Stable Carbon Isotope Analysis of Hexachlorocyclohexanes by Liquid-Liquid Extraction Gas Chromatography Isotope Ratio Mass Spectrometry: Method Evaluation and Applications

Compound specific isotope analysis (CSIA) and enantiomer specific isotope analysis (ESIA) are powerful tools for assessing the fate of hexachlorocyclohexanes (HCHs) in the environment. However, there is no systematic study on the CSIA and ESIA analysis test methods of the carbon isotopes of HCHs in water and soil environments, in particular the isotope fractionation in the pre-concentration process. We endeavored to test the compatibility of CSIA and ESIA with the liquid-liquid extraction method of HCHs in water. The results showed that there were negligible changes in the delta C-13 of HCHs after extraction, indicating that liquid-liquid extraction can be used as a pre-concentration method for the determination of delta C-13 of HCHs in water. The optimized method was validated and then applied to differentiate three HCHs from different manufacturers, to identify in situ degradation of HCHs of groundwater from a contaminated site and to resolve the carbon isotope fractionation occurring in the alpha-HCH oxidation by CaO2/Fe(II) Fenton system. The results showed that the same reagents from different manufacturers have different carbon isotope compositions, and different isomers from the same manufacturer also have different isotope compositions, showing useful evidence in identifying the source of HCHs. The more enriched delta C-13 in the down-gradient wells indicated that HCHs have undergone biodegradation or/and chemical reactions in the groundwater system of the site. Carbon isotopic enrichment factors (epsilon(C)) of -1.90 +/- 0.10 parts per thousand were obtained in the oxidation process. Hence, the method validated in this study has great potential as a method for identifying the degradation of HCHs in a water environment.

Automated summary

Compound specific isotope analysis (CSIA) and enantiomer specific isotope analysis (ESIA) were used to assess the fate of hexachlorocyclohexanes (HCHs) in water. The liquid-liquid extraction method was compatible with CSIA and ESIA, and showed negligible changes in the carbon isotopes of HCHs. This method was validated and successfully used to differentiate HCHs from different manufacturers, identify in situ degradation of HCHs in groundwater, and resolve carbon isotope fractionation. The results showed the potential of this method for identifying HCH degradation in water.