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A reconnaissance spatial and temporal assessment of methane and inorganic constituents in groundwater in bedrock aquifers, Pike County, Pennsylvania, 2012-13

July 22, 2014

Pike County in northeastern Pennsylvania is underlain by the Devonian-age Marcellus Shale and other shales, formations that have potential for natural gas development. During 2012–13, the U.S. Geological Survey in cooperation with the Pike County Conservation District conducted a reconnaissance study to assess baseline shallow groundwater quality in bedrock aquifers prior to possible shale-gas development in the county. For the spatial component of the assessment, 20 wells were sampled in summer 2012 to provide data on the occurrence 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. For the temporal component of the assessment, 4 of the 20 wells sampled in summer 2012 were sampled monthly from July 2012 through June 2013 to provide data on seasonal variability in groundwater quality. All water samples were analyzed for major ions, nutrients, selected inorganic trace constituents (including metals and other elements), stable isotopes of water, radon-222, gross alpha- and gross beta-particle activity, dissolved gases (methane, ethane, and ethene), and, if possible, isotopic composition of methane. Additional analyses for boron and strontium isotopes, age-dating of water, and radium-226 were done on water samples collected from six wells in June 2013.

Results of the summer 2012 sampling show that water from 16 (80 percent) of 20 wells had detectable concentrations of methane, but concentrations were less than 0.1 milligram per liter (mg/L) in most well-water samples; only two well-water samples had concentrations greater than 1 mg/L. The groundwater with elevated methane also had a chemical composition that differed in some respects (pH, selected major ions, and inorganic trace constituents) from groundwater with low methane concentrations. The two well-water samples with the highest methane concentrations (about 3.7 and 5.8 mg/L) also had the highest pH values (8.7 and 8.3, respectively) and the highest concentrations of sodium, lithium, boron, fluoride, and bromide. Elevated concentrations of some other constituents, such as barium, strontium, and chloride, were not limited to well-water samples with elevated methane, although the two samples with elevated methane also had among the highest concentrations of these constituents.

One sample with elevated methane concentrations also had elevated arsenic concentrations, with the arsenic concentration of 30 micrograms per liter (μg/L) exceeding the drinking-water standard of 10 µg/L for arsenic. No other sample from the 20 wells sampled in summer 2012 had concentrations of constituents that exceeded any established primary drinking-water standards. However, radon-222 activities ranging up to 4,500 picocuries per liter (pCi/L) exceeded the proposed drinking-water standard of 300 pCi/L in 85 percent of the 20 well-water samples.

The isotopic composition methane in the two high-methane samples (δCCH4 values of -64.55 and -64.41 per mil and δDCH4 values of -216.9 and -201.8 per mil, respectively) indicates a predominantly microbial source for the methane formed by a carbon dioxide reduction process. The stable isotopic composition of water (δDH20 and δ18OH20) in samples from all 20 wells falls on the local meteoric line, indicating water in the wells was of relatively recent meteoric origin (modern precipitation), including samples with elevated methane concentrations.

Analytical results for 4 of the 20 wells sampled monthly for 1 year ending June 2013 in order to assess temporal variability in groundwater quality show that concentrations of major ions generally varied by less than 20 percent, with most differences less than 4 mg/L. Concentrations of methane varied by less than 1 μg/L (0.001 mg/L) in samples from three wells with low methane and by as much as 1 mg/L (1,000 μg/L) in samples from one well with relatively high methane. The isotopic composition of methane in the one well with relatively high methane varied slightly in the monthly samples, ranging from about -64.5 to -64.8 per mil for δ13CCH4 and from about -217 to -228 per mil for δDCH4. The δ13C values for dissolved inorganic carbon (DIC) in water from this well were consistent with microbial methane formation by carbon dioxide reduction (drift-type methane) and varied little in the temporal samples, ranging from -10.5 to -10.1 per mil.

Additional analyses of samples collected in late June 2013 from six wells with a range of methane and trace constituent concentrations provided baseline data on strontium and boron isotopic compositions (87Sr/86Sr ratios and δ11B, respectively) that potentially may be used to differentiate among sources of these constituents. The strontium and boron isotopic composition determined in the six shallow Pike County groundwater samples had 87Sr/86Sr ratios of 0.71426 to 0.71531 and δ11B values of 11.7 to 27.0 per mil, which differ from those reported for brines in Devonian-age formations in Pennsylvania.

The June 2013 samples were also analyzed for radium-226 and age-dating dissolved gases. Activities of radium-226 ranged from 0.041 to 0.29 pCi/L in water samples from the six wells and were less than the drinking-water standard of 5 pCi/L for combined radium-226 and radium-228. Age-dating of groundwater using a method based on the presence of anthropogenic gases (chlorofluorocarbons and sulfur hexafluoride) released into the atmosphere yielded estimated recharge dates for water from these six wells that ranged from the 1940s to early 2000s. The oldest water was in samples from wells that had the highest methane concentrations and the youngest water was in samples from a continuously pumped 300-foot deep production well.

Publication Year 2014
Title A reconnaissance spatial and temporal assessment of methane and inorganic constituents in groundwater in bedrock aquifers, Pike County, Pennsylvania, 2012-13
DOI 10.3133/sir20145117
Authors Lisa A. Senior
Publication Type Report
Publication Subtype USGS Numbered Series
Series Title Scientific Investigations Report
Series Number 2014-5117
Index ID sir20145117
Record Source USGS Publications Warehouse
USGS Organization Pennsylvania Water Science Center