Transformation of Chlorofluorocarbons Investigated via Stable Carbon Compound-Specific Isotope Analysis.

Compound-specific isotope analysis (CSIA) is a valuable tool in contaminant remediation studies. Chlorofluorocarbons (CFCs) are ozone-depleting substances previously thought to be persistent in groundwater under most geochemical conditions but more recently have been found to (bio)transform in some laboratory experiments. To date, limited applications of CSIA to CFCs have been undertaken. Here, biotransformation-associated carbon isotope enrichment factors, εC,bulk for CFC-113 (εC,bulk = -8.5 ± 0.4‰) and CFC-11 (εC,bulk = -14.5 ± 1.9‰), were determined. δ13C signatures of pure-phase CFCs and hydrochlorofluorocarbons were measured to establish source signatures. These findings were applied to investigate potential in situ CFC transformation in groundwater at a field site, where carbon isotope fractionation of CFC-11 suggests naturally occurring biotransformation by indigenous microorganisms. The maximum extent of CFC-11 transformation is estimated to be up to 86% by an approximate calculation using the Rayleigh concept. CFC-113 δ13C values in contrast were not resolvably different from pure-phase sources measured to date, demonstrating that CSIA can aid in identifying which compounds may, or may not, be undergoing reactive processes at field sites. Science and public attention remains focused on CFCs, as unexplained source inputs to the atmosphere have been recently reported, and the potential for CFC biotransformation in surface and groundwaters remains unclear. This study proposes δ13C CSIA as a novel application to study the fate of CFCs in groundwater.

Determination of in situ biodegradation rates via a novel high resolution isotopic approach in contaminated sediments.

A key challenge in conceptual models for contaminated sites is identification of the multiplicity of processes controlling contaminant concentrations and distribution as well as quantification of the rates at which such processes occur. Conventional protocol for calculating biodegradation rates can lead to overestimation by attributing concentration decreases to degradation alone. This study reports a novel approach of assessing in situ biodegradation rates of monochlorobenzene (MCB) and benzene in contaminated sediments. Passive diffusion samplers allowing cm-scale vertical resolution across the sediment-water interface were coupled with measurements of concentrations and stable carbon isotope signatures to identify zones of active biodegradation of both compounds. Large isotopic enrichment trends in 13C were observed for MCB (1.9-5.7‰), with correlated isotopic depletion in 13C for benzene (1.0-7.0‰), consistent with expected isotope signatures for substrate and daughter product produced by in situ biodegradation. Importantly in the uppermost sediments, benzene too showed a pronounced 13C enrichment trend of up to 2.2‰, providing definitive evidence for simultaneous degradation as well as production of benzene. The hydrogeological concept of representative elementary volume was applied to CSIA data for the first time and identified a critical zone of 10-15 cm with highest biodegradation potential in the sediments. Using both stable isotope-derived rate calculations and numerical modeling, we show that MCB degraded at a slower rate (0.1-1.4 yr-1 and 0.2-3.2 yr-1, respectively) than benzene (3.3-84.0 yr-1) within the most biologically active zone of the sediment, contributing to detoxification.