Variation in Lithium Isotopes During Fluid-Shale Interactions at Elevated Pressure and Temperature

Abstract:

Naturally-occurring isotopes are useful tracers of fluid mixing in complex natural systems, and have been applied towards evaluating the sources of elevated total dissolved solids in water produced from unconventional oil and gas operations. Prior investigations showed that elevated Li in saline waters co-produced with natural gas during Marcellus Shale development resulted from mixing of hydraulic fracturing fluid (HFF) and Li-rich formation water. However, specific contributions to the Li isotope signature from reactions between the HFF and shale remained unclear. This study focused on HFF-shale reactions that could affect the Li budget and isotope composition in Marcellus Shale produced water in a series of flow through experiments conducted at fixed temperature and pressure (66^oC, 20MPa) comparable to formation conditions. Synthetic HFF was prepared by mixing either freshwater or a lab-derived saline water with chemical additives commonly used in hydraulic fracturing. Outcrop cores of Marcellus Shale were artificially fractured either parallel to or perpendicular to bedding prior to loading into the flow-through apparatus, and each experiment was performed with a unique HFF composition continuously pumped through a fresh core (15 cm in length, 3.8 cm in diameter). Initial fluid and cumulative effluents collected after 2 days and 7 days from the start of the experiment were measured for concentrations of cations and anions. Multi-collector ICP-MS was used to measure lithium isotope ratios (δ⁷Li).

Preliminary results show that dissolution of carbonate minerals occurred in both replicate experiments with freshwater-based HFF (pH 2) as shown by a large decrease in Li/Ca from 0.8 (initial fluid) to 0.003 (effluents on day 2 and day 7) with no significant change in Li concentration. This is consistent with low Li in carbonate cement (<2%) and water soluble (<8%) and exchangeable (<2%) fractions of Marcellus Shale. Variation in δ⁷Li values is within analytical uncertainty (2SD=1‰) in comparison to an increase of at least 3‰ (from 1^st day to >45 days after production) in produced water samples from the field. Results to date suggest that HFF-shale reactions have a minimal effect on the Li isotopic signature of Marcellus Shale produced waters.