The number of Marcellus Shale gas wells drilled in the Appalachian basin has increased rapidly over the past decade, leading to increased interest in the highly saline water produced with the natural gas which must be recycled, treated, or injected into deep disposal wells. New geochemical and isotopic analyses of produced water for 3 time-series and 13 grab samples from Marcellus Shale gas wells in southwest and north central Pennsylvania (PA) are used to address the origin of the water and solutes produced over the long term (>12 months). The question of whether the produced water originated within the Marcellus Shale, or whether it may have been drawn from adjacent reservoirs via fractures is addressed using measurements of and activity. These parameters indicate that the water originated in the Marcellus Shale, and can be more broadly used to trace water of Marcellus Shale origin.

During the first 1–2 weeks of production, rapid increases in salinity and positive shifts in values were observed in the produced water, followed by more gradual changes until a compositional plateau was reached within approximately 1 yr. The values and relationships between Na, Cl, and Br provide evidence that the water produced after compositional stabilization is natural formation water, the salinity for which originated primarily from evaporatively concentrated paleoseawater. The rapid transition from injected water to chemically and isotopically distinct water while of the injected water volume had been recovered, supports the hypothesis that significant volumes of injected water were removed from circulation by imbibition.