Highly chlorinated unintentionally produced persistent organic pollutants generated during the methanol-based production of chlorinated methanes: A case study in China

• Numerous unintentionally produced POPs observed in the CCl4 byproduct.
• Emission profiles of these hazardous substances were distinctive.
• Top three emissions were perchlorinated cyclopentadiene, butadiene, and benzenes.
• TEQ for PCNs was considerably higher than PCDDs/DFs.
• Emission factor of PCDDs/DFs was 364 μg TEQ t−1 product for residues.

The formation of unintentionally produced persistent organic pollutants (POPs) may occur during various chlorination processes. In this study, emissions of unintentionally produced POPs during the methanol-based production of chlorinated methanes were investigated. High concentrations of highly chlorinated compounds such as decachlorobiphenyl, octachloronaphthalene, octachlorostyrene, hexachlorobutadiene, hexachlorocyclopentadiene, hexachlorobenzene, and pentachlorobenzene were found in the carbon tetrachloride byproduct of the methanol-based production of chlorinated methanes. The total emission amounts of hexachlorocyclopentadiene, hexachlorobutadiene, polychlorinated benzenes, polychlorinated naphthalenes, octachlorostyrene, and polychlorinated biphenyls released during the production of chlorinated methanes in China in 2010 were estimated to be 10 080, 7350, 5210, 427, 212, and 167 kg, respectively. Moreover, polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) were formed unintentionally during chlorinated methanes production, the emission factor for PCDDs/DFs was 364 μg toxic equivalency quotient (TEQ) t−1 product for residues, which should be added into the UNEP toolkit for updating. It was worth noting that a high overall toxic equivalency quotient from polychlorinated naphthalenes and PCDDs/DFs was generated from the chlorinated methanes production in China in 2010. The values reached 563 and 32.8 g TEQ, respectively. The results of the study indicate that more research and improved management systems are needed to ensure that the methanol-based production of chlorinated methanes can be achieved safely.

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