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USGS2015

Characterizing toxicity of metal-contaminated sediments from mining areas

This paper reviews methods for testing the toxicity of metals associated with freshwater sediments, linking toxic effects with metal exposure and bioavailability, and developing sediment quality guidelines. The most broadly applicable approach for characterizing metal toxicity is whole-sediment toxicity testing, which attempts to simulate natural exposure conditions in the laboratory. Standard methods for whole-sediment testing can be adapted to test a wide variety of taxa. Chronic sediment tests that characterize effects on multiple endpoints (e.g., survival, growth, and reproduction) can be highly sensitive indicators of adverse effects on resident invertebrate taxa. Methods for testing of aqueous phases (pore water, overlying water, or elutriates) are used less frequently. Analysis of sediment toxicity data focuses on statistical comparisons between responses in sediments from the study area and responses in one or more uncontaminated reference sediments. For large or complex study areas, a greater number of reference sediments is recommended to reliably define the normal range of responses in uncontaminated sediments – the ‘reference envelope’. Data on metal concentrations and effects on test organisms across a gradient of contamination may allow development of concentration-response models, which estimate metal concentrations associated with specified levels of toxic effects (e.g. 20% effect concentration or EC20). Comparisons of toxic effects in laboratory tests with measures of impacts on resident benthic invertebrate communities can help document causal relationships between metal contamination and biological effects. Total or total-recoverable metal concentrations in sediments are the most common measure of metal contamination in sediments, but metal concentrations in labile sediment fractions (e.g., determined as part of selective sediment extraction protocols) may better represent metal bioavailability. Metals released by the weak-acid extraction of acid-volatile sulfide (AVS), termed simultaneously-extracted metals (SEM), are widely used to estimate the ‘potentially-bioavailable’ fraction of metals that is not bound to sulfides (i.e., SEM-AVS). Metal concentrations in pore water are widely considered to be direct measures of metal bioavailability, and predictions of toxicity based on pore-water metal concentrations may be further improved by modeling interactions of metals with other pore-water constituents using Biotic Ligand Models. Data from sediment toxicity tests and metal analyses has provided the basis for development of sediment quality guidelines, which estimate thresholds for toxicity of metals in sediments. Empirical guidelines such as Probable Effects Concentrations or (PECs) are based on associations between sediment metal concentrations and occurrence of toxic effects in large datasets. PECs do not model bioavailable metals, but they can be used to estimate the toxicity of metal mixtures using by calculation of probable effect quotients (PEQ = sediment metal concentration/PEC). In contrast, mechanistic guidelines, such as Equilibrium Partitioning Sediment Benchmarks (ESBs) attempt to predict both bioavailability and mixture toxicity. Application of these simple bioavailability models requires more extensive chemical characterization of sediments or pore water, compared to empirical guidelines, but may provide more reliable estimates of metal toxicity across a wide range of sediment types.

Applied Geochemistry↗

USGS1985

Hydrogeology, digital solute-transport simulation, and geochemistry of the Lower Cretaceous aquifer system near Baltimore, Maryland

