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Is your wardrobe making you sick?: Textile Chemicals with Focus on Skin Sensitizers – Analytical Methods, Occurrence and Dermal Exposure
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).ORCID iD: 0000-0001-9724-210X
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 [en]
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: urn:nbn:se:su:diva-230791ISBN: 978-91-8014-835-1 (print)ISBN: 978-91-8014-836-8 (electronic)OAI: oai:DiVA.org:su-230791DiVA, id: diva2:1868829
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
List of papers
1. Disperse azo dyes, arylamines and halogenated dinitrobenzene compounds in synthetic garments on the Swedish market
Open this publication in new window or tab >>Disperse azo dyes, arylamines and halogenated dinitrobenzene compounds in synthetic garments on the Swedish market
2022 (English)In: Contact Dermatitis, ISSN 0105-1873, E-ISSN 1600-0536, Vol. 87, no 4, p. 315-324Article in journal (Refereed) Published
Abstract [en]

Background: Azobenzene disperse dyes (azo DDs) are well-known as textile allergens, but the knowledge of their occurrence in garments is low. The numerous azo DDs and dye components found in textiles constitute a potential health risk, but only seven azo DDs are included in the European baseline patch test series (EBS).

Objectives: To investigate non-regulated azo DDs and dye components in synthetic garments on the Swedish market.

Methods: High-performance liquid chromatography/mass spectrometry, gas chromatography/mass spectrometry and computerized data mining.

Results: Sixty-two azo DDs were detected, with Disperse Red 167:1 occurring in 67%, and 14 other DDs each found in >20% of the garments. Notably, the EBS dyes were less common, three even not detected, while arylamines were frequently detected and exceeded 1 mg/g in several garments. Also, halogenated dinitrobenzenes were identified in 25% of the textiles.

Conclusion: Azo DDs and dye components, in complex compositions and with large variations, occurred frequently in the synthetic garments. The arylamines were shown to occur at much higher levels compared to the azo DDs, suggesting the former constitute a potentially higher health risk. The role of arylamines and halogenated dinitrobenzenes in textile allergy has to be further investigated.

Keywords
arylamines, clothing, contact allergy, disperse azo dyes, halogenated dinitrobenzenes, screening, textile dye mix
National Category
Respiratory Medicine and Allergy Chemical Sciences
Identifiers
urn:nbn:se:su:diva-206850 (URN)10.1111/cod.14163 (DOI)000809815200001 ()35611449 (PubMedID)2-s2.0-85131535325 (Scopus ID)
Available from: 2022-07-01 Created: 2022-07-01 Last updated: 2024-06-12Bibliographically approved
2. Solvent-free automated thermal desorption-gas chromatography/mass spectrometry for direct screening of hazardous compounds in consumer textiles
Open this publication in new window or tab >>Solvent-free automated thermal desorption-gas chromatography/mass spