Hydraulic fracturing for gas production is now ubiquitous in shale plays, but relatively little is known about shale-hydraulic fracturing fluid (HFF) reactions within the reservoir. To investigate reactions during the shut-in period of hydraulic fracturing, experiments were conducted flowing different HFFs through fractured Marcellus shale cores at reservoir temperature and pressure (66 °C, 20 MPa) for one week. Results indicate HFFs with hydrochloric acid cause substantial dissolution of carbonate minerals, as expected, increasing effective fracture volume (fracture volume + near-fracture matrix porosity) by 56-65%. HFFs with reused produced water composition cause precipitation of secondary minerals, particularly barite, decreasing effective fracture volume by 1-3%. Barite precipitation occurs despite the presence of antiscalants in experiments with and without shale contact and is driven in part by addition of dissolved sulfate from the decomposition of persulfate breakers in HFF at reservoir conditions. The overall effect of mineral changes on the reservoir has yet to be quantified, but the significant amount of barite scale formed by HFFs with reused produced water composition could reduce effective fracture volume. Further study is required to extrapolate experimental results to reservoir-scale and to explore the effect that mineral changes from HFF interaction with shale might have on gas production.

CO2 sequestration in the form of carbonate minerals via alteration of oceanic crust and upper mantle is an important part of the global carbon cycle, but the annual rate of CO2 mineralization is not well quantified. This study aimed to constrain groundwater ages within the Samail ophiolite, Sultanate of Oman. Such ages could provide upper bounds on the time required for ongoing low temperature CO2 mineralization. While we were able to estimate apparent groundwater ages for modern waters, results from hyperalkaline boreholes and springs were disappointing. Waters from boreholes and hyperalkaline springs within the ophiolite were characterized using multiple environmental tracers including tritium (3 H), noble gases (He, 4 He, Ne, Ar, Kr, Xe), stable isotopes (δ 18 O, δ 2 H), and chemical parameters (pH, Ca, Mg, DIC, etc.). Shallow peridotite groundwater and samples from boreholes near the mantle transition zone have a pH < 9.3, are 4-40 years old, have little to no non-atmospheric He accumulation, NGTs (noble gas temperatures) equivalent to the modern mean annual ground temperature, and stable isotopes within the range of current local precipitation. In contrast, hyperalkaline springs and deeper samples from peridotite boreholes have pH > 10, are pre-H-bomb (older than 1952), have significant non-atmospheric helium accumulation (30-70% of dissolved helium), often are isotopically heavier (enriched in δ 18 O), and can have NGTs 6-7 o C lower than the modern ground temperature. These differences suggest that groundwater in deep (> 50 m) peridotite aquifers is considerably older than shallow groundwater in peridotite and water in deeper aquifers near the mantle transition zone. Unfortunately, how much older remains an open question. The low NGT of groundwater from one deep (300 m) peridotite borehole indicates it is probably glacial in origin. If so, it must date back to at least the late Pleistocene, the most recent glacial period; He accumulation suggests it could be from 20-220 ka. The inefficacy of this suite of environmental tracers to quantitatively estimate apparent groundwater age for hyperalkaline fluids necessitates the use of different techniques. Future work to constrain groundwater ages should utilize a packer system to isolate discrete depth intervals within boreholes and less common environmental tracers such as 39 Ar and 81 Kr.