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Kinetics and mechanism of diclofenac removal using ferrate(VI): roles of Fe3+, Fe2+, and Mn2+

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Abstract

In this study, the effect of Fe3+, Fe2+, and Mn2+ dose, solution pH, reaction temperature, background water matrix (i.e., inorganic anions, cations, and natural organic matters (NOM)), and the kinetics and mechanism for the reaction system of Fe(VI)/Fe3+, Fe(VI)/Fe2+, and Fe(VI)/Mn2+ were investigated systematically. Traces of Fe3+, Fe2+, and Mn2+ promoted the DCF removal by Fe(VI) significantly. The pseudo-first-order rate constant (kobs) of DCF increased with decreasing pH (9–6) and increasing temperature (10–30 °C) due to the gradually reduced stability and enhanced reactivity of Fe(VI). Cu2+ and Zn2+ ions evidently improved the DCF removal, while CO32− restrained it. Besides, SO42−, Cl−, NO3−, Mg2+, and Ca2+ almost had no influence on the degradation of DCF by Fe(VI)/Fe3+, Fe(VI)/Fe2+, and Fe(VI)/Mn2+ within the tested concentration. The addition of 5 or 20 mg L−1 NOM decreased the removal efficiency of DCF. Moreover, Fe2O3 and Fe(OH)3, the by-products of Fe(VI), slightly inhibited the DCF removal, while α-FeOOH, another by-product of Fe(VI), showed no influence at pH 7. In addition, MnO2 and MnO4−, the by-products of Mn2+, enhanced the DCF degradation due to catalysis and superposition of oxidation capacity, respectively. This study indicates that Fe3+ and Fe2+ promoted the DCF removal mainly via the self-catalysis for Fe(VI), and meanwhile, the catalysis of Mn2+ and the effect of its by-products (i.e., MnO2 and MnO4−) contributed synchronously for DCF degradation.

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Funding

This work was supported by the Key R & D project of Science and Technology Department of Sichuan Province [No. 2017SZ0175], the Science and Technology Huimin Project of Chengdu [No. 2014-HM01-00278-SF], and the Joint Research Program about Sustainable Use of Water and Resources in the Upper Yangtze River [No. 2012DFG91520].

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  1. Faculty of Geosciences and Environmental Engineering, Southwest Jiaotong University, Chengdu, 611756, China

    Junfeng Zhao, Qun Wang, Yongsheng Fu, Bo Peng & Gaofeng Zhou

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  1. Junfeng Zhao
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  2. Qun Wang
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  3. Yongsheng Fu
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  4. Bo Peng
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Correspondence to Qun Wang or Yongsheng Fu.

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Responsible editor: Vítor Pais Vilar

Highlights

• DCF removal using Fe(VI) was promoted by Cu2+ and Zn2+ but restrained by CO32−.

• Fe2O3 and Fe(OH)3 inhibited DCF removal, while α-FeOOH showed no influence at pH 7.

• MnO2 and MnO4− enhanced DCF oxidation using Fe(VI) via catalysis and superposition of oxidizability.

• Fe3+ and Fe2+ promoted DCF removal efficiency mainly through the self-catalysis of Fe(VI).

• The catalysis of Mn2+ and the effect of by-products contributed for DCF degradation greatly.

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Zhao, J., Wang, Q., Fu, Y. et al. Kinetics and mechanism of diclofenac removal using ferrate(VI): roles of Fe3+, Fe2+, and Mn2+. Environ Sci Pollut Res 25, 22998–23008 (2018). https://doi.org/10.1007/s11356-018-2375-6

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