Michelle Chartrand1, Elodie Passeport2,3, Carla Rose1, Georges Lacrampe-Couloume1, Terry F Bidleman4, Liisa M Jantunen5, Barbara Sherwood Lollar1. 1. Department of Earth Sciences, University of Toronto, 22 Russell Street, Toronto, ON, M5S 3B1, Canada. 2. Department of Civil Engineering, University of Toronto, 35 Russell Street, Toronto, ON, M5S 1A4, Canada. 3. Department of Chemical Engineering and Applied Chemistry, University of Toronto, 200 College Street, Toronto, ON, M5S 3E5, Canada. 4. Dept. of Chemistry, Umeå University, Linnaeus väg 6, SE-901 87, Umeå, Sweden. 5. Air Quality Processes Research Section, Environment Canada, 6248 Eighth Line, Egbert, ON, L0L1N0, Canada.
Abstract
RATIONALE: The manufacturing and uses of hexachlorocyclohexane (HCH) have resulted in a serious environmental challenge and legacy. This study highlights the ability of compound specific isotope analysis (CSIA) to distinguish among various HCH sources and to support the evaluation of the potential for in situ biodegradation in contaminated groundwater. METHODS: Tests were conducted to verify the absence of significant isotope fractionation during HCH sample pre-concentration including dichloromethane extraction, solvent exchange into iso-octane, and H2SO4 clean-up, and analysis by gas chromatography/combustion-isotope ratio mass spectrometry (GC/C-IRMS). The method was then applied to four Technical Grade (TG) HCH mixtures procured from different sources and to groundwater samples from a contaminated site. RESULTS: The pre-concentration method enabled determination of carbon isotope ratios (δ(13)C values) of HCH isomers with no significant isotopic fractionation. The TG-HCH mixtures had significantly different δ(13)C values. Moreover, for any given TG-HCH, all isomers had δ(13)C values within 1.1‰ of each other - a distinctly uniform fingerprint. At the HCH-contaminated field site, compared with source wells, downgradient wells showed significant (up to 5.1‰) enrichment in (13)C and the δ(13)C values of the HCH isomers were significantly different from each other. CONCLUSIONS: A method was successfully developed for the CSIA of HCH isomers that showed potential for HCH source differentiation and identification of HCH in situ biodegradation. At the HCH-contaminated site, the observed preferential isotopic enrichment of certain isomers relative to others for a given source allows differentiation between biodegraded and non-biodegraded HCH.
RATIONALE: The manufacturing and uses of hexachlorocyclohexane (HCH) have resulted in a serious environmental challenge and legacy. This study highlights the ability of compound specific isotope analysis (CSIA) to distinguish among various HCH sources and to support the evaluation of the potential for in situ biodegradation in contaminated groundwater. METHODS: Tests were conducted to verify the absence of significant isotope fractionation during HCH sample pre-concentration including dichloromethane extraction, solvent exchange into iso-octane, and H2SO4 clean-up, and analysis by gas chromatography/combustion-isotope ratio mass spectrometry (GC/C-IRMS). The method was then applied to four Technical Grade (TG) HCH mixtures procured from different sources and to groundwater samples from a contaminated site. RESULTS: The pre-concentration method enabled determination of carbon isotope ratios (δ(13)C values) of HCH isomers with no significant isotopic fractionation. The TG-HCH mixtures had significantly different δ(13)C values. Moreover, for any given TG-HCH, all isomers had δ(13)C values within 1.1‰ of each other - a distinctly uniform fingerprint. At the HCH-contaminated field site, compared with source wells, downgradient wells showed significant (up to 5.1‰) enrichment in (13)C and the δ(13)C values of the HCH isomers were significantly different from each other. CONCLUSIONS: A method was successfully developed for the CSIA of HCH isomers that showed potential for HCH source differentiation and identification of HCH in situ biodegradation. At the HCH-contaminated site, the observed preferential isotopic enrichment of certain isomers relative to others for a given source allows differentiation between biodegraded and non-biodegraded HCH.