The Discovery and Analysis of PFAS (‘Forever Chemicals’) in Human Blood and Biological Materials
Published 2024-03-04
Keywords
- Forever chemicals,
- Organic fluorine in biological materials,
- PFAS,
- PFOA,
- PFOS
- exposure to PFAS ...More
How to Cite
Copyright (c) 2024 Anthony S. Travis
This work is licensed under a Creative Commons Attribution 4.0 International License.
Abstract
This paper reviews the development of analytical techniques used prior to the early 1980s in the identification of organofluorine compounds in human blood. The compounds of interest are industrial products, the so-called Forever Chemicals, which are stable long-chain per- and polyfluoroalkyl substances (PFAS) that are highly resistant to breakdown. Because of their special properties they have been used since the 1950s in a wide range of commercial and domestic products. Academic research in the 1960s and 1970s that originally focused on fluoride in dentistry and human health led to the finding that PFAS were present in the blood of residents of several cities in the United States. This, and concerns over their toxic properties, encouraged industrial research into analytical methods for their detection. Notably, and because long-chain PFAS are nonvolatile, special techniques were developed for analysis by gas chromatography.
References
- Belisle, Jon, and Donald F. Hagen. 1978. “Method for the determination of the total fluorine content of whole blood, serum/plasma, and other biological samples,” Anal. Biochem. 87(2)(July):545-555.
- Belisle, Jon, and Donald F. Hagen. 1980. "A method for the determination of perfluorooctanoic acid in blood and other biological samples," Anal. Biochem 101(2):369-376.
- Belisle, Jon. 1981. “Organic fluorine in human serum: Natural versus industrial sources,” Science 212 (26 June):1509-1510.
- Bilott, Robert, with Tom Shroder. 2019. Exposure: Poisoned Water, Corporate Greed, and One Lawyer’s Twenty-Year Battle Against DuPont. New York: Atria Books.
- Blum, A., et al., “The Madrid Statement on poly- and perfluoroalkyl substances (PFASs).” 2015. Environ. Health. Perspect. 123(5):A107-11. doi: 10.1289/ehp.1509934. PMID: 25932614; PMCID: PMC4421777.
- Bock, R., and H. J. Semmler. 1967. “Abtrennung und Bestimmung des Fluorid-Ions mit Hilfe Silicium organisher Verbindungen,” Z. Anal. Chem. 230:161-184.
- Brunn, Hubertus, et al. 2023. “PFAS: Forever chemicals—persistent, bioaccumulative and mobile. Reviewing the status and the need for their phase out and remediation of contaminated sites,” Environ. Sci. Eur. 35, article 30. https://doi.org/10.1186/s12302-023-00730-7
- Bryson, Christopher. 2004. The Fluoride Deception. New York: Seven Stories Press.
- Chemical Industries. 1950. August, p. 266.
- Dickinson, Denis. 1950. The Chemical Analysis of Waters, Boiler- and Feed-waters, Sewage, and Effluents. London: Blackie.
- Dubocq, Florian, et al. 2020. “Characterization of the chemical contents of fluorinated and fluorine-free firefighting foams using a novel workflow combining nontarget screening and total fluorine analysis,” Environ. Sc. Technol. 54(1):245-254.
- Elliott, Donald E. 1977. “Anomalous response of[f] the flame ionization detector to perfluorinated carboxylic acids,” J. Chromatogr. Sc. 15(10):475‐477.
- Environmental Working Group [n.d.], “For 50 years, polluters knew PFAS chemicals were dangerous but hid risks from public.” 3M-DuPont-Timeline_sm.pdf.
- Ettre, Leslie S. 1977. “American instrument companies and the early development of gas chromatography,” J. Chromatogr. Sc. 15:90-110.
- Fenn, John B. 2002. “Electrospray ionization mass spectrometry: How it all began,” J. Biomol. Tech. 13(3) (September):101-118.
- “Fluorineophyte: New company in New Jersey turns out polytrifluorochloroethylene oils, greases and waxes.” 1950. Chemical Industries, June, p. 23.
- Fresen, J. A., F. H. Cox, and M. J. Witter. 1968. “The determination of fluoride in biological materials by means of gas chromatography,” Pharm. Weekbl. 103:909-914.
- Gaber, Nadi, Lisa Bero, and Tracy J. Woodruff. 2023. “The devil they knew: Chemical documents analysis of industry influence on PFAS science,” Ann Global Health 89(1):37, 1-17. DOI: https://doi. org/10.5334/aogh.4013.
- Gaines, Linda G. T., 2023. “Historical and current usage of per- and polyfluoroalkyl substances (PFAS): A literature review,” Am. J. Ind. Med. 66(5):353-378.
