The mobility and bioavailability of selenium is a major health and environmental issue and a main concern for geological disposal of high-level radioactive waste. Chemically and/or microbially mediated oxidation of insoluble Se-bearing particulate, such as iron selenides, to dissolved and mobile phases controls the transport and distribution of Se in the environment. The oxidation of ferroselite(FeSe2) by ferric iron was investigated in anoxic conditions. The redox reaction can be represented by: FeSe2 + 2Fe3+ = 2Se0 + 3Fe2+. Kinetic studies indicated that the reaction can be described by second-order rate law, with rate constants of 0.49±0.01, 0.85±0.02, 1.84±0.04, and 3.29±0.13 L mol-1 s-1 at pH 1.62, 1.87, 2.23, and 2.49, respectively. The positive correlation between reaction rate and pH implies that diffusion of Fe3+ oxidant to the mineral surface is the rate-determining step. The strong reactivity of FeSe2 towards Fe3+ suggests that ferric iron may play a significant role in FeSe2 oxidation process(e.g., by Se4+, O2, etc.) and Se0 should be the first reaction product. Also, it was shown that the reduction rate of Fe3+ or Se4+ by pyrite(FeS2) can be significantly increased in the presence of FeSe2, suggesting a stronger reactivity of FeSe2 compared with pyrite. The results obtained extend our knowledge about the subtle interaction between Se, pyrite and iron selenides in the environment, and give insight into the transfer of selenium from iron selenides to bio-available selenium(i.e., selenite and selenate) in the Se-rich environment. The mobility and bioavailability of selenium is a major health and environmental issue and a main concern for geological disposal of high-level radioactive waste. Chemically and / or microbially mediated oxidation of insoluble Se-bearing particulate, such as iron selenides, to dissolved and mobile phases controls the transport and distribution of Se in the environment. The oxidation of ferroselite (FeSe2) by ferric iron was investigated in anoxic conditions. The redox reaction can be represented by: FeSe2 + 2Fe3 + = 2Se0 + 3Fe2 +. Kinetic studies indicated that the reaction can be described by second-order rate law with rate constants of 0.49 ± 0.01, 0.85 ± 0.02, 1.84 ± 0.04, and 3.29 ± 0.13 L mol-1 s-1 at pH 1.62, 1.87, 2.23, and 2.49, respectively. The positive correlation between reaction rate and pH implies that diffusion of Fe3 + oxidant to the mineral surface is the rate-determining step. The strong reactivity of FeSe2 towards Fe3 + suggests that ferric iron may play a significant role in Also, it was shown that the reduction rate of Fe3 + or Se4 + by pyrite (FeS2) can be greatly increased in the presence of FeSe2 (eg, by Se4 +, O2, etc.) and Se0 should be the first reaction product , suggesting a stronger reactivity of FeSe2 compared with pyrite. The results obtained extend our knowledge about the subtle interaction between Se, pyrite and iron selenides in the environment, and give insight into the transfer of selenium from iron selenides to bio-available selenium (ie , selenite and selenate) in the Se-rich environment.