Calibration bias of experimentally determined chlorine isotope enrichment factors: the need for a two-point calibration in compound-specific chlorine isotope analysis.

RATIONALE: The recent development of compound-specific online chlorine isotope analysis (37 Cl-CSIA) methods has fostered dual chlorine-carbon isotope studies to gain better insights into sources and environmental transformation reactions of chlorinated ethenes. One-point and two-point calibration schemes are currently used to convert raw data to the international δ37 ClSMOC scale, but a critical evaluation of best practices to arrive at reliable δ37 ClSMOC signatures and enrichment factors was missing and is presented here.

METHODS

Aqueous solutions of neat perchloroethylene and trichloroethylene (TCE) and aqueous samples from a TCE biodegradation experiment with pure cultures of Desulfitobacterium hafniense Y51 were analysed for their chlorine isotope ratios using GC/qMS and GC/IRMS. The δ37 ClSMOC values were obtained using one-point and two-point calibration schemes. Chlorine isotope enrichment factors, εCl , were calculated using both approaches and the corresponding bias of δ37 ClSMOC values introduced by the different types of calibration was determined.

RESULTS

Different calibration methods resulted in significant differences (up to 30%) in both δ37 Cl signatures and εCl values.

CONCLUSIONS

Our results demonstrate that a two-point calibration together with comprehensive information on reference materials is indispensable and should become standard practice for reliable 37 Cl-CSIA of organic compounds. Copyright © 2016 John Wiley & Sons, Ltd.