Oxidation mechanisms and chemical bioavailability of chromium in agricultural soil – pH as the master variable

Abstract

Chromium (Cr) is a heavy metal that exists in soils in two stable oxidation states, +III and +VI. The trivalent species is an essential nutrient, whereas the hexavalent species is highly toxic. This study investigated the environmental impact of CrIII potentially released into soil from wastes and various materials by determining the risk of oxidation of initially soluble inorganic CrIII into hazardous CrVI. The principal aim was to describe the pH-dependent mechanisms that regulate 1) the formation of CrVI from the easily soluble CrIII and 2) the potential bioavailability of CrIII and that of CrVI species produced in the oxidation of CrIII in agricultural soil (fine sand, organic carbon 3.2%). The amount of CrVI formed in oxic soil conditions was regulated by two counteracting reactions: 1) oxidation of CrIII into CrVI by manganese oxide (MnIVO2) and 2) the subsequent reduction of CrVI by organic matter back to CrIII. The effect of pH on this net-oxidation of CrIII and on the chemical availability of both CrIII and CrVI species was investigated in soil samples incubated with or without excessive amounts of synthetic MnO2, over the chemically adjusted pH range of 3.9–6.3 (+22 °C, 47 d). In soil subsamples without added MnO2, the net-oxidation of CrIII into CrVI (1 mM CrCl3 in soil suspensions, 1:10 w/V) was negligible. As for the MnO2-treated soils, at maximum only 4.7% of added CrIII was oxidized – regardless of the high oxidation potential of these subsamples. The lowest production of CrVI was observed under acidic soil conditions at pH ∼4. At low pH, the net-oxidation diminished as result of enhanced reduction of CrVI back to CrIII. At higher pHs, the oxidation was limited by enhanced precipitation (or adsorption) of CrIII, which lowered the overall amount of CrIII susceptible for oxidation. Moreover, the oxidation reactions by MnO2 were inhibited by formation of Cr(OH)3 coverage on its surface. The pH-dependent chemical bioavailability of added CrIII differed from that of the CrVI formed. At elevated pHs the chemical availability of CrIII decreased, whereas that of CrVI produced increased. However, the risk of CrVI formation through oxidation of the easily soluble inorganic CrIII was considered to be low in agricultural soils high in organic matter and low in innate MnO2.