This study was made to develop information on the hydrogeology and ground-water geochemistry of the Patuxent and Patapsco aquifers (Lower Cretaceous) near Baltimore, Maryland. This information is needed to evaluate the availability and chemical quality of water from these aquifers. The Patuxent aquifer unconformably overlies Lower Paleozoic and Precambrian basement rocks and consists primarily of medium- to coarse-grained quartz sand. Discontinuous lenses of gravel and silty clay are commonly interbedded with the sand-sized material. The Patuxent aquifer in this area attains a thickness of 250 feet and transmissivities range from 2,000 to 8,000 feet squared per day. The Patuxent is the most productive source of ground water in the Baltimore area. In 1982, approximately 11 million gallons of water per day was produced from this unit. Several cones of depression, ranging from 30 to 50 feet below sea level, have developed in response to this pumping stress. The Arundel Formation conformably overlies the Patuxent aquifer. The Arundel is composed predominantly of clay and ranges from 0 to 150 feet thick. The Arundel exhibits very low vertical hydraulic conductivities that are on the order of 10 -9 to 10 -11 feet per second. This unit acts as the upper confining bed of the Patuxent aquifer in much of the project area. The Patapsco aquifer unconformably overlies the Arundel Formation and is a medium- to fine-grained quartz sand. The Patapsco functions as a water-table aquifer in much of the project area. Although the Patapsco has been heavily pumped in the past, pumpage from that aquifer in Baltimore was negligible in 1982. Brackish-water contamination of the Patuxent and Patapsco aquifers has been a major water-quality problem since the early 1900's. The Patuxent aquifer presently (1982) contains a circular plume of brackish-water contamination about 5 miles in diameter. This plume is centered on the Harbor district and has enlarged measurably since 1945. The Patapsco aquifer has a smaller zone of brackish-water contamination that has decreased in size since 1945. Borehole data demonstrate that the Arundel Formation has been breached by Pleistocene river channels near the Harbor district. These erosional channels provide a conduit for brackish water to intrude into the Patuxent aquifer. A two-dimensional areal solute-transport model of the Patuxent aquifer was constructed. This model was designed to estimate the future movement of the brackish-water plume based on alternative scenarios of aquifer use. Model simulations suggest that the plume will remain relatively immobile if 1982 pumping patterns continue into the foreseeable future. However, increased pumpage in the Marley Neck peninsula could draw the plume to the southeast and increase contamination of the Fairfield area. The water quality of the Patuxent aquifer is extremely variable. Because of this variability, it is useful to divide the aquifer into three water-quality zones: Zone 1 -- This zone corresponds to the plume of brackish-water contamination. Zone 2 -- This zone exhibits evidence of urbanization-related contamination such as measurable concentrations of organic chemicals and elevated concentrations of trace elements and total organic carbon. Zone 3 -- Water composition in this zone is controlled exclusively by naturally occurring chemical processes. These processes are dominated by reactions involving dissolved iron. Near the outcrop area, oxidation of pyrite and lignite consumes dissolved oxygen and produces ledges of iron hydroxide-cemented sandstones and conglomerates. The predominant dissolved iron species in oxic water is Fe(OH) 2 + . Downgradient, the water becomes anoxic and sulfate reduction becomes an important process. The predominant dissolved iron species in anoxic water is Fe 2+ .

Maryland↗

USGS2021

Relative risk of groundwater-quality degradation near California (USA) oil fields estimated from 3H, 14C, and 4He

Relative risks of groundwater-quality degradation near selected California oil fields are estimated by examining spatial and temporal patterns in chemical and isotopic data in the context of groundwater-age categories defined by tritium and carbon-14. In the Coastal basins, western San Joaquin Valley (SJV), and eastern SJV; 82, 76, and 0% of samples are premodern (pre-1953 recharge), respectively; and 3, 0, and 31% are modern (recharged during or after 1953), respectively. Carbon-14 and helium-4 data indicate most premodern samples are 1000 to 10,000 (33%) or >10,000 (50%) years old. Organic chemicals that could be associated with deeper hydrocarbon reservoirs (e.g. thermogenic gases and benzene) occur most frequently in premodern groundwater, suggesting premodern groundwater has a higher risk of degradation from upward migration of hydrocarbons than modern and mixed-age groundwater. Low sulfate concentrations in some premodern groundwater containing high thermogenic-methane concentrations (>28 mg/L) indicate methane attenuation associated with sulfate reduction can be limited in premodern groundwater. The more common occurrence of manufactured compounds, like tetrachloroethene, in modern and mixed-age groundwater than in premodern groundwater indicates modern and mixed-age groundwater has a higher risk of degradation from land-surface sources than premodern groundwater. Time-series data for chloride in groundwater affected by disposal of oil-field water in unlined ponds indicate some modern and mixed-age groundwater are susceptible to chemical migration within 2–3 km of surface sources. Timescales for diluting chloride concentrations in groundwater with fresh recharge once disposal ponds are decommissioned are shorter in mixed-age groundwater with large fractions of modern water (9–14 years in one example) than in mixed-age groundwater with large fractions of premodern water (no evidence of dilution after 12 years of monitoring in one example). The presence of predominantly premodern groundwater in the Coastal basins and western SJV indicates these areas have relatively high risk from upward migration of hydrocarbons, reduced methane attenuation capacity, and long dilution times, whereas predominantly modern- and mixed-age groundwater in the eastern SJV indicates this area has relatively high risk from chemical migration from land-surface sources and subsequent extensive spreading. Age-based characterizations of relative risk could inform the design of groundwater-monitoring programs near oil fields in terms of the spatial distribution of monitoring points relative to source areas and monitoring frequency and duration.

