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ACI Avances en Ciencias e Ingenierías

SECTION A: EXACT SCIENCES

Vol. 3 No. 2 (2011): Número especial por el Año Internacional de la Química

Development of Analytical Methods to Quantify Perfluorooctane Sulfonate and Related Compounds in the Environment

DOI
https://doi.org/10.18272/aci.v3i2.63
Submitted
July 29, 2015

Abstract

Analytical techniques based on 19F NMR spectroscopy and HPLC-suppressed conductivity detection were developed to detect and quantify aqueous perfluoroctane sulfonate (PFOS), perfluoroctanoic acid (PFOA), and perfluorobutane sulfonate (PFBS). Chromatographic separation of the perfluoroalkyl surfactants (PFAS) was performed using a C18 reversed-phase column and a mobile phase consisting of a mixture of boric acid and acetonitrile. The detection limit for PFOS by 19F NMR was 3.6 mg L-1. The detection limit for PFOS, PFOA and PFBS by HPLC-suppressed conductivity detection was 1 mg L-1. The detection limits were shown to improve considerably if samples were pre-concentrated by solid-phase extraction. The detection limits for PFOS of pre-concentrated samples were 3.6 mg L-1 and 10 ug L-1 by 19F NMR and HPLC-suppressed conductivity detection, respectively. Comparison of these two methodologies showed that HPLC-suppressed conductivity detection should be preferred for routine quantification of these contaminants due to its simplicity, time efficiency, and accuracy. Conversely, 19F NMR can be used to characterize changes in the chemical structure of fluorinated compounds due to its inherent advantage of high specificity and no matrix interferences. The feasibility of utilizing total organic carbon (TOC) and chemical oxygen demand (COD) analysis for the quantitative detection of PFOS in aqueous samples was also investigated. Although, the TOC analysis provided reliable quantification of PFAS in aqueous samples, the non-specificity is a drawback of the technique. The dichromate-based COD method was found unsuitable for the analysis of PFOS due to the incomplete oxidation of the highly stable perfluorinated compound under the conditions evaluated.

