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Enhanced carbon tetrachloride degradation by hydroxylamine in ferrous ion activated calcium peroxide in the presence of formic acid

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Abstract

Hydroxyl radicals (HO•) show low reactivity with perchlorinated hydrocarbons, such as carbon tetrachloride (CT), in conventional Fenton reactions, therefore, the generation of reductive radicals has attracted increasing attention. This study investigated the enhancement of CT degradation by the synergistic effects of hydroxylamine (HA) and formic acid (FA) (initial [CT] = 0.13 mmol/L) in a Fe (II) activated calcium peroxide (CP) Fenton process. CT degradation increased from 56.6% to 99.9% with the addition of 0.78 mmol/L HA to the CP/Fe(II)/FA/CT process in a molar ratio of 12/6/12/1. The results also showed that the presence of HA enhanced the regeneration of Fe(II) from Fe(III), and the production of HO• increased one-fold when employing benzoic acid as the HO• probe. Additionally, FA slightly improves the production of HO•. A study of the mechanism confirmed that the carbon dioxide radical (CO2•−), a strong reductant generated by the reaction between FA and HO•, was the dominant radical responsible for CT degradation. Almost complete CT dechlorination was achieved in the process. The presence of humic acid and chloride ion slightly decreased CT removal, while high doses of bicarbonate and high pH inhibited CT degradation. This study helps us to better understand the synergistic roles of FA and HA for HO• and CO2•− generation and the removal of perchlorinated hydrocarbons in modified Fenton systems.

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Acknowledgements

This study was financially supported by a grant from the National Key R&D Program of China (No. 2018YFC1802500) and Chinese Scholar Council (CSC, No. 201806740035). The authors also acknowledge the support from Prof. Dionysios. D. Dionysiou at the Department of Chemical and Environmental Engineering (DCEE) at the University of Cincinnati.

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Authors and Affiliations

  1. State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, East China University of Science and Technology, Shanghai, 200237, China

    Wenchao Jiang, Ping Tang, Qian Sui & Shuguang Lyu

  2. Environmental Engineering and Science Program, Department of Chemical and Environmental Engineering, University of Cincinnati, Cincinnati, OH, 45221-0071, USA

    Wenchao Jiang, Zhen Liu & Huan He

Authors
  1. Wenchao Jiang
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  2. Ping Tang
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  3. Zhen Liu
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  4. Huan He
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  5. Qian Sui
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  6. Shuguang Lyu
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Corresponding author

Correspondence to Shuguang Lyu.

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Highlights

• Complete CT degradation was achieved by employing HA to CP/Fe(II)/FA process.

• Quantitative detection of Fe(II) regeneration and HO• production was investigated.

• Benzoic acid outcompeted FA for the reaction with HO•.

• CO2•− was the dominant reductive radical for CT removal.

• Effects of solution matrix on CT removal were conducted.

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Jiang, W., Tang, P., Liu, Z. et al. Enhanced carbon tetrachloride degradation by hydroxylamine in ferrous ion activated calcium peroxide in the presence of formic acid. Front. Environ. Sci. Eng. 14, 18 (2020). https://doi.org/10.1007/s11783-019-1197-1

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  • DOI: https://doi.org/10.1007/s11783-019-1197-1

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