al concentrations of 3.6 mg/L, indicating stream response during storms was closely linked to chemistry of soil leachate. Poorly buffered streams did not support reproducing populations of trout ( Salmonidae sp.) or other fishes. In contrast, one well-buffered stream (20 mg/L CaCO 3 ) exhibited drops to pH 5.5 during peak flow and supported reproducing trout and sculpin ( Cottus bairdi ) populations. The acidification of the four streams studied was attributed to atmospheric deposition.

Journal of Environmental Quality↗

Decomposition of soil organic matter from boreal black spruce forest: Environmental and chemical controls

Black spruce forests are a dominant covertype in the boreal forest region, and they inhabit landscapes that span a wide range of hydrologic and thermal conditions. These forests often have large stores of soil organic carbon. Recent increases in temperature at northern latitudes may be stimulating decomposition rates of this soil carbon. It is unclear, however, how changes in environmental conditions influence decomposition in these systems, and if substrate controls of decomposition vary with hydrologic and thermal regime. We addressed these issues by investigating the effects of temperature, moisture, and organic matter chemical characteristics on decomposition of fibric soil horizons from three black spruce forest sites. The sites varied in drainage and permafrost, and included a “Well Drained” site where permafrost was absent, and “Moderately well Drained” and “Poorly Drained” sites where permafrost was present at about 0.5 m depth. Samples collected from each site were incubated at five different moisture contents (2, 25, 50, 75, and 100% saturation) and two different temperatures (10°C and 20°C) in a full factorial design for two months. Organic matter chemistry was analyzed using pyrolysis gas chromatography-mass spectrometry prior to incubation, and after incubation on soils held at 20°C, 50% saturation. Mean cumulative mineralization, normalized to initial carbon content, ranged from 0.2% to 4.7%, and was dependent on temperature, moisture, and site. The effect of temperature on mineralization was significantly influenced by moisture content, as mineralization was greatest at 20°C and 50–75% saturation. While the relative effects of temperature and moisture were similar for all soils, mineralization rates were significantly greater for samples from the “Well Drained” site compared to the other sites. Variations in the relative abundances of polysaccharide-derivatives and compounds of undetermined source (such as toluene, phenol, 4-methyl phenol, and several unidentifiable compounds) could account for approximately 44% of the variation in mineralization across all sites under ideal temperature and moisture conditions. Based on our results, changes in temperature and moisture likely have similar, additive effects on in situ soil organic matter (SOM) decomposition across a wide range of black spruce forest systems, while variations in SOM chemistry can lead to significant differences in decomposition rates within and among forest sites.

Biogeochemistry↗

Irrigation-induced contamination of water, sediment, and biota in the western United States-synthesis of data from the National Irrigation Water Quality Program

