Baseline assessment of groundwater quality in Wayne County, Pennsylvania, 2014
The Devonian-age Marcellus Shale and the Ordovician-age Utica Shale, geologic formations which have potential for natural gas development, underlie Wayne County and neighboring counties in northeastern Pennsylvania. In 2014, the U.S. Geological Survey, in cooperation with the Wayne Conservation District, conducted a study to assess baseline shallow groundwater quality in bedrock aquifers in Wayne County prior to potential extensive shale-gas development. The 2014 study expanded on previous, more limited studies that included sampling of groundwater from 2 wells in 2011 and 32 wells in 2013 in Wayne County. Eighty-nine water wells were sampled in summer 2014 to provide data on the presence of methane and other aspects of existing groundwater quality throughout the county, including concentrations of inorganic constituents commonly present at low levels in shallow, fresh groundwater but elevated in brines associated with fluids extracted from geologic formations during shale-gas development. Depths of sampled wells ranged from 85 to 1,300 feet (ft) with a median of 291 ft. All of the groundwater samples collected in 2014 were analyzed for bacteria, major ions, nutrients, selected inorganic trace constituents (including metals and other elements), radon-222, gross alpha- and gross beta-particle activity, selected man-made organic compounds (including volatile organic compounds and glycols), dissolved gases (methane, ethane, and propane), and, if sufficient methane was present, the isotopic composition of methane. Results of the 2014 study show that groundwater quality generally met most drinking-water standards, but some well-water samples had one or more constituents or properties, including arsenic, iron, pH, bacteria, and radon-222, that exceeded primary or secondary maximum contaminant levels (MCLs). Arsenic concentrations were higher than the MCL of 10 micrograms per liter (µg/L) in 4 of 89 samples (4.5 percent) with concentrations as high as 20 µg/L; arsenic concentrations were higher than the Health Advisory level of 2 µg/L in 27 of 89 samples (30 percent). Total iron concentrations exceeded the secondary maximum contaminant level (SMCL) of 300 µg/L in 9 of 89 samples (10 percent). The pH ranged from 5.4 to 9.3 and did not meet the SMCL range of greater than 6.5 to less than 8.5 in 27 samples (30 percent); 22 samples had pH values less than 6.5, and 5 samples had pH values greater than 8.5. Total coliform bacteria were detected in 22 of 89 samples (25 percent); Escherichia coli were detected in only 2 of those 22 samples. Radon-222 activities ranged from 25 to 7,400 picocuries per liter (pCi/L), with a median of 2,120 pCi/L, and exceeded the proposed drinking-water standard of 300 pCi/L in 86 of 89 samples (97 percent); radon-222 activities were higher than the alternative proposed standard of 4,000 pCi/L in 12 of 89 samples (13.5 percent). Water from 8 of the 89 wells (9 percent) had concentrations of methane greater than the reporting level of 0.24 milligrams per liter (mg/L) with the detectable methane concentrations ranging from 0.74 to 9.6 mg/L. Of 16 replicate samples submitted to another laboratory with a lower reporting level of 0.0002 mg/L, 15 samples had detectable methane concentrations that ranged from 0.0011 to 9.7 mg/L. Of these 15 samples, low levels of ethane (0.00032 to 0.0017 mg/L) were detected in 6 of 7 samples with methane concentrations greater than 0.75 mg/L. The isotopic composition of methane in 6 of 8 samples with sufficient dissolved methane (about 1 mg/L) for isotopic analysis is consistent with a predominantly thermogenic methane source (sample carbon isotopic ratio δ13C CH4 values ranging from -56.36 to -45.97 parts per thousand (‰) and hydrogen isotopic ratio δD CH4 values ranging from -233.1 to -141.1 ‰). However, the low levels of ethane relative to methane indicate that the methane may be of microbial origin and subsequently underwent oxidation. Isotopic compositions indicated a possibly mixed thermogenic and microbial source (carbon dioxide reduction process) for the methane in 1 of the 8 samples (δ 13 C CH4 of -63.72 and δD CH4 of -192.3 ‰) and potential oxidation of microbial and (or) thermogenic methane in the remaining sample (δ 13 C CH4 of -46.56 and δD CH4 of -79.7 ‰). Groundwater samples with relatively elevated methane concentrations (near or greater than 1 mg/L) had a chemical composition that differed in some respects (pH, selected major ions, and inorganic trace constituents) from groundwater with relatively low methane concentrations (less than 0.75 mg/L). The seven well-water samples with the highest methane concentrations (from about 1 to 9.6 mg/L) also had among the highest pH values (8.1 to 9.3, respectively) and the highest concentrations of sodium, lithium, boron, fluoride, arsenic, and bromide. Relatively elevated concentrations of some other constituents, such as barium, strontium, and chloride, commonly were present in, but not limited to, those well-water samples with elevated methane. Groundwater samples with the highest methane concentrations had chloride/bromide ratios that indicate mixing with a small amount of brine (0.02 percent or less, by volume) similar in composition to that reported for gas and oil well brines in Pennsylvania. Most other samples with low methane concentrations (less than about 1 mg/L) had chloride/bromide ratios that indicate predominantly man-made sources of chloride, such as road salt, septic systems, and (or) animal waste. Although naturally occurring brines may originate from deeper parts of the aquifer system, the man-made sources are likely to affect shallow groundwater. Geochemical modeling showed that the water chemistry of samples with elevated pH, sodium, lithium, bromide, and alkalinity could result from dissolution of calcite (calcium carbonate) combined with cation exchange and mixing with a small amount of brine. Through cation exchange reactions (which are equivalent to processes in a water softener) calcium ions released by calcite dissolution are exchanged for sodium ions on clay minerals. The spatial distribution of groundwater compositions generally shows that (1) relatively dilute, slightly acidic, oxygenated, calcium-carbonate type waters tend to occur in the uplands along the western border of Wayne County; (2) waters of near neutral pH with the highest amounts of hardness (calcium and magnesium) generally occur in areas of intermediate altitudes; and (3) waters with pH values greater than 8, low oxygen concentrations, and the highest arsenic, sodium, lithium, bromide, and methane concentrations can occur in deep wells in uplands but most frequently occur in stream valleys, especially at low elevations (less than about 1,200 ft above North American Vertical Datum of 1988) where groundwater may be discharging regionally, such as to the Delaware River. Thus, the baseline assessment of groundwater quality in Wayne County prior to gas-well development shows that shallow (less than about 1,000 ft deep) groundwater is generally of good quality, but methane and some constituents present in high concentrations in brine (and produced waters from gas and oil wells) may be present at low to moderate concentrations in some parts of Wayne County.