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Substantial defluorination of polychlorofluorocarboxylic acids triggered by anaerobic microbial hydrolytic dechlorination

Jin, Bosen, Liu, Huaqing, Che, Shun, Gao, Jinyu, Yu, Yaochun, Liu, Jinyong, Men, Yujie·2023·Nature Water
DOI 10.1038/s44221-023-00077-6

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Figure 1 Biotransformation and defluorination pathways of CTFE oligomer carboxylic acids by the anaerobic microbial community. a , Parent compound decay and F -formation over 84 days. Data are presented as mean values. Error bars represent the s.d. from n = 3 replicates. b , The proposed general biotransformation pathways. Green arrows represent dechlorinating reactions. Red arrows represent defluorinating reactions. The thicknesses of the red arrows represent the number of F release. The green-shaded panel represents the non-defluorinating pathway via reductive dechlorination (-Cl+H). The grey-shaded panel represents the defluorinating pathway via eliminative dechlorination (-ClCl or -ClF). The pink-shaded panel represents the defluorinating pathway via hydrolytic dechlorination (-Cl+OH). Note: Aerobic biotransformation or abiotic transformation was not observed, except for the slight fluoride
Figure 1 Biotransformation and defluorination pathways of CTFE oligomer carboxylic acids by the anaerobic microbial community. a , Parent compound decay and F -formation over 84 days. Data are presented as mean values. Error bars represent the s.d. from n = 3 replicates. b , The proposed general biotransformation pathways. Green arrows represent dechlorinating reactions. Red arrows represent defluorinating reactions. The thicknesses of the red arrows represent the number of F release. The green-shaded panel represents the non-defluorinating pathway via reductive dechlorination (-Cl+H). The grey-shaded panel represents the defluorinating pathway via eliminative dechlorination (-ClCl or -ClF). The pink-shaded panel represents the defluorinating pathway via hydrolytic dechlorination (-Cl+OH). Note: Aerobic biotransformation or abiotic transformation was not observed, except for the slight fluorideCC-BY-NC-ND · From the PDF
Figure 2 Biotransformation and defluorination pathways of CTFE2 by the anaerobic microbial community. a , The decay of CTFE2 and the formation of fluoride and TPs. TP170 was quantified using the reference standard and shown on the left y-axis, while the other TPs were represented as peak areas on the right y-axis. Data are presented as mean values. Error bars represent the s.d. from n = 3 replicates. b , Proposed biotransformation pathways. Green arrows indicate dechlorinating reactions. Red arrows indicate defluorinating reactions. Arrow thicknesses suggest the relative proportion of CTFE2 undergoing different pathways. -Cl+H: reductive dechlorination. -2Cl: eliminative dechlorination. -Cl+OH: hydrolytic dechlorination. HF: eliminative defluorination. -F+OH: hydrolytic defluorination. In brackets are unstable transient intermediates, and in dashed boxes are proposed TPs not detected by LC-HRMS. See Figure S3a - d for the LC-HRMS/MS detection of the four identified TPs.
