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Solvent-free automated thermal desorption-gas chromatography/mass spectrometry for direct screening of hazardous compounds in consumer textiles
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).ORCID iD: 0000-0001-9724-210X
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).ORCID iD: 0000-0003-1636-0214
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).ORCID iD: 0000-0002-2981-3617
Number of Authors: 42023 (English)In: Analytical and Bioanalytical Chemistry, ISSN 1618-2642, E-ISSN 1618-2650, Vol. 415, no 19, p. 4675-4687Article in journal (Refereed) Published
Abstract [en]

The global production of textiles utilizes numerous large-volume chemicals that may remain to some extent in the finished garments. Arylamines, quinolines, and halogenated nitrobenzene compounds are possible mutagens, carcinogens and/or skin sensitizers. For prevention, control of clothing and other textiles must be improved, especially those imported from countries without regulations of textile chemicals. An automated analytical methodology with on-line extraction, separation, and detection would largely simplify screening surveys of hazardous chemicals in textiles. Automated thermal desorption-gas chromatography/mass spectrometry (ATD-GC/MS) was developed and evaluated as a solvent-free, direct chemical analysis for screening of textiles. It requires a minimum of sample handling with a total run time of 38 min including sample desorption, chromatographic separation, and mass spectrometric detection. For most of the studied compounds, method quantification limit (MQL) was below 5 mu g/g for 5 mg of textile sample, which is sufficiently low for screening and control of quinoline and arylamines regulated by EU. Several chemicals were detected and quantified when the ATD-GC/MS method was applied in a limited pilot screening of synthetic fiber garments. A number of arylamines were detected, where some of the halogenated dinitroanilines were found in concentrations up to 300 mu g/g. This is ten times higher than the concentration limit for similar arylamines listed by the EU REACH regulation. Other chemicals detected in the investigated textiles were several quinolines, benzothiazole, naphthalene, and 3,5-dinitrobromobenzene. Based on the present results, we suggest ATD-GC/MS as a screening method for the control of harmful chemicals in clothing garments and other textiles.

Place, publisher, year, edition, pages
2023. Vol. 415, no 19, p. 4675-4687
Keywords [en]
ATD-GC/MS, Textiles, Arylamines, Quinoline, Halogenated nitroaromatic compounds, Skin sensitizer
National Category
Biological Sciences Analytical Chemistry
Identifiers
URN: urn:nbn:se:su:diva-221113DOI: 10.1007/s00216-023-04780-xISI: 001015527200001PubMedID: 37338566Scopus ID: 2-s2.0-85162231222OAI: oai:DiVA.org:su-221113DiVA, id: diva2:1798487
Available from: 2023-09-19 Created: 2023-09-19 Last updated: 2025-04-11Bibliographically approved
In thesis
1. Is your wardrobe making you sick?: Textile Chemicals with Focus on Skin Sensitizers – Analytical Methods, Occurrence and Dermal Exposure
Open this publication in new window or tab >>Is your wardrobe making you sick?: Textile Chemicals with Focus on Skin Sensitizers – Analytical Methods, Occurrence and Dermal Exposure
2024 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Textile production includes the use of a large diversity of chemicals, often in high amounts, and their presence in the finished textiles has become a topic of increasing concern. One of the health concerns associated with several of these compounds is skin sensitization, which may lead to the development of textile allergy. This thesis has a special focus on skin allergens and presents analytical methods and workflows to gain a deeper understanding of these chemicals in clothing.

In Paper I, a suspect screening of disperse azo dyes in synthetic clothing was conducted using liquid chromatography/high-resolution mass spectrometry (LC/HRMS). In addition, gas chromatography/mass spectrometry (GC/MS) was applied to screen for volatile/semi-volatile dye components. Various disperse azo dyes and arylamines were identified. Notably, most of the dyes used today to diagnose textile allergy were rarely identified. Further, the well-known skin sensitizer 2,4-dinitrochlorobenzene was shown to occur in garments for the first time. Paper II presents a screening method for textiles with automated thermal desorption (ATD) coupled to GC/MS. This method was used for accurate quantification of more than 30 volatile/semi-volatile compounds in textiles, but is also suitable for a wider range of semi-volatiles. Most analytes had method detection limits below 1 µg/g (26 out of 31 analytes) with a relative standard deviation <15%. The ATD-GC/MS method would allow companies to simultaneously screen for multiple components with a minimum of sample preparation, significantly enhancing efficiency and the ability to comply with regulations. 

