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Defluorination of Per- and Polyfluoroalkyl Substances (PFASs) with Hydrated Electrons: Structural Dependence and Implications to PFAS Remediation and Management

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Bentel, Michael J., Yu, Yaochun, Xu, Lihua, Li, Zhong, Wong, Bryan M., Men, Yujie, Liu, Jinyong·2019·Environmental Science & Technology
DOI 10.1021/acs.est.8b06648
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Abstract

Abstract This study investigates critical structure–reactivity relationships within 34 representative per- and polyfluoroalkyl substances (PFASs) undergoing defluorination with UV-generated hydrated electrons. While CnF2n+1–COO– with variable fluoroalkyl chain lengths (n = 2 to 10) exhibited a similar rate and extent of parent compound decay and defluorination, the reactions of telomeric CnF2n+1–CH2CH2–COO– and CnF2n+1–SO3– showed an apparent dependence on the length of the fluoroalkyl chain. Cross comparison of experimental results, including different rates of decay and defluorination of specific PFAS categories, the incomplete defluorination from most PFAS structures, and the surprising 100% defluorination from CF3COO–, leads to the elucidation of new mechanistic insights into PFAS degradation. Theoretical calculations on the C–F bond dissociation energies (BDEs) of all PFAS structures reveal strong relationships among (i) the rate and extent of decay and defluorination, (ii) head functional groups, (iii) fluoroalkyl chain length, and (iv) the position and number of C–F bonds with low BDEs. These relationships are further supported by the spontaneous cleavage of specific bonds during calculated geometry optimization of PFAS structures bearing one extra electron, and by the product analyses with high-resolution mass spectrometry. Multiple reaction pathways, including H/F exchange, dissociation of terminal functional groups, and decarboxylation-triggered HF elimination and hydrolysis, result in the formation of variable defluorination products. The selectivity and ease of C–F bond cleavage highly depends on molecular structures. These findings provide critical information for developing PFAS treatment processes and technologies to destruct a wide scope of PFAS pollutants and for designing fluorochemical formulations to avoid releasing recalcitrant PFASs into the environment.

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Citations

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Metadata

Authors
Bentel, M. J., Yu, Y., Xu, L., Li, Z., Wong, B. M., Men, Y., & Liu, J.
Venue
Environmental Science & Technology
Publisher
American Chemical Society (ACS)
Published
2019-03-15
Volume
53
Issue
7
Pages
3718-3728
ISSN
  • 0013-936X (ISSN-L)
  • 1520-5851
DOI
10.1021/acs.est.8b06648
OpenAlex
W2921364395
Cited by
648
References
14
FWCI
19.88
Type
journal article
Language
en
Open access
hybrid
Licence
pubs.acs.org/page/policy/authorchoice_termsofuse.html (vor, 2 d)
Funders
  • National Science Foundation (NA)
  • Division of Chemistry (CHE-1709286, CHE-1709719)
  • University of California, Riverside (NA)
  • Strategic Environmental Research and Development Program (ER-1289, ER-1497)

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