Journal of Environmental Chemical Engineering
·
2023
·
IF 7.7
Yiqing Liu,Ting Wang,Zhengjie Chen,Shenglan Liu,Yongsheng Fu
Currently, the research on bisulfite (BS) activation by Mn(II) is very limited probably because of the low catalytic efficiency of Mn(II). Adding ligands to Mn(II)/BS system is likely to improve the BS activation, but the relative information is very rare. Therefore, the effect of nitrilotriacetic acid (NTA) on Mn(II)/BS system was investigated in this work using sulfamethoxazole (SMX) as the target contaminant. The results showed that the addition of NTA enhanced SMX removal in Mn(Ⅱ)/BS system through forming Mn(Ⅱ/III)-NTA complexes driving Mn(III)/Mn(II) cycle and stabilizing Mn(III). Alcohol scavenging experiments and competitive kinetic experiments indicated that sulfate radical (SO 4 •− ) and hydroxyl radical (HO • ) were not the main reactive species in Mn(II)/NTA/BS system. Mn(Ⅲ) was the primary oxidant for SMX elimination in this system and its existence was proved by UV-Vis absorption spectrum of reaction solution. Mn(Ⅱ)/NTA/BS system could greatly degrade SMX in near-neutral conditions, while nearly no SMX removal was observed at pH 3.0. The decrease of dissolved oxygen concentration significantly inhibited BS autocatalytic stage, thus suppressing the removal of SMX. Due to the competitive complexation of HCO 3 − and FA with NTA for Mn(II), their addition in Mn(Ⅱ)/NTA/BS system obviously inhibited SMX degradation . Four intermediates were detected during SMX degradation in Mn(Ⅱ)/NTA/BS system, and the possible SMX transformation pathways were speculated as N-S bond breaking, hydroxylation, amino oxidation and coupling reaction.
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ENVIRONMENTAL SCIENCE & TECHNOLOGY
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2015
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IF 5.33
Bo Sun,Xiaohong Guan,Jingyun Fang,Paul G. Tratnyek
MnO4– was activated by HSO3–, resulting in a process that oxidizes organic contaminants at extraordinarily high rates. The permanganate/bisulfite (PM/BS) process oxidized phenol, ciprofloxacin, and methyl blue at pHini 5.0 with rates (kobs ≈ 60–150 s–1) that were 5–6 orders of magnitude faster than those measured for permanganate alone, and ∼5 to 7 orders of magnitude faster than conventional advanced oxidation processes for water treatment. Oxidation of phenol was fastest at pH 4.0, but still effective at pH 7.0, and only slightly slower when performed in tap water. A smaller, but still considerable (∼3 orders of magnitude) increase in oxidation rates of methyl blue was observed with MnO2 activated by HSO3– (MO/BS). The above results, time-resolved spectroscopy of manganese species under various conditions, stoichiometric analysis of pH changes, and the effect of pyrophosphate on UV absorbance spectra suggest that the reactive intermediate(s) responsible for the extremely rapid oxidation of organic contaminants in the PM/BS process involve manganese(III) species with minimal stabilization by complexation. The PM/BS process may lead to a new category of advanced oxidation technologies based on contaminant oxidation by reactive manganese(III) species, rather than hydroxyl and sulfate radicals.
