Degradation study of δ-hexachlorocyclohexane by iron sulfide nanoparticles: Elucidation of reaction pathway using compound specific isotope analysis and pH variation

pH influences the reactivity of iron (II) minerals towards halogenated pollutants like hexachlorocyclohexanes (HCHs). To explore these incompletely understood interactions, we investigated the carbon isotope fractionation of the δ-HCH isomer during dehalogenation by iron sulfide at pHs spanning a pH range across slightly acidic to alkaline domains (5.8-9.6). The δ-1,3,4,5,6-pentachlorocyclohex-1-ene (δ-PCCH) was the intermediate degradation product, while benzene, monochlorobenzene (MCB), but especially 1,2-dichlorobenzene (1,2-DCB), and 1,2,4-trichlorobenzene (1,2,4-TCB), were the main degradation products of δ-HCH. These degradation products suggested dehydrochlorination as the main degradation pathway of δ-HCH by iron sulfide. Different kinetic experiments indicate that the rate constants (k_a) during dechlorination of δ-HCH by iron sulfide rose with pH: 0.003 d^-1 (pH 5.8) < 0.034 d^-1 (pH 8) < 0.085 (pH 9.3) < 0.286 d^-1 (pH 9.6). Upon Rayleigh model calculations, an enrichment factor (εC) of -7.8 ± 1.0 ‰ was calculated for δ-HCH dehalogenation by FeS at pH 8.0. This suggests an apparent kinetic isotope effect (AKIE_C) value of 1.049 ± 0.006 for dehydrohalogenation. The magnitude of the isotope effect from this paper furthermore supports dehydrohalogenation and opens the possibility to study the degradation of HCHs by iron (II) minerals containing FeS as mackinawite in oxygen-deprived environments.