Enrichment Factors of Perfluoroalkyl Oxoanions at the Air/Water Interface
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.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
Claims other papers make about this one
Each is checked against this paper’s own text: does it say what the citing paper says it does?
The lack of a relationship between precursor Kai and number of perfluorinated carbons may reflect chemical saturation.
“The lack of a relationship between precursor Kai and number of perfluorinated carbons may therefore reflect chemical saturation.42”
From Centurial Persistence of Forever Chemicals at Military Fire Training Sites (2023) · cites this paper as [42]
Cites
Atmospheric chemistry and physics: from air pollution to climate change
(1998) · Choice Reviews Online · doi:10.5860/choice.35-5721 · Cited by 5,162 · see citing works
Atmospheric chemistry and physics: from air pollution to climate change
(2007) · Choice Reviews Online · doi:10.5860/choice.44-4512 · Cited by 4,437 · see citing works
Global Distribution of Perfluorooctane Sulfonate in Wildlife
Giesy, J. P., & Kannan, K. (2001) · Environmental Science & Technology · doi:10.1021/es001834k · Cited by 2,750 · see citing works
Sources, fate and transport of perfluorocarboxylates
Prevedouros, K., Cousins, I. T., Buck, R. C., & Korzeniowski, S. H. (2006) · Environmental Science & Technology · doi:10.1021/es0512475 · Cited by 2,594 · see citing works
Chemistry of the Upper and Lower Atmosphere
(2000) · Elsevier eBooks · doi:10.1016/b978-0-12-257060-5.x5000-x · Cited by 1,796 · see citing works
Biological Monitoring of Polyfluoroalkyl Substances: A Review
Houde, M., Martin, J. W., Letcher, R. J., Solomon, K. R., & Muir, D. C. G. (2006) · Environmental Science & Technology · doi:10.1021/es052580b · Cited by 1,259 · see citing works
Food WebSpecific Biomagnification of Persistent Organic Pollutants
Kelly, B. C., Ikonomou, M. G., Blair, J. D., Morin, A. E., & Gobas, F. A. P. C. (2007) · Science · doi:10.1126/science.1138275 · Cited by 1,055 · see citing works
Compound-specific, quantitative characterization of organic fluorochemicals in biological matrices
Hansen, K. J., Clemen, L. A., Ellefson, M. E., & Johnson, H. O. (2001) · Environmental Science & Technology · doi:10.1021/es001489z · Cited by 923 · see citing works
Negative ion production with the electrospray ion source
Yamashita, M., & Fenn, J. B. (1984) · The Journal of Physical Chemistry · doi:10.1021/j150664a046 · Cited by 582 · see citing works
Rapid freshening of the deep North Atlantic Ocean over the past four decades
Dickson, B., Yashayaev, I., Meincke, J., Turrell, W. R., Dye, S. R., & Holfort, J. (2002) · Nature · doi:10.1038/416832a · Cited by 540 · see citing works
The Sea Surface and Global Change
(1997) · Cambridge University Press eBooks · doi:10.1017/cbo9780511525025 · Cited by 490 · see citing works
Accumulation of Perfluorooctane Sulfonate in Marine Mammals
Kannan, K., Koistinen, J., Beckmen, K. B., Evans, T. J., Gorzelany, J. F., Hansen, K. J., Jones, P. D., Helle, E., Nyman, M., & Giesy, J. P. (2001) · Environmental Science & Technology · doi:10.1021/es001873w · Cited by 489 · see citing works
Ninham, B. W., & Parsegian, V. A. (1970) · Biophysical Journal · doi:10.1016/s0006-3495(70)86326-3 · Cited by 484 · see citing works
Pegram, L. M., & Record, M. T. (2007) · The Journal of Physical Chemistry B · doi:10.1021/jp070245z · Cited by 482 · see citing works
