Oxidation and mobilization of selenium by nitrate in irrigation drainage

Abstract

Selenium (Se) can be oxidized by nitrate (NO − 3 ) from irrigation on Cretaceous marine shale in western Colorado. Dissolved Se concentrations are positively correlated with dissolved NO − 3 concentrations in surface water and ground water samples from irrigated areas. Redox conditions dominate in the mobilization of Se in marine shale hydrogeologic settings; dissolved Se concentrations increase with increasing platinum-electrode potentials. Theoretical calculations for the oxidation of Se by NO − 3 and oxygen show favorable Gibbs free energies for the oxidation of Se by NO − 3 , indicating NO − 3 can act as an electron acceptor for the oxidation of Se. Laboratory batch experiments were performed by adding Mancos Shale samples to zero-dissolved-oxygen water containing 0, 5, 50, and 100 mg/L NO − 3 as N (mg N/L). Samples were incubated in airtight bottles at 25°C for 188 d; samples collected from the batch experiment bottles show increased Se concentrations over time with increased NO − 3 concentrations. Pseudo first-order rate constants for NO − 3 oxidation of Se ranged from 0.0007 to 0.0048/d for 0 to 100 mg N/L NO − 3 concentrations, respectively. Management of N fertilizer applications in Cretaceous shale settings might help to control the oxidation and mobilization of Se and other trace constituents into the environment.