Please wait a minute...
Frontiers of Environmental Science & Engineering

ISSN 2095-2201

ISSN 2095-221X(Online)

CN 10-1013/X

Postal Subscription Code 80-973

2018 Impact Factor: 3.883

Front. Environ. Sci. Eng.    2019, Vol. 13 Issue (5) : 67    https://doi.org/10.1007/s11783-019-1145-0
RESEARCH ARTICLE
Screening of textile finishing agents available on the Chinese market: An important source of per- and polyfluoroalkyl substances to the environment
Mehvish Mumtaz1, Yixiang Bao1, Wenchao Li2, Lingxiao Kong2, Jun Huang1(), Gang Yu1
1. State Key Joint Laboratory of Environment Simulation and Pollution Control (SKJLESPC), Beijing Key Laboratory for Emerging Organic Contaminants Control (BKLEOC), School of Environment, Tsinghua University, Beijing 100084, China
2. CSD IDEA (Beijing) Environment Test & Analysis Co., Ltd., Beijing 100192, China
 Download: PDF(619 KB)   HTML
 Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks
Abstract

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.

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.

Keywords Textile finishing agents      Kendrick mass defect      Total oxidizable precursor assay     
Corresponding Author(s): Jun Huang   
Issue Date: 10 July 2019
 Cite this article:   
Mehvish Mumtaz,Yixiang Bao,Wenchao Li, et al. Screening of textile finishing agents available on the Chinese market: An important source of per- and polyfluoroalkyl substances to the environment[J]. Front. Environ. Sci. Eng., 2019, 13(5): 67.
 URL:  
https://academic.hep.com.cn/fese/EN/10.1007/s11783-019-1145-0
https://academic.hep.com.cn/fese/EN/Y2019/V13/I5/67
PFASs Recoverya
(%)
LODb
(ng/mL)
LOQc
(ng/mL)
PFBA 101±0.3 0.3 2.7
PFPeA 104±15.8 0.4 3.6
PFHxA 112±18.5 0.3 2.6
PFHpA 100±7.0 0.3 2.7
PFOA 115±17.5 0.2 2.3
PFNA 106±12.7 0.2 2.0
PFDA 133±13.6 0.2 2.4
PFUnDA 90±9.8 0.2 2.1
PFBS 100±7.4 0.3 3.2
PFPeS 115±9.5 0.2 2.0
PFHxS 98±10.5 0.4 3.6
PFHpS 85±6.1 0.3 2.9
PFOS 100±14.8 0.2 2.2
PFNS 84±3.2 0.1 1.33
PFDS 94±4 0.2 1.96
4:2FTOH 119±5.0 8.6 28.7
6:2FTOH 112±12.3 2.7 9.0
8:2FTOH 112±8.0 1.8 5.8
10:2FTOH 124±1.1 1.1 3.7
Tab.1  Calculated recovery of PFASs, LOD and LOQ (ng/mL)
Fig.1  KMD against KM plot for the entire mass in FA10, representing the overviewed PFASs among the selected list of 58 PFASs.
Fig.2  KMD against KM plot for the entire mass spectrum in FA4, representing the overviewed PFASs among the selected list of 58 PFASs.
Fig.3  Directly quantified PFASs in ECF-based TFAs.
Fig.4  Directly quantified PFASs in telomerization-based TFAs.
Fig.5  Observed increase in the concentration (mg/L) of PFCAs after oxidative treatment.
Fig.6  Percentage contribution by unidentified precursors [PFCAs generated upon oxidation that could not be related to measured precursors, and calculated by the difference between the oxidation products (i.e., all PFCAs) and the identified precursors (i.e., FTOH)].
1 K A Barzen-Hanson, J A Field (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
https://doi.org/10.1021/acs.estlett.5b00049
2 S Brendel, E Fetter, C Staude, L Vierke, A Biegel‑Engler (2018). Short‑chain perfluoroalkyl acids: Environmental concerns and a regulatory strategy under REACH. Environmental Sciences Europe, 30(1):9
https://doi.org/10.1186/s12302-018-0134-4 pmid: 29527446
3 K A Barzen-Hanson, S C Roberts, S Choyke, K Oetjen, A McAlees, N Riddell, R McCrindle, P L Ferguson, C P Higgins, J A Field (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
https://doi.org/10.1021/acs.est.6b05843 pmid: 28098989