Since several compounds identified in Papers I and II are suspected to cause skin sensitization, this was further studied and is the focus of Paper III. A combination of in vitro methods was employed to study the first and third key events of contact allergy as well as mutagenicity. Two hitherto unreported skin sensitizers and two mutagenic compounds were discovered. Despite this, the risks for skin sensitization or other non-carcinogenic health effects from exposure to these compounds in textiles were estimated as acceptable, at least when considering individual compounds and the levels so far reported.

In Paper IV, cellulose nanocrystals (CNCs) produced from upcycling post-consumer garments were screened for textile chemicals using a non-target/suspect screening approach with GC/MS and LC/HRMS. Generally, lower levels were detected in the cellulose nanocrystals. However, phthalates were found to remain mainly in the CNCs. Although the levels of phthalates in this case were below the EU regulation, this emphasizes the need for control of the garments.

In conclusion, this thesis has developed analytical methods and approaches that can be used for the surveillance and screening of chemicals in textiles, facilitating future identification of substances that constitute potential health risks.

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry, Stockholm University, 2024. p. 67
Keywords
Textile chemicals, textile allergens, disperse azo dyes, arylamines, halogenated aromatic compounds, non-target/suspect screening, LC/HRMS, GC/MS, ATD-GC/MS
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-230791 (URN)978-91-8014-835-1 (ISBN)978-91-8014-836-8 (ISBN)
Public defence
2024-09-13, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16B, Stockholm, 10:00 (English)
Opponent
Supervisors
Available from: 2024-08-21 Created: 2024-06-12 Last updated: 2024-09-16Bibliographically approved
2. Towards safe and sustainable fashion: Screening methodologies to detect health-hazardous chemicals in textiles and textile processing
Open this publication in new window or tab >>Towards safe and sustainable fashion: Screening methodologies to detect health-hazardous chemicals in textiles and textile processing
2025 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

As one of the top global industries, textile manufacturing utilizes several thousands of industrial chemicals, many of which end up in the finished garments. These residues constitute a widespread, possibly hazardous, exposure of the general population, yet the long-term health effects remain largely unknown. Skin allergy - a life-long, incurable condition – is one health effect of repeated skin exposure to one or several chemicals. Among the Western population, textile allergy is estimated to have a prevalence of around 1%.

Fast-fashion trends make the chemical content in everyday textile apparel hard to predict, as non-regulated chemicals are rapidly introduced into production. Only a tiny fraction of the used chemicals is hitherto regulated, and there is a lack of oversight regarding the content in everyday garments. A recently introduced EU legislation concerning handling textile waste motivates the development of alternative recycling methods for worn-out textile apparel. Upcycling methods are also important to reduce the environmental burden from incineration and landfilling.

This thesis focuses on developing analytical tools for the quantitative chemical screening of textiles. A novel, fully automated analytical methodology based on thermal desorption - gas chromatography-mass spectrometry (ATD-GC/MS) was developed for polyester, synthetic polyester blends, and cotton, constituting at least 75% of the retail market. The method is especially suitable for detecting semi-volatile compounds capable of skin permeation. Recently, the method was proposed for evaluation as a potential EU standard. Ultimately, the method could help ensure regulatory compliance within the textile industry. 

In addition, a high-resolution mass spectrometry workflow was developed to investigate the fate of hazardous substances during the upcycling of polycotton waste into cellulose nanocrystals. Most hazardous textile chemicals were found to remain in the polyester, while the upcycled product contained much less contaminants. Chemical release into waste streams is correlated with solubility under acidic conditions, highlighting target compounds for removal during upscaling.

Together, the developed methods contribute to a robust analytical toolbox with the potential to improve chemical oversight in textiles, support regulatory expansion, and promote safer, more sustainable fashion.

Place, publisher, year, edition, pages
Stockholm: Department of Chemistry, Stockholm University, 2025. p. 97
Keywords
Sustainable fashion, Textile screening, Thermal desorption
National Category
Textile, Rubber and Polymeric Materials
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-241997 (URN)978-91-8107-244-0 (ISBN)978-91-8107-245-7 (ISBN)
Public defence
2025-06-04, Magnelisalen, Kemiska övningslaboratoriet, Svante Arrenhius Väg 16B, and online via Zoom, public link is available at the department website, Stockholm, 13:00 (English)
Opponent
Supervisors
Funder
Mistra - The Swedish Foundation for Strategic Environmental Research, 2018/11
Available from: 2025-05-12 Created: 2025-04-11 Last updated: 2025-07-14Bibliographically approved

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Carlsson, JosefineÅström, TimÖstman, ConnyNilsson, Ulrika

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