Investigation of Sources of Fluorinated Compounds in Private Water Supplies in an Oil and Gas-Producing Region of Northern West Virginia.

Per- and polyfluoroalkyl substances (PFASs) are a class of toxic organic compounds that have been widely used in consumer applications and industrial activities, including oil and gas production. We measured PFAS concentrations in 45 private wells and 8 surface water sources in the oil and gas-producing Doddridge, Marshall, Ritchie, Tyler, and Wetzel Counties of northern West Virginia and investigated relationships between potential PFAS sources and drinking water receptors. All surface water samples and 60% of the water wells sampled contained quantifiable levels of at least one targeted PFAS compound, and four wells (8%) had concentrations above the proposed maximum contaminant level (MCL) for perfluorooctanoic acid (PFOA). Individual concentrations of PFOA and perfluorobutanesulfonic acid exceeded those measured in finished public water supplies. Total targeted PFAS concentrations ranged from nondetect to 36.8 ng/L, with surface water concentrations averaging 4-fold greater than groundwater. Semiquantitative, nontargeted analysis showed concentrations of emergent PFAS that were potentially higher than targeted PFAS. Results from a multivariate latent variable hierarchical Bayesian model were combined with insights from analyses of groundwater chemistry, topographic characteristics, and proximity to potential PFAS point sources to elucidate predictors of PFAS concentrations in private wells. Model results reveal (i) an increased vulnerability to contamination in upland recharge zones, (ii) geochemical controls on PFAS transport likely driven by adsorption, and (iii) possible influence from nearby point sources.

Conventional Fossil Fuel Extraction, Associated Biogeochemical Processes, and Topography Influence Methane Groundwater Concentrations in Appalachia.

The production of fossil fuels, including oil, gas, and coal, retains a dominant share in US energy production and serves as a major anthropogenic source of methane, a greenhouse gas with a high warming potential. In addition to directly emitting methane into the air, fossil fuel production can release methane into groundwater, and that methane may eventually reach the atmosphere. In this study, we collected 311 water samples from an unconventional oil and gas (UOG) production region in Pennsylvania and an oil and gas (O&G) and coal production region across Ohio and West Virginia. Methane concentration was negatively correlated to distance to the nearest O&G well in the second region, but such a correlation was shown to be driven by topography as a confounding variable. Furthermore, sulfate concentration was negatively correlated with methane concentration and with distance to coal mining in the second region, and these correlations were robust even when considering topography. We hypothesized that coal mining enriched sulfate in groundwater, which in turn inhibited methanogenesis and enhanced microbial methane oxidation. Thus, this study highlights the complex interplay of multiple factors in shaping groundwater methane concentrations, including biogeochemical conversion, topography, and conventional fossil extraction.

Assessing Unconventional Oil and Gas Exposure in the Appalachian Basin: Comparison of Exposure Surrogates and Residential Drinking Water Measurements.

Health studies report associations between metrics of residential proximity to unconventional oil and gas (UOG) development and adverse health endpoints. We investigated whether exposure through household groundwater is captured by existing metrics and a newly developed metric incorporating groundwater flow paths. We compared metrics with detection frequencies/concentrations of 64 organic and inorganic UOG-related chemicals/groups in residential groundwater from 255 homes (Pennsylvania n = 94 and Ohio n = 161). Twenty-seven chemicals were detected in ≥20% of water samples at concentrations generally below U.S. Environmental Protection Agency standards. In Pennsylvania, two organic chemicals/groups had reduced odds of detection with increasing distance to the nearest well: 1,2-dichloroethene and benzene (Odds Ratio [OR]: 0.46, 95% confidence interval [CI]: 0.23-0.93) and m- and p-xylene (OR: 0.28, 95% CI: 0.10-0.80); results were consistent across metrics. In Ohio, the odds of detecting toluene increased with increasing distance to the nearest well (OR: 1.48, 95% CI: 1.12-1.95), also consistent across metrics. Correlations between inorganic chemicals and metrics were limited (all |ρ| ≤ 0.28). Limited associations between metrics and chemicals may indicate that UOG-related water contamination occurs rarely/episodically, more complex metrics may be needed to capture drinking water exposure, and/or spatial metrics in health studies may better reflect exposure to other stressors.

Groundwater Methane in Northeastern Pennsylvania Attributable to Thermogenic Sources and Hydrogeomorphologic Migration Pathways.

Conflicting evidence exists as to whether or not unconventional oil and gas (UOG) development has enhanced methane transport into groundwater aquifers over the past 15 years. In this study, recent groundwater samples were collected from 90 domestic wells and 4 springs in Northeastern Pennsylvania located above the Marcellus Shale after more than a decade of UOG development. No statistically significant correlations were observed between the groundwater methane level and various UOG geospatial metrics, including proximity to UOG wells and well violations, as well as the number of UOG wells and violations within particular radii. The δ13C and methane-to-higher chain hydrocarbon signatures suggested that the elevated methane levels were not attributable to UOG development nor could they be explained by using simple biogenic-thermogenic end-member mixing models. Instead, groundwater methane levels were significantly correlated with geochemical water type and topographical location. Comparing a subset of contemporary methane measurements to their co-located pre-drilling records (n = 64 at 49 distinct locations) did not indicate systematic increases in methane concentration but did reveal several cases of elevated concentration (n = 12) across a spectrum of topographies. Multiple lines of evidence suggested that the high-concentration groundwater methane could have originated from shallow thermogenic methane that migrated upward into groundwater aquifers with Appalachian Basin brine.

