Road salting and natural brine migration revealed as major sources of groundwater contamination across regions of northern Appalachia with and without unconventional oil and gas development.

High methane and salt levels in groundwater have been the most widely cited unconventional oil and gas development (UOGD) related water impairments. The attribution of these contaminants to UOGD is usually complex, especially in regions with mixed land uses. Here, we compiled a large hydrogeochemistry dataset containing 13 geochemical analytes for 17,794 groundwater samples from rural northern Appalachia, i.e., 19 counties located on the boundary between Pennsylvania (PA; UOGD is permitted) and New York (NY; UOGD is banned). With this dataset, we explored if statistical and geospatial tools can help shed light on the sources of inorganic solutes and methane in groundwater in regions with mixed land uses. The traditional Principal Component Analysis (PCA) indicates salts in NY and PA groundwater are mainly from the Appalachian Basin Brine (ABB). In contrast, the machine learning tool - Non-negative Matrix Factorization (NMF) highlights that road salts (in addition to ABB) account for 36%-48% of total chloride in NY and PA groundwaters. The PCA fails to identify road salts as one water/salt source, likely due to its geochemical similarity with ABB. Neither PCA nor NMF detects a regional impact of UOGD on groundwater quality. Our geospatial analyses further corroborate (1) road salting is the major salt source in groundwater, and its impact is enhanced in proximity to highways; (2) UOGD-related groundwater quality deterioration is only limited to a few localities in PA.

Geochemical Evidence of Potential Groundwater Contamination with Human Health Risks Where Hydraulic Fracturing Overlaps with Extensive Legacy Hydrocarbon Extraction.

Unconventional oil and gas development (UOGD) sometimes impacts water resources, including incidents of methane (CH4) migration from compromised wells and spills that degrade water with salts, organics, and metals. We hypothesized that contamination may be more common where UOGD overlaps with legacy coal, oil, and gas extraction. We tested this hypothesis on ∼7000 groundwater analyses from the largest U.S. shale gas play (Marcellus), using data mining techniques to explore UOGD contamination frequency. Corroborating the hypothesis, we discovered small, statistically significant regional correlations between groundwater chloride concentrations ([Cl]) and UOGD proximity and density where legacy extraction was extremely dense (southwestern Pennsylvania (SWPA)) but no such correlations where it was minimal (northeastern Pennsylvania). On the other hand, legacy extraction of shallow gas in SWPA may have lessened today's gas leakage, as no regional correlation was detected for [CH4] in SWPA. We identify hotspots where [Cl] and [CH4] increase by 3.6 and 3.0 mg/L, respectively, per UOG well drilled in SWPA. If the [Cl] correlations document contamination via brines leaked from wellbores, impoundments, or spills, we calculate that thallium concentrations could exceed EPA limits in the most densely developed hotspots, thus posing a potential human health risk.