Effects of oxalic acid on Cr(VI) reduction by phenols in ice.

Since Cr(VI) is highly toxic, the environmental reduction of Cr(VI) to Cr(III) has attracted significant attention. Oxalic acid, a primary component of dissolved organic matter (DOM), is widely distributed throughout the natural environment but the reduction of Cr(VI) by oxalic acid is insignificant at the low concentrations present in the environment; however, the reduction of Cr(VI) is accelerated significantly in ice. In terms of combined pollution, Cr(VI) can coexist with other organic pollutants in the environment but the impact of organic pollutants on the reduction of Cr(VI), changes to the organic pollutants themselves, and the role of oxalic acid in these reactions are unknown. In this study, we investigated redox reactions between Cr(VI) and phenolic compounds in ice (- 15 °C) in the presence of oxalic acid and compared these to room temperature redox reactions in aqueous solutions (20 °C). While these redox reactions were negligible in aqueous solution, they were significantly accelerated in ice under acidic conditions, which was primarily attributed to the freeze concentration effect. Oxalic acid has two functions in these redox reactions; the first is to provide the H+ required for the reaction and the second is to serve as a reducing agent. When oxalic acid and phenolic pollutants coexist, Cr(VI) preferentially reacts with the phenolic compounds. Phenol, 4-chlorophenol (4-CP), and 2,4-dichlorophenol (2,4-DCP) were each demonstrated to reduce Cr(VI) in ice, but the reaction rate and overall reactivity of these three phenolic compounds are different.