Role of iron in controlling speciation and mobilization of arsenic in subsurface environment

Widespread arsenic contamination of groundwater has been reported of late in Bangladesh and West Bengal state of India. On the basis of arsenic geochemistry, three probable mechanisms have been cited for arsenic mobility in aquifers of West Bengal and Bangladesh. First, mobilization of arsenic due to the oxidation of arsenic-bearing pyrite minerals. Second, dissolution of arsenic-contaminated iron oxy-hydroxides (FeOOH) due to onset of reducing conditions in the subsurface. Third, due to the release of arsenic sorbed to aquifer minerals by competitive exchange with phosphate ions, that migrates into aquifers due to application of fertilizer to surface soil. Based on the review of field data from the affected region, it appears that the second mechanism described above is the most probable. Two reduction processes associated with this mechanism were investigated, viz., reduction of iron oxy-hydroxide to iron (II), which results in the mobilization of arsenic, and reduction of arsenic (V) to arsenic (III), which may enhance mobility of arsenic under certain conditions. These reactions, in the opinion of some researchers, are possible in subsurface environments mainly through microbial intervention. However, through the data presented in this paper, it has been demonstrated that above red–ox reactions involving iron and arsenic are also possible through predominantly abiotic pathways. While these results do not necessarily imply that abiotic red–ox processes are dominant in all subsurface environments containing iron and arsenic, it is entirely possible that abiotic interactions as described here may be responsible for a substantial amount of transformations involving iron and arsenic in anoxic subsurface environments.