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Influence of iron and copper oxides on polychlorinated diphenyl ether formation in heterogeneous reactions

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Abstract

Polychlorinated diphenyl ether (PCDE) has attracted great attention recently as an important type of environmental pollutant. The influence of iron and copper oxides on formation of PCDEs was investigated using laboratory-scale flow reactors under air and under nitrogen at 350 °C, a temperature corresponding to the post-combustion zone of a municipal solid waste incinerator. The results show that the 2,2′,3,4,4′,5,5′,6-otachlorodiphenyl ether (OCDE) formed from the condensation of pentachlorophenol (PCP) and 1,2,4,5-tetrachlorobenzene (Cl4Bz) is the predominant congener formed on the SiO2/Fe2O3 surface with and without oxygen. This indicated that HCl elimination between PCP and 1,2,4,5-Cl4Bz molecules formed 2,2′,3,4,4′,5,5′,6-OCDE in the presence of Fe2O3. On the other hand, decachlorodiphenyl ether, nonachlorodiphenyl ether, and OCDE were the dominant products on the SiO2/CuO surface without oxygen, although the 2,2′,3,4,4′,5,5′,6-OCDE was the dominant product on the SiO2/CuO surface with oxygen. Therefore, the presence of Fe2O3 and CuO influences the formation and homologue distribution of PCDEs, which shifted towards the lower chlorinated species. Fe2O3 can promote both the condensation and dechlorination reaction without oxygen. On the contrary, with oxygen, Fe2O3 suppresses the condensation of chlorobenzene and chlorophenol to form PCDEs and polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). CuO can increase the formation of lower chlorinated PCDEs and PCDDs without oxygen. In conclusion, the different fly ash components have a major influence on PCDE emissions.

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Abbreviations

Cl4Bz:

Tetrachlorobenzene

MSWI:

Municipal solid waste incinerator

HxCDD:

Hexachlorodibenzo-p-dioxin

HxCDE:

Hexachlorodiphenyl ether

HxCDF:

Hexachlorodibenzofurans

HpCDD:

Heptachlorodibenzo-p-dioxin

HpCDE:

Heptachlorodiphenyl ether

HpCDF:

Heptachlorodibenzofuran

OCDD:

Octachlorodibenzo-p-dioxin

OCDE:

Octachlorodiphenyl ether

NonaCDE:

Nonachlorodiphenyl ether

DecaCDE:

Decachlorodiphenyl ether

PCDDs:

Polychlorinated dibenzo-p-dioxins

PCDEs:

Polychlorinated diphenyl ethers

PCDFs:

Polychlorinated dibenzofurans

PCP:

Pentachlorophenol

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Acknowledgments

This study was supported by the National Natural Science Foundation of China (21037003), the National 973 program (2009CB421606), and open fund of State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences (KF2012-10).

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Authors and Affiliations

  1. Department of Environmental Sciences, Henan Agricultural University, Zhengzhou, 450002, China

    Wenxia Liu, Lianfeng Shen, Fawen Zhang & Xitian Yang

  2. State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, P.O. Box 2871, Beijing, 100085, China

    Wenxia Liu, Wenbin Liu & Minghui Zheng

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  1. Wenxia Liu
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  2. Lianfeng Shen
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  3. Fawen Zhang
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  4. Wenbin Liu
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  5. Minghui Zheng
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Correspondence to Wenxia Liu.

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Responsible editor: Hongwen Sun

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Liu, W., Shen, L., Zhang, F. et al. Influence of iron and copper oxides on polychlorinated diphenyl ether formation in heterogeneous reactions. Environ Sci Pollut Res 20, 5569–5576 (2013). https://doi.org/10.1007/s11356-013-1539-7

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  • DOI: https://doi.org/10.1007/s11356-013-1539-7

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