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CHEMOSPHERE
·
2018
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IF 4.427
Xinghao Wang,Jiayi Yao,Siyuan Wang,Xiaoxue Pan,Ruiyang Xiao,Qingguo Huang,Zunyao Wang,Ruijuan Qu
Photodegradation of pollutants is classically explained by reaction with reactive oxygen species. However Mn(III) may also remove pollutants, but direct evidence is actually lacking. Here we investigated the role of soluble Mn(III) on phototransformation of four typical estrogens, namely estrone (E1), 17β-estradiol (E2), estriol (E3), and 17α-ethynylestradiol (EE2), in the presence of Mn(II) and humic acid . Conversion rates of 60.2%, 89.0%, 87.6%, and 80.2% were achieved for E1, E2, E3, and EE2, respectively, after 72 h visible light irradiation. A detailed quenching experiments revealed that soluble Mn(III), and not reactive oxygen species, was the oxidant responsible for estrogen removal. The determination of Mn(III) concentration provided direct proof of the role of Mn(III)-based oxidizers in the conversion of estrogens. Soluble Mn(III) can form complexes with humic acid, and about 6.51 μM of Mn(III)-humic acid was formed from 20 μM of Mn(II) in the presence of 5 mg/L of humic acid. Furthermore, product identification and theoretical computation demonstrated that estrogens are mainly converted into oligomers (dimers, trimers, tetramers, etc.) via a single-electron process. According to these results, the oxidation of Mn(II) to Mn(III) is initiated by superoxide ion (O 2 •- ) generated from dissolved oxygen in the presence of humic acid under visible light irradiation. The formed soluble Mn(III) strips the estrogens of a single electron to generate phenoxyl radicals, which undergo oligomerization, while leads to regeneration of Mn(II). Hence, the photochemical Mn(II)-Mn(III) redox cycling may significantly influence the fate and transformation of estrogens in waters.
研究领域:
环境科学
·
生物学
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JOURNAL OF HAZARDOUS MATERIALS
·
2024
·
IF 12.2
Yuxi Zhang,Yamin Deng,Jiangkai Xue,Yihan Cheng,Yulun Nie,Kunfu Pi,Yao Du,Xianjun Xie,Jianbo Shi,Yanxin Wang
The environmental fate of arsenic (As) relies substantially on its speciation, which occurs frequently coupled to the redox transformation of manganese. While trivalent manganese (Mn(III)), which is known for its high reactivity, is believed to play a role in As mobilization by iron (oxyhydr)oxides in dynamic aquifers, the exact roles and underlying mechanisms are still poorly understood. Using increasingly complex batch experiments that mimick As-affected aquifer conditions in combination with time-resolved characterization, we demonstrate that Mn(III)-NOM complexes play a crucial role in the manganese-mediated immobilization of As(III) by ferrihydrite and goethite . Under anaerobic condition , Mn(III)-fulvic acid (FA) rapidly oxidized 31.8% of aqueous As(III) and bound both As(III) and As(V). Furthermore, Mn(III)-FA exerted significantly different effects on the adsorption of As by ferrihydrite and goethite. Mn(III)-FA increased the adsorption of As by 6–16% due to the higher affinity of oxidation-produced As(V) for ferrihydrite under circumneutral conditions. In contrast, As adsorption by crystalline goethite was eventually inhibited due to the competitive effect of Mn(III)-FA. To summarize, our results reveal that Mn(III)-NOM complexes play dual roles in As retention by iron oxides , depending on the their crystallization. This highlights the importance of Mn(III) for the fate of As particularly in redox fluctuating groundwater environments.
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Journal of Cleaner Production
·
2021
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IF 9.297
Chuankun Yin,Siji Zhou,Keyi Zhang,Jiale Bai,Yangyang Lv,Xuewen Zhang,Xiaoxia Li,Aihua Xu
p-Nitrophenol (PNP) is one of the highly toxic and mutagenic pollutants existed in aquatic environment. In this work, the crednerite CuMnO 2 nanoflake was prepared and used to degrade PNP with peroxymonosulfate (PMS) as the oxidant. It was found that CuMnO 2 exhibited much higher activity than other Cu-based catalysts such as CuO, Cu 2 O, CuFe 2 O 4 and CuFeO 2 , with 90% of PNP degraded after 10 min under mild reaction conditions. The catalyst was also stable during five successive runs. Sulfate and hydroxyl radicals produced from PMS reduction by Cu(I) species, as well as superoxide ions and single oxygen, contribute to the degradation of PNP. More importantly, the interactions between Mn and Cu species in CuMnO 2 were identified by X-ray photoelectron spectroscopy (XPS), fourier transform infrared spectroscopy (FT-IR) and linear sweep voltammetry (LSV), and were further confirmed by the control experiment with the mixture of Cu 2 O + Mn 2 O 3 . The results implied that the high valent Mn(III) species acted as Lewis acids to withdraw electron from PMS, resulting that the Cu(I) species can be easier oxidized to Cu(II) by PMS with the formation of radicals. These findings provide an ideal bimetallic heterogeneous catalyst and a new mechanism for PMS-mediated reaction.