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References

  1. Houde, M., Martin, J. W., Letcher, R. J., Solomon, K. R., and Muir, D. C. G. 2006. "Biological monitoring of polyfluoroalkyl substances: A review". Environmental Science & Technology. 40 (11), 3463-3473.
  2. Lau, C., Anitole, K., Hodes, C., Lai, D., Pfahles-Hutchens, A., and Seed, J. 2007. "Perfluoroalkyl acids: A review of monitoring and toxicological findings". Toxicological Sciences. 99 (2), 366-394.
  3. Conder, J. M., Hoke, R. A., De Wolf, W., Russell, M. H., and Buck, R. C. 2008. "Are PFCAs bioaccumulative? a critical review and comparison with regulatory lipophilic compounds". Environmental Science & Technology. 42 (4), 995-1003.
  4. Kannan, K., Corsolini, S., Falandysz, J., Fillmann, G., Kumar, K. S., Loganathan, B. G., Mohd, M. A., Olivero, J., Van Wouwe, N., Yang, J. H., and Aldous, K. M. 2004. "Perfluorooctanesulfonate and related fluorochemicals in human blood from several countries". Environmental Science & Technology. 38 (17), 4489-4495.
  5. Butenhoff, J. L., Olsen, G. W., and Pfahles-Hutchens, A. 2006. "The applicability of biomonitoring data for perfluorooctanesulfonate to the environmental public health continuum". Environmental Health Perspectives. 114 (11), 1776-1782.
  6. Giesy, J. P., and Kannan, K. 2001. "Global distribution of perfluorooctane sulfonate in wildlife". Environmental Science & Technology. 35 (7), 1339-1342.
  7. Martin, J. W., Smithwick, M. M., Braune, B. M., Hoekstra, P. F., Muir, D. C. G., and Mabury, S. A. 2004. "Identification of long-chain perfluorinated acids in biota from the Canadian Arctic". Environmental Science & Technology. 38 (2), 373-380.
  8. Tao, L., Kannan, K., Kajiwara, N., Costa, M. M., Fillmann, G., Takahashi, S., and Tanabe, S. 2006. "Perfluorooctanesulfonate and related fluorochemicals in albatrosses, elephant seals, penguins, and Polar Skuas from the Southern Ocean". Environmental Science & Technology. 40 (24), 7642-7648.
  9. Higgins, C. P., Field, J. A., Criddle, C. S., and Luthy, R. G. 2005. "Quantitative determination of perfluorochemicals in sediments and domestic sludge". Environmental Science & Technology. 39 (11), 3946-3956.
  10. Senthilkumar, K., Ohi, E., Sajwan, K., Takasuga, T., and Kannan, K. 2007. "Perfluorinated compounds in river water, river sediment, market fish, and wildlife samples from Japan". Bulletin of Environmental Contamination and Toxicology. 79 (4), 427-431.
  11. Prevedouros, K., Cousins, I. T., Buck, R. C., and Korzeniowski, S. H. 2006. "Sources, fate and transport of perfluorocarboxylates". Environmental Science & Technology. 40 (1), 32-44.
  12. EPA 2003a. "Preliminary Risk Assesment of the Developmental Toxicity Associated with Exposure to Perfluorooctanoic Acid and its Salts". Technical report. U. S. Environmental Protection Agency.
  13. Brooke, D., Footitt, A., and Nwaogu, T. A. 2004. "Environmental risk evaluation report: Perfluorooctanesulphonate (PFOS) ". Environment Agency, Chemicals Assessment Section, Wallingford, UK.
  14. Ochoa-Herrera, V and Sierra-Alvarez, R. 2008. "Removal of prefluorinated surfactants by sorption onto granular activated carbon, zeolite and sludge". Chemosphere. 72, 1588-1593.
  15. Higgins, C. P., and Luthy, R. G. 2006. "Sorption of perfluorinated surfactants on sediments". Environmental Science & Technology. 40 (23), 7251-7256.
  16. Saito, N., Harada, K., Inoue, K., Sasaki, K., Yoshinaga, T., and Koizumi, A. 2004. "Perfluorooctanoate and perfluorooctane sulfonate concentrations in surface water in Japan". Journal of Occupational Health. 46 (1), 49-59.
  17. So, M. K., Taniyasu, S., Yamashita, N., Giesy, J. P., Zheng, J., Fang, Z., Im, S. H., and Lam, P. K. S. 2004. "Perfluorinated compounds in coastal waters of Hong Kong, South China, and Korea". Environmental Science & Technology. 38 (15), 4056-4063.
  18. Yamashita, N., Kannan, K., Taniyasu, S., Horii, Y., Petrick, G., and Gamo, T. 2005. "A global survey of perfluorinated acids in oceans." Marine Pollution Bulletin. 51 (8-12), 658-668.
  19. Loos, R., Wollgast, J., Huber, T., and Hanke, G. 2007. "Polar herbicides, pharmaceutical products, perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), and nonylphenol and its carboxylates and ethoxylates in surface and tap waters around Lake Maggiore in Northern Italy". Analytical and Bioanalytical Chemistry. 387 (4), 1469-1478.
  20. Konwick, B. J., Tomy, G. T., Ismail, N., Peterson, J. T., Fauver, R. J., Higginbotham, D., and Fisk, A. T. 2008. "Concentrations and patterns of perfluoroalkyl acids in georgia, USA surface waters near and distant to a major use source". Environmental Toxicology and Chemistry. 27 (10), 2011-2018.
  21. Sinclair, E., Mayack, D. T., Roblee, K., Yamashita, N., and Kannan, K. 2006. "Occurrence of perfluoroalkyl surfactants in water, fish, and birds from New York State". Archives of Environmental Contamination and Toxicology. 50 (3), 398-410.
  22. Skutlarek, D., Exner, M., and Farber, H. 2006. "Perfluorinated surfactants in surface and drinking water". Environmental Science and Pollution Research. 13 (5), 299-307.
  23. Villagrasa, M., deAlda, M. L., and Barcelo, D. 2006. "Environmental analysis of fluorinated alkyl substances by liquid chromatography (tandem) mass spectrometry: a review". Analytical and Bioanalytical Chemistry. 386 (4), 953-972.
  24. Richardson, S. D. 2008. "Environmental mass spectrometry: Emerging contaminants and current issues". Analytical Chemistry. 80 (12), 4373-4402.
