Development of an enantiomer-specific stable carbon isotope analysis (ESIA) method for assessing the fate of α‐hexachlorocyclohexane in the environment

α‐Hexachlorocyclohexane (α‐HCH) is the only chiral isomer of the eight 1,2,3,4,5,6‐HCHs and we have developed an enantiomer‐specific stable carbon isotope analysis (ESIA) method for the evaluation of its fate in the environment.The carbon isotope ratios of the α‐HCH enantiomers were determined for a commercially available α‐HCH sample using a gas chromatography‐combustion‐isotope ratio mass spectrometry (GC‐C‐IRMS) system equipped with a chiral column. The GC‐C‐IRMS measurements revealed δ‐values of −32.5 ± 0.8‰ and −32.3 ± 0.5‰ for (−) α‐HCH and (+) α‐HCH, respectively. The isotope ratio of bulk α‐HCH was estimated to be −32.4 ± 0.6‰ which was in accordance with the δ‐values obtained by GC‐C‐IRMS (−32.7 ± 0.2‰) and elemental analyzer‐isotope ratio mass spectrometry (EA‐IRMS) of the bulk α‐HCH (−32.1 ± 0.1‰). The similarity of the isotope ratio measurements of bulk α‐HCH by EA‐IRMS and GC‐C‐IRMS indicates the accuracy of the chiral GC‐C‐IRMS method. The linearity of theα‐HCH ESIA method shows that carbon isotope ratios can be obtained for a signal size above 100mV. The ESIA measurements exhibited standard deviations (2σ) that were mostly < ± 0.5‰. In order to test the chiral GC‐C‐IRMS method, the isotope compositions of individual enantiomers in biodegradation experiments of α‐HCH withClostridium pasteurianum and samples from a contaminated field site were determined. The isotopic compositions of theα‐HCHenantiomers show a range of enantiomeric and isotope patterns, suggesting that enantiomeric and isotopefractionation can serve as an indicator for biodegradation and source characterization of α‐HCH in the environment.