- Guy, W. S., D. R. Taves, and W. S. Brey. 1976. “Organic fluorocompounds in human plasma: Prevalence and characteristics,” in R. Filler, ed., Biochemistry Involving Carbon-Fluorine Bonds. Washington DC: American Chemical Society, pp. 117-134
- Guy, Warren S. 1979. “Inorganic and organic fluorine in human blood.” In E. Johansen, D. R. Taves, and T. O. Olsen, eds, Continuing Evaluation of the Use of Fluorides, AAAS Selected Symposium Series 11. Washington DC: American Association for the Advancement of Science/Boulder CO: Westview Press, pp.125-147.
- Hagan, Donald R., Jon Belisle, James D. Johnson, and P. Venkateswarlu. 1981. “Characterization of fluorinated metabolites by a gas chromatographic-helium microwave plasma detector: the bio transformation of 1H,1H,2H,2H-perfluorodecanol to perfluorooctanooate,” Anal. Biochem. 118:336-343.
- Homburg, Ernst, and Elisabeth Vaupel, eds. 2019. Hazardous Chemicals: Agents of Risk and Change, 1800-2000. New York: Berghahn.
- Jahnke, A., and U. Berge. 2009. “Trace analysis of per- and polyfluorinated alky substances in various matrices. How do current methods perform?” J. Chromatogr. A 1216(3):410-421.
- Kissa, Erik. 2001. Fluorinated Surfactants and Repellents,” 2nd ed. New York: CRC Press.
- Krafft, Marie Pierre, and Jean G. Riess. 2015. “Per- and polyfluorinated substances (PFASs): Environmental challenges,” Curr. Opin. Colloid Interface Sc. 20(3):192-212;
- Lerner, Sharon. 2018 “3M knew about the dangers of PFOA and PFOS decades ago, internal documents show,” The Intercept, 31 July.
- Liggett, L. M. 1954. “Determination of organic halogen with sodium biphenyl reagent,” Anal. Chem. 26(4):748-750.
- Lovelock, James. 1971. “Atmospheric fluorine compounds as indicators of air movements,” Nature 230 (April 9):379.
- MacDonald, Patrick D. 2008. “Waters Corporation: Fifty years of innovation in analysis and purification,” Chemical Heritage 26(2):32-37.
- Matuszak, M. P., and D. R. Brown. 1945. “Thorium nitrate titration of fluoride with special reference to determining fluorine and sulfur in hydrocarbons,” Ind. Eng. Chem., Anal. Ed. 17(2):100–106.
- McClure, F. J. 1939. “Microdetermination of fluorine by thorium nitrate titration,” Ind. Eng. Chem. 11(3):171-173.
- Mayer, Caroline E., and David Brown. 2000. “3M to discontinue some Scotchgard repellent products,” Washington Post/Los Angeles Times, 17 May.
- Methods of Analysis of the Association of Agricultural Analysts.1960. 9th edition. Washington DC: Association of Agricultural Chemists.
- Moody, Cheryl A., and Jennifer A. Field. 2000, “Perfluorinated surfactants and the environmental implications of their use in fire-fighting foams,” Environ. Sci. Technol. 34(18):3864–3870.
- Morris, Peter J. T. 2015. The Matter factory: A History of the Chemistry Laboratory. London: Reaktion Books.
- O’Hagan, David, and David B. Harper. 1999. “Fluorine-containing natural products,” J. Fluor. 100(1-2):127-133.
- Reuters. 2023. “3Ms $10.3 billion PFAS settlement gets preliminary approval,” 29 August.
- Rich, Nathaniel. 2016. "The lawyer who became DuPont's worst nightmare," The New York Times, 10 January. http://www.nytimes.com/2016/01/10/magazine/the-lawyer-who-became-duponts-worst-nightmare.html?_r=0.
- Ritter, Evelyn E., et al. 2017. “PIGE as a screening tool for per- and polyfluorinated substances in papers and textiles,” Nucl. Instr. Meth. Phys. Res., B 407:47-54.
- Simons, J. H. 1950. “Fluorochemicals and their production.” In J. H. Simons, ed., Fluorine Chemistry, vol. 1. New York: Academic Press.
- Singer, Leon, and W. D. Armstrong. 1954. “Fluoride determination by electron transfer catalysis,” Anal. Chem. 26(5):904-906.
- Singer, Leon, and W. D. Armstrong. 1959. “Determination of fluoride in blood serum,” Anal. Chem. 31(1):105-109.
- Singer, Leon, and W. D. Armstrong. 1960. “Regulation of human plasma fluoride concentration,” J. Appl. Physiol. 15:508–510.
- Singer, Leon, and W. D. Armstrong. 1965. “Determination of fluoride: Procedure based upon diffusion of hydrogen fluoride,” Anal. Biochem. 10:495-500.
- Singer, Leon, and W. D. Armstrong. 1967. “Normal human serum fluoride concentrations,” Nature 214 (June 10):1161-1162.