Domestic groundwater wells in Appalachia show evidence of low-dose, complex mixtures of legacy pollutants.

Lack of water quality data for private drinking water sources prevents robust evaluation of exposure risk for communities co-located with historically contaminated sites and ongoing industrial activity. Areas of the Appalachian region of the United States (i.e., Pennsylvania, Ohio and West Virginia) contain extensive hydraulic fracturing activity, as well as other extractive and industrial technologies, in close proximity to communities reliant on private drinking water sources, creating concern over potential groundwater contamination. In this study, we characterized volatile organic compound (VOC) occurrence at 307 private groundwater well sites within Pennsylvania, Ohio, and West Virginia. The majority (97%) of water samples contained at least one VOC, while the average number of VOCs detected at a given site was 5 ± 3. The majority of individual VOC concentrations fell below applicable U.S. Environmental Protection Agency (EPA) Maximum Contamination Levels (MCLs), except for chloroform (MCL of 80 µg L-1; n = 1 at 98 µg L-1), 1,2-dibromoethane (MCL of 0.05 µg L-1; n = 3 ranging from 0.05 to 0.35 µg L-1), and 1,2-dibromo-3-chloropropane (MCL of 0.2 µg L-1; n = 7 ranging from 0.20 to 0.58 µg L-1). To evaluate well susceptibility to VOCs from industrial activity, distance to hydraulic fracturing site was used to assess correlations with contaminant occurrences. Proximity to closest hydraulic fracturing well-site revealed no statistically significant linear relationships with either individual VOC concentrations, or frequency of VOC detections. Evaluation of other known industrial contamination sites (e.g., US EPA Superfund sites) revealed elevated levels of three VOCs (chloroform, toluene, benzene) in groundwaters within 10 km of those Superfund sites in West Virginia and Ohio, illuminating possible point source influence. Lack of correlation between VOC concentrations and proximity to specific point sources indicates complex geochemical processes governing trace VOC contamination of private drinking water sources. While individual concentrations of VOCs fell well below recommended human health levels, the low dose exposure to multiple VOCs occurring in drinking supplies for Appalachian communities was noted, highlighting the importance of groundwater well monitoring.

Social Vulnerability and Groundwater Vulnerability to Contamination From Unconventional Hydrocarbon Extraction in the Appalachian Basin.

Unconventional oil and gas (UOG) development, made possible by horizontal drilling and high-volume hydraulic fracturing, has been fraught with controversy since the industry's rapid expansion in the early 2000's. Concerns about environmental contamination and public health risks persist in many rural communities that depend on groundwater resources for drinking and other daily needs. Spatial disparities in UOG risks can pose distributive environmental injustice if such risks are disproportionately borne by marginalized communities. In this paper, we analyzed groundwater vulnerability to contamination from UOG as a physically based measure of risk in conjunction with census tract level sociodemographic characteristics describing social vulnerability in the northern Appalachian Basin. We found significant associations between elevated groundwater vulnerability and lower population density, consistent with UOG development occurring in less densely populated rural areas. We also found associations between elevated groundwater vulnerability and lower income, higher proportions of elderly populations, and higher proportion of mobile homes, suggesting a disproportionate risk burden on these socially vulnerable groups. We did not find a statistically significant association between elevated groundwater vulnerability and populations of racial/ethnic minorities in our study region. Household surveys provided empirical support for a relationship between sociodemographic characteristics and capacity to assess and mitigate exposures to potentially contaminated water. Further research is needed to probe if the observed disparities translate to differences in chemical exposure and adverse health outcomes.

Groundwaters in Northeastern Pennsylvania near intense hydraulic fracturing activities exhibit few organic chemical impacts.

Horizontal drilling with hydraulic fracturing (HDHF) relies on the use of anthropogenic organic chemicals in proximity to residential areas, raising concern for groundwater contamination. Here, we extensively characterized organic contaminants in 94 domestic groundwater sites in Northeastern Pennsylvania after ten years of activity in the region. All analyzed volatile and semi-volatile compounds were below recommended United States Environmental Protection Agency maximum contaminant levels, and integrated concentrations across two volatility ranges, gasoline range organic compounds (GRO) and diesel range organic compounds (DRO), were low (0.13 ± 0.06 to 2.2 ± 0.7 ppb and 5.2-101.6 ppb, respectively). Following dozens of correlation analyses with distance-to-well metrics and inter-chemical indicator correlations, no statistically significant correlations were found except: (1) GRO levels were higher within 2 km of violations and (2) correlation between DRO and a few inorganic species (e.g., Ba and Sr) and methane. The correlation of DRO with inorganic species suggests a potential high salinity source, whereas elevated GRO may result from nearby safety violations. Highest-concentration DRO samples contained bis-2-ethylhexyl phthalate and N,N-dimethyltetradecylamine. Nevertheless, the overall low rate of contamination for the analytes could be explained by a spatially-resolved hydrogeologic model, where estimated transport distances from gas wells over the relevant timeframes were short relative to the distance to the nearest groundwater wells. Together, the observations and modeled results suggest a low probability of systematic groundwater organic contamination in the region.