Temperature-dependent Li isotope ratios in Appalachian Plateau and Gulf Coast Sedimentary Basin saline water

Lithium (Li) concentrations of produced water from unconventional (horizontally drilled and hydraulically fractured shale) and conventional gas wells in Devonian reservoirs in the Appalachian Plateau region of western Pennsylvania range from 0.6 to 17mmolkg(-1), and Li isotope ratios, expressed as in Li-7, range from +8.2 to +15 parts per thousand. Li concentrations are as high as 40mmolkg(-1) in produced waters from Plio-Pleistocene through Jurassic-aged reservoirs in the Gulf Coast Sedimentary Basin analyzed for this study, and Li-7 values range from about +4.2 to +16.6 parts per thousand. Because of charge-balance constraints and rock buffering, Li concentrations in saline waters from sedimentary basins throughout the world (including this study) are generally positively correlated with chloride (Cl), the dominant anion in these fluids. Li concentrations also vary with depth, although the extent of depth dependence differs among sedimentary basins. In general, Li concentrations are higher than expected from seawater or evaporation of seawater and therefore require water-mineral reactions that remove lithium from the minerals. Li isotope ratios in these produced waters vary inversely with temperature. However, calculations of temperature-dependent fractionation of Li-7 between average shale Li-7 (-0.7 parts per thousand) and water result in Li-7(water) that is more positive than that of most produced waters. This suggests that aqueous Li-7 may reflect transport of water from depth and/or reaction with rocks having Li-7 lighter than average shale.