Experimental reduction of aqueous sulphate by hydrogen under hydrothermal conditions: Implication for the nuclear waste storage

Abstract

Sulphate reduction by hydrogen, likely to occur in deep geological nuclear waste storage sites, was studied experimentally in a two-phase system (water + gas) at 250–300 °C and under 4–16 bars H 2 partial pressure in hydrothermal-vessels. The calculated activation energy is 131 kJ/mol and the half-life of aqueous sulphate in the presence of hydrogen and elemental sulphur ranges from 210,000 to 2.7 × 10 9 years at respective temperatures of 90 °C, the thermal peak in the site and 25 °C, the ambient temperature far from the site. The features and rate of the sulphate reduction by H 2 are close to those established for TSR in oil fields. The experiments also show that the rate of sulphate reduction is not significantly affected in the H 2 pressure range of 4–16 bars and in the pH range of 2–5, whereas a strong increase is measured at pH below 2. We suggest that the condition for the reaction to occur is the speciation of sulphate dominated by non symmetric species ( HSO 4 - at low pH), and we propose a three steps reaction, one for each intermediate-valence sulphur species, the first one requiring H 2S as electron donor rather than H 2. We distinguish two possible reaction pathways for the first step, depending on pH: reduction of sulphate into sulphur dioxide below pH 2 or into thiosulphate or sulphite + elemental sulphur in the pH range 2–5.