In situ measurement-based partitioning behavior of perfluoroalkyl acids in the atmosphere

  • Kim, Seung-Kyu (Department of Marine Science, College of Natural Sciences, Incheon National University) ;
  • Li, Donghao (Key Laboratory of Nature Resource of the Changbai Mountain and Functional Molecular, Yanbian Univeristy, Ministry of Education) ;
  • Kannan, Kurunthachalam (Wadsworth Center, New York State Department of Health, and Department of Environmental Health Sciences, School of Public Health, State University of New York at Albany)
  • Received : 2019.03.30
  • Accepted : 2019.04.23
  • Published : 2020.06.30


Environmental fate of ionizable organic pollutants such as perfluoroalkyl acids (PFAAs) are of increasing interest but has not been well understood because of uncertain values for parameters related with atmospheric interphase partitioning behavior. In the present study, not only the values for air-water partition coefficient (KAW) and dissociation constant (pKa) of PFAAs were induced by adjusting to in situ measurements of air-water distribution coefficient between vapor phase and rainwater but also gas-particle partition coefficients were also estimated using three-phase partitioning model of ionizable organic pollutants, in situ measurements of PFAAs in aerosol and air vapor phase, and obtained parameter values. The pKa values of PFAAs we obtained were close to the minimum values suggested in literature except for perfluorooctane sulfonic acids, and COSMOtherm-modeled KAW values were assessed to more appropriate among suggested values. When applying parameter values we obtained, it was predicted that air particle-associated fate and transport of PFAAs could be negligible and PFAAs could distribute ubiquitously along the transection from urban to rural region by pH-dependent phase transfer in air. Our study is expected to have some implications in prediction of the environmental redistribution of other ionizable organic compounds.



  1. Wang T, Wang Y, Liao C, Cai Y, Jiang G. Perspectives on the inclusion of perfluorooctane sulfonate into the Stockholm Convention on persistent organic pollutants. Environ. Sci. Technol. 2009;43:5171-5175.
  2. Gouin T, Wania F. Time trends of Arctic contamination in relation to emission history and chemical persistence and partitioning properties. Environ. Sci. Technol. 2007;41:5986-5992.
  3. Wang Z, Xie Z, Moller A, Mi W, Wolschke H, Ebinghaus R. Atmospheric concentrations and gas/particle partitioning of neutral poly- and perfluroalkyl substances in Northern German coast. Atmos. Environ. 2014;95:207-213.
  4. Xie Z, Wang Z, Mi W, Moller A, Wolschke H, Ebinghaus R. Neutral poly-/perfluoroalkyl substances in air and snow from the Arctic. Sci. Rep. 2015;5:8912.
  5. Buck RC, Franklin J, Berger U, et al. Perfluoroalkyl and polyfluoroalkyl substances in the environment: Terminology, classification, and origins. Int. Environ. Assess. Manage. 2011;7:513-541.
  6. Ellis DA, Martin JW, De Silva AO, et al. Degradation of fluorotelomer alcohols: A likely atmospheric source of perfluorinated carboxylic acids. Environ. Sci. Technol. 2004;38:3316-3321.
  7. Wallington TJ, Hurley MD, Xia J, et al. Formation of C7F15COOH (PFOA) and other perfluorocarboxylic acids during the atmospheric oxidation of 8:2 fluorotelomer alcohol. Environ. Sci. Technol. 2006;40:924-930.
  8. Kim S-K, Kannan K. Perfluorinated acids in air, rain, snow, surface runoff, and lakes: Relative importance of pathways to contamination of urban lakes. Environ. Sci. Technol. 2007;41:8328-8334.
  9. Yarwood G, Kemball-Cook S, Keinath M, et al. High-resolution atmospheric modeling of fluorotelomer alcohols and perfluorocarboxylic acids in the North American troposphere. Environ. Sci. Technol. 2007;41:5756-5762.
  10. Kim S-K, Li D-H, Shoeib M, Zoh K-D. Contribution of diffuse inputs to the aqueous mass load of perfluoroalkyl acids in river and stream catchments in Korea. Sci. Total Environ. 2014;470- 471:1430-1440.