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CHEMICAL ENGINEERING SCIENCE
·
2026
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IF 5.1
Shangyi Zhao,Jing Li,Yanchanjuan Yang,Shuaiqi Zhao,Aihua Xu,Xiuying Liu,Xiaoxia Li
Sulfite (SO 3 2− ) has emerged as an economical and eco-friendly precursor for reactive species generation in advanced oxidation processes (AOPs). However, conventional activation strategies typically require high sulfite inputs and generate non-selective radicals, limiting their efficiency and practicality. Here, we demonstrate that a trace amount of water‑soluble manganese porphyrin complex (Mn(III)‑TCPP, as low as 4 μM), can efficiently activate Na 2 SO 3 at ultralow concentrations (10–100 μM) to degrade sulfadiazine. The Mn(III)-TCPP/Na 2 SO 3 system exhibited an initial rate 41 times faster than the Mn 2+ /Na 2 SO 3 system and 4.2 times greater than the reported -Mn(III)-NTA/Na 2 SO 3 system. A linear correlation between the degradation rate constant and the Hammett constant (σ + ) of porphyrin substituents confirms that ligand electronic structure modulates Mn redox cycling during SO 3 2− oxidation by dissolved O 2 . Mechanistic studies, including time‑resolved spectroscopy, electrochemical analysis, and reactive species trapping, reveal that the reaction proceeds primarily via superoxide radical and singlet oxygen, representing a distinct departure from conventional sulfate radical or high-valent Mn(V) that has been reported in other metal–ligand AOP systems. This work establishes a new, highly efficient sulfite activation driven by an ultralow-dose metalloporphyrin catalyst and provides fundamental insight into non‑radical oxidation routes for sulfite-based AOPs.
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Nano Research
·
2023
·Vol. 16
·期 8
·10748-10755
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IF 9.9
Li Junhua,Jiang Yi,Zhang Xu,Huo Yidan,Du Fanglin,Tuo Yongxiao,Guo Zhiyan,Chen Dawei,Chen Shenghua
The electrooxidation of the alcohol and aldehyde molecules instead of water coupled with H 2 production has been proven to be effective for producing high-value fine chemicals under alkaline conditions. It is also noteworthy that under acidic conditions, the stability of non-noble metal water oxidation catalysts remains a great challenge due to the lattice oxygen mechanism. Hence, we coupled the biomass-derived glucose oxidation for high-value D-glucaric acid (GRA) with ultra-durable hydrogen in acid solution over a Yb-MnO 2 catalyst. The Mn 3+ regulated by Yb atoms doped in MnO 2 can effectively optimize the adsorption and desorption processes of the alcohol and aldehyde group and improve the intrinsic activity but cannot for H 2 O. The catalyst exhibited extremely high activity and stability after 50 h for glucose oxidation, inhibiting the lattice oxygen process and MnO 4− formation, while the activity was quickly lost within 0.5 h for water oxidation. Density functional theory (DFT) calculations further demonstrated that glucose oxidation reaction proceeds preferentially due to the oxidation of aldehyde group with lower adsorption-free energy (−0.4 eV) than water (Δ G > 0 eV), avoiding the lattice oxygen mechanism. This work suggests that biomass-derived glucose oxidation not only provides a cost-effective approach for high-value chemicals, but also shows an extremely potential as an alternative to acidic oxygen evolution reaction (OER) for ultradurable H 2 production.
