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

Autor: Badea SL; National Research and Development Institute for Cryogenic and Isotopic Technologies - ICSI Rm. Vâlcea, 4th Uzinei Street, 240050, Ramnicu Valcea, Romania. Electronic address: silviu.badea@qlab.usamv.ro., Cristea NI; National Research and Development Institute for Industrial Ecology, 57-73 Drumul Podu Dambovitei, District 6, 060652, Bucharest, Romania., Niculescu VC; National Research and Development Institute for Cryogenic and Isotopic Technologies - ICSI Rm. Vâlcea, 4th Uzinei Street, 240050, Ramnicu Valcea, Romania., Korolova Y; National Research and Development Institute for Cryogenic and Isotopic Technologies - ICSI Rm. Vâlcea, 4th Uzinei Street, 240050, Ramnicu Valcea, Romania., Enache S; National Research and Development Institute for Cryogenic and Isotopic Technologies - ICSI Rm. Vâlcea, 4th Uzinei Street, 240050, Ramnicu Valcea, Romania., Soare A; National Research and Development Institute for Cryogenic and Isotopic Technologies - ICSI Rm. Vâlcea, 4th Uzinei Street, 240050, Ramnicu Valcea, Romania., Tiliakos A; National Research and Development Institute for Cryogenic and Isotopic Technologies - ICSI Rm. Vâlcea, 4th Uzinei Street, 240050, Ramnicu Valcea, Romania; Babeş-Bolyai University of Cluj-Napoca, Department of Engineering Science, Centre for Vibrodiagnostics for Equipment Testing and Automation (CVDTEA), 1 Mihail Kogălniceanu str., RO-400084, Cluj-Napoca, Romania., Botoran OR; National Research and Development Institute for Cryogenic and Isotopic Technologies - ICSI Rm. Vâlcea, 4th Uzinei Street, 240050, Ramnicu Valcea, Romania., Ionete RE; National Research and Development Institute for Cryogenic and Isotopic Technologies - ICSI Rm. Vâlcea, 4th Uzinei Street, 240050, Ramnicu Valcea, Romania., Höhener P; Aix-Marseille University - Environmental Chemistry Laboratory (LCE), UMR 7376, 3 place Victor Hugo - Case 29, 13331, Marseille Cedex 3, France.
Jazyk: angličtina
Zdroj: Environmental pollution (Barking, Essex : 1987) [Environ Pollut] 2025 Jan 01; Vol. 364 (Pt 1), pp. 125278. Date of Electronic Publication: 2024 Nov 08.
DOI: 10.1016/j.envpol.2024.125278
Abstrakt: 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.
Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: None If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
(Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)
Databáze: MEDLINE
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