Iron-reducing conditions in subsurface environments promote dechlorination reactions via both biotic and abiotic pathways, the latter often mediated via biologically activated minerals formed by dissimilatory iron-reducing bacteria (DIRB). Here we report the major products and pathways associated with the abiotic transformation of carbon tetrachloride (CT) by nanoscale biogenic magnetite/maghemite particles produced by the DIRB Geobacter metallireducens. Product formation and free radical/carbene trapping studies indicate that CT transformation occurs via three parallel pathways. The first pathway (hydrogenolysis) results in the formation of chloroform (45-50%) via a trichloromethyl free radical (·CCl{sub}3) and possibly a trichloromethyl carbanion (:(CCl{sub}3){sup}-). The second and third pathways involve a dichlorocarbene intermediate (:CCl{sub}2), which either hydrolyzes to form CO (～38%) (carbene hydrolysis), or undergoes further reduction to yield methane (8-10%) (carbene reduction). The mechanism of methane formation from:CCl{sub}2 is not known, but is speculated to involve a sequence of surface coordinated carbenoid and free radical complexes. The large fraction of relatively benign products formed by the carbene-mediated pathways suggests that magnetite/maghemite particles may have a beneficial application in the remediation of CT contaminated environments.
展开▼