  11. Ahrens L, Harner T, Shoeib M, Lane DA, Murphy JG. Improved characterization of gas-particle partitioning for per- and polyfluoroalkyl substances in the atmosphere using annular diffusion denuder samplers. Environ. Sci. Technol. 2012;46:7199-7206.
  12. Vierke L, Ahrens L, Shoeib M, et al. In situ air-water and particle-water partitioning of perfluorocarboxylic acids, perfluorosulfonic acids and perfluorooctyl sulfonamide at a waste-water treatment plant. Chemosphere 2013;92:941-948.
  13. Liu W, He W, Wu J, Wu W, Xu F. Distribution, partitioning and inhalation exposure of perfluoroalkyl acids (PFAAs) in urban and rural air near Lake Chaohu, China. Environ. Pollut. 2018;243:13-151.
  14. McMurdo C, Ellis D, Webster E, Butler J, Christensen RD, Reid LK. Aerosol enrichment of the surfactant PFO and mediation of the water-air transport of gaseous PFOA. Environ. Sci. Technol. 2008;42:3969-3974.
  15. Ju X, Jin Y, Sakaki K, Saito N. Perfluorinated surfactants in surface, subsurface water and microlayer from Dalian coastal waters in China. Environ. Sci. Technol. 2009;42:3538-3542.
  16. Cho Y-K, Kim M-O, Kim B-C. Sea fog around the Korean peninsula. J. Appl. Meteorol. 2000;39:2473-2479.<2473:SFATKP>2.0.CO;2
  17. Wang T, Wang P, Meng J, et al. A review of sources, multimedia distribution and health risks of perfluoroalkyl acids (PFAAs) in China. Chemosphere 2015;129:87-99.
  18. Tian Z, Kim S-K, Shoeib M, Oh J-E, Park J-E. Human exposure to per- and polyfluoroalkyl substances (PFASs) via house dust in Korea: Implication to exposure pathway. Sci. Total Environ. 2016;553:266-275.
  19. Schwarzenbach RP, Gschwend PM, Imboden DM. Environmental organic chemistry. 2nd ed. Hoboken: John Wiley & Sons; 2002.
  20. Qureshi A, MacLeod M, Hungerbühler K. Modeling aerosol suspension soils and oceans as sources of micropollutants to air. Chemosphere 2009;77:495-500.
  21. Franco A, Haushild M, Jolliet O, Trapp S. Atmospheric fate of non-volatile and ionizable compounds. Chemosphere 2011;85:1353-1359.
  22. Gomis MI, Wang Z, Scheringer M, Cousins IT. A modeling assessment of the physicochemical properties and environmental fate of emerging and novel per- and polyfluoroalkyl substances. Sci. Total Environ. 2015;505:981-991.
  23. Pankow JF. Review and comparative analysis of the theories on partitioning between the gas and aerosol particulate phases in the atmosphere. Atmos. Environ. 1987;21:2275-2283.
  24. Masiol M, Hopke PK, Felton HD, et al. Analysis of major air pollutants and submicron particles in New York City and Long Island. Atmos. Environ. 2017;148:203-214.
  25. Squizzato S, Masiol M, Rich DQ, Hopke PK. A long-term source apportionment of $PM_{2.5}$ in New York State during 2005-2016. Atmos. Environ. 2018;192:35-47.
  26. Mackay D. Multimedia environmental models - The fugacity approach. 2nd ed. Boca Raton (FL): Taylor & Francis; 2001.
  27. Jenkins J, Roy K, Driscoll C, Buerkett C. Acid rain in the Adirondacks: An environmental history. New York: Cornell Univ. Press; 2007.
  28. Rayne S, Forest K. Perfluoroalkyl sulfonic and carboxylic acids: A critical review of physicochemical properties, levels and patterns in waters and wastewaters, and treatment methods. J. Environ. Sci. Health A 2009;44:1145-1199.
  29. Rayne S, Forest K, Friesen KJ. Computational approaches may underestimate pKa values of longer-chain perfluorinated carboxylic acids: Implication for assessing environmental and biological effects. J. Environ. Sci. Health A 2009b;44:317-326.
