Publication Details

Reference Category Journals
DOI / URL link
Title (Primary) Stable isotope fractionation associated with the synthesis of hexachlorocyclohexane isomers for characterizing sources
Author Liu, X.; Wu, L.; Kümmel, S.; Richnow, H.H.
Journal Chemosphere
Year 2022
Department ISOBIO
Volume 296
Page From art. 133938
Language englisch
Topic T7 Bioeconomy
Keywords Photochemical chlorination; CSIA; Source identification; By-products; Chlorine radical substitution; Isotope forensic
Abstract The stable isotope fingerprints of hexachlorocyclohexane (HCH) isomers have potential for identifying sources as they are related to the synthesis processes and isotopic compositions of raw materials. However, the isotopic fractionation associated with the synthesis processes has not been investigated. Therefore, photochemical synthesis experiments using benzene and chlorine gas were conducted to characterize the associated isotopic fractionation under different conditions. Different pattern of isotopic fractionation factors (αC, αCl, and αH) was observed in each experiment. The large variability of αH is related to the accumulating secondary hydrogen isotope effects or the rearrangement of C–H bond at the cyclohexane ring. An increase of δ13C and δ37Cl values of HCH isomers was observed during synthesis, which is related to the C–Cl bond formation in the radical dichlorination forming HCH and the subsequent chlorine substitution forming heptachlorocyclohexanes. The large variability of δ2H values is related to the secondary and primary hydrogen isotope effects. Different δ13C, δ37Cl and δ2H values among HCH isomers were observed, indicating that conformational complexity of HCH caused by arrangement C–Cl bond in planar and axial positions also influence the isotope values. The understanding of isotopic fractionation during HCH synthesis can be indicative for source identification in the field.
Persistent UFZ Identifier https://www.ufz.de/index.php?en=20939&ufzPublicationIdentifier=25768
Liu, X., Wu, L., Kümmel, S., Richnow, H.H. (2022):
Stable isotope fractionation associated with the synthesis of hexachlorocyclohexane isomers for characterizing sources
Chemosphere 296 , art. 133938