Cited by 64Per- and polyfluoroalkyl substances researchMass Spectrometry Techniques and ApplicationsSurfactants and Colloidal Systems

Enrichment Factors of Perfluoroalkyl Oxoanions at the Air/Water Interface

Psillakis, Elefteria, Cheng, Jie, Hoffmann, M. R., Colussi, A. J.·2009·The Journal of Physical Chemistry A

Abstract

The refractory, water-bound perfluoro-n-alkyl carboxylate F(CF2)nCO2- and sulfonate F(CF2)nSO3- surfactant anions reach remote locations by mechanisms that are not well understood. Here we report experiments in which the relative concentrations of these anions on the surface of microdroplets produced by nebulizing their aqueous solutions are measured via electrospray ionization mass spectrometry. Enrichment factors f (relative to Br-: f(Br-) identical with 1) increase with n, asymptotically reaching f[F(CF2)nSO3-] approximately 2 f[F(CF2)nCO2-] approximately 200 f(Br-) values above n approximately 8. The larger f values for F(CF2)nSO3- over their F(CF2)nCO2- congeners are consistent with a closer approach of the bulkier, less hydrated -SO3- headgroup to the air/water interface. A hyperbolic, rather than the predicted linear log f[F(CF2)nCO2-] vs n dependence suggests the onset of conformational restrictions to interfacial enrichment above n approximately 4. Marine aerosols produced from contaminated ocean surface waters are therefore expected to be highly enriched in F(CF2)nCO2-/F(CF2)nSO3- species.

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Crossref · 10.1021/jp902795m

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  • The lack of a relationship between precursor Kai and number of perfluorinated carbons may reflect chemical saturation.

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Authors
Psillakis, E., Cheng, J., Hoffmann, M. R., & Colussi, A. J.
Affiliations
California Institute of Technology (US)
Corresponding author
Colussi, A. J.
Venue
The Journal of Physical Chemistry A
Published
2009-05-29
Volume
113
Issue
31
Pages
8826-8829
ISSN
  • 1089-5639 (ISSN-L)
  • 1520-5215
OpenAlex
W1985193004
Cited by
64
References
75
Citations by year
2026: 2 · 2025: 5 · 2024: 6 · 2023: 8 · 2022: 3 · 2021: 2 · 2020: 4 · 2019: 4 · 2018: 1 · 2017: 5 · 2016: 3 · 2015: 1 · 2014: 1 · 2013: 3 · 2012: 3
FWCI
4.05
Type
journal article
Language
en
Open access
closed
Locations
  • The Journal of Physical Chemistry A (publishedVersion)
  • PubMed (publishedVersion)
  • CaltechAUTHORS (California Institute of Technology) (submittedVersion)
Topics
  • Physical Sciences › Environmental Science › Environmental Chemistry › Per- and polyfluoroalkyl substances research
  • Physical Sciences › Chemistry › Spectroscopy › Mass Spectrometry Techniques and Applications
  • Physical Sciences › Chemistry › Organic Chemistry › Surfactants and Colloidal Systems
Keywords
perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, air-water interface, interfacial enrichment, enrichment factor, microdroplets, nebulization, electrospray ionization mass spectrometry, headgroup hydration, conformational restriction, marine aerosols, perfluorinated surfactants
MeSH terms
Air, Carboxylic Acids, Fluorocarbons, Models, Molecular, Molecular Biology, Sulfonic Acids, Surface Properties, Surface-Active Agents, Thermodynamics, Water

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