  30. Klamt A, Eckert F, Diedenhofen M, Beck ME. First principles calculations of aqueous pKa values for organic and inorganic acids using COSMO-RS reveal an inconsistency in the slope of the pKa scale. J. Phys. Chem. A 2003;107:9380-9386.
  31. Eckert F, Klamt A. Accurate prediction of basicity in aqueous solution with COSMO-RS. J. Comput. Chem. 2006;27:11-19.
  32. Hilal SH, Karickhoff SW, Carreira LAA. Rigorous test for SPARC's chemical reactivity models: Estimation of more than 4300 ionization pKas. Quant. Struct.-Act. Relat. 1995;14:348-355.
  33. Igarashi S, Yotsuyanagi T. Homogeneous liquid-liquid extraction by pH dependent phase separation with a fluorocarbon ionic surfactants and its application to the preconcentration of porphyrin compounds. Microchim. Acta 1992;106:37-44.
  34. Moroi Y, Yano H, Shibata O, Yonemitsu T. Determination of acidity constants of perfluoroalkanoic acids. Bull. Chem. Soc. Jpn. 2001;74:667-672.
  35. Burns D, Ellis DA, Li H, McMurdo CJ, Webster E. Experimental pKa determination for perfluorooctanoic acid (PFOA) and the potential impact of pKa concentration dependence on laboratory- measured partitioning phenomena and environmental modeling. Environ. Sci. Technol. 2008;42:9283-9288.
  36. Arp HPH, Niederer C, Goss K-U. Predicting the partitioning behavior of various highly fluorinated compounds. Environ. Sci. Technol. 2006;40:7298-7304.
  37. Kim M, Li LY, Grace JR, Ye C. Selecting reliable physicochemical properties of perfluoroalkyl and polyfluoroalkyl substances (PFASs) based on molecular descriptors. Environ. Pollut. 2015;196:462-472.
  38. Wania FA. A global mass balance analysis of the source of perfluorocarboxylic acids in the Arctic Ocean. Environ. Sci. Technol. 2007;41:4529-4535.
  39. Li H, Ellis DA, Mackay D. Measurement of low air-water partition coefficients of organic acids by evaporation from a water surface. J. Chem. Eng. Data 2007;52:1580-1584.
  40. Kutsuna S, Hori H. Experimental determination of Henry's law constant of perfluorooctanoic acid (PFOA) at 298 K by means of an inert-gas stripping method with a helical plate. Atmos. Environ. 2008;42:8883-8892.
  41. Khwaja HA, Husain L. Chemical characterization of acid precipitation in Albany, New York. Atmos. Environ. 1990;24:1869-1882.
  42. Singh S, Elumalai SP, Pal AK. Rain pH estimation based on the particulate matter pollutants and wet deposition study. Sci. Total Environ. 2016;563-564:293-301.
  43. Ding G, Peijnenburg WJGM. Physicochemical properties and aquatic toxicity of poly- and perfluorinated compounds. Crit. Rev. Environ. Sci. Technol. 2013;43:598-678.
  44. Arp HPH, Goss K-U. Gas/particle partitioning behavior of perfluorocarboxylic acids with terrestrial aerosols. Environ. Sci. Technol. 2009;43:8542-8547.
  45. Brooke D, Footitt A, Nwaogu TA. Environmental risk evaluation report: Perfluorooctanesulphonate (PFOS) [Internet]. Environmental Agency; c2004. Available from:
  46. Wang Z, MacLeod M, Cousins IT, Scheringer M, Hungerbuhler K. Using COSMOtherm to predict physicochemical properties of poly- and perfluorinated alkyl substances (PFASs). Environ. Chem. 2011;8:389-398.
  47. Labadie P, Chevreuil M. Partitioning behavior of perfluorinated alkyl contaminants between water, sediment and fish in the Orge River (nearby Paris, France). Environ. Pollut. 2011;159:391-397.
  48. Higgins CP, Luthy RG. Sorption of perfluorinated surfactants on sediments. Environ. Sci. Technol. 2006;40:7251-7256.