The yield and isotopic composition of radiolytic H2, a potential energy source for the deep subsurface biosphere

The production rate and isotopic composition of H₂ derived from radiolytic reactions in H₂O were measured to assess the importance of radiolytic H₂ in subsurface environments and to determine whether its isotopic signature can be used as a diagnostic tool. Saline and pure, aerobic and anaerobic water samples with pH values of 4, 7, and 10 were irradiated in sealed vials at room temperature with an artificial γ source, and the H₂ abundance in the headspace and its isotopic composition were measured. The H₂ concentrations were observed to increase linearly with dosage at a rate of 0.40 ± 0.04 molecules (100 eV)⁻¹ within the dosage range of 900 to 3500 Gray (Gy; Gy = 1 J Kg⁻¹) with no indication of a maximum limit on H₂ concentration. At ∼2000 Gy, the H₂ concentration varied only by 16% across the experimental range of pH, salinity, and O₂. Based upon this measured yield and H₂ yields for α and β particles, a radiolytic H₂ production rate of 10⁻⁹ to 10⁻⁴ nM s⁻¹ was estimated for the range of radioactive element concentrations and porosities typical of crustal rocks. The δD of H₂ was independent of the dosage, pH (except for pH 4), salinity, and O₂ and yielded an αD_H2O-H2 of 2.05 ± 0.07 (αD_H2O-H2 = (D/H)_H2O to (D/H)_H2), slightly less than predicted radiolytic models. Although this radiolytic fractionation value is significantly heavier than that of equilibrium isotopic exchange between H₂ and H₂O, the isotopic exchange rate between H₂ and H₂O will erase the heavy δD of radiolytic H₂ if the age of the groundwater is greater than ∼10³ to 10⁴ yr. The millimolar concentrations of H₂ observed in the groundwater of several Precambrian Shields are consistent with radiolysis of water that has resided in the subsurface for a few million years. These concentrations are well above those required to support H₂-utilizing microorganisms and to inhibit H₂-producing, fermentative microorganisms.