JOURNAL OF HAZARDOUS MATERIALS
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2025
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IF 11.3
Pengtao Cai,Tong Chen,Mingxiu Zhan,Xiaojun Ma,Masaki Takaoka,Chen Sun,Xiaodong Li
Per- and polyfluoroalkyl substances (PFAS) are known for their strong C-F bonds, which make them highly persistent in the environment and resistant to degradation. Among PFAS, perfluorobutane sulfonate (PFBS), a short-chain PFSA widely used as a replacement for long-chain PFAS like perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), has garnered attention due to its environmental persistence and toxicity. Although PFBS has lower bioaccumulation potential than its long-chain counterparts, it remains a significant pollutant with limited data available on its degradation mechanisms. To address this, the present study investigates PFBS degradation under subcritical water hydrothermal conditions. Various alkaline substances and additives were tested, and degradation products were analyzed by liquid and gas chromatography-mass spectrometry. Results show that 2 M NaOH at 325°C achieved an ∼99.4 % PFBS removal rate, and the degradation pathway began with the breakdown of the S-C bond, followed by C-F bond cleavage, resulting in the formation of smaller fluorinated compounds, including trifluoroacetic acid. Density functional theory (DFT) calculations provided detailed insights into the degradation mechanism, identifying hydroxide ion attack on the sulfonic acid group as the initial step and elucidating three distinct pathways for subsequent reactions. This study provides key insights into PFBS degradation mechanisms, emphasizing the synergistic effect of alkaline bases and additives. The findings support the optimization of subcritical hydrothermal treatment for PFAS removal, providing a scalable and environmentally sustainable solution.
研究领域:
环境科学
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化学工程
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理论计算
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
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2024
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IF 12.2
Lijie Duan,Mengbin Gu,Minghao Wang,Liquan Liu,Xue Cheng,Xueqi Fan,Jun Huang
Widespread detection in soils and sediments underscores the potential threats posed by persistent, bioaccumulative and toxic perfluorooctane sulfonate (PFOS) to ecosystems and organisms. Nevertheless, the formidable energy of the C-F bond imparts stability and hampers degradation. This study investigates the potential of boron carbide (B 4 C), a hard-ceramic material often utilized in armor and abrasion contexts, for degrading solid-phase PFOS through ball milling. Following a 60-minute reaction period, PFOS degradation reached 100 %, while desulfurization stabilized at 13.9 %. Defluorination initially rose to 23.7 % but subsequently displayed a gradual decline. Fluoride ions, once released, were secured and the stable reservoir surface of B 4 C during the ball-milling process, leading to the formation of B-C-B-F chemical bonds, which was confirmed through characterization by XPS, FTIR, and solid-state NMR analyses. Furthermore, intermediate byproducts formed during the degradation of PFOS, encompassing perfluoroalkyl sulfonic acids (PFSAs) and perfluoro carboxylic acids (PFCAs), were identified. Eventually, the generation of free electrons, contributing to the facilitation of degradation for both PFOS and its intermediates, was confirmed through the DPPH experiment. This identification underscores the intricacy of the PFOS degradation pathway, which encompasses the generation and subsequent breakdown of these intermediates. These discoveries hold significance for pioneering sustainable and inventive methods to combat PFOS pollution across diverse applications. Furthermore, they enrich the comprehension of how mechanical forces can be leveraged for the eco-friendly removal of PFOS contaminants.
研究领域:
环境科学
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材料科学
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
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2023
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IF 13.6
Li Li,Ruoning Guo,Jie Gao,Jie Liu,Zhiwei Zhao,Xin Sheng,JunYu Fan,Fuyi Cui
Perfluorooctanoic acid (PFOA) is a representative persistent organic pollutant and its disposal by mechanochemical (MC) technology emerges in recent years. However, degradation mechanism of PFOA especially rupture of C−F bonds during MC process is still unclear. Therefore, we innovatively employed barium titanate as co-milling reagent in MC system to disclose an electron-dominated reduction process. By stimulating piezoelectric effect of BaTiO 3 under MC impact, free electrons were generated. The results implied more than 95.00% degradation and 60.00% defluorination efficiency were obtained after 6 h′ ball milling. DPPH• was used as probe to confirm the existence of piezo-excited electrons, which were further verified to be major reactive species by atmosphere experiments. Thus, PFOA destruction was dominated by reduction process, characterizing by breakage of C−F bonds induced by electrons. Accordingly, the fate of organic fluorides was explored and BaF 2 was identified as final product. The cleavage of carboxyl group initiated PFOA decomposition, following by successive removal of CF 2 groups and elimination of F − . Moreover, the practical experiments and reusable trials implied promising application of this method. Overall, this paper provides a novel perspective for reductive decomposition of PFOA by MC technology and reveals the major role of electrons during reaction process.
研究领域:
环境科学
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
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