Biomimetic degradation of perfluorinated acids by vitamin B12 with nano-zero-valent iron/nickel bimetal: effects of their self-structure and coexisting substances
. Xiamen Engineering & Technology Research Center for Urban Water Environment Planning and Remediation, College of Civil Engineering, Huaqiao University, Xiamen 361021, China . Ningde City Investment Logistics Group Co., Ltd., Ningde 352000, China . Analytical and Testing Center of Huaqiao University, Xiamen 361021, China
Perfluorinated acids (PFAs) are a new class of persistent organic pollutants that are difficult to defluorinate or remove. The reductive degradation of various representative PFAs in a biomimetic system composed of vitamin B12 (VB12) as a catalyst and nano-zero-valent iron-nickel bimetal (nFe0/Ni0) as a reductant was investigated in this study. The effects of the self-structures of PFAs and the coexisting substances in natural water were also discussed. The results indicated that the defluorination and removal rates of PFAs were highly dependent on the length and terminal functional groups of the perfluorocarbon chain. Only Perfluorocarboxylates with C > 11 and Perfluorosulfonates with C > 6 were significantly degraded. Based on the analysis of the degradation products of perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHxS), prefluorooctanesulfonate (PFOS), and 2-perfluoroctyl ethanol (8:2 FTOH), hydrolysis followed by the scission of C–S or C–C connecting the terminal functional groups was the dominant degradation pathway of long-chain PFAs instead of cleavage of C–C in the perfluorocarbon chain. The perfluorocarbon chain length affects the product type. It is speculated that the high bond dissociation energies of C–F bonds in short-chain PFAs hinder the occurrence of the decarboxylation-hydroxylation-elimination-hydrolysis (DHEH) pathway and make the addition of (–CF2–)n dominant. Meanwhile, the inhibition of SO42– removal by PFOS was significant, whereas humic acid, Cl–, and dissolved oxygen had only a slight influence. Overall, this study provides new insights on the degradation of PFAs containing multiple structures and highlights the impact of the self-structure on PFAs removal.
Fan Wei,Jiaqi Zhang,Zhimin Yang, et al. Biomimetic degradation of perfluorinated acids by vitamin B12 with nano-zero-valent iron/nickel bimetal: effects of their self-structure and coexisting substances[J]. Front. Environ. Sci. Eng.,
2025, 19(2): 18.
Fig.1 Time profiles of defluorination rate of adsorption controls (a), and decomposition treatments (b), removal rate of adsorption controls (c), and decomposition treatments (d) for PFCAs. The experiment conditions: [PFCAs]0 = 200 μmol/L, [VB12]0 = 200 μmol/L, [0.5 wt% nFe0/Ni0]0 = 3.0 g/L, pHi = 9.5, and t = 60 °C.
Fig.2 Time profiles of defluorination rate of adsorption controls and decomposition treatments (a), removal rate of adsorption controls (b), and decomposition treatments (c) for PFSAs. The experiment conditions: [PFSAs]0 = 200 μmol/L, [VB12]0 = 200 μmol/L, [0.5 wt% nFe0/Ni0]0 = 3.0 g/L, pHi = 9.5, and t = 60 °C.
Fig.3 The (a) defluorination and (b) removal rates of PFCAs and PFSAs with the same chain length at 72 h.
Fig.4 Proposed degradation pathways of PFOS, PFHxS, PFBS, and 8:2FTOH. The solid arrows indicate transformation steps that are expected to occur based on degradation product analysis. The dashed arrows indicate potential transformation steps that are in doubt. The double arrows indicate multiple transformation steps that are omitted. The structural formula of polyfluorinated acids is not shown because the substitution position is uncertain.
Fig.5 The effect of (a) HA, (b) FA, (c) SO42–, (d) Cl–, (e) DO concentration on PFOS removal; (f) DO concentration in the system after reaction. The experiment conditions: [PFOS]0 = 200 μmol/L, [VB12]0 = 200 μmol/L, [0.5 wt% nFe0/Ni0]0 = 3.0 g/L, pHi = 9.5, and t = 60 °C.
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