  25. deVoogt, P. and Saez, M. 2006. "Analytical chemistry of perfluoroalkylated substances". Trac-Trends in Analytical Chemistry. 25 (4), 326-342.
  26. Hernandez, F., Sancho, J. V, and Pozo, O. J. 2005. "Critical review of the application of liquid chromatography/mass spectrometry to the determination of pesticide residues in biological samples". Analytical and Bioanalytical Chemistry. 382 (4), 934-946.
  27. Barcelo, D. and Petrovic, M. 2007. "Challenges and achievements of LC-MS in environmental analysis: 25 years on". Trac-Trends in Analytical Chemistry. 26 (1), 2-11.
  28. Martin, J. W., Muir, D. C. G., Moody, C. A., Ellis, D. A., Kwan, W. C., Solomon, K. R., and Mabury, S. A. 2002. "Collection of airborne fluorinated organics and analysis by gas chromatography/chemical ionization mass spectrometry". Analytical Chemistry. 74 (3), 584-590.
  29. Jahnke, A., Ahrens, L., Ebinghaus, R., Berger, U., Barber, J. L., and Temme, C. 2007. "An improved method for the analysis of volatile polyfluorinated alkyl substances in environmental air samples". Analytical and Bioanalytical Chemistry. 387 (3), 965-975.
  30. Moody, C. A. and Field, J. A. 2000. "Perfluorinated surfactants and the environmental implications of their use in firefighting foams". Environmental Science & Technology. 34 (18), 3864-3870.
  31. Langlois, I., Berger, U., Zencak, Z., and Oehme, M. 2007. "Mass spectral studies of perfluorooctane sulfonate derivatives separated by high resolution gas chromatography". Rapid Communications in Mass Spectrometry. 21 (22), 3547-3553.
  32. Moody, C. A., Kwan, W. C., Martin, J. W., Muir, D. C. G., and Mabury, S. A. 2001. "Determination of perfluorinated surfactants in surface water samples by two independent analytical techniques: Liquid chromatography/tandem mass spectrometry and f-19 nmr". Analytical Chemistry. 73 (10), 2200-2206.
  33. Arsenault, G., McCrindle, R., Chittim, B., and McAlees, A. 2005. "Separation and fluorine nuclear magnetic resonance spectroscopy (19F-NMR) analysis of the individual branched isomers present in technical perfluorooctanesulfonic acid (PFOS) ". Organohalogen Compounds. 67, 818-822.
  34. Vyas, S. M., Kania-Korwel, I., and Lehmler, H. J. 2007. "Differences in the isomer composition of perfluoroctanesulfonyl (PFOS) derivatives". Journal of Environmental Science and Health Part a Toxic/Hazardous Substances & Environmental Engineering. 42 (3), 249-255.
  35. M 1997. "Fluorochemical isomer distribution by 19F NMR spectroscopy". Technical report. U. S. Evironmental Protection Agency Public Docket AR226-0564.
  36. Kissa, E. 2001. "Fluorinated surfactants and repellants". Marcel Dekker, Inc., New York,.
  37. Arsenault, G., Chittim, B., McAlees, A., McCrindle, R., Riddell, N., and Yeo, B. 2008. "Some issues relating to the use of perfluoro octane sulfonate (PFOS) samples as reference standards". Chemosphere. 70 (4), 616-625.
  38. Ochoa-Herrera, V., Sierra-Alvarez, R., Somogyi, A., Jacobsen, N. E., Wysocki, V. H., and Field, J. A. 2008. "Reductive defluorination of perfluorooctane sulfonate". Environmental Science & Technology. 42 (9), 3260-3264.
  39. Martin, J. W., Kannan, K., Berger, U., De Voogt, P, Field, J., Franklin, J., Giesy, J. P, Harner, T., Muir, D. C. G., Scott, B., Kaiser, M., Jarnberg, U., Jones, K. C., Mabury, S. A., Schroeder, H., Simcik, M., Sottani, C., Van Bavel, B., Karrman, A., Lindstrom, G., and Van Leeuwen, S. 2004. "Analytical challenges hamper perfluoroalkyl research". Environmental Science & Technology. 38 (13), 248A-255A.
  40. Murakami, M. and Takada, H. 2008. "Perfluorinated surfactants (PFSS) in size-fractionated street in Tokyo". Chemosphere. 73, 1172-1177.
  41. Tugnait, M., Lenz, E. M., Phillips, P, Hofmann, M., Spraul, M., Lindon, J. C., Nicholson, J. K., and Wilson, I. D. 2002. "The metabolism of 4-trifluoromethoxyaniline and [C-13]-4-trifluoromethoxyacetanilide in the rat: detection and identification of metabolites excreted in the urine by NMR and HPLC-NMR". Journal of Pharmaceutical and Biomedical Analysis. 28 (5), 875-885.
  42. Buchanan, G. W., Munteanu, E., Dawson, B. A., and Hodgson, D. 2005. "Concerning the origin of F-19-F-19 NMR COSY and NOESY connections in the spectra of perfluorooctanoic acid, R-F-palmitic acid-F-13 and diethyl perfluorosuberate". Magnetic Resonance in Chemistry. 43 (7), 528-534.
  43. Takasaki, M., Kimura, K., Kawaguchi, K., Abe, A., and Katagiri, G. 2005. "Structural analysis of a perfluorosulfonate ionomer in solution by F-19 and C-13 NMR". Macromolecules. 38 (14), 6031-6037.
  44. Bruch, M. D. 1996. NMR Spectroscopy Techniques, CRC Press, Boca Raton, FL.
  45. Hebert, G. N., Odom, M. A., Craig, P. S., Dick, D. L., and Strauss, S. H. 2002. "Method for the determination of sub-ppm concentrations of perfluoroalkylsulfonate anions in water". Journal ofEnvironmental Monitoring. 4 (1), 90-95.
  46. Langlois, I. and Oehme, M. 2006. "Structural identification of isomers present in technical perfluorooctane sulfonate by tandem mass spectrometry". Rapid Communications in Mass Spectrometry. 20 (5), 844-850.
  47. Hori, H., Hayakawa, E., Yamashita, N., Taniyasu, S., Nakata, F., and Kobayashi, Y. 2004. "High-performance liquid chromatography with conductimetric detection of perfluorocarboxylic acids and perfluorosulfonates". Chemosphere. 57 (4), 273-282.
  48. APHA 2005. Standard Methods for the Examination of Water and Wastewater., American Public Health Association, Washington, DC, 21st edition.
  49. Mara, D. and Horan, N. J. 2003. Handbook ofWater and Wastewater Microbiology, Academic Press.

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