- Singer, Leon, and Aaron S. Posner. 1984. “Wallace D. Armstrong (1905-1984),” Calcified Tissue International 36:347-348.
- Standard Methods for the Examination of Water, Sewage, and Industrial Wastes. 1955. 10th edition. New York: American Public Health Association.
- Stein, T. P., Winston K. Robbins, Helene E. Brooks, and Herbert W. Wallace. 1975. “Determination of fluorocarbon in blood,” J. Biomed. Mater. Res. 9:479-485.
- Sweetser, P. B. 1956. “Decomposition of organic fluorine compounds by Wickbold oxyhydrogen flame combustion method,” Anal. Chem. 28:1766–1768.
- Taves, Donald R. 1966. “Normal human serum fluoride concentrations,” Nature 211 (July 9):192-193.
- Taves, Donald R. 1967. “Use of urine to serum fluoride concentration ratios to confirm serum fluoride analyses,” Nature 215 (September 23):1380.
- Taves, Donald R. 1968a. “Evidence that there are two forms of fluoride in human serum,” Nature 217 (March 16):1050-1051.
- Taves, Donald R. 1968b. “Separation of fluoride by rapid diffusion using hexamethyldisiloxane,” Talanta 15:969-974.
- Taves, Donald R. 1968c. “Electrophoretic mobility of serum fluoride,” Nature 220 (November 9):582-583.
- Taves, Donald R. 2022. “Fluoride: From nutrient to suspected neurotoxin,” Nutrients 14:3507. https://doi.org/10.3390/nu14173507.
- Ubel, F.A., S. D. Sorenson, and D. E. Roach. 1980. “Health status of plant workers exposed to fluorochemicals – A preliminary report, Am. Ind. Hyg. Assoc. J. 41(8):384-389.
- US EPA. 2009. “Determination of selected perfluorinated alkyl acids in drinking water by solid phase extraction and liquid chromatography/tandem mass spectrometry (LC/MS/MS),” Method 537 (September).
- US EPA press office. 2024. “Biden-Harris administration finalizes rule to prevent inactive PFAS from reentering commerce,” 8 January.
- Venkateswarlu, Pothapragada, and D. Narayana Rao. 1954. “Estimation of fluorine in biological material,” Anal. Chem. 26(4):766-767.
- Venkteswarlu, Pothapragada, and P. Sita. 1971a. “A new approach to the microdetermination of fluoride. Adsorption-diffusion technique,” Anal. Chem. 43(6):758–760.
- Venkateswarlu, Pothapragada, Leon Singer, and W. D. Armstrong. 1971b. “Determination of ionic (plus ionizable) fluoride in biological fluids: Procedure based on adsorption of fluoride ion on calcium phosphate,” Anal. Biochem. 42:350-359.
- Venkateswarlu, Pothapragada. 1974. “Reverse extraction technique for the determination of fluoride in biological materials,” Anal. Chem. 46(7):878-882.
- Venkateswarlu, Pothapragada. 1975. “Fallacies in the determination of total fluorine and nonionic fluorine in the diffusates of unashed sera and ultrafiltrates,” Biochem. Med. 14(4):368-377.
- Venkateswarlu, Pothapragada. 1977. “Determination of fluorine in biological materials.” In Methods Biochem. Anal. vol. 24. Chichester: Wiley.
- Venkateswarlu, Pothapragada. 1982. “Sodium biphenyl method for determination of covalently bound fluorine in organic compounds and biological materials,” Anal. Chem. 54:1132-1137.
- Venkateswarlu, Pothapragada, Larry D. Winter, Robert A. Prokop, and Donald F. Hagen. 1983. “Automated molecular absorption spectrometry for determination of fluorine in biological samples,” Anal. Chem. 55(14):2232-2236.
- Venkateswarlu, Pothapragada. 1994. “Determination of fluorine in biological material: A review,” Adv. Dent. Res. 8(1):80-86.
- Villagrasa, M., M. L. de Alda, and D. Barcelo. 2006. “Environmental analysis of fluorinated alkyl substances by liquid chromatography-(tandem) mass spectrometry. A Review,” Anal. Bioanal. Chem. 386(40):935-972
- Waldblott, G. L., and J. Yiamouyiannis. 1977. “Special Report. AAAS Fluoride Symposium in Denver,” Fluoride 10(3) (July):141-144.
- Wickbold, R. 1954. “Die quantitative Verbrennung Fluor-haltiger organischer Substanzen,” Angew. Chem. 66:173–174.
- Williams, Deena. 2022. "Toxic: 3M knew its chemicals were harmful decades ago, but didn't tell the public, government," Minnesota Reformer, 15 December.
- Ylinen, M., H. Hahnijarvi, P. Peura, and O. Ramo. 1985. “Quantitative gas chromatographic determination of perfluorooctanoic acid as the benzyl ester in plasma and urine,” Arch. Environ. Contam. Toxicol. 14(6):713-717.