4 J Bečanová, L Melymuk, Š Vojta, K Komprdová, J Klánová (2016). Screening for perfluoroalkyl acids in consumer products, building materials and wastes. Chemosphere, 164: 322–329
https://doi.org/10.1016/j.chemosphere.2016.08.112 pmid: 27592321
5 R C Buck, J Franklin, U Berger, J M Conder, I T Cousins, P de Voogt, A A Jensen, K Kannan, S A Mabury, S P van Leeuwen (2011). Perfluoroalkyl and polyfluoroalkyl substances in the environment: Terminology, classification, and origins. Integrated Environmental Assessment and Management, 7(4): 513–541
https://doi.org/10.1002/ieam.258 pmid: 21793199
6 C M Butt, D C Muir, S A Mabury (2014). Biotransformation pathways of fluorotelomer-based polyfluoroalkyl substances: A review. Environmental Toxicology and Chemistry, 33(2): 243–267
https://doi.org/10.1002/etc.2407 pmid: 24114778
7 L A D’Agostino, S A Mabury (2014). Identification of novel fluorinated surfactants in aqueous film forming foams and commercial surfactant concentrates. Environmental Science & Technology, 48(1): 121–129
https://doi.org/10.1021/es403729e pmid: 24256061
8 I K Dimzon, X Trier, T Frömel, R Helmus, T P Knepper, P de Voogt (2016). High resolution mass spectrometry of polyfluorinated polyether-based formulation. Journal of the American Society for Mass Spectrometry, 27(2): 309–318
https://doi.org/10.1007/s13361-015-1269-9 pmid: 26519300
9 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)
10 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
11 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
12 P Favreau, C Poncioni-Rothlisberger, B J Place, H Bouchex-Bellomie, A Weber, J Tremp, J A Field, M Kohler (2017). Multianalyte profiling of per- and polyfluoroalkyl substances (PFASs) in liquid commercial products. Chemosphere, 171: 491–501
https://doi.org/10.1016/j.chemosphere.2016.11.127 pmid: 28038421
13 S Fernando, K J Jobst, V Y Taguchi, P A Helm, E J Reiner, B E McCarry (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
https://doi.org/10.1021/es503428j pmid: 25133985
14 J P Giesy, K Kannan (2001). Global distribution of perfluorooctane sulfonate in wildlife. Environmental Science & Technology, 35(7): 1339–1342
https://doi.org/10.1021/es001834k pmid: 11348064
15 Greenpeace (2011). Dirty laundry, unraveling the corporate connections to toxic water pollution in China. Amsterdam: Greenpeace International.
16 C Gremmel, T Frömel, T P Knepper (2016). Systematic determination of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in outdoor jackets. Chemosphere, 160: 173–180
https://doi.org/10.1016/j.chemosphere.2016.06.043 pmid: 27376856
17 D Herzke, E Olsson, S Posner (2012). Perfluoroalkyl and polyfluoroalkyl substances (PFASs) in consumer products in Norway: A pilot study. Chemosphere, 88(8): 980–987
https://doi.org/10.1016/j.chemosphere.2012.03.035 pmid: 22483730
18 F Heydebreck, J Tang, Z Xie, R Ebinghaus (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
https://doi.org/10.1021/acs.est.6b03213 pmid: 27617679
19 H Holmquist, S Schellenberger, I van der Veen, G M Peters, P E G Leonards, I T Cousins (2016). Properties, performance and associated hazards of state-of-the-art durable water repellent (DWR) chemistry for textile finishing. Environment International, 91: 251–264
https://doi.org/10.1016/j.envint.2016.02.035 pmid: 26994426
20 M Houde, J W Martin, R J Letcher, K R Solomon, D C G Muir (2006). Biological monitoring of polyfluoroalkyl substances: A review. Environmental Science & Technology, 40(11): 3463–3473
https://doi.org/10.1021/es052580b pmid: 16786681
21 E F Houtz, C P Higgins, J A Field, D L Sedlak (2013). Persistence of perfluoroalkyl acid precursors in AFFF-impacted groundwater and soil. Environmental Science & Technology, 47(15): 8187–8195