Figure 2 Biotransformation and defluorination pathways of CTFE2 by the anaerobic microbial community. a , The decay of CTFE2 and the formation of fluoride and TPs. TP170 was quantified using the reference standard and shown on the left y-axis, while the other TPs were represented as peak areas on the right y-axis. Data are presented as mean values. Error bars represent the s.d. from n = 3 replicates. b , Proposed biotransformation pathways. Green arrows indicate dechlorinating reactions. Red arrows indicate defluorinating reactions. Arrow thicknesses suggest the relative proportion of CTFE2 undergoing different pathways. -Cl+H: reductive dechlorination. -2Cl: eliminative dechlorination. -Cl+OH: hydrolytic dechlorination. HF: eliminative defluorination. -F+OH: hydrolytic defluorination. In brackets are unstable transient intermediates, and in dashed boxes are proposed TPs not detected by LC-HRMS. See Figure S3a - d for the LC-HRMS/MS detection of the four identified TPs.CC-BY-NC-ND · From the PDF
Image 3
CC-BY-NC-ND · From the PDF
Figure 4 Proposed biotransformation pathways of CTFE3 and CTFE4 . a , proposed pathways for CTFE3 . b , the proposed key defluorination pathways via hydrolytic dechlorination and chain-shortening reactions for CTFE4 . See Figure S5a - f for CTFE4 TP formation curves, Figure S3e - p and Figure S5G for the LC-HRMS/MS detection of the identified TPs of CTFE3 and CTFE4 , respectively.
Figure 4 Proposed biotransformation pathways of CTFE3 and CTFE4 . a , proposed pathways for CTFE3 . b , the proposed key defluorination pathways via hydrolytic dechlorination and chain-shortening reactions for CTFE4 . See Figure S5a - f for CTFE4 TP formation curves, Figure S3e - p and Figure S5G for the LC-HRMS/MS detection of the identified TPs of CTFE3 and CTFE4 , respectively.CC-BY-NC-ND · From the PDF
Figure 5 Biotransformation of terminal-Cl PFCAs by the anaerobic microbial community. a-c , Parent compound decay, F release, and TP formation of Cl-C5a , Cl-C7a , and Cl-C9a , respectively. Data are presented as mean values. Error bars represent the s.d. from n = 3 replicates. d , the proposed biotransformation pathways in common. Red arrows: defluorinating reactions. Green arrows: dechlorinating reactions. In brackets: unstable transient TPs. No aerobic or abiotic transformation or adsorption was observed, as shown in Figure S1 and Figure. S2g i . See Figure S9 for the LC-HRMS/MS detection of the identified TPs.
Figure 5 Biotransformation of terminal-Cl PFCAs by the anaerobic microbial community. a-c , Parent compound decay, F release, and TP formation of Cl-C5a , Cl-C7a , and Cl-C9a , respectively. Data are presented as mean values. Error bars represent the s.d. from n = 3 replicates. d , the proposed biotransformation pathways in common. Red arrows: defluorinating reactions. Green arrows: dechlorinating reactions. In brackets: unstable transient TPs. No aerobic or abiotic transformation or adsorption was observed, as shown in Figure S1 and Figure. S2g i . See Figure S9 for the LC-HRMS/MS detection of the identified TPs.CC-BY-NC-ND · From the PDF
Image 6
CC-BY-NC-ND · From the PDF
Figure 7 CTFE4 defluorination in subcultures of the anaerobic communities, the isolated colony, and the pure cultures. a , defluorination of 50 μM CTFE4 in subcultures. Data are presented as mean values. Error bars represent the s.d. from n = 3 replicates, except for the 4 th subculture, the error bars of which represent the s.d. from n = 2 replicates. b , Defluorination of 50 μM CTFE4 in the colony isolated from the 3 rd subculture. c , Information of the two major
Figure 7 CTFE4 defluorination in subcultures of the anaerobic communities, the isolated colony, and the pure cultures. a , defluorination of 50 μM CTFE4 in subcultures. Data are presented as mean values. Error bars represent the s.d. from n = 3 replicates, except for the 4 th subculture, the error bars of which represent the s.d. from n = 2 replicates. b , Defluorination of 50 μM CTFE4 in the colony isolated from the 3 rd subculture. c , Information of the two majorCC-BY-NC-ND · From the PDF

