The reductive immobilization of aqueous Se(IV) by natural pyrrhotite

The interaction of Se(IV) with natural pyrrhotite was investigated at pH conditions ranging from acidic to nearly neutral. The results indicate that the reduction rate can be described in terms of a pseudo-first order reaction. At pH ∼4.0 to ∼5.0, the rate decreased with increasing pH. Unexpectedly, at pH ∼5.0, the rate increased with increasing reaction time. This response was also observed at pH ∼6.0. Two different reaction mechanisms were proposed to explain pyrrhotite oxidation by Se(IV). Because pyrrhotite is acid-soluble and can be attacked by both Fe(3+) and protons, direct reduction by the released aqueous sulfide dominates the reaction at low pH, whereas the cyclic oxidation of aqueous Fe(2+) adsorbed on pyrrhotite surfaces becomes predominant at high pH. Phosphate, which can be irreversibly bound to Fe(3+) intermediates even under acidic conditions, can significantly decrease the reaction rate by an order of magnitude at pH ∼4.5. In contrast to the thermodynamic calculations and the predicted prevalence of FeSe based on previous reports of aqueous Se(IV) reduction by synthetic mackinawite or troilite, only Se(0) was observed as the reaction product in this study. This observation confirmed that a slow reaction favors the formation of Se(0) rather than iron selenides.