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Screening of textile finishing agents available on the Chinese market: An important source of per- and polyfluoroalkyl substances to the environment

Abstract

Organofluorinated surfactants are widely employed in textile finishing agents (TFAs) to achieve oil, water, and stain repellency. This has been regarded as an important emission source of per-and polyfluoroalkyl substances (PFASs) to the environment. China is the biggest manufacturer of clothes, and thus TFA production is also a relevant industrial activity. Nevertheless, to date, no survey has been conducted on PFAS contents in commercially available TFAs. In the present study, TFA products were investigated by the Kendrick mass defect method. The quantification results demonstrated a significant presence of perfluorooctane sulfonate (0.37 mg/L) in TFAs manufactured by electrochemical fluorination technology. The products obtained by short-chain PFAS-based telomerization were dominated by perfluorooctanoic acid (mean concentration: 0.29 mg/L), whose values exceeded the limits stated in the European Chemical Agency guidelines (0.025 mg/L). Moreover, the total oxidizable precursor assay indicated high levels of indirectly quantified precursors with long alkyl chains (C7-C9). Together, these results suggest that there is currently a certain of environmental and health risks in China that originates from the utilization of TFAs, and a better manufacturing processes are required to reduce such risks.

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References

  • Barzen-Hanson K A, Field J A (2015). Discovery and implications of C2 and C3 perfluoroalkyl sulfonates in aqueous film-forming foams and groundwater. Environmental Science & Technology Letters, 2(4): 95–99

    Article  CAS  Google Scholar 

  • Brendel S, Fetter E, Staude C, Vierke L, Biegel-Engler A (2018). Short-chain perfluoroalkyl acids: Environmental concerns and a regulatory strategy under REACH. Environmental Sciences Europe, 30(1):9

    Article  CAS  Google Scholar 

  • Barzen-Hanson K A, Roberts S C, Choyke S, Oetjen K, McAlees A, Riddell N, McCrindle R, Ferguson P L, Higgins C P, Field J A (2017). Discovery of 40 classes of per- and polyfluoroalkyl substances in historical aqueous film-forming foams (AFFFs) and AFFF-impacted groundwater. Environmental Science & Technology, 51(4): 2047–2057

    Article  CAS  Google Scholar 

  • Bečanová J, Melymuk L, Vojta Š, Komprdová K, Klánová J (2016). Screening for perfluoroalkyl acids in consumer products, building materials and wastes. Chemosphere, 164: 322–329

    Article  CAS  Google Scholar 

  • Buck R C, Franklin J, Berger U, Conder J M, Cousins I T, de Voogt P, Jensen A A, Kannan K, Mabury S A, van Leeuwen S P (2011). Perfluoroalkyl and polyfluoroalkyl substances in the environment: Terminology, classification, and origins. Integrated Environmental Assessment and Management, 7(4): 513–541

    Article  CAS  Google Scholar 

  • Butt C M, Muir D C, Mabury S A (2014). Biotransformation pathways of fluorotelomer-based polyfluoroalkyl substances: A review. Environmental Toxicology and Chemistry, 33(2): 243–267

    Article  CAS  Google Scholar 

  • D’Agostino L A, Mabury S A (2014). Identification of novel fluorinated surfactants in aqueous film forming foams and commercial surfactant concentrates. Environmental Science & Technology, 48(1): 121–129

    Article  CAS  Google Scholar 

  • Dimzon I K, Trier X, Frömel T, Helmus R, Knepper T P, de Voogt P (2016). High resolution mass spectrometry of polyfluorinated polyether-based formulation. Journal of the American Society for Mass Spectrometry, 27(2): 309–318

    Article  CAS  Google Scholar 

  • ECHA (2016). Opinion on an Annex XV dossier proposing restrictions on perfluorooctanoic acid (PFOA), its salts and PFOA-related substances. Committee for risk assessment (RAC); Committee for socio-economic analysis (SEAC)

  • EPA-537 (2009). Determination of selected perfluorinated alkyl acids in drinking water by solid phase extraction and liquid chromatography/tandem mass spectrometry (LC/MS/MS), EPA Document #: EPA/600/R-08/092

