Co-present Pb(II) accelerates the oxidation of organic contaminants by permanganate: Role of Pb(III)

doi:10.1007/s11783-022-1530-y

Front. Environ. Sci. Eng.

2022, Vol. 16

Issue (8) : 109 https://doi.org/10.1007/s11783-022-1530-y

RESEARCH ARTICLE

Co-present Pb(II) accelerates the oxidation of organic contaminants by permanganate: Role of Pb(III)

Lei Dong^1,², Pin Xie¹, Xin Zhang², Junlian Qiao¹, Dandan Rao¹, Yuankui Sun³(

), Xiaohong Guan³

¹. College of Environmental Science and Engineering, Tongji University, Shanghai 200092, China
². Shanghai Municipal Engineering Design Institute (group) Co., Ltd., Shanghai 200092, China
³. Shanghai Key Laboratory for Urban Ecological Processes and Eco-Restoration, Shanghai Engineering Research Center of Biotransformation of Organic Solid Waste, Institute of Eco-Chongming (IEC), School of Ecological and Environmental Science, East China Normal University, Shanghai 200241, China

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Abstract

• Simultaneous removal of organic contaminants and Pb(II) was achieved by Mn(VII).

• Pb(II) enhanced Mn(VII) oxidation performance over a wide pH range.

• Pb(II) did not alter the pH-rate profile for contaminants oxidation by Mn(VII).

• Mn(VII) alone cannot oxidize Pb(II) effectively at pH below 5.0.

• Pb(III) plays important roles on enhancing Mn(VII) decontamination process.

The permanganate (Mn(VII)) oxidation has emerged as a promising technology for the remediation and treatment of the groundwater and surface water contaminated with the organic compounds. Nonetheless, only a few studies have been conducted to explore the role of the heavy metals (especially the redox-active ones) during the Mn(VII) oxidation process. In this study, taking Pb(II) as an example, its influence on the Mn(VII) decontamination performance has been extensively investigated. It was found that, with the presence of Pb(II), Mn(VII) could degrade diclofenac (DCF), 2,4-dichlorophenol, and aniline more effectively than without. For instance, over a wide pH range of 4.5–8.0, the dosing of 10 μmol/L Pb(II) accelerated the DCF removal rate from 0.006–0.25 min⁻¹ to 0.05–0.46 min⁻¹ with a promotion factor of 1.9–9.4. Although the UV-vis spectroscopic and high resolution transmission electron microscopy analyses suggested that Mn(VII) could react with Pb(II) to produce Mn(IV) and Pb(IV) at pH 6.0–8.0, further experiments revealed that Pb(II) did not exert its enhancing effect through promoting the generation of MnO₂, as the reactivity of MnO₂ was poor under the employed pH range. At pH below 5.0, it was interesting to find that, a negligible amount of MnO₂ was formed in the Mn(VII)/Pb(II) system in the absence of contaminants, while once MnO₂ was generated in the presence of contaminants, it could catalyze the Pb(II) oxidation to Pb(IV) by Mn(VII). Collectively, by highlighting the conversion process of Pb(II) to Pb(IV) by either Mn(VII) or MnO₂, the reactive Pb(III) intermediates were proposed to account for the Pb(II) enhancement effect.

Keywords Permanganate Pb(II) oxidation MnO₂ pH effect

Corresponding Author(s): Yuankui Sun

About author:

Tongcan Cui and Yizhe Hou contributed equally to this work.

Issue Date: 27 December 2021

Cite this article:

Lei Dong,Pin Xie,Xin Zhang, et al. Co-present Pb(II) accelerates the oxidation of organic contaminants by permanganate: Role of Pb(III)[J]. Front. Environ. Sci. Eng., 2022, 16(8): 109.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-022-1530-y
https://academic.hep.com.cn/fese/EN/Y2022/V16/I8/109

Fig.1 Effect of PbCl₂ on the kinetics of DCF oxidation by KMnO₄ over the pH range of 4.5−8.0 (a)–(e) and summary of the corresponding rate constants (f). Reaction conditions: [DCF]₀ = 10 μmol/L, [KMnO₄]₀ = 100 μmol/L, [NaCl] = 5 mmol/L, T = 25 ^oC. The solid lines in panels (a)–(e) represent the fitting curves with pseudo first-order law and the dotted lines are provided to guide to the eye only. Error bars not shown are smaller than markers.

Fig.2 Variation of dissolved Pb(II) during the reaction between KMnO₄ and Pb(II) in the presence (a) and absence (b) of DCF over the pH range of 5.0−8.0. Reaction conditions: [DCF]₀ = 10 μmol/L (if any), [KMnO₄]₀ = 100 μmol/L, [NaCl] = 5.0 mmol/L, T = 25 ^oC. Error bars not shown are smaller than markers.

Fig.3 Effect of PbCl₂ on the kinetics of 2,4-DCP oxidation by KMnO₄ over the pH range of 5.0−9.0 (a)–(j) and summary of the corresponding rate constants. Reaction conditions: [2,4-DCP]₀ = 10 μmol/L, [KMnO₄]₀ = 100 μmol/L, [NaCl] = 5.0 mmol/L, T = 25 ^oC. The solid lines in panels (a)–(f) represent the fitting curves with pseudo first-order law and the dotted lines are provided to guide to the eye only. Error bars not shown are smaller than markers.

Fig.4 Effect of Pb(II) concentration on the kinetics of DCF (a) and 2,4-DCP (b) oxidation by KMnO₄. (c) Summary of rate constants of DCF and 2,4-DCP oxidation by KMnO₄ with the presence of various Pb(II) concentrations. Reaction conditions: [KMnO₄]₀ = 100 μmol/L, [NaCl] = 5 mmol/L, T = 25 ^oC, [DCF]₀ = [2,4-DCP]₀ = 10 μmol/L, pH= 5.0 and 8.0 for DCF and 2,4-DCP, respectively.

Fig.5 Variation of UV-vis spectra during the reaction between KMnO₄ and DCF in the absence or presence of Pb(II) over the pH range of 5.0−8.0. Peaks at 418 nm and 526 nm are the characteristic UV-vis absorption peaks of MnO₂ and MnO₄^–, respectively. Reaction conditions: [DCF]₀ = 10 μmol/L, [KMnO₄]₀ = 100 μmol/L, [NaCl] = 5.0 mmol/L, T= 25 ^oC. The lines ascribed to “0 min” represent the spectra of solution containing Mn(VII) but without Pb(II) and DCF.

Fig.6 XRD patterns, TEM, HRTEM, and energy dispersive spectroscopy mapping images of the solid products collected after the reaction of Mn(VII) and DCF in the presence of Pb(II). Reaction conditions: pH= 7.0, [DCF]₀ = 10 μmol/L, [KMnO₄]₀ = 100 μmol/L, [NaCl] = 5.0 mmol/L, T = 25 ^oC. The pre-formed MnO₂ was prepared by mixing the appropriate amounts of KMnO₄ and Na₂S₂O₃ solutions.

Fig.7 XPS spectra of solid samples obtained from the reactions between KMnO₄ and Pb(II) in the presence of 0 μmol/L (a) and 40 μmol/L (b) DCF. Reaction conditions: pH= 7.0, [KMnO₄]₀ = 100 μmol/L, [Pb(II)]₀ = 80 μmol/L, [NaCl] = 5.0 mmol/L, T = 25 ^oC, reaction time= 60 min.

Scheme 1 Proposed role of Pb(III) intermediates during the reaction of KMnO₄ with organic pollutants.

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