Chemical and isotopic characteristics of methane in groundwater of Ohio, 2016

Abstract

In 2016, the U.S. Geological Survey, in cooperation with the Ohio Water Development Authority, investigated the hydrogeologic setting, chemical and isotopic characteristics, and origin of methane in groundwater of Ohio. Understanding the occurrence and distribution of methane in groundwater is important in terms of public safety because methane in water wells can pose a risk of explosion. In addition, documenting the chemical and isotopic characteristics of methane in groundwater can make an important contribution to future stray gas investigations. Water samples were collected from 15 domestic water wells known to produce methane, which were in 12 counties in diverse parts of Ohio. The wells were 75–345 feet deep and tapped a range of aquifer types, including glacial deposits and bedrock of Upper Ordovician, Upper Devonian, Lower Mississippian, and Pennsylvanian ages. Although the hydrogeologic settings were varied, there was a broad similarity among the well sites in that the bedrock was predominantly shale and the glacial deposits were predominantly clay. The wells were sampled for dissolved inorganic constituents; dissolved organic carbon; methane and other dissolved gases; stable isotopes (carbon, hydrogen, and oxygen) of methane, water, and dissolved inorganic carbon; and carbon-14 of methane. Gas composition and stable isotopes of methane were used to differentiate thermogenic and microbial methane. The degree of fractionation of hydrogen and carbon isotopes was used to evaluate the pathway of microbial methanogenesis (carbon dioxide [CO 2 ] reduction or acetate fermentation) and the effects of secondary processes such as oxidation, mixing, and migration. The concentration of carbon-14 of methane was used to evaluate the relative age of the carbon source. The quality of water from the 15 wells differed greatly; water types ranged from CaMgHCO 3 to NaCl, and total dissolved solids concentrations ranged from 318 to 2,940 milligrams per liter (mg/L). Methane concentrations ranged from 1.2 to 120 mg/L. Of the 15 samples, 12 had methane concentrations greater than 28 mg/L, the level that can pose a risk of explosion. Of the 15 samples, 12 had chemical and isotopic characteristics or "signatures" consistent with microbial methane formed by CO 2 reduction. CO 2 reduction is commonly associated with microbial degradation of organic matter in anaerobic aquifers and with the formation of microbial shale gas and coalbed methane along margins of sedimentary basins. Two of 15 samples were interpreted as having a component of thermogenic methane based on the δ 13 C of methane (−50.96 and −47.74 parts per thousand [per mil]) and gas dryness (28 and 5). One of 15 samples (from the shallowest well) had chemical and isotopic characteristics consistent with methane oxidation by sulfate reduction based on light δ 13 C of dissolved inorganic carbon (−31.6 per mil) and evidence of sulfate reduction in terms of the odor and appearance of the water. For the 12 samples interpreted as microbial methane formed by CO 2 reduction, the δ 13 C of methane varied from −75 to −56 per mil. Multiple samples from the same aquifer demonstrated a general trend of increasing δ 13 C of methane with depth. Samples with lighter δ 13 C of methane (−75 to −62 per mil) were from shallower wells (or wells with shallow open intervals), and the isotopic signature of the water was consistent with modern or postglacial groundwater recharge. Three samples with heavier δ 13 C of methane (−61 to −56 per mil) were from deeper wells or more confined aquifers where the isotopic signature of water was consistent with older (glacial) recharge. In addition, δ 13 C of dissolved inorganic carbon was enriched (+12 to +18.9 per mil), and carbon-14 of methane was consistent with carbon associated with Paleozoic bedrock or older glacial deposits. These observations are generally consistent with increased Rayleigh-type fractionation at greater depths; however, other interpretations are possible. Isotopic signatures can be ambiguous, especially in areas with complex geologic histories that include multiple episodes of migration, mixing, and (or) oxidation. Many of the wells were in proximity to multiple potential natural and anthropogenic pathways of methane migration; however, it is not possible to determine if the methane in any of the wells is related to human activities based on the chemical and isotopic data collected for this study.