California↗

USGS2008

Anthropogenic influences on the input and biogeochemical cycling of nutrients and mercury in Great Salt Lake, Utah, USA

Despite the ecological and economic importance of Great Salt Lake (GSL), little is known about the input and biogeochemical cycling of nutrients and trace elements in the lake. In response to increasing public concern regarding anthropogenic inputs to the GSL ecosystem, the US Geological Survey (USGS) and US Fish and Wildlife Service (USFWS) initiated coordinated studies to quantify and evaluate the significance of nutrient and Hg inputs into GSL. A 6??? decrease in ??15N observed in brine shrimp (Artemia franciscana) samples collected from GSL during summer time periods is likely due to the consumption of cyanobacteria produced in freshwater bays entering the lake. Supporting data collected from the outflow of Farmington Bay indicates decreasing trends in ??15N in particulate organic matter (POM) during the mid-summer time period, reflective of increasing proportions of cyanobacteria in algae exported to GSL on a seasonal basis. The C:N molar ratio of POM in outflow from Farmington Bay decreases during the summer period, supportive of the increased activity of N fixation indicated by decreasing ??15N in brine shrimp and POM. Although N fixation is only taking place in the relatively freshwater inflows to GSL, data indicate that influx of fresh water influences large areas of the lake. Separation of GSL into two distinct hydrologic and geochemical systems from the construction of a railroad causeway in the late 1950s has created a persistent and widespread anoxic layer in the southern part of GSL. This anoxic layer, referred to as the deep brine layer (DBL), has high rates of SO42 - reduction, likely increasing the Hg methylation capacity. High concentrations of methyl mercury (CH3Hg) (median concentration = 24 ng/L) were observed in the DBL with a significant proportion (31-60%) of total Hg in the CH3Hg form. Hydroacoustic and sediment-trap evidence indicate that turbulence introduced by internal waves generated during sustained wind events can temporarily mix the elevated CH3Hg concentrations in the DBL with the more biologically active upper brine layer (UBL). Brine shrimp collected during the summer/fall time periods contained elevated Hg concentrations (median concentration = 0.34 mg/kg, dry weight (dw)) relative to samples collected during the spring (median concentration < 0.2 mg/kg, dw). Higher Hg in brine shrimp during the summer and fall may reflect the higher proportion of adult brine shrimp during this time period, resulting in an increased time for bioaccumulation of Hg. Eared grebes (Podiceps nigricollis) consume brine shrimp from GSL during the fall molting period. Median Hg concentrations in eared grebe livers increased by almost three times during the 3-5 month fall molting period. Selected duck species utilizing GSL have consistently exceeded the US Environmental Protection Agency (USEPA) screening level for Hg (0.3 mg/kg Hg wet weight), resulting in the issuance of warnings against unlimited human consumption of breast muscle tissue.

