Chromium(VI) formation via heating of Cr(III)-Fe(III)-(oxy)hydroxides: A pathway for fire-induced soil pollution

Mixed Cr(III)-Fe(III) (oxy)hydroxides are important Cr-bearing phases in natural, unpolluted soil. Fires frequently affect large areas of land around the world, causing the temporary development of elevated soil temperatures. This study examines the hypothesis that heating Cr(III)-Fe(III) (oxy)hydroxides at temperatures which occur in surface soils during fires can drive rapid oxidation of Cr(III) to hazardous Cr(VI). To test this, poorly-ordered Cr(III)_x-Fe(III)_1-x (oxy)hydroxides, with x spanning 0.1 to 0.9, were heated at up to 800 °C for 2 h. Heating at 400-800 °C produced a highly crystalline hematite-eskolaite solid-solution (Fe^III_2-nCr^III_nO₃, where n ranges from 0 to 2). Chromium K-edge X-ray absorption spectroscopy showed that during heating up to ∼40% of the initial Cr(III) was oxidized to Cr(VI), with the greatest extent of Cr(VI) formation occurring at 200-400 °C. At these temperatures, a substantial proportion (17%-70%) of the newly-formed Cr(VI) was exchangeable (i.e. extracted by a pH 7.2, 10 mM PO₄^3- solution). This suggests that much of the Cr(VI) formed by heating of Cr(III)_x-Fe(III)_1-x (oxy)hydroxides at 200-400 °C is likely to be relatively mobile in fire-impacted soils. The results of this study provide new insights into a potentially-important pathway for the in-situ formation of Cr(VI) in soil.