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Journal of Water Process Engineering
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2023
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IF 7
Jinbing Huang,Xiaoyan Liu,Shiwei Xie
Although electrochemical activation of permanganate ( E -PM) is a green and efficient method to degrade refractory organics by in-situ generated reactive Mn( III ) aq , this process highlights on the presence of promoter and/or stabilizer. Oxalate (OA) is a widespread organic chelate in natural water bodies (with concentrations up to 1 mM), but whose effect on the E -PM process is still unclear. In this study, we found electrolysis and the presence of OA both promote the activation of PM for the degradation of diclofenac (DCF), showing a high synergistic coefficient (3.23) and elevated reaction constant (0.1395 min −1 ). Nevertheless, this process is highly pH-dependent, behaving decreased reactivity as pH value increasing from 3 to 11. Sufficient concentration of OA (≥0.5 mM in this study) is required for stabilizing Mn(III). UV–vis spectra, visual evidence and quenching experiments identified the presence and dominant role of Mn(III)-OA on the degradation of DCF. Using chronoamperometry, we confirmed Mn(III)-OA was primarily generated from the electro-reduction of PM in the presence of OA at pH 5.
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JOURNAL OF HAZARDOUS MATERIALS
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2020
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IF 9.038
Wei Ding,Huaili Zheng,Yongjun Sun,Zhiwei Zhao,Xinyu Zheng,Yuyang Wu,Weilong Xiao
As(III) oxidation to As(V) is deemed necessary for better arsenic removal, and separation is still the optimal approach for water remediation from As(III). Herein, sulfite (SIV) was adopted to activate MnFe 2 O 4 for simultaneous oxidation and adsorption of As(III) in neutral water. The As(III) removal was more efficient than a peroxidation of As(III) followed by adsorption. The adsorption capacity of MnFe 2 O 4 /S(IV) for As(III) (26.257 mg g −1 ) was much higher than those of MnFe 2 O 4 alone for As(III) (9.491 mg g −1 ) and As(V) (9.142 mg g −1 ). The mechanistic study corroborated that intermediate Mn(III) was the dominant oxidant responsible for rapid oxidation of As(III), and the dual roles of S(IV) as a complexing ligand and a precursor of oxysulfur radicals accelerated the redox cycle of Mn(II)/Mn(III). Moreover, S(IV) enhanced arsenic adsorption by driving more production of monodentate complexes. As(III) can be effectively removed over a wide range of temperatures (283.15–313.15 K) and pH (3–10) with the optimal pH of 7. The effect of coexisting ions and reusability of MnFe 2 O 4 were also investigated. Especially, the superior performance of MnFe 2 O 4 /S(IV) for As(III) removal in various water matrixes may help develop new removal technologies based on active Mn(III) for the water decontamination from As(III).
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CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Wei Sun,Mushan Xie,Bo Shi,Zhixuan Zhu,Jian Zhang,Ying Wang,Jing Bian,Haibo Wang,Chun Zhao
The selective and simultaneous removal of antibiotics (ABs), antibiotic-resistant bacteria (ARBs), and antibiotic resistance genes (ARGs) from complex water matrices is crucial but remains challenging. Herein, relatively pure nonradical oxidation systems of singlet oxygen ( 1 O 2 ) and reactive trivalent manganese (Mn( III ) aq ) were established through electrofiltration-activated peroxymonosulfate and permanganate processes, respectively. Both systems simultaneously removed ABs, ARBs, and > 99 % of 20 selected ARGs within 15 min, while the addition of anions and nature organic matter slightly inhibited ARB inactivation. A multiperspective investigation confirmed that 1 O 2 demonstrated superior efficacy in ARB inactivation and protein damage compared to Mn( III ) aq , whereas Mn( III ) aq destroyed the ARB cell membrane, induced oxidative stress, and damaged almost all ARGs more rapidly than 1 O 2 . In particular, 1 O 2 exhibited selectivity toward four ARGs, which was attributed to a positive dependence on the 5′-GG-3′ doublet content. Moreover, 1 O 2 and Mn( III ) aq significantly reduced the risks of ARB regrowth and horizontal gene transfer of ARGs while providing resilience in real water matrices with improved energy-effectiveness. The findings of this study offer new insights into nonradical reactive species dominated advanced oxidation processes for controlling antibiotic resistance in real water.
