Carbon isotope fractionation during permanganate oxidation of chlorinated ethylenes (cDCE, TCE, PCE)

Permanganate oxidation of chlorinated ethylenes is an attractive technique to effect remediation of these important groundwater contaminants. Stable carbon isotope fractionation associated with permanganate oxidation of trichloroethylene (TCE), tetrachloroethylene (PCE), and cis-1,2-dichloroethylene (cDCE) has been measured, to study the possibility of applying stable carbon isotope analysis as a technique to assess the efficacy of remediation implemented by permanganate oxidation. Average carbon isotope fractionation factors of α_TCE = 0.9786, α_PCE = 0.9830, and α_cDCE = 0.9789 were obtained, although the fractionation factor for PCE may be interpreted to change from a value of 0.9779-0.9871 during the course of the reaction. The fractionation factors for all three compounds are quite similar, in contrast to the variation of fractionation factors vs degree of chlorination observed for other degradative processes, such as microbial dechlorination. This may be due to a common rate-determining step for permanganate oxidation of all three compounds studied. The large fractionation factors and the relative lack of dependence of the fractionation factors upon other environmental factors (e.g. oxidation rate, presence of multiple contaminants, incomplete oxidation, presence of chloride in solution) indicate that monitoring δ¹³C values of chlorinated ethylenes during oxidation with permanganate may be a sensitive, and potentially quantitative, technique to investigate the extent of degradation.