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.
Article PDF
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.Avoid common mistakes on your manuscript.
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
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
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
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
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
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
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
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
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
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
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
Giesy J P, Kannan K (2001). Global distribution of perfluorooctane sulfonate in wildlife. Environmental Science & Technology, 35(7): 1339–1342
Greenpeace (2011). Dirty laundry, unraveling the corporate connections to toxic water pollution in China. Amsterdam: Greenpeace International.
Gremmel C, Frömel T, Knepper T P (2016). Systematic determination of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in outdoor jackets. Chemosphere, 160: 173–180
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
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
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
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
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
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
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
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)
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
Kissa E (2001). Fluorinated surfactants and repellents (Vol. 97). Boca Raton: CRC Press
Knepper T P, Lange F T (2011). Polyfluorinated Chemicals and Transformation Products (Vol. 17). New York: Springer Science & Business Media
Lacasse K, Baumann W (2004). Textile Chemicals: Environmental Data and Facts. New York: Springer Science & Business Media
Lindstrom A B, Strynar M J, Libelo E L (2011). Polyfluorinated compounds: Past, present, and future. Environmental Science & Technology, 45(19): 7954–7961
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
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
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
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
McKeen L W (2015). Fluorinated Coatings and Finishes Handbook: The Definitive User’s Guide. Cambridge: William Andrew
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
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
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
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
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
Rao N S, Baker B E (1994). Textile Finishes and Fluorosurfactants. New York: Plenum
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
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
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
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
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
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
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
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
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
Xiao F (2017). Emerging poly- and perfluoroalkyl substances in the aquatic environment: A review of current literature. Water Research, 124: 482–495
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
Ye F, Zushi Y, Masunaga S (2015). Survey of perfluoroalkyl acids (PFAAs) and their precursors present in Japanese consumer products. Chemosphere, 127: 262–268
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).
Author information
Authors and Affiliations
Corresponding author
Additional information
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.
Supporting information
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
Rights and permissions
About this article
Cite this article
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
Received:
Revised:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11783-019-1145-0