The Redox Environment of Deep Groundwaters Associated with the Tono Uranium Deposit, Japan

Abstract

ABSTRACTAn unconformity underlying the Tono uranium deposit in central Japan represents the approximate location of a redox front separating relatively oxidizing groundwaters (Eh ≈0 mV) in the weathered, fractured Toki granite (TG) from strongly reducing pore fluids (Eh ≈-360 mV) in sedimentary rocks of the overlying Lower Toki Lignite-bearing Formation (TL). Uranium has been effectively immobilized in the TL during the past 10 million years. Stable and reversible redox potentials measured in-situ in boreholes penetrating the sedimentary rocks and granite appear to be controlled by the Fe(III)-oxyhydroxide – Fe2+ redox couple. A simplified analytical model of front migration suggests that chemical buffering by pyrite alone would limit the propagation velocity of the front into the TL to less than 8x10−6 m yr−1. The model is constrained by Darcy fluxes derived from groundwater flow models and relative 14C groundwater ages, average modal abundances of pyrite in the TL, and the analytical detection limit for dissolved oxygen in TG groundwaters (2 ppm). Model results also suggest that the redox buffering capacity of the TL would be exhausted within 10 million years if an upper bound O2(aq) concentration in TG groundwaters fixed by equilibrium with atmospheric O2(g) (8.5 ppm) is assumed. Immobilization of uranium in the TL is thus attributable to oxidation-reduction reactions that minimize O2(aq) concentrations primarily in the TG, and secondarily in the TL.