Applied Geochemistry↗

USGS2012

Groundwater quality in the Columbia Plateau, Snake River Plain, and Oahu basaltic-rock and basin-fill aquifers in the Northwestern United States and Hawaii, 1992-2010

This assessment of groundwater-quality conditions of the Columbia Plateau, Snake River Plain, and Oahu for the period 1992–2010 is part of the U.S. Geological Survey’s National Water Quality Assessment (NAWQA) program. It shows where, when, why, and how specific water-quality conditions occur in groundwater of the three study areas and yields science-based implications for assessing and managing the quality of these water resources. The primary aquifers in the Columbia Plateau, Snake River Plain, and Oahu are mostly composed of fractured basalt, which makes their hydrology and geochemistry similar. In spite of the hydrogeologic similarities, there are climatic differences that affect the agricultural practices overlying the aquifers, which in turn affect the groundwater quality. Understanding groundwater-quality conditions and the natural and human factors that control groundwater quality is important because of the implications to human health, the sustainability of rural agricultural economies, and the substantial costs associated with land and water management, conservation, and regulation. The principal regional aquifers of the Columbia Plateau, Snake River Plain, and Oahu are highly vulnerable to contamination by chemicals applied at the land surface; essentially, they are as vulnerable as many shallow surficial aquifers elsewhere. The permeable and largely unconfined character of principal aquifers in the Columbia Plateau, Snake River Plain, and Oahu allow water and chemicals to infiltrate to the water table despite depths to water commonly in the hundreds of feet. The aquifers are essentially unconfined over large areas, having few extensive clay layers to impede infiltration through permeable volcanic rock and alluvial sediments. Agriculture is intensive in all three study areas, and heavy irrigation has imposed large artificial flows of irrigation recharge that rival or exceed natural recharge rates. Fertilizers and pesticides applied at land surface are leached from soil and transported to deep water tables with the infiltrating irrigation recharge, resulting in a layer of degraded water quality overlying better quality regional groundwater beneath. This “irrigation-recharge layer” is best known on Oahu, where it has been studied since the 1960s; however, the extent of nitrate and pesticide contamination in the Columbia Plateau and Snake River Plain indicate that the same situation exists in those areas. Contamination from agricultural and urban activities is present not only at shallow depths in surficial materials of the three areas, but extends regionally in the deep, principal bedrock aquifers that are tapped for drinking water by domestic and public-supply wells. Naturally occurring constituents and nitrate concentrations above human-health benchmarks—Maximum Contaminant Levels (MCLs), and Health-Based Screening Levels (HBSLs)—were more common in the Columbia Plateau and the Snake River Plain than in Oahu. Concentrations of anthropogenic constituents (constituents related to human activities) above human-health benchmarks were more common in Oahu. Naturally occurring contaminants, such as arsenic and radon, may be present in groundwater at concentrations of potential concern for human health in relatively undeveloped settings that otherwise may not be perceived as susceptible to contamination. Even though the median depth to groundwater in Oahu is more than 300 feet, the common occurrence of anthropogenic compounds in groundwater indicates that Oahu has a high susceptibility to contamination. Nitrate concentrations in groundwater were above the national background concentrations of 1 milligram per liter (mg/L) in all three study areas. In the Columbia Plateau, nitrate exceeded the human-health benchmark of 10 mg/L in 20 percent of the wells sampled. In the Snake River Plain, nitrate exceeded the human-health benchmark of 10 mg/L in 3 percent of the wells sampled. Nitrate can persist in groundwater for years and even decades in the oxygen-rich groundwater of the Columbia Plateau and the Snake River Plain, so prudent groundwater protection measures are critical to protect drinking water resources by reducing nitrate leaching from the land surface. Nitrate logistic regression models indicated that areas with a high percentage of land in crops (such as potatoes or sugarcane) and soils with low amounts of organic matter are most likely to have elevated nitrate concentrations in the groundwater. Areas where agricultural activities were absent had much lower probabilities of detecting elevated nitrate concentrations. The Columbia Plateau had a much higher probability of having elevated nitrate concentrations, with most of the land area having greater than a 50 percent probability of elevated nitrate concentrations. Oahu and the Snake River Plain had a much lower probability of having elevated nitrate concentrations because of their lower percentage of agricultural land. Pesticides were detected at many sites in groundwater of the Columbia Plateau, Snake River Plain, and Oahu but generally at low concentrations below human-health benchmarks. Atrazine and its degradate (a compound produced from the breakdown of a parent pesticide), deethylatrazine, were the most commonly detected pesticides in groundwater sampled in the Columbia Plateau and Snake River Plain. Bromacil was the most commonly detected pesticide on Oahu. The other pesticides most commonly detected in the study areas include simazine, hexazinone, metribuzin, diuron, prometon, metolachlor, p,p’ -DDE, dieldrin, 2-4-D, and alachlor. DDE (a degradate of DDT) and dieldrin are still being detected in groundwater despite having been banned for more than 30 years. Codetection of multiple pesticides in water from a single well was common. The widespread occurrence of pesticides in groundwater in the study areas indicates that the groundwater is highly susceptible to pesticide contamination. Some pesticides were detected in groundwater samples from all three study areas, but other pesticides were detected only in samples from Oahu, or only in samples from the Columbia Plateau and Snake River Plain. This is because some pesticides (such as atrazine) are broad-spectrum pesticides that are used on many crops in many different areas of the United States. Other pesticides (such as simazine, metribuzin, and metolachlor) are used on row crops (such as potatoes, barley, and alfalfa) grown in the Columbia Plateau and Snake River Plain, but not on pineapple or sugarcane grown in Oahu. Atrazine logistic-regression models indicate that areas with a high percentage of land in crops (such as potatoes or sugarcane), a low percentage of fallow land, and highly permeable soils with low amounts of organic matter are most likely to have atrazine detected in the groundwater. Areas where agricultural activities were absent had much lower probabilities of atrazine being detected. The Snake River Plain had a much higher probability of atrazine detections, with more than 50 percent of the land area having greater than a 50 percent probability of atrazine contamination. Oahu had a much lower probability of atrazine contamination, with only 24 percent of the land area having greater than a 50 percent probability of atrazine contamination. Oahu and the Columbia Plateau had some of the highest percentages of soil fumigant detections in groundwater in the United States. Soil fumigants are volatile organic compounds (VOCs) used as pesticides, which are applied to soils to reduce populations of plant parasitic nematodes (harmful rootworms), weeds, fungal pathogens, and other soil-borne microorganisms. They are used in Oahu and the Columbia Plateau on crops such as pineapple and potatoes. All three areas (Columbia Plateau, Snake River Plain, and Oahu) had fumigant concentrations exceeding human-health benchmarks for drinking water.