In October 1985 the U.S. Department of the Interior (DOI), through the National Irrigation Water Quality Program (NIWQP), began a series of field investigations at 26 areas in the Western United States to determine whether irrigation drainage has had harmful effects on fish, wildlife, and humans or has reduced beneficial uses of water. In 1992 NIWQP initiated the Data Synthesis Project to evaluate data collected during the field investigations. Geologic, climatologic, and hydrologic data were evaluated and water, sediment, and biota from the 26 areas were analyzed to identify commonalities and dominant factors that result in irrigation-induced contamination of water and biota. Data collected for the 26 area investigations have been compiled and merged into a common data base. The structure of the data base is designed to enable assessment of relations between contaminant concentrations in water, sediment, and biota. The data base is available to the scientific community through the World Wide Web at URL http://www.usbr.gov/niwqp . Analysis of the data base for the Data Synthesis included use of summary statistics, factor analysis, and logistic regression. A Geographic Information System was used to store and analyze spatially oriented digital data such as land use, geology and evaporation rates. In the U.S. Department of the Interior (DOI) study areas, samples of water, bottom sediment, and biota were collected for trace-element and pesticide analysis. Contaminants most commonly associated with irrigation drainage were identified by comparing concentrations in water with established criteria. For surface water, the criteria used were typically chronic criteria for the protection of freshwater aquatic life. Because ground water can discharge to the surface where wildlife can be exposed to it, the criteria used for ground water were both the maximum contaminant levels (MCL's) for drinking water and the chronic criteria for the protection of freshwater aquatic life. Data collected by the NIWQP studies indicated that, in surface water, filtered and unfiltered samples had nearly the same concentrations of arsenic, boron, molybdenum, and selenium for concentrations greater than about 10 micrograms per liter. Therefore, in this concentration range, filtered concentrations can be directly compared to biological-effect levels developed for unfiltered samples. In the range of 1 to 10 micrograms per liter there may be a tendency for unfiltered arsenic concentrations to be greater than filtered concentrations. For selenium, however, the data suggest differences from equality in that range result from analytical imprecision and not a general tendency for unfiltered concentrations to be greater than filtered concentrations. This relation may not be true in lentic, nutrient-rich waters because in such settings algae can bioaccumulate large amounts of selenium and other trace elements. Selenium was the trace element in surface water that most commonly exceeded chronic criteria for the protection of freshwater aquatic life; more than 40 percent of the selenium concentrations in surface-water samples exceeded the U.S. Environmental Protection Agency (USEPA) aquatic-life chronic criterion (5 micrograms per liter). In 12 of the 26 areas at least 25 percent of the surface water-samples had selenium concentrations that either equaled or exceeded the chronic criterion (5 micrograms per liter). More than 28 percent of boron concentrations and almost 17 percent of the molybdenum concentrations exceeded the aquatic life criteria established by the State of California (550 and 19 micrograms per liter, respectively). In ground water, more than 22 percent of the arsenic concentrations and more than 35 percent of the selenium concentrations exceeded the MCL (10 and 50 micrograms per liter, respectively). Few samples of uranium in surface water exceeded a criterion for the protection of aquatic life (300 micrograms per liter), but 44 percent of the uranium concentrations in ground water exceeded the MCL (30 micrograms per liter). Molybdenum, selenium and uranium were the trace elements most commonly found in bottom-sediment samples that exceeded the upper limit of the 95th percentile expected range in soils of the Western United States. Selenium is the only trace element for which ecological sediment guidelines are used in this report. Selenium concentrations commonly exceeded the ecological sediment guideline of two micrograms per gram. DDT and its degradation products DDD and DDE were the most common pesticide residues found in surface water at concentrations exceeding criteria. However, almost all the samples exceeding the criteria were from a single study area, the Owyhee-Vale Reclamation Project areas in Oregon and Idaho. The organochlorine pesticide chlordane was detected in 30 percent of the bottom-sediment samples, and undegraded DDT was detected in 21 percent. DDT or its degradation products were detected in all 21 study areas where bottom-sediment samples were analyzed for organochlorine pesticides. A principal-components analysis indicated that elevated selenium concentrations in surface water are not associated with elevated boron, molybdenum, or arsenic concentrations. The occurrence of selenium is associated with sulfate and uranium. The association of boron and molybdenum with chloride suggests that evaporative processes control their concentrations. Arsenic is not associated with any other measured trace element and is associated negatively with selenium. This report focuses on selenium because it was the trace element most frequently found at concentrations exceeding criteria for the protection of aquatic life. Selenium concentrations in water are dynamic, and, at a given site, the selenium concentration can change by an order of magnitude during a year and from one year to another. In some areas, selenium contamination may not occur during normal or wet periods. However, during a drought, reduced water deliveries may result in selenium contamination by evaporative concentration. Marine sedimentary rocks, especially those of Late Cretaceous age, are likely to be seleniferous. Irrigation of soils derived from them can contribute large amounts of selenium to drainwater; shallow wells in and near irrigated areas contained hundreds to thousands of micrograms per liter of selenium. The median selenium concentration in surface-water samples from NIWQP sites associated with Upper Cretaceous marine sedimentary rocks is 7 micrograms per liter (range less than 1 to 8,300 micrograms per liter) and from sites not associated with such rocks is 0.4 micrograms per liter (range less than 1 to 390 micrograms per liter). Irrigation-induced selenium contamination has been observed only in arid or semiarid areas. In those NIWQP study areas having local geologic sources of selenium, typically more than 25 percent of the surface-water samples exceed the chronic criterion for selenium if the evaporation rate is 3.0 times greater than the annual precipitation. In terminal water bodies, selenium accumulates and is not flushed out. In both terminal and flow-through lakes and ponds, the median selenium concentrations in surface water for samples collected from June through August are nearly the same (1.0 and 0.8 micrograms per liter, respectively). However, the 75th-percentile selenium concentration for terminal water bodies (24 µg/L) is significantly higher than for flow-through systems (4 µg/L). Selenium concentrations in biota were compared with concentrations that have been demonstrated to have adverse effects on similar species (the effect level) or to have adverse effects on another species if consumed (the dietary effect level). Twenty-five percent of the plant samples had selenium concentrations exceeding the dietary effect level (3 micrograms per gram dry weight) whereas more than 57 percent of the invertebrate samples and 61 percent of the fish samples exceeded the dietary effect level. Of the more than 2,000 bird eggs collected, 44 percent had