The p <i>K</i> <sub>a</sub> Values of PFOA and Other Highly Fluorinated Carboxylic Acids
Goss, K.-U. (2008) · Environmental Science & Technology · doi:10.1021/es702192c · Cited by 471 · see citing works
Cavalli, F., Facchini, M. C., Decesari, S., et al. (2004) · Journal of Geophysical Research Atmospheres · doi:10.1029/2004jd005137 · Cited by 412 · see citing works
Perfluorinated Acids in Arctic Snow: New Evidence for Atmospheric Formation
Young, C. J., Furdui, V. I., Franklin, J., Koerner, R. M., Muir, D. C. G., & Mabury, S. A. (2007) · Environmental Science & Technology · doi:10.1021/es0626234 · Cited by 406 · see citing works
Physicochemical properties of aqueous solutions of fluorinated surfactants
Shinoda, K., Hato, M., & Hayashi, T. (1972) · The Journal of Physical Chemistry · doi:10.1021/j100650a021 · Cited by 396 · see citing works
The Influence of Organic Films at the Air−Aqueous Boundary on Atmospheric Processes
Donaldson, D. J., & Vaida, V. (2006) · Chemical Reviews · doi:10.1021/cr040367c · Cited by 390 · see citing works
Dilution of the Northern North Atlantic Ocean in Recent Decades
Curry, R., & Mauritzen, C. (2005) · Science · doi:10.1126/science.1109477 · Cited by 376 · see citing works
Perfluorinated acids as novel chemical tracers of global circulation of ocean waters
Yamashita, N., Taniyasu, S., Petrick, G., Wei, S., Gamo, T., Lam, P. K. S., & Kannan, K. (2008) · Chemosphere · doi:10.1016/j.chemosphere.2007.07.079 · Cited by 364 · see citing works
Trajectory Shifts in the Arctic and Subarctic Freshwater Cycle
Peterson, B. J., McClelland, J. W., Curry, R., et al. (2006) · Science · doi:10.1126/science.1122593 · Cited by 357 · see citing works
On the mechanisms by which the charged droplets produced by electrospray lead to gas phase ions
Kebarle, P., & Peschke, M. (2000) · Analytica Chimica Acta · doi:10.1016/s0003-2670(99)00598-x · Cited by 351 · see citing works
Perfluorinated Chemicals in the Arctic Atmosphere
Shoeib, M., Harner, T., & Vlahos, P. (2006) · Environmental Science & Technology · doi:10.1021/es0618999 · Cited by 309 · see citing works
Berkel, G. J. V., Pasilis, S. P., & Ovchinnikova, O. S. (2008) · Journal of Mass Spectrometry · doi:10.1002/jms.1440 · Cited by 299 · see citing works
Sea-to-Air Transport of Surface Active Material
Blanchard, D. C. (1964) · Science · doi:10.1126/science.146.3642.396 · Cited by 294 · see citing works
Sonic Spray Ionization Method for Atmospheric Pressure Ionization Mass Spectrometry
Hirabayashi, A., Sakairi, M., & Koizumi, H. (1994) · Analytical Chemistry · doi:10.1021/ac00096a025 · Cited by 273 · see citing works
Modeling Global-Scale Fate and Transport of Perfluorooctanoate Emitted from Direct Sources
Armitage, J. M., Cousins, I. T., Buck, R. C., Prevedouros, K., Russell, M. H., MacLeod, M., & Korzeniowski, S. H. (2006) · Environmental Science & Technology · doi:10.1021/es0614870 · Cited by 253 · see citing works
Predicting the Partitioning Behavior of Various Highly Fluorinated Compounds
Arp, H. P. H., Niederer, C., & Goss, K. (2006) · Environmental Science & Technology · doi:10.1021/es060744y · Cited by 250 · see citing works
Olsen, G. W., Mair, D. C., Church, T. R., Ellefson, M. E., Reagen, W. K., Boyd, T. M., Herron, R. M., Medhdizadehkashi, Z., Nobiletti, J. B., Rios, J. A., et al. (2008) · Environmental Science & Technology · doi:10.1021/es800071x · Cited by 244 · see citing works
Gas-phase ions of solute species from charged droplets of solutions