  • EU (2006). European, Directive 2006/122/EC of the European Parliament and of the council of 12 December 2006, Off. J. Eur. Union L372/32(2006) 32–34

    Google Scholar 

  • Favreau P, Poncioni-Rothlisberger C, Place B J, Bouchex-Bellomie H, Weber A, Tremp J, Field J A, Kohler M (2017). Multianalyte profiling of per- and polyfluoroalkyl substances (PFASs) in liquid commercial products. Chemosphere, 171: 491–501

    Article  CAS  Google Scholar 

  • Fernando S, Jobst K J, Taguchi V Y, Helm P A, Reiner E J, McCarry B E (2014). Identification of the halogenated compounds resulting from the 1997 Plastimet Inc. fire in Hamilton, Ontario, using comprehensive two-dimensional gas chromatography and (ultra)high resolution mass spectrometry. Environmental Science & Technology, 48(18): 10656–10663

    Article  CAS  Google Scholar 

  • Giesy J P, Kannan K (2001). Global distribution of perfluorooctane sulfonate in wildlife. Environmental Science & Technology, 35(7): 1339–1342

    Article  CAS  Google Scholar 

  • Greenpeace (2011). Dirty laundry, unraveling the corporate connections to toxic water pollution in China. Amsterdam: Greenpeace International.

    Google Scholar 

  • Gremmel C, Frömel T, Knepper T P (2016). Systematic determination of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in outdoor jackets. Chemosphere, 160: 173–180

    Article  CAS  Google Scholar 

  • Herzke D, Olsson E, Posner S (2012). Perfluoroalkyl and polyfluoroalkyl substances (PFASs) in consumer products in Norway: A pilot study. Chemosphere, 88(8): 980–987

    Article  CAS  Google Scholar 

  • Heydebreck F, Tang J, Xie Z, Ebinghaus R (2016). Emissions of per- and polyfluoroalkyl substances in a textile manufacturing plant in China and their relevance for workers’ exposure. Environmental Science & Technology, 50(19): 10386–10396

    Article  CAS  Google Scholar 

  • Holmquist H, Schellenberger S, van der Veen I, Peters G M, Leonards P E G, Cousins I T (2016). Properties, performance and associated hazards of state-of-the-art durable water repellent (DWR) chemistry for textile finishing. Environment International, 91: 251–264

    Article  CAS  Google Scholar 

  • Houde M, Martin J W, Letcher R J, Solomon K R, Muir D C G (2006). Biological monitoring of polyfluoroalkyl substances: A review. Environmental Science & Technology, 40(11): 3463–3473

    Article  CAS  Google Scholar 

  • Houtz E F, Higgins C P, Field J A, Sedlak D L (2013). Persistence of perfluoroalkyl acid precursors in AFFF-impacted groundwater and soil. Environmental Science & Technology, 47(15): 8187–8195

    Article  CAS  Google Scholar 

  • Houtz E F, Sedlak D L (2012). Oxidative conversion as a means of detecting precursors to perfluoroalkyl acids in urban runoff. Environmental Science & Technology, 46(17): 9342–9349

    Article  CAS  Google Scholar 

  • Houtz E F, Sutton R, Park J S, Sedlak M (2016). Poly- and perfluoroalkyl substances in wastewater: Significance of unknown precursors, manufacturing shifts, and likely AFFF impacts. Water Research, 95(Supplement C): 142–149

    Article  CAS  Google Scholar 

  • Huang C H, Li X S, Jin G (2010). Electro fluorination and its fine-fluorine production branches. Chemical Production and Technology, 17(6): 15–17, 52 (in Chinese)

    Google Scholar 

  • Kendrick E (1963). A Mass Scale Based on CH2 = 14.0000 for High resolution mass spectrometry of organic compounds. Analytical Chemistry, 35(13): 2146–2154

    Article  CAS  Google Scholar 

  • Kissa E (2001). Fluorinated surfactants and repellents (Vol. 97). Boca Raton: CRC Press

    Google Scholar 

  • Knepper T P, Lange F T (2011). Polyfluorinated Chemicals and Transformation Products (Vol. 17). New York: Springer Science & Business Media

