Radium release mechanisms during hydraulic fracturing of Marcellus Shale

Wastewater co-produced with methane from Devonian Marcellus Shale is hypersaline and enriched in Ra. Recent studies find that water injected during hydraulic fracturing can leach out significant quantities of Na, Ca, Ba and Sr from solid phases in the shale over just hours to days. Here, we show with water-rock leaching experiments that the measured 226Ra/228Ra ratios of Marcellus wastewater could also derive from rapid leaching of mineral and organic phases of the shale. Radium isotopes 226Ra (t1/2 = 1600 a) and 228Ra (t1/2 = 5.8 a) are produced through radioactive decay of 238U (t1/2 = 4.5 Ga) and 232Th (t1/2 = 14 Ga), respectively. In the absence of processes that fractionate U, Th and Ra from one another, the decay rates of each parent-daughter pair become identical over 5 half-lives of the daughter radionuclide reaching a condition of secular equilibrium. Water-rock interaction may induce pronounced deviations from secular equilibrium in the water phase, however. Such is the case during hydraulic fracturing, where Ra is soluble and mobile, and is orphaned from insoluble U and Th parents. Once 226Ra and 228Ra are mobilized no fractionation between these isotopes is expected during their transport to the surface. Thus the 226Ra/228Ra ratio in wastewater provides a fingerprint of Ra source(s). Leaching Marcellus Shale with pure water under anoxic conditions releases mainly 228Ra from clays; extraction of 228Ra from radiation damaged sites is likely the dominant contributing mechanism. Using a novel isotope dilution technique we find that 90% of the Ra released in pure water partitions back onto rock (possibly clays). In comparison, leaching with high ionic strength solutions induces the release of 226Ra from mainly organics; the breakdown of organic matter in these solutions may be the driving mechanism controlling 226Ra release in solution. Radium released by high ionic strength solutions strongly partitions into water and results in the development of leachates with high 226Ra/228Ra ratios that are comparable to those of Marcellus wastewaters. Our results suggest that hydraulic fracturing using dilute HCl solution releases Ca and Na from the shale and effects rapid Ra release from the rock. Hypersaline and radioactive wastewater is thus a consequence of active leaching of shale during hydraulic fracturing.