Carbon Isotopic Fractionation of CFCs during Abiotic and Biotic Degradation

Carbon stable isotope (C-13) fractionation in chlorofluorocarbon (CFC) compounds arising from abiotic (chemical) degradation using zero-valent iron (ZVI) and biotic (landfill gas attenuation) processes is investigated. Batch tests (at 25 degrees C) for CFC-113 and CFC-11 using ZVI show quantitative degradation of CFC-113 to HCFC-123a and CFC-1113 following pseudo-first-order kinetics corresponding to a half-life (tau(1/2)) of 20.5 h, and a ZVI surface-area normalized rate constant (k(SA)) of -(9.8 +/- 0.5) x 10(-5) L m(-2) h(-1). CFC-11 degraded to trace HCFC-21 and HCFC-31 following pseudo-first-order kinetics corresponding to tau(1/2) = 17.3 h and k(SA) = -(1.2 +/- 0.5) x 10(-4) L m(-2) h(-1). Significant kinetic isotope effects of epsilon(parts per thousand) = -5.0 +/- 0.3 (CFC-113) and -17.8 +/- 4.8 (CFC-11) were observed. Compound-specific carbon isotope analyses also have been used here to characterize source signatures of CFC gases (HCFC-22, CFC-12, HFC-134a, HCFC-142b, CFC-114, CFC-11, CFC-113) for urban (UAA), rural/remote (RAA), and landfill (LAA) ambient air samples, as well as in situ surface flux chamber (FLUX; NO FLUX) and landfill gas (LFG) samples at the Dargan Road site, Northern Ireland. The latter values reflect biotic degradation and isotopic fractionation in LFG production, and local atmospheric impact of landfill emissions through the cover. Isotopic fractionations of Delta C-13 similar to -13 parts per thousand (HCFC-22), Delta C-13 similar to -35 parts per thousand (CFC-12) and Delta C-13 similar to -15 parts per thousand (CFC-11) were observed for LFG in comparison to characteristic solvent source signatures, with the magnitude of the isotopic effect for CFC-11 apparently similar to the kinetic isotope (abiotic) ZVI degradation.