    Google Scholar 

  • Lacasse K, Baumann W (2004). Textile Chemicals: Environmental Data and Facts. New York: Springer Science & Business Media

    Book  Google Scholar 

  • Lindstrom A B, Strynar M J, Libelo E L (2011). Polyfluorinated compounds: Past, present, and future. Environmental Science & Technology, 45(19): 7954–7961

    Article  CAS  Google Scholar 

  • Liu X, Guo Z, Folk IV E E, Roache N F (2015a). Determination of fluorotelomer alcohols in selected consumer products and preliminary investigation of their fate in the indoor environment. Chemosphere, 129: 81–86

    Article  CAS  Google Scholar 

  • Liu Y, Pereira A D S, Martin J W (2015b). Discovery of C5–C17 poly- and perfluoroalkyl substances in water by in-line SPE-HPLC-Orbitrap with in-source fragmentation flagging. Analytical Chemistry, 87(8): 4260–4268

    Article  CAS  Google Scholar 

  • Lin B, Chen Y, Zhang G (2018). Impact of technological progress on China’s textile industry and future energy saving potential forecast. Energy, 161, 859–869

    Article  Google Scholar 

  • Lu G H, Gai N, Zhang P, Piao H T, Chen S, Wang X C, Jiao X C, Yin X C, Tan K Y, Yang Y L (2017). Perfluoroalkyl acids in surface waters and tapwater in the Qiantang River watershed-Influences from paper, textile, and leather industries. Chemosphere, 185: 610–617

    Article  CAS  Google Scholar 

  • McKeen L W (2015). Fluorinated Coatings and Finishes Handbook: The Definitive User’s Guide. Cambridge: William Andrew

    Google Scholar 

  • Moody C A, Martin J W, Kwan W C, Muir D C. G, Mabury S A (2002). Monitoring perfluorinated surfactants in biota and surface water samples following an accidental release of fire-fighting foam into Etobicoke Creek. Environmental Science & Technology, 36(4): 545–551

    Article  CAS  Google Scholar 

  • Mumtaz M, Bao Y, Liu L, Huang J, Cagnetta G, Yu G (2019). Per- and polyfluoroalkyl substances in representative fluorocarbon surfactants used in Chinese film-forming foams: Levels, profile shift, and environmental implications. Environmental Science and Technology Letters, 6(5): 259–264

    Article  CAS  Google Scholar 

  • Myers A L, Jobst K J, Mabury S A, Reiner E J (2014). Using mass defect plots as a discovery tool to identify novel fluoropolymer thermal decomposition products. Journal of Mass Spectrometry, 49(4): 291–296

    Article  CAS  Google Scholar 

  • Place B J, Field J A (2012). Identification of novel fluorochemicals in aqueous film-forming foams used by the US military. Environmental Science & Technology, 46(13): 7120–7127

    Article  CAS  Google Scholar 

  • Rankin K, Mabury S A, Jenkins T M, Washington J W (2016). A North American and global survey of perfluoroalkyl substances in surface soils: Distribution patterns and mode of occurrence. Chemosphere, 161: 333–341

    Article  CAS  Google Scholar 

  • Rao N S, Baker B E (1994). Textile Finishes and Fluorosurfactants. New York: Plenum

    Book  Google Scholar 

  • Ritscher A, Wang Z, Scheringer M, Boucher J M, Ahrens L, Berger U, Bintein S, Bopp S K, Borg D, Buser A M, Cousins I, DeWitt J, Fletcher T, Green C, Herzke D, Higgins C, Huang J, Hung H, Knepper T, Lau C S, Leinala E, Lindstrom A B, Liu J, Miller M, Ohno K, Perkola N, Shi Y, Småstuen Haug L, Trier X, Valsecchi S, van der Jagt K, Vierke L (2018). Zürich statement on future actions on per- and polyfluoroalkyl substances (PFASs). Environmental Health Perspectives, 126(8): 084502

    Article  Google Scholar 

  • Roach P J, Laskin J, Laskin A (2011). Higher-order mass defect analysis for mass spectra of complex organic mixtures. Analytical Chemistry, 83(12): 4924–4929