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Research works printed but not linked: 35

  1. Dolbier, W. R. Fluorine chemistry at the millennium. J. Fluor. Chem. 126, 157–163 (2005). · DOI
  2. Lohmann, R. et al. Are fluoropolymers really of low concern for human and environmental health and separate from other PFAS. Environ. Sci. Technol. 54, 12820–12828 (2020). · DOI
  3. Xiao, F. Emerging poly- and perfluoroalkyl substances in the aquatic environment: a review of current literature. Water Res. 124, 482–495 (2017). · DOI · Paper page
  4. Dams, R. & Hintzer, K. in Fluorinated Polymers: Applications Vol. 2 1–31 (The Royal Society of Chemistry, 2017).
  5. Vanbrocklin, C. Military applications of chlorotrifluoroethylene oligomer base nonflammable hydraulic fluid. J. Fire Sci. 11, 232–241 (1993). · DOI
  6. Gschweder, L., Mattie, D., Syder, C., Warer, W. & van Brocklin, C. Chlorotrifluoroethylene oligomer based nonflammable hydraulic fluid. 1 Fluid, additive, and elastomer development. J. Synth. Lubr. 9, 187–203 (1992). · DOI
  7. Ellis, D. A., Mabury, S. A., Martin, J. W. & Muir, D. C. Thermolysis of fluoropolymers as a potential source of halogenated organic acids in the environment. Nature 412, 321–324 (2001). · DOI · Paper page
  8. Dias, J. et al. Thermal degradation behavior of ionic liquid/fluorinated polymer composites: effect of polymer type and ionic liquid anion and cation. Polymer 229, 123995 (2021). · DOI
  9. DelRaso, N. J., Auten, K. L., Higman, H. C. & Leahy, H. F. Evidence of hepatic conversion of C6 and C8 chlorotrifluoroethylene (CTFE) oligomers to their corresponding CTFE acids. Toxicol. Lett. 59, 41–49 (1991). · DOI
  10. Brashear, W. T., Greene, R. J. & Mahle, D. A. Structural determination of the carboxylic acid metabolites of polychlorotrifluoroethylene. Xenobiotica 22, 499–506 (1992). · DOI
  11. Song, X., Vestergren, R., Shi, Y., Huang, J. & Cai, Y. Emissions, transport, and fate of emerging per- and polyfluoroalkyl substances from one of the major fluoropolymer manufacturing facilities in China. Environ. Sci. Technol. 52, 9694–9703 (2018). · DOI
  12. Yin, H., Anders, M. W. & Jones, J. P. Metabolism of 1,2-dichloro-1-fluoroethane and 1-fluoro-1,2,2-trichloroethane: electronic factors govern the regioselectivity of cytochrome P450-dependent oxidation. Chem. Res. Toxicol. 9, 50–57 (1996). · DOI
  13. Harris, J. W. & Anders, M. W. Metabolism of the hydrochlorofluorocarbon 1,2-dichloro-1,1-difluoroethane. Chem. Res. Toxicol. 4, 180–186 (1991). · DOI
  14. Yu, Y. et al. Microbial cleavage of C–F bonds in two C6 per- and polyfluorinated compounds via reductive defluorination. Environ. Sci. Technol. 54, 14393–14402 (2020). · DOI · Paper page
  15. Yu, Y. et al. Microbial defluorination of unsaturated per- and polyfluorinated carboxylic acids under anaerobic and aerobic conditions: a structure specificity study. Environ. Sci. Technol. 56, 4894–4904 (2022). · DOI · Paper page
  16. Adrian, L. & Löffler, F. E. Organohalide-Respiring Bacteria (Springer, 2016). · DOI
  17. Zhang, B. et al. Novel and legacy poly- and perfluoroalkyl substances (PFASs) in indoor dust from urban, industrial, and e-waste dismantling areas: the emergence of PFAS alternatives in China. Environ. Pollut. 263, 114461 (2020). · DOI · Paper page
  18. Liu, W. et al. Atmospheric chlorinated polyfluorinated ether sulfonate and ionic perfluoroalkyl acids in 2006 to 2014 in Dalian, China. Environ. Toxicol. Chem. 36, 2581–2586 (2017). · DOI · Paper page
  19. Wang, Y. et al. Suspect and nontarget screening of per- and polyfluoroalkyl substances in wastewater from a fluorochemical manufacturing park. Environ. Sci. Technol. 52, 11007–11016 (2018). · DOI
  20. MacInnis, J. J., Lehnherr, I., Muir, D. C. G., Quinlan, R. & De Silva, A. O. Characterization of perfluoroalkyl substances in sediment cores from High and Low Arctic lakes in Canada. Sci. Total Environ. 666, 414–422 (2019). · DOI
