Biomimetic degradation of perfluorinated acids by vitamin B12 with nano-zero-valent iron/nickel bimetal: effects of their self-structure and coexisting substances

Highlights

	● Degradation of long-chain PFAs is better than short-chain in VB12 + nFe0/Ni0 systems.
	● PFSAs are more susceptible to defluorination and removal than PFCAs in this system.
	● Degradation products of some PFAs were identified and possible pathways were proposed.
	● The system has good anti-interference ability to common natural water components.

Abstract

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 SO₄^2– 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.

Graphical abstract

Keywords

Perfluorinated compounds / Vitamin B₁₂ / nFe⁰/Ni⁰ / Biomimetic reduction

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Acknowledgements

This study was supported by the National Natural Science Foundation of China (No. 51878300), the Promotion Program for Young and Middle-aged Teacher in Science and Technology Research of Huaqiao University (No. ZQN-YX602), the Science and Technology Program of Quanzhou City (No. 2018C084R) and the Experimental Teaching and Management Reform Project of Huaqiao University in 2023 (No. SY2023J03).

Conflict of Interests

The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11783-025-1938-2 and is accessible for authorized users.

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