Chemical and isotopic tracers of the contribution of microbial gas in Devonian organic-rich shales and reservoir sandstones, northern Appalachian Basin

Stephen G. Osborn, Jennifer C. McIntosh

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In this study, the geochemistry and origin of natural gas and formation waters in Devonian age organic-rich shales and reservoir sandstones across the northern Appalachian Basin margin (western New York, eastern Ohio, northwestern Pennsylvania, and eastern Kentucky) were investigated. Additional samples were collected from Mississippian Berea Sandstone, Silurian Medina Sandstone and Ordovician Trenton/Black River Group oil and gas wells for comparison. Dissolved gases in shallow groundwaters in Devonian organic-rich shales along Lake Erie contain detectable CH4 (0.01-50.55 mol%) with low δ13C-CH4 values (-74.68 to -57.86‰) and no higher chain hydrocarbons, characteristics typical of microbial gas. Nevertheless, these groundwaters have only moderate alkalinity (1.14-8.72 meq/kg) and relatively low δ13C values of dissolved inorganic C (DIC) (-24.8 to -0.6‰), suggesting that microbial methanogenesis is limited. The majority of natural gases in Devonian organic-rich shales and sandstones at depth (>168 m) in the northern Appalachian Basin have a low CH4 to ethane and propane ratios (3-35 mol%; C1/C2 + C3) and high δ13C and δD values of CH4 (-53.35 to -40.24‰, and -315.0 to -174.6‰, respectively), which increase in depth, reservoir age and thermal maturity; the molecular and isotopic signature of these gases show that CH4 was generated via thermogenic processes. Despite this, the geochemistry of co-produced brines shows evidence for microbial activity. High δ13C values of DIC (>+10‰), slightly elevated alkalinity (up to 12.01 meq/kg) and low SO4 values (<1 mmole/L) in select Devonian organic-rich shale and sandstone formation water samples suggest the presence of methanogenesis, while low δ13C-DIC values (<-22‰) and relatively high SO4 concentrations (up to 12.31 mmole/L) in many brine samples point to SO4 reduction, which likely limits microbial CH4 generation in the Appalachian Basin. Together the formation water and gas results suggest that the vast majority of CH4 in the Devonian organic-rich shales and sandstones across the northern Appalachian Basin margin is thermogenic in origin. Small accumulations of microbial CH4 are present at shallow depths along Lake Erie and in western NY.

Original languageEnglish (US)
Pages (from-to)456-471
Number of pages16
JournalApplied Geochemistry
Issue number3
StatePublished - Mar 1 2010


ASJC Scopus subject areas

  • Environmental Chemistry
  • Pollution
  • Geochemistry and Petrology

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