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SECCIÓN A: CIENCIAS EXACTAS

Vol. 3 Núm. 2 (2011): Número especial por el Año Internacional de la Química

Desarrollo de métodos analíticos para cuantificar perfluorooctano sulfonato y compuestos relacionados en el medio ambiente

DOI
https://doi.org/10.18272/aci.v3i2.63
Enviado
julio 29, 2015

Resumen

Métodos analíticos basados en 19F NMR y HPLC con detector de conductividad suprimida fueron desarrollados para detectar y cuantificar sulfonato de perfluorooctano (PFOS), ácido perfluorooctanoico (PFOA) y sulfonato de perfluorobutano (PFBS) en muestras ambientales. La separación de los surfactantes perfluorinados (PFAS) se realizó con una columna C18 de fase reversa y una fase móvil compuesta de ácido bórico y acetonitrilo. El límite de detección para PFOS con 19F NMR fue 3.6 mg L-1, mientras que para PFAS con HPLC con detector de conductividad suprimida fue 1 mg L-1. Los límites de detección mejoraron considerablemente si las muestras fueron pre-concentradas a través de una extracción en fase sólida (SPE) registrando valores para PFOS con 19F NMR y HPLC con detector de conductividad suprimida de 3.6 mg L-1 y 10 ug L-1, respectivamente. Esta última demostró ser la mejor técnica para análisis rutinario de cuantificación de contaminantes fluorinados debido a su simplicidad, rapidez y precisión. 19F NMR fue muy efectiva para detectar y caracterizar cambios en la estructura química de los compuestos fluorinados ya que es una técnica analítica altamente específica en la que la matriz ambiental no interfiere con el análisis. El análisis de carbono orgánico total (TOC) y la determinación de la demanda química de oxígeno (COD) para la cuantificación de PFOS en muestras acuosas también fueron estudiados. A pesar de que los análisis de TOC permitieron cuantificar exitosamente PFAS, la falta de especificidad de este método es una limitación considerable. Finalmente, el análisis de PFOS a través de la determinación de COD no fue posible debido a una oxidación incompleta de los altamente estables compuestos fluorinados bajo las condiciones de operación evaluadas.

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Citas

  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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