Nguyen, S., & Fenn, J. B. (2007) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.0609969104 · Cited by 233 · see citing works
Hirabayashi, A., Sakairi, M., & Koizumi, H. (1995) · Analytical Chemistry · doi:10.1021/ac00113a023 · Cited by 224 · see citing works
The North Atlantic Oscillation controls air pollution transport to the Arctic
Eckhardt, S., Stohl, A., Beirle, S., Spichtinger, N., James, P. M., Forster, C., Junker, C., Wagner, T., Platt, U., & Jennings, S. G. (2003) · Atmospheric chemistry and physics · doi:10.5194/acp-3-1769-2003 · Cited by 221 · see citing works
A Global Mass Balance Analysis of the Source of Perfluorocarboxylic Acids in the Arctic Ocean
Wania, F. (2007) · Environmental Science & Technology · doi:10.1021/es070124c · Cited by 220 · see citing works
Bossi, R., Rigét, F. F., Dietz, R., Sonne, C., Fauser, P., Dam, M., & Vorkamp, K. (2005) · Environmental Pollution · doi:10.1016/j.envpol.2004.12.020 · Cited by 217 · see citing works
Aerosol Enrichment of the Surfactant PFO and Mediation of the Water−Air Transport of Gaseous PFOA
McMurdo, C. J., Ellis, D. A., Webster, E. M., Butler, J. E., Christensen, R. D., & Toose, L. (2008) · Environmental Science & Technology · doi:10.1021/es7032026 · Cited by 193 · see citing works
Chemical Fractionation at the Air/Sea Interface
Duce, R. A., & Hoffman, E. J. (1976) · Annual Review of Earth and Planetary Sciences · doi:10.1146/annurev.ea.04.050176.001155 · Cited by 178 · see citing works
Partitioning of atmospherically relevant ions between bulk water and the water/vapor interface
Pegram, L. M., & Record, M. T. (2006) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.0606256103 · Cited by 174 · see citing works
Polyfluorinated chemicals in a spatially and temporally integrated food web in the Western Arctic
Powley, C. R., George, S. W., Russell, M. H., Hoke, R. A., & Buck, R. C. (2007) · Chemosphere · doi:10.1016/j.chemosphere.2007.06.067 · Cited by 170 · see citing works
Oppo, C., Bellandi, S., Innocenti, N. D., et al. (1999) · Marine Chemistry · doi:10.1016/s0304-4203(98)00065-6 · Cited by 168 · see citing works
Charge Separation in the Aerodynamic Breakup of Micrometer-Sized Water Droplets
Zilch, L. W., Maze, J. T., Smith, J. W., et al. (2008) · The Journal of Physical Chemistry A · doi:10.1021/jp806995h · Cited by 161 · see citing works
Jing, P., Rodgers, P. J., & Amemiya, S. (2009) · Journal of the American Chemical Society · doi:10.1021/ja807961s · Cited by 158 · see citing works
Experimental Anion Affinities for the Air/Water Interface
Cheng, J., Vecitis, C. D., Hoffmann, M. R., & Colussi, A. J. (2006) · The Journal of Physical Chemistry B · doi:10.1021/jp066197k · Cited by 152 · see citing works
Self-citationSmithwick, M., Norstrom, R. J., Mabury, S. A., Solomon, K. R., Evans, T. J., Stirling, I., Taylor, M. K., & Muir, D. C. G. (2006) · Environmental Science & Technology · doi:10.1021/es051750h · Cited by 150 · see citing works
Dietz, R., Bossi, R., Rigét, F. F., Sonne, C., & Born, E. W. (2008) · Environmental Science & Technology · doi:10.1021/es7025938 · Cited by 145 · see citing works
Atmospheric pressure ion evaporation-mass spectrometry
Iribarne, J. V., Dziedzic, P. J., & Thomson, B. A. (1983) · International Journal of Mass Spectrometry and Ion Physics · doi:10.1016/0020-7381(83)87009-0 · Cited by 136 · see citing works
Contribution of Volatile Precursor Substances to the Flux of Perfluorooctanoate to the Arctic
Schenker, U., Scheringer, M., MacLeod, M., Martin, J. W., Cousins, I. T., & Hungerbühler, K. (2008) · Environmental Science & Technology · doi:10.1021/es703165m · Cited by 134 · see citing works
