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.