Barium Isotopes Track the Source of Dissolved Solids in Produced Water from the Unconventional Marcellus Shale Gas Play.

Waters coproduced with hydrocarbons from unconventional oil and gas reservoirs such as the hydraulically fractured Middle Devonian Marcellus Shale in the Appalachian Basin, USA, contain high levels of total dissolved solids (TDS), including Ba, which has been variously ascribed to drilling mud dissolution, interaction with pore fluids or shale exchangeable sites, or fluid migration through fractures. Here, we show that Marcellus Shale produced waters contain some of the heaviest Ba (high 138Ba/134Ba) measured to date (δ138Ba = +0.36‰ to +1.49‰ ± 0.06‰) and are distinct from overlying Upper Devonian/Lower Mississippian reservoirs (δ138Ba = -0.83‰ to -0.52‰). Marcellus Shale produced water values do not overlap with drilling mud barite (δ138Ba ≈ 0.0‰) and are significantly offset from Ba reservoirs within the producing portion of the Marcellus Shale, including exchangeable sites and carbonate cement. Precipitation, desorption, and diffusion processes are insufficient or in the wrong direction to produce the observed enrichments in heavy Ba. We hypothesize that the produced water is derived primarily from brines adjacent to and most likely below the Marcellus Shale, although such deep brines have not yet been obtained for Ba isotope analysis. Barium isotopes show promise for tracking formation waters and for understanding water-rock interaction under downhole conditions.

Application of isotopic and geochemical signals in unconventional oil and gas reservoir produced waters toward characterizing in situ geochemical fluid-shale reactions.

Optimizing hydrocarbon production and waste management from unconventional oil and gas extraction requires an understanding of the fluid-rock chemical interactions. These reactions can affect flow pathways within fractured shale and produced water chemistry. Knowledge of these chemical reactions also provides valuable information for planning wastewater treatment strategies. This study focused on characterizing reservoir reactions through analysis of produced water chemistry from the Marcellus Shale Energy and Environmental Laboratory field site in Morgantown, WV, USA. Analysis of fracturing fluids, time-series produced waters (PW) over 16 months of operation of two hydraulically fractured gas wells, and shale rocks from the same well for metal concentrations and multiple isotope signatures (δ2H and δ18O of water, δ7Li, δ11B, 87Sr/86Sr) showed that the chemical and isotopic composition of early (<10 days) PW samples record water-rock interactions during the fracturing period. Acidic dissolution of carbonate minerals was evidenced by the increase in TOC, B/Na, Sr/Na, Ca/Na, and the decrease in 87Sr/86Sr in PW returning in the first few days toward the 87Sr/86Sr signature of carbonate cement. The enrichment of 6Li in these early (e.g., day 1) PW samples is most likely a result of desorption of Li from clays and organic matter due to the injection of fracturing fluid. Redox-active trace elements appear to be controlled by oxidation-reduction reactions and potentially reactions involving wellbore steel. Overall, PW chemistry is primarily controlled by mixing between early PW with local in-situ formation water however certain geochemical reactions (e.g., carbonate cement dissolution and desorption of 6Li from clays and organic matter) can be inferred from PW composition monitored immediately over the first ten days of water return.