    Article  CAS  Google Scholar 

  • Robel A E, Marshall K, Dickinson M, Lunderberg D, Butt C, Peaslee G, Stapleton H M, Field J A (2017). Closing the mass balance on fluorine on papers and textiles. Environmental Science & Technology, 51(16): 9022–9032

    Article  CAS  Google Scholar 

  • Strynar M, Dagnino S, McMahen R, Liang S, Lindstrom A, Andersen E, McMillan L, Thurman M, Ferrer I, Ball C (2015). Identification of novel perfluoroalkyl ether carboxylic acids (PFECAs) and sulfonic acids (PFESAs) in natural waters using accurate mass time-of-flight mass spectrometry (TOFMS). Environmental Science & Technology, 49(19): 11622–11630

    Article  CAS  Google Scholar 

  • Trier X, Granby K, Christensen J H (2011). Polyfluorinated surfactants (PFS) in paper and board coatings for food packaging. Environmental Science and Pollution Research International, 18(7): 1108–1120

    Article  CAS  Google Scholar 

  • Vestergren R, Herzke D, Wang T, Cousins I T (2015). Are imported consumer products an important diffuse source of PFASs to the Norwegian environment? Environmental Pollution, 198: 223–230

    Article  CAS  Google Scholar 

  • Wang Z, DeWitt J C, Higgins C P, Cousins I T (2017). A never-ending story of per- and polyfluoroalkyl substances (PFASs)? Environmental Science & Technology, 51(5): 2508–2518

    Article  CAS  Google Scholar 

  • Washington J W, Jenkins T M (2015). Abiotic hydrolysis of fluorotelomer-based polymers as a source of perfluorocarboxylates at the global scale. Environmental Science & Technology, 49(24): 14129–14135

    Article  CAS  Google Scholar 

  • Winkens K, Koponen J, Schuster J, Shoeib M, Vestergren R, Berger U, Karvonen A M, Pekkanen J, Kiviranta H, Cousins I T (2017). Perfluoroalkyl acids and their precursors in indoor air sampled in children’s bedrooms. Environmental Pollution, 222: 423–432

    Article  CAS  Google Scholar 

  • Xiao F (2017). Emerging poly- and perfluoroalkyl substances in the aquatic environment: A review of current literature. Water Research, 124: 482–495

    Article  CAS  Google Scholar 

  • Xie S, Wang T, Liu S, Jones K C, Sweetman A J, Lu Y (2013). Industrial source identification and emission estimation of perfluorooctane sulfonate in China. Environment International, 52: 1–8

    Article  CAS  Google Scholar 

  • Ye F, Zushi Y, Masunaga S (2015). Survey of perfluoroalkyl acids (PFAAs) and their precursors present in Japanese consumer products. Chemosphere, 127: 262–268

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported by the Major Science and Technology Program for Water Pollution Control and Treatment in China (Grant Nos. 2017ZX07202-001 & 2017ZX07202-004).

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Correspondence to Jun Huang.

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Highlights

• Kendrick mass defect was used for PFASs screening in textile finishing agents (TFAs).

• Total oxidizable precursor assay provides insight into unknown precursors.

• Perfluorooctane sulfonate was found as impurity in short ECF technology based TFAs.

• Perfluorooctanoate was also detected in C6 telomerization based TFAs.

• Long chain precursors were also observed in both types of TFAs.

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11783_2019_1145_MOESM1_ESM.pdf

Screening of textile finishing agents available on the Chinese market: An important source of per- and polyfluoroalkyl substances to the environment

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Mumtaz, M., Bao, Y., Li, W. et al. Screening of textile finishing agents available on the Chinese market: An important source of per- and polyfluoroalkyl substances to the environment. Front. Environ. Sci. Eng. 13, 67 (2019). https://doi.org/10.1007/s11783-019-1145-0

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  • DOI: https://doi.org/10.1007/s11783-019-1145-0

Keywords

  • Textile finishing agents
  • Kendrick mass defect
  • Total oxidizable precursor assay