Controlled variation of redox conditions in a floodplain soil: Impact on metal mobilization and biomethylation of arsenic and antimony

An automated biogeochemical microcosm system allowing the control of redox potential (E-H) in soil suspensions was used to assess the effect of E-H on the mobility of cadmium (Cd), copper (Cu), nickel (Ni), zinc (Zn), iron (Fe), and manganese (Mn) as well as on the methylation of arsenic (As) and antimony (Sb) in a contaminated and slightly acidic floodplain soil. The experiment was conducted under stepwise variation from reducing (approximately -300 mV at pH 5) to oxidizing (+600 mV at pH 5) conditions. The E-H was found to be an important factor controlling the dynamics of studied compounds and elements. Concentrations of Cd, Cu, Mn, Ni, and Zn in solution were low at low E-H and increased with rising E-H what might be attributed to the interaction with dissolved organic carbon (DOC), Mn, and precipitation as sulphides. Redox potential and pH correlate significantly with Cd, Ni, Cu, Zn, and Mn. Total Fe concentrations in solution were high at low E-H and dropped sharply at E-H> 350 mV at pH 5 to lower values due to the formation of Fe (hydr)oxides. Other metals did not adsorb to or co-precipitate with Fe, which may be attributed to the low pH (between 4.4 and 5.3) amongst other factors. Concentrations of inorganic arsenic (As-i) and antimony (Sb-i), momomethyl arsenic (MMAs), monomethyl antimony (MMSb), and dimethyl arsenic (DMAs) in solution decreased significantly with rising E-H, indicating that low E-H promotes the mobility of these compounds. (C) 2010 Elsevier B.V. All rights reserved.