Electrospray ionization source geometry for mass spectrometry: past, present, and future
Manisali, I., Chen, D. D. Y., & Schneider, B. B. (2005) · TrAC Trends in Analytical Chemistry · doi:10.1016/j.trac.2005.07.007 · Cited by 132 · see citing works
Surfactants in Atmospheric Aerosols
Latif, M. T., & Brimblecombe, P. (2004) · Environmental Science & Technology · doi:10.1021/es049109n · Cited by 116 · see citing works
The Statistics of Liquid Spray and Dust Electrification by the Hopper and Laby Method
Dodd, E. E. (1953) · Journal of Applied Physics · doi:10.1063/1.1721137 · Cited by 114 · see citing works
Bubbles. Boundary-layer "microtome" for micronthick samples of a liquid surface
MacIntyre, F. (1968) · The Journal of Physical Chemistry · doi:10.1021/j100848a034 · Cited by 100 · see citing works
Physical/chemical separations in the break-up of highly charged droplets from electrosprays
Tang, K., & Smith, R. (2001) · Journal of the American Society for Mass Spectrometry · doi:10.1016/s1044-0305(01)00222-7 · Cited by 95 · see citing works
Global Inorganic Source of Atmospheric Bromine
Enami, S., Vecitis, C. D., Cheng, J., et al. (2007) · The Journal of Physical Chemistry A · doi:10.1021/jp074903r · Cited by 89 · see citing works
Self-citationGeneral Relationships of the Adsorption Behavior of Surfactants at the Water/Air Interface
Fainerman, V. B., Miller, R., & Möhwald, H. (2002) · The Journal of Physical Chemistry B · doi:10.1021/jp012672x · Cited by 88 · see citing works
Changes in the pool of Labrador Sea Water in the subpolar North Atlantic
Kieke, D., Rhein, M., Stramma, L., et al. (2007) · Geophysical Research Letters · doi:10.1029/2006gl028959 · Cited by 88 · see citing works
Arp, H. P. H., Schwarzenbach, R. P., & Goss, K. (2008) · Environmental Science & Technology · doi:10.1021/es703094u · Cited by 86 · see citing works
What Is So Special about the Sorption Behavior of Highly Fluorinated Compounds?
Goss, K., & Bronner, G. (2006) · The Journal of Physical Chemistry A · doi:10.1021/jp062684o · Cited by 85 · see citing works
Arp, H. P. H., Schwarzenbach, R. P., & Goss, K. (2008) · Environmental Science & Technology · doi:10.1021/es703096p · Cited by 80 · see citing works
The dominant influence of the Icelandic Low on the position of the Gulf Stream northwall
Hameed, S., & Piontkovski, S. A. (2004) · Geophysical Research Letters · doi:10.1029/2004gl019561 · Cited by 73 · see citing works
Cincinelli, A., Stortini, A. M., Checchini, L., et al. (2005) · Journal of Environmental Monitoring · doi:10.1039/b507321a · Cited by 59 · see citing works
Barreiro, M., Fedorov, A. V., Pacanowski, R. C., et al. (2007) · Annual Review of Earth and Planetary Sciences · doi:10.1146/annurev.earth.36.090507.143219 · Cited by 55 · see citing works
Kihara, S., Suzuki, M., Sugiyama, M., et al. (1988) · Journal of Electroanalytical Chemistry · doi:10.1016/0022-0728(88)80352-8 · Cited by 52 · see citing works
Geochemical fractionation during mass transfer from sea to air by breaking bubbles
MacIntyre, F. (1970) · Tellus A Dynamic Meteorology and Oceanography · doi:10.3402/tellusa.v22i4.10238 · Cited by 50 · see citing works
Tyrode, E. C., Johnson, C. M., Rutland, M. W., et al. (2006) · The Journal of Physical Chemistry C · doi:10.1021/jp063912h · Cited by 46 · see citing works
Determination of the Octanol−Air Partition Coefficients (KOA) of Fluorotelomer Alcohols