https://doi.org/10.1021/es4018877 pmid: 23886337
22 E F Houtz, D L Sedlak (2012). Oxidative conversion as a means of detecting precursors to perfluoroalkyl acids in urban runoff. Environmental Science & Technology, 46(17): 9342–9349
https://doi.org/10.1021/es302274g pmid: 22900587
23 E F Houtz, R Sutton, J S Park, M Sedlak (2016). Poly- and perfluoroalkyl substances in wastewater: Significance of unknown precursors, manufacturing shifts, and likely AFFF impacts. Water Research, 95(Supplement C): 142–149
https://doi.org/10.1016/j.watres.2016.02.055 pmid: 26990839
24 C H Huang, X S Li, G Jin (2010). Electro fluorination and its fine-fluorine production branches. Chemical Production and Technology, 17(6): 15–17, 52 (in Chinese)
25 E Kendrick (1963). A Mass Scale Based on CH2 = 14.0000 for High resolution mass spectrometry of organic compounds. Analytical Chemistry, 35(13): 2146–2154
https://doi.org/10.1021/ac60206a048
26 E Kissa (2001). Fluorinated surfactants and repellents (Vol. 97). Boca Raton: CRC Press
27 T P Knepper, F T Lange (2011). Polyfluorinated Chemicals and Transformation Products (Vol. 17).New York: Springer Science & Business Media
28 K Lacasse, W Baumann (2004). Textile Chemicals: Environmental Data and Facts. New York: Springer Science & Business Media
29 A B Lindstrom, M J Strynar, E L Libelo (2011). Polyfluorinated compounds: Past, present, and future. Environmental Science & Technology, 45(19): 7954–7961
https://doi.org/10.1021/es2011622
30 X Liu, Z Guo, E E Folk IV, N F Roache (2015a). Determination of fluorotelomer alcohols in selected consumer products and preliminary investigation of their fate in the indoor environment. Chemosphere, 129: 81–86
https://doi.org/10.1016/j.chemosphere.2014.06.012 pmid: 24997516
31 Y Liu, A D S Pereira, J W Martin (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
https://doi.org/10.1021/acs.analchem.5b00039 pmid: 25818392
32 B Lin, Y Chen, G Zhang(2018). Impact of technological progress on China's textile industry and future energy saving potential forecast. Energy, 161, 859–869
https://doi.org/10.1016/j.energy.2018.07.178
33 G H Lu, N Gai, P Zhang, H T Piao, S Chen, X C Wang, X C Jiao, X C Yin, K Y Tan, Y L Yang (2017). Perfluoroalkyl acids in surface waters and tapwater in the Qiantang River watershed-Influences from paper, textile, and leather industries. Chemosphere, 185: 610–617
https://doi.org/10.1016/j.chemosphere.2017.06.139 pmid: 28719881
34 L W McKeen (2015). Fluorinated Coatings and Finishes Handbook: The Definitive User’s Guide.   Cambridge: William Andrew
35 C A Moody, J W Martin, W C Kwan, D C. G Muir, S A Mabury (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
https://doi.org/10.1021/es011001+ pmid: 11883418
36 M Mumtaz, Y Bao, L Liu, J Huang, G Cagnetta, G Yu (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
https://doi.org/10.1021/acs.estlett.9b00154
37 A L Myers, K J Jobst, S A Mabury, E J Reiner (2014). Using mass defect plots as a discovery tool to identify novel fluoropolymer thermal decomposition products. Journal of Mass Spectrometry, 49(4): 291–296
https://doi.org/10.1002/jms.3340 pmid: 24719344
38 B J Place, J A Field (2012). Identification of novel fluorochemicals in aqueous film-forming foams used by the US military. Environmental Science & Technology, 46(13): 7120–7127
https://doi.org/10.1021/es301465n pmid: 22681548
39 K Rankin, S A Mabury, T M Jenkins, J W Washington (2016). A North American and global survey of perfluoroalkyl substances in surface soils: Distribution patterns and mode of occurrence. Chemosphere, 161: 333–341