Hawai'i, Idaho, Nevada, Oregon, Utah, Washington, ↗

USGS2001

Geologic studies in Alaska by the U.S. Geological Survey, 1999

The collection of nine papers that follow continue the series of U.S. Geological Survey (USGS) investigative reports in Alaska under the broad umbrella of the geologic sciences. The series presents new and sometimes preliminary findings that are of interest to earth scientists in academia, government, and industry; to land and resource managers; and to the general public. Reports presented in Geologic Studies in Alaska cover a broad spectrum of topics from various parts of the State (fig. 1), serving to emphasize the diversity of USGS efforts to meet the Nation's needs for earth-science information in Alaska. The papers in this volume are organized under the topics: Hazards, Geologic Framework, Environment and Climate, and Resources. This organization is intended to reflect the scope and objectives of USGS geologic programs currently active in Alaska. The two Hazards studies discuss volcano-related topics in the seismically active southcentral Alaska region. The first paper revisits the eruptive events of Redoubt Volcano that occurred more than a decade ago and the subsequent development of the Alaska Volcano Observatory (AVO). This treatise documents the historic impact of this eruption and briefly summarizes the state of our knowledge of the other Cook Inlet, Alaska Peninsula, and Aleutian Island volcanoes. Finally, it discusses the recent role that AVO has had in seismic station installation and hazard assessment at volcanically active sites throughout the world. The second paper discusses the eruptive history of Snowy Mountain in the upper Alaska Peninsula. Because subsets of its 25-30 lava flows erupted as packages in short episodes, calculation of the volcano's lifetime average volumetric eruption rate is problematic. A portion of the cone was hydrothermally weakened and collapsed in the late Holocene producing a 22-km2 debris avalanche. Geologic Framework studies provide background information that is the scientific basis for present and future earth science investigations. The first paper compares and contrasts the Insular-Intermontane suture zone (IISZ) of southeast Alaska with the Adria-Europe suture zone (AESZ) of Switzerland and Hungary. The study develops the hypothesis that the zones have distinct differences as well as similarities and neither is a simple lithotectonic terrane boundary. The second paper discusses the relation among volcanic, glacial, and tectonic activity in the Cold Bay and False Pass 1 :250,000-scale quadrangles on the Alaska Peninsula. During Pleistocene time, continental-shelf glaciations and two massive volcanic centers were the dominant controls over landscape development. The third paper gives detailed geologic information for Paleozoic rocks within the Taylor Mountains D-1 quadrangle portion of the Holitna Lowland of southwestern Alaska. Because of the excellent preservation of megafossils, these Silurian and Ordovician strata lend themselves to detailed statigraphic investigations. Further, low thermal alteration indices of this area have made them a potential target of petroleum exploration. The final report in this section discusses the development of a new spectral enhancement approach for interpreting Multispectral Scanner (MSS) and Thematic Mapper (TM) satellite images. This technique enhances the use of remote sensing data in identifying geologic units in areas that have been poorly investigated. This study used this technique to better define the distribution of a JMtu (mafic, ultramafic, and sedimentary) unit and a PzZrqs (pelitic and quartzitic schist) unit. Environment and climate studies are the emphasis of two papers. One presents the first radiocarbon-dated postglacial vegetation history of the Kenai Mountains of southcentral Alaska. This reconstruction is the result of the analysis of pollen assemblages and peat from sediments collected in Tern Lake and presents a minimum age for deglaciation of these interior valleys at 9,31 0±200 yr B .P. Current vegetation, however, developed within the past ca. 2,500 years. A