Atmospheric heterogeneous reaction of chlorobenzene on mineral α-Fe₂O₃ particulates: a chamber experiment study

Highlights

● Photochemical conversion of chlorobenzene (CB) on α-Fe₂O₃ was evaluated.

● CB can be considerably degraded by α-Fe₂O₃ under light irradiation.

● Photochemical conversion of CB is markedly suppressed by adding SO₂ or NO₂.

● CB can be ultimately converted into PCDD/Fs under dark state or light irradiation.

● Photochemical conversion complements an overlooked source of natural PCDD/Fs.

Abstract

Despite the large emission of chlorinated volatile organic compounds (CVOCs) into the atmosphere, the ultimate fate of these compounds remains largely unknown. Herein, we explore the photochemical conversion of an important class of CVOCs, namely chlorobenzene (CB), on mineral α-Fe₂O₃ particulates under atmospheric relevant conditions. A series of chamber reactions composed of the CB with/without SO₂ or NO₂ are performed, followed by in situ diffuse reflectance infrared Fourier transform spectroscopy measurements and density functional theory calculations. We show that CB can be considerably degraded by α-Fe₂O₃ under light irradiation, whereas the reaction is markedly suppressed by adding SO₂ or NO₂ owing to their competitive adsorption and surface acidification. In particular, we discover that CB can be ultimately converted into polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) under dark state or light irradiation, suggesting a possible origin of atmospheric PCDD/Fs from this overlooked photochemical source.

Graphical abstract

Keywords

Photochemical conversion / Chlorobenzene / α-Fe₂O₃ / PCDD/Fs / Mineral particulate

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 22176169, 52070168), the Key R&D Plan of Zhejiang Province (No. 2023C03127), and the Fundamental Research Funds for the Central Universities (No. 226-2022-00150).

Competing Interests

The authors declare no conflict of interest.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11783-023-1734-9 and is accessible for authorized users.

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