Constraining the fate of chlorinated ethenes in groundwater systems using stable carbon compound specific isotope analysis

grantor: University of TorontoThe isotopic effects of subsurface processes on the stable carbon isotopic composition, [delta]13C, of chlorinated ethenes were investigated using Compound Specific Isotope Analysis (CSIA). Headspace analysis was determined to be a robust, simple and effective method for sample preparation and analysis using Gas Chromatography-Combustion-Isotope Ratio Mass Spectrometry (GC-C-IRMS). No significant isotopic fractionation (>0.5 ‰) was observed during equilibrium volatilization of the chlorinated ethenes from aqueous solution. Further, no significant isotopic fractionation (>0.5 ‰) was associated with equilibrium sorption of TCE and PCE. These results confirmed the hypothesis that non-degradative, physical subsurface processes would not result in significant isotopic fractionation of the [delta]13C of the chlorinated ethenes. In contrast, degradation of the chlorinated ethenes resulted in large isotopic enrichments of the residual reactant in 13C, consistent with preferential reaction of molecules containing the lighter 12C isotope. This isotopic enrichment could be described by a Rayleigh model enrichment factor ([epsilon]). Rayleigh enrichment factors ([epsilon]) described isotopic fractionation of the chlorinated ethenes during microbial reductive dechlorination of most of the chlorinated ethenes, during abiotic reductive dechlorination of TCE by zero-valent iron, and during aerobic co-metabolic degradation of TCE by toluene ortho-monooxygenase. Enrichment factors varied with specific microbial consortia, with degradation pathway (reductive dechlorination versus aerobic co-metabolism); and for abiotic experiments, with different iron types and surface treatments. The observation of these isotopic enrichment trends indicated that CSIA can provide direct evidence of the occurrence of chlorinated ethene degradation in the field, independent of mass loss due to non-degradative subsurface processes. CSIA was applied at three field sites. These studies confirmed that the [delta] 13CTCE can be conserved at a site where plume geometry is controlled by advective and partitioning processes. Most importantly, they confirmed that CSIA could give direct confirmation of the occurrence of degradation of the chlorinated ethenes at field sites. Therefore CSIA of the [delta] 13C of the chlorinated ethenes represents a powerful tool for the investigation and monitoring of sources and fate of chlorinated ethenes in subsurface systems.Ph.D