second study discusses the cycling of arsenic and cadmium in sub-arctic boreal forest ecosystems typical of interior Alaska and defines the importance of various natural (geogenic) sources. The transport and uptake into vegetation of these elements from soils developed from loess as well as soils developed from the major rock units is presented. The bioaccumulation of cadmium in willow (Salix sp.) and its potential consequence to the health of browsing animals is discussed. Papers related to resource issues comprise the topic of the final report. This paper presents a brief statistical summary of the geochemistry of rock samples collected in the east-central portion of the Eagle 1 :250,000-scale quadrangle. This study helps define the rock unit source of both resource- and environmental-based chemical elements of interest in the Fortymile mining district. Two bibliographies at the end of the volume list reports covering Alaska earth science topics in USGS publications during 1999 and reports about Alaska by USGS authors in non-USGS publications during the same period.

Alaska↗

USGS2014

From headwaters to coast: Influence of human activities on water quality of the Potomac River Estuary

The natural aging process of Chesapeake Bay and its tributary estuaries has been accelerated by human activities around the shoreline and within the watershed, increasing sediment and nutrient loads delivered to the bay. Riverine nutrients cause algal growth in the bay leading to reductions in light penetration with consequent declines in sea grass growth, smothering of bottom-dwelling organisms, and decreases in bottom-water dissolved oxygen as algal blooms decay. Historically, bay waters were filtered by oysters, but declines in oyster populations from overfishing and disease have led to higher concentrations of fine-sediment particles and phytoplankton in the water column. Assessments of water and biological resource quality in Chesapeake Bay and tributaries, such as the Potomac River, show a continual degraded state. In this paper, we pay tribute to Owen Bricker’s comprehensive, holistic scientific perspective using an approach that examines the connection between watershed and estuary. We evaluated nitrogen inputs from Potomac River headwaters, nutrient-related conditions within the estuary, and considered the use of shellfish aquaculture as an in-the-water nutrient management measure. Data from headwaters, nontidal, and estuarine portions of the Potomac River watershed and estuary were analyzed to examine the contribution from different parts of the watershed to total nitrogen loads to the estuary. An eutrophication model was applied to these data to evaluate eutrophication status and changes since the early 1990s and for comparison to regional and national conditions. A farm-scale aquaculture model was applied and results scaled to the estuary to determine the potential for shellfish (oyster) aquaculture to mediate eutrophication impacts. Results showed that (1) the contribution to nitrogen loads from headwater streams is small (about 2 %) of total inputs to the Potomac River Estuary; (2) eutrophic conditions in the Potomac River Estuary have improved in the upper estuary since the early 1990s, but have worsened in the lower estuary. The overall system-wide eutrophication impact is high, despite a decrease in nitrogen loads from the upper basin and declining surface water nitrate nitrogen concentrations over that period; (3) eutrophic conditions in the Potomac River Estuary are representative of Chesapeake Bay region and other US estuaries; moderate to high levels of nutrient-related degradation occur in about 65 % of US estuaries, particularly river-dominated low-flow systems such as the Potomac River Estuary; and (4) shellfish (oyster) aquaculture could remove eutrophication impacts directly from the estuary through harvest but should be considered a complement—not a substitute—for land-based measures. The total nitrogen load could be removed if 40 % of the Potomac River Estuary bottom was in shellfish cultivation; a combination of aquaculture and restoration of oyster reefs may provide larger benefits.