selenium concentrations exceeding 6 micrograms per gram, a threshold value for reduced hatchability. In 14 areas, selenium concentrations in eggs from some populations of birds exceeded 6 micrograms per gram. Selenium-caused deformities of bird embryos were found in four of the NIWQP study areas; however, most study areas were not systematically surveyed for such deformities. Eggs were sampled from 34 species of birds belonging to 10 orders. Nearly all the eggs collected come from aquatic species of birds, with American coots, mallards, and American avocets being the three species most frequently collected. Of the 34 species, at least one set of eggs from 16 species had a geometric-mean selenium concentration of at least 12.5 micrograms per gram, a high-risk threshold. All three species of grebes yielded at least one set of high risk eggs, as did four of five species of shorebirds and five of eleven species of waterfowl. Egg-set data were examined to determine if some feeding guilds are more at risk to selenium poisoning than others. Analysis of data for waterbird eggs from the study areas where the 75th percentile selenium concentration in surface water exceeded 5 µg/L suggests that herbivorous birds may bioaccumulate less selenium than insect- and fish-eating birds. For birds from these study areas, selenium concentrations for 39 percent of the egg sets from herbivorous birds fell in the normal range (less than 3 µg/g) while only 7 and 0 percent, respectively, of egg sets from insect- and fish-eating birds fall in the normal range. Although herbivorous birds may bioaccumulate less selenium, it does not appear that any waterbird feeding guilds are particularly well buffered from exposure to selenium contamination. Predictive tools were developed to aid managers in identifying specific land areas at risk for irrigation-induced selenium contamination. The tools range from identifying broad geographic regions where selenium contamination is likely, to assessing the probability that selenium concentrations in a specific stream or lake exceed the chronic criterion for selenium. A geographic information system was used to prepare a map that identifies land areas in the Western United States that are susceptible to selenium contamination if irrigated. On the basis of the 75th percentile, selenium concentration in surface water, 12 of the 26 NIWQP study areas were classified as contaminated, two as seleniferous, and 12 as uncontaminated. The map correctly identified both seleniferous areas and 10 of 12 selenium-contaminated areas as susceptible; 10 of 12 uncontaminated areas were correctly identified as not being susceptible. About 160,000 square miles are identified as being susceptible; of that area, about 4,100 square miles have been identified by satellite imagery as actively being irrigated. Principal-components analysis and pattern-recognition techniques indicate that major-ion chemistry of water samples alone can be used to identify selenium- and nonselenium-producing areas in the Western United States. Water samples composed of simple salts of sulfate typically have concentrations of selenium that exceed 3 µg/g, whereas samples composed of simple salts of chloride or carbonate typically have low selenium concentrations. Weathering of soils that contain reduced-sulfur minerals, such as pyrite, mobilizes sulfur and selenium because selenium commonly substitutes for sulfur in these minerals. In areas where the bedrock is composed of Upper Cretaceous marine sedimentary rocks, logistic regression of data from the NIWQP sites indicates that if the dissolved-solids concentration equals 1,000 milligrams per liter, the probability is about 69 percent that the selenium concentration will exceed 5 micrograms per liter, the U.S. Environmental Protection Agency chronic criterion. In areas where the bedrock is not composed of such rocks, the probability is only about 10 percent. The avian-egg data within the biotic data base were used to make a quantitative toxicological risk assessment. Of the 23 study areas where avian eggs were sampled, 14 areas yielded at least one egg containing 6 µg/g selenium, the threshold for embryotoxicity. However, only 6 of the study areas yielded eggs containing enough selenium to expect selenium-induced teratogenesis of duck embryos. Predicted probabilities of discovering embryo teratogenesis matched field observations in 13 of the 14 study areas reporting results of embryo assessments. Bird eggs were collected from 161 individual sampling sites and at 79 of those sites selenium concentrations in one or more eggs exceeded 6 µg/g. At the 79 sites where biological effects are expected on the basis of selenium concentrations in the eggs, the median rate was 3.9 percent of the hens losing at least one egg to selenium-induced embryotoxicity. This corresponds to about 1.2 percent selenium-induced egg inviability among otherwise viable eggs. Across all NIWQP study areas, the overall rate of hens projected to lose at least one egg to selenium-induced embryotoxicity is estimated to be 1.9 percent, which corresponds to about 0.3 percent selenium-induced egg inviability among otherwise viable eggs. After accounting for increased mortality of selenium poisoned-hatchlings due to other factors such as weather and predators, it was estimated that that increases of 0.3 and 1.2 percent in inviable eggs would cause approximately a 1.4 and 5.4 percent depression in nesting success. Regional surveys of nesting success among ducks revealed that duck populations commonly exist near their demographic break-even point. The vulnerable demographic condition of North American duck populations during the mid-1960's to mid-1980's was primarily due to noncontaminant factors, such as poor-quality nesting habitat and dry climatic cycles. Under such conditions, rates of 1.4- to 5.4-percent depression in nesting success caused by exposure to selenium from irrigation projects can be crucial for avian populations already close to their demographic break-even point. Even the worst-case levels of contaminant effects, however, could be tolerated by populations of ducks existing just modestly above demographic break-even points. This suggests the biotic risk to ducks could be addressed by reducing irrigation-induced water pollution but more effectively by restoring high-quality (more predator-safe) nesting habitat. An analysis at the nesting-site level was made of the relation between selenium content of water and bird eggs. Eggs from 93 bird populations were collected from nesting sites where the water sample collected during April-July contained less than 5 µg/L selenium. The average selenium concentration in egg sets was embryotoxic in 19 of the 93 populations. Of the populations collected at sites where the selenium in the water was less than 1 microgram per liter, only four of 54 populations contained embryotoxic concentrations. Eggs from 65 populations of birds were collected from nesting sites where selenium concentrations in water samples collected during April-July equaled or exceeded 5 µg/L, and 55 of those 65 populations contained embryotoxic concentrations of selenium in the eggs. An analysis at the study-area level was made of the relation between selenium contamination of water and selenium contamination of the food chain and egg loss due to selenium poisoning. Most food organisms, particularly aquatic invertebrates and fish, contained potentially harmful amounts of selenium in study areas where selenium concentrations in more than 25 percent of the water samples exceed 5 µg/L. The analysis also indicates that some hens are predicted to lose eggs to selenium poisoning in all study areas where selenium concentrations in more than 25 percent of the water samples exceed 5 µg/L. These results suggest that areas where selenium contamination of the food chain and loss of eggs to selenium poisoning is occurring may be identified using the same methods developed to identify areas where selenium contamination of water is likely to occur.

