Perchlorate removal in Fe0/H2O systems: Impact of oxygen availability and UV radiation

In this study, the removal of perchlorate (0.016 mM ) using Fe⁰-only (325 mesh, 10 g L⁻¹) and Fe⁰ (10 g L⁻¹) with UV (254 nm) reactions were investigated under oxic and anoxic conditions (nitrogen purging). Under anoxic conditions, only 2% and 5.6% of perchlorate was removed in Fe⁰-only and Fe⁰/UV reactions, respectively, in a 12 h period. However, under oxic conditions, perchlorate was removed completely in the Fe⁰-only reaction, and reduced by 40% in the Fe⁰/UV reaction, within 9 h. The pseudo-first-order rate constant (k₁) was 1.63 × 10⁻³ h⁻¹ in Fe⁰-only and 4.94 × 10⁻³ h⁻¹ in Fe⁰/UV reaction under anoxic conditions. Under oxic conditions, k₁ was 776.9 × 10⁻³ h⁻¹ in Fe⁰-only reaction and 35.1 × 10⁻³ h⁻¹ in the Fe⁰/UV reaction, respectively. The chlorine in perchlorate was recovered as chloride ion in Fe⁰-only and Fe⁰/UV reactions, but lower recovery of chloride under oxic conditions might due to the adsorption/co-precipitation of chloride ion with the iron oxides. The removal of perchlorate in Fe⁰/UV reaction under oxic conditions increased in the presence of methanol (73%, 9 h), a radical scavenger, indicating that OH radical can inhibit the removal of perchlorate. The removal of perchlorate by Fe⁰-only reaction under oxic condition was highest at neutral pH. Application of the Langmuir-Hinshelwood model indicated that removal of perchlorate was accelerated by adsorption/co-precipitation reactions onto iron oxides and subsequent removal of perchlorate during further oxidation of Fe⁰. The results imply that oxic conditions are essential for more efficient removal of perchlorate in Fe⁰/H₂O system.