Thuens, S., Dreyer, A., Sturm, R., Temme, C., & Ebinghaus, R. (2007) · Journal of Chemical & Engineering Data · doi:10.1021/je700522f · Cited by 40 · see citing works
Charges on particles of different size from bubbles of Mediterranean Sea surf and from waterfalls
Reiter, R. (1994) · Journal of Geophysical Research Atmospheres · doi:10.1029/93jd03268 · Cited by 26 · see citing works
Analysis of Organic Compounds in Antarctic Snow and Their Origin
Desideri, P. G., Lepri, L., Udisti, R., et al. (1998) · International Journal of Environmental & Analytical Chemistry · doi:10.1080/03067319808032637 · Cited by 25 · see citing works
Microchip Sonic Spray Ionization
Pól, J., Kauppila, T. J., Haapala, M., et al. (2007) · Analytical Chemistry · doi:10.1021/ac070003v · Cited by 23 · see citing works
Aquatic Processes and Systems in PerspectiveGlobal transport and fate of perfluorochemicals
Simcik, M. F. (2005) · Journal of Environmental Monitoring · doi:10.1039/b509482h · Cited by 21 · see citing works
Rontu, N., & Vaida, V. (2007) · The Journal of Physical Chemistry C · doi:10.1021/jp070484m · Cited by 20 · see citing works
Humic Marine Matter and Insoluble Materials in Antarctic Snow
Calace, N., Petronio, B. M., Cini, R., et al. (2001) · International Journal of Environmental & Analytical Chemistry · doi:10.1080/03067310108044393 · Cited by 17 · see citing works
Hutterli, M. A., Crueger, T., Fischer, H., et al. (2006) · Climate Dynamics · doi:10.1007/s00382-006-0211-z · Cited by 17 · see citing works
Renner, R. (2008) · Environmental Science & Technology · doi:10.1021/es0871614 · Cited by 14 · see citing works
Arctic Tropospheric Winds Derived from TOVS Satellite Retrievals
Francis, J. A., Hunter, E., & Zou, C. (2005) · Journal of Climate · doi:10.1175/jcli3407.1 · Cited by 14 · see citing works
Renner, R. (2008) · Environmental Science & Technology · doi:10.1021/es0871715 · Cited by 10 · see citing works
Flagged first, then by citations
Cited by
Sorted by citations
Brusseau, M. L. (2018) · Science of The Total Environment · doi:10.1016/j.scitotenv.2017.09.065 · Cited by 306 · see citing works
Adsorption of PFOA at the air-water interface during transport in unsaturated porous media
Lyu, Y., Brusseau, M. L., Chen, W., Yan, N., Fu, X., & Lin, X. (2018) · Environmental Science & Technology · doi:10.1021/acs.est.8b02348 · Cited by 259 · see citing works
Fate and transport of per- and polyfluoroalkyl substances (PFASs) in the vadose zone
Sharifan, H., Bagheri, M., Wang, D., Burken, J. G., Higgins, C. P., Liang, Y., Liu, J., Schaefer, C. E., & Blotevogel, J. (2021) · Science of The Total Environment · doi:10.1016/j.scitotenv.2021.145427 · Cited by 180 · see citing works
Brusseau, M. L. (2019) · Water Research · doi:10.1016/j.watres.2018.12.057 · Cited by 157 · see citing works
Centurial Persistence of Forever Chemicals at Military Fire Training Sites
Ruyle, B. J., Thackray, C. P., Butt, C. M., LeBlanc, D. R., Tokranov, A. K., Vecitis, C. D., & Sunderland, E. M. (2023) · Environmental Science & Technology · doi:10.1021/acs.est.3c00675 · Cited by 142 · see citing works
PFAS on atmospheric aerosol particles: A review
Faust, J. A. (2023) · Environmental Science: Processes & Impacts · doi:10.1039/d2em00002d · Cited by 139 · see citing works
- 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
- Publisher
- American Chemical Society (ACS)
- 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
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review