Maryland, Pennsylvania, Virginia, West Virginia↗

USGS2013

Tracing groundwater with low-level detections of halogenated VOCs in a fractured carbonate-rock aquifer, Leetown Science Center, West Virginia, USA

Measurements of low-level concentrations of halogenated volatile organic compounds (VOCs) and estimates of groundwater age interpreted from 3 H/ 3 He and SF 6 data have led to an improved understanding of groundwater flow, water sources, and transit times in a karstic, fractured, carbonate-rock aquifer at the Leetown Science Center (LSC), West Virginia. The sum of the concentrations of a set of 16 predominant halogenated VOCs (TDVOC) determined by gas chromatography with electron-capture detector (GC–ECD) exceeded that possible for air–water equilibrium in 34 of the 47 samples (median TDVOC of 24,800 pg kg −1 ), indicating that nearly all the water sampled in the vicinity of the LSC has been affected by addition of halogenated VOCs from non-atmospheric source(s). Leakage from a landfill that was closed and sealed nearly 20 a prior to sampling was recognized and traced to areas east of the LSC using low-level detection of tetrachloroethene (PCE), methyl chloride (MeCl), methyl chloroform (MC), dichlorodifluoromethane (CFC-12), and cis-1,2-dichloroethene (cis-1,2-DCE). Chloroform (CHLF) was the predominant VOC in water from domestic wells surrounding the LSC, and was elevated in groundwater in and near the Fish Health Laboratory at the LSC, where a leak of chlorinated water occurred prior to 2006. The low-level concentrations of halogenated VOCs did not exceed human or aquatic-life health criteria, and were useful in providing an awareness of the intrinsic susceptibility of the fractured karstic groundwater system at the LSC to non-atmospheric anthropogenic inputs. The 3 H/ 3 He groundwater ages of spring discharge from the carbonate rocks showed transient behavior, with ages averaging about 2 a in 2004 following a wet climatic period (2003–2004), and ages in the range of 4–7 a in periods of more average precipitation (2008–2009). The SF 6 and CFC-12 data indicate older water (model ages of 10s of years or more) in the low-permeability shale of the Martinsburg Formation located to the west of the LSC. A two-a record of specific conductance, water temperature, and discharge recorded at 30-min intervals demonstrated an approximately 3-month lag in discharge at Gray Spring. The low groundwater ages of waters from the carbonate rocks support rapid advective transport of contaminants from the LSC vicinity, yet the nearly ubiquitous occurrence of low-level concentrations of halogenated VOCs at the LSC suggests the presence of long-term persistent sources, such as seepage from the closed and sealed landfill, infiltration of VOCs that may persist locally in the epikarst, exchange with low-permeability zones in fractured rock, and upward leakage of older water that may contain elevated concentrations of halogenated VOCs from earlier land use activities.

West Virginia↗