https://doi.org/10.1016/j.chemosphere.2016.06.109 pmid: 27441993
40 N S Rao, B E Baker (1994). Textile Finishes and Fluorosurfactants. New York: Plenum
41 A Ritscher, Z Wang, M Scheringer, J M Boucher, L Ahrens, U Berger, S Bintein, S K Bopp, D Borg, A M Buser, I Cousins, J DeWitt, T Fletcher, C Green, D Herzke, C Higgins, J Huang, H Hung, T Knepper, C S Lau, E Leinala, A B Lindstrom, J Liu, M Miller, K Ohno, N Perkola, Y Shi, L Småstuen Haug, X Trier, S Valsecchi, K van der Jagt, L Vierke (2018). Zürich statement on future actions on per- and polyfluoroalkyl substances (PFASs). Environmental Health Perspectives, 126(8): 084502
https://doi.org/10.1289/EHP4158 pmid: 30235423
42 P J Roach, J Laskin, A Laskin (2011). Higher-order mass defect analysis for mass spectra of complex organic mixtures. Analytical Chemistry, 83(12): 4924–4929
https://doi.org/10.1021/ac200654j pmid: 21526851
43 A E Robel, K Marshall, M Dickinson, D Lunderberg, C Butt, G Peaslee, H M Stapleton, J A Field (2017). Closing the mass balance on fluorine on papers and textiles. Environmental Science & Technology, 51 (16): 9022–9032
https://doi.org/10.1021/acs.est.7b02080
44 M Strynar, S Dagnino, R McMahen, S Liang, A Lindstrom, E Andersen, L McMillan, M Thurman, I Ferrer, C Ball (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
https://doi.org/10.1021/acs.est.5b01215 pmid: 26392038
45 X Trier, K Granby, J H Christensen (2011). Polyfluorinated surfactants (PFS) in paper and board coatings for food packaging. Environmental Science and Pollution Research International, 18(7): 1108–1120
https://doi.org/10.1007/s11356-010-0439-3 pmid: 21327544
46 R Vestergren, D Herzke, T Wang, I T Cousins (2015). Are imported consumer products an important diffuse source of PFASs to the Norwegian environment? Environmental Pollution, 198: 223–230
https://doi.org/10.1016/j.envpol.2014.12.034 pmid: 25644935
47 Z Wang, J C DeWitt, C P Higgins, I T Cousins (2017). A never-ending story of per- and polyfluoroalkyl substances (PFASs)? Environmental Science & Technology, 51(5): 2508–2518
https://doi.org/10.1021/acs.est.6b04806 pmid: 28224793
48 J W Washington, T M Jenkins (2015). Abiotic hydrolysis of fluorotelomer-based polymers as a source of perfluorocarboxylates at the global scale. Environmental Science & Technology, 49(24): 14129–14135
https://doi.org/10.1021/acs.est.5b03686 pmid: 26526296
49 K Winkens, J Koponen, J Schuster, M Shoeib, R Vestergren, U Berger, A M Karvonen, J Pekkanen, H Kiviranta, I T Cousins (2017). Perfluoroalkyl acids and their precursors in indoor air sampled in children’s bedrooms. Environmental Pollution, 222: 423–432
https://doi.org/10.1016/j.envpol.2016.12.010 pmid: 28012670
50 F Xiao (2017). Emerging poly- and perfluoroalkyl substances in the aquatic environment: A review of current literature. Water Research, 124: 482–495
https://doi.org/10.1016/j.watres.2017.07.024 pmid: 28800519
51 S Xie, T Wang, S Liu, K C Jones, A J Sweetman, Y Lu (2013). Industrial source identification and emission estimation of perfluorooctane sulfonate in China. Environment International, 52: 1–8
https://doi.org/10.1016/j.envint.2012.11.004 pmid: 23266910
52 F Ye, Y Zushi, S Masunaga (2015). Survey of perfluoroalkyl acids (PFAAs) and their precursors present in Japanese consumer products. Chemosphere, 127: 262–268
https://doi.org/10.1016/j.chemosphere.2015.02.026 pmid: 25753850
[1] FSE-19053-OF-MM_suppl_1 Download
Viewed
Full text


Abstract

Cited

  Shared   
  Discussed