western United States↗

Use of 234U and 238U isotopes to evaluate contamination of near-surface groundwater with uranium-mill effluent: A case study in south-central Colorado, U.S.A.

The 234U/238U alpha activity ratio (AR) was determined in 47 samples of variably uraniferous groundwater from the vicinity of a uranium mill near Canon City, Colorado. The results illustrate that uranium isotopes can be used to determine the distribution of uranium contamination in groundwater and to indicate processes such as mixing and chemical precipitation that affect uranium concentrations. Highly to moderately contaminated groundwater samples collected from the mill site and land immediately downgradient from the mill site contain more than 100 ??g/l of dissolved uranium and typically have AR values in the narrow range of 1.0-1.06. Other samples from the shallow alluvial aquifer farther downgradient from the mill contain 10-100 ??g/1 uranium and plot along a broad trend of increasing AR (1.06-1.46) with decreasing uranium concentration. The results are consistent with mixing of liquid mill waste (AR ??? 1.0) with alluvial groundwater of small, but variable, uranium concentrations and AR of 1.31.5. In the alluvial aquifer, the spatial distribution of wells with AR values less than 1.3 is consistent with previous estimates of the probable distribution of contamination, based on water chemistry and hydrology. Wells more distant from the area of probable contamination have AR values that are consistently greater than 1.3 and are indicative of little or no contamination. The methodology of this study can be extended usefully to similar sites of uranium mining, milling, or processing provided that local geohydrologic settings promote uranium mobility and that introduced uranium contamination is isotopically distinct from that of local groundwater.