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SCIENCE OF THE TOTAL ENVIRONMENT
·
2024
·
IF 8.2
Song Gao,Xinghao Wang,Xinhao Wang,Xiru Chen,Sijia Liang,Ziyan Zhou,Shuxia Xu,Yanfen Fang,Juan Gao,Cheng Gu
Aqueous trivalent manganese [Mn(III)], an important reactive intermediate, is ubiquitous in natural surface water containing humic acid (HA). However, the effect of low-molecular-weight organic acids (LMWOAs) on the formation, stability and reactivity of Mn(III) intermediate is still unknown. In this study, six LMWOAs, including oxalic acid (Oxa), salicylic acid (Sal), catechol (Cat), caffeic acid (Caf), gallic acid (Gal) and ethylene diamine tetraacetic acid (EDTA), were selected to investigate the effects of LMWOAs on the degradation of BPA induced by in situ formed Mn(III)-L in the HA/Mn(II) system under light irradiation. The chromophoric constituents of HA could absorb light radiation and generate superoxide radical to promote the oxidation of Mn(II) to form Mn(III), which was further involved in transformation of BPA. Our results implied that different LMWOAs did significantly impact on Mn(III) production and its degradation of BPA due to their different functional group. EDTA, Oxa and Sal extensively increased the Mn(III) concentration from 50 to 100 μM compared to the system without LMWOAs, following the order of EDTA > Oxa > Sal, and also enhanced the degradation of BPA with the similar patterns. In contrast, Cat, Caf and Gal had an inhibitory effect on the formation of Mn(III), which is likely because they consumed the superoxide radicals generated from irradiated HA, resulting in the inhibition of Mn(II) oxidation and further BPA removal. The product identification and theoretical calculation indicated that a single electron transfer process occurred between Mn(III)-L and BPA, forming BPA radicals and subsequent self-coupling products. Our results demonstrated that the LMWOAs with different structures could alter the cycling process of Mn via complexation and redox reactions, which would provide new implications for the removal of organic pollutants in surface water.
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WATER RESEARCH
·
2024
·
IF 11.4
Shiqi Tian,Yuwei Ma,Yuanyuan Xu,Yingzi Lin,Jun Ma,Gang Wen
Dissolved Mn(III), as a potent one-electron transfer oxidant, is ubiquitous in natural waters and sediments and actively involved in the transformation of organics in biogeochemical processes and water treatment. However, the important role of Mn(III) has long been overlooked because of its short life. This study was the first to investigate the performance of Mn(III) in organoarsenic transformation and to highlight the environmental implications. Both homogeneous and heterogeneous Mn(III)-based systems were effective to remove p -arsanilic acid ( p -ASA, 15 μ M) with degradation efficiency approaching 40.4 %–98.3 %. Two degradation pathways of p -ASA were proposed, in which As-C bond and amino group were vulnerable sites to Mn(III) attack, leading to the formation of more toxic arsenate (As(V)) and nitarsone. Through transforming organoarsenic to inorganic arsenic species, the removal efficiency of total arsenic and dissolved organics were enhanced to 65.1 %–95.5 % and 16.6 %–36.6 %, respectively, by post-treatment of coagulation or adsorption, accompanied with significant reduction of cytotoxicity and environmental risks. Particularly, polymeric ferric sulfate and granular activated alumina showed superior performance in the total As removal. Moreover, oxidation efficiency of Mn(III) was hardly affected by common cations and anions (e.g., Ca 2+ , Mg 2+ , NH 4 + , NO 3 ˉ, SO 4 ˉ), halide ions (e.g., Clˉ, Brˉ) and natural organic matter, showing high robustness for organoarsenic removal under complicated water matrices. Overall, this study shed light on the significance of Mn(III) to the fate of organoarsenics in manganese-rich environments, and demonstrated the promising potential of Mn(III)-based strategies to achieve targeted decontamination in water/wastewater purification.
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