  21. Yi, S., Zhu, L. & Mabury, S. A. First report on in vivo pharmacokinetics and biotransformation of chlorinated polyfluoroalkyl ether sulfonates in rainbow trout. Environ. Sci. Technol. 54, 345–354 (2020). · DOI
  22. Yi, S., Yang, D., Zhu, L. & Mabury, S. A. Significant reductive transformation of 6:2 chlorinated polyfluorooctane ether sulfonate to form hydrogen-substituted polyfluorooctane ether sulfonate and their toxicokinetics in male Sprague–Dawley rats. Environ. Sci. Technol. 56, 6123–6132 (2021). · DOI
  23. Lieberman, I. & Barker, H. A. β-Keto acid formation and decomposition by preparations of Clostridium kluyveri. J. Bacteriol. 68, 329–333 (1954). · DOI
  24. Buschmann, J., Angst, W. & Schwarzenbach, R. P. Iron porphyrin and cysteine mediated reduction of ten polyhalogenated methanes in homogeneous aqueous solution: product analyses and mechanistic considerations. Environ. Sci. Technol. 33, 1015–1020 (1999). · DOI
  25. Che, S. et al. Structure-specific aerobic defluorination of short-chain fluorinated carboxylic acids by activated sludge communities. Environ. Sci. Technol. Lett. 8, 668–674 (2021). · DOI · Paper page
  26. Chen, G. et al. Anaerobic microbial metabolism of dichloroacetate. mBio https://doi.org/10.1128/mBio.00537-21 (2021). · DOI
  27. Möller, B., Oßmer, R., Howard, B. H., Gottschalk, G. & Hippe, H. Sporomusa, a new genus of gram-negative anaerobic bacteria including Sporomusa sphaeroides spec. nov. and Sporomusa ovata spec. nov. Arch. Microbiol. 139, 388–396 (1984). · DOI
  28. Temme, H. R., Carlson, A. & Novak, P. J. Presence, diversity, and enrichment of respiratory reductive dehalogenase and non-respiratory hydrolytic and oxidative dehalogenase genes in terrestrial environments. Front. Microbiol. 10, 1258 (2019). · DOI
  29. Duhamel, M. & Edwards, E. A. Microbial composition of chlorinated ethene-degrading cultures dominated by Dehalococcoides. FEMS Microbiol. Ecol. 58, 538–549 (2006). · DOI
  30. Baena, S. et al. Desulfovibrio aminophilus sp. nov., a novel amino acid degrading and sulfate reducing bacterium from an anaerobic dairy wastewater lagoon. Syst. Appl. Microbiol. 21, 498–504 (1998). · DOI
  31. Yang, Y., Pesaro, M., Sigler, W. & Zeyer, J. Identification of microorganisms involved in reductive dehalogenation of chlorinated ethenes in an anaerobic microbial community. Water Res. 39, 3954–3966 (2005). · DOI
  32. Evich, M. G. et al. Environmental fate of Cl-PFPECAs: predicting the formation of PFAS transformation products in New Jersey soils. Environ. Sci. Technol. 56, 7779–7788 (2022). · DOI
  33. Men, Y. et al. Sustainable syntrophic growth of Dehalococcoides ethenogenes strain 195 with Desulfovibrio vulgaris Hildenborough and Methanobacterium congolense: global transcriptomic and proteomic analyses. ISME J. 6, 410–421 (2012). · DOI
  34. Tonomura, K., Futai, F., Tanabe, O. & Yamakoka, T. Defluorination of monofluoroacetate by bacteria. Part I. Isolation of bacteria and their activity of defluorination. Agric. Biol. Chem. 29, 124–128 (1965).
  35. Davis, C. K., Webb, R. I., Sly, L. I., Denman, S. E. & McSweeney, C. S. Isolation and survey of novel fluoroacetate-degrading bacteria belonging to the phylum Synergistetes. FEMS Microbiol. Ecol. 80, 671–684 (2012). · DOI · Paper page

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Metadata

Authors
Jin, B., Liu, H., Che, S., Gao, J., Yu, Y., Liu, J., & Men, Y.
ORCID
Venue
Nature Water
Publisher
Springer Science and Business Media LLC
Published
2023-05-15
Volume
1
Issue
5
Pages
451-461
ISSN
2731-6084
DOI
10.1038/s44221-023-00077-6
Cited by
79
References
12
Language
en
Licence
Funders
  • United States Department of Defense | Strategic Environmental Research and Development Program (ER20-1541)
  • U.S. Department of Health & Human Services | NIH | National Institute of Environmental Health Sciences (R01ES032668)

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