Environmental Geology↗

Ground-water models as a management tool in Florida

Highly sophisticated computer models provide powerful tools for analyzing historic data and for simulating future water levels, water movement, and water chemistry under stressed conditions throughout the ground-water system in Florida. Models that simulate the movement of heat and subsidence of land in response to aquifer pumping also have potential for application to hydrologic problems in the State. Florida, with 20 ground-water modeling studies reported since 1972, has applied computer modeling techniques to a variety of water-resources problems. Models in Florida generally have been used to provide insight to problems of water supply, contamination, and impact on the environment. The model applications range from site-specific studies, such as estimating contamination by wastewater injection at St. Petersburg, to a regional model of the entire State that may be used to assess broad-scale environmental impact of water-resources development. Recently, groundwater models have been used as management tools by the State regulatory authority to permit or deny development of water resources. As modeling precision, knowledge, and confidence increase, the use of ground-water models will shift more and more toward regulation of development and enforcement of environmental laws. (USGS)

Water-Resources Investigations Report↗

Characterization of bottom-sediment, water, and elutriate chemistry at selected stations at Reelfoot Lake, Tennessee

To better-understand and predict the potential effect of dredging on water quality at Reelfoot Lake, chemical analyses were conducted on samples of lake water, bottom sediment, and elutriate water. Chemical analyses were conducted on samples of lake water, bottom sediment, and elutriate water collected at five stations in the lake during November 1988. Lake water was of the calcium magnesium bicarbonate type with an average dissolved-solids concentration of 120 milligrams per liter. Trace constituents were present in bottom sediments at concentrations representative of their average relative abundance in the earth?s crust. Elutriate waters prepared by mixing bottom sediment and lake water had suspended-solids concentrations as high as 2,000 milligrams per liter which exerted significant oxygen demand Trace constituents in the unfiltered elutriate waters were elevated with respect to lake water; elevated concentrations were attributable to the increased suspended-solids concentrations. Concentrations of total-recoverable copper, lead., and zinc in many elutriate waters exceeded U.S. Environmental Protection Agency?s water-quality criteria for the protection of freshwater aquatic life. The toxicity of elutriate waters, as measured by a 48-hour bioassay with Ceriodaphnia dubia, was low.

Tennessee↗

Pathology of sea otters

In the months following the Exxon Valdez oil spill (EVOS), 994 sea otters ( Enhydra lutris ) from oil-spill-affected areas died (Doroff et al. 1993). Carcasses collected from these areas and otters that died in rehabilitation centers are included in this number. The actual number that died was probably much greater. Within days of the spill, the Exxon Company (USA) funded an effort to rehabilitate oil-contaminated sea otters (Davis 1990). Initially, clinical veterinarians working on the rehabilitation effort performed partial necropsies on some of the sea otters that died. Soon, veterinary pathologists from the University of Alaska and the U.S. Environmental Protection Agency provided assistance. Later, rehabilitation centers were constructed and other veterinarians with special training in pathology were hired by Exxon to provide diagnostic support. In late April 1989, veterinary pathologists from the U.S. Fish and Wildlife Service (USFWS) assumed responsibility for pathologic evaluation of oil-spill-affected sea otters. The USFWS requested assistance from veterinary pathologists of the Armed Forces Institute of Pathology (AFIP) in June 1989. Eventually, as part of the Natural Resources Damage Assessment program, AFIP veterinary pathologists were asked to carry out histopathological studies of the tissue specimens collected by all parties and to perform necropsies on carcasses that had been collected and frozen. A veterinary clinical pathologist was requested to assess hematology and clinical chemistry findings in otters that had been held in the rehabilitation centers. In spite of the best efforts of many dedicated people working under extremely difficult conditions, there are significant limitations in the pathological studies. The absence of a detailed necropsy protocol and of full documentation of necropsy findings during the first several weeks after the spill resulted in important data being lost. Often, samples of all major organs were not collected. In some cases, no necropsy report was available. Specimens for toxicologic analysis for petroleum hydrocarbons were not consistently collected. The absence of a detailed toxicology protocol suggests that the samples may not have been collected properly. The lack of a consistent numbering system for identification of specimens caused major problems; some samples were useless because they could not be identified. Many blood samples could not be transported to laboratories quickly enough to prevent significant deterioration of the samples because of inclement weather and the remote locations of the rehabilitation centers. Thus, in a number of cases, data could not be used because significant deterioration of the specimens was considered likely to have occurred. Since more than one laboratory was used to analyze blood samples, problems with comparability of results were encountered. The laboratory tests were performed to aid the clinical veterinarians in diagnosis and treatment of individual animals, not as part of a consistent protocol; thus, there is variation in the amount and type of laboratory data available for each otter. These problems illustrate the need for development of contingency plans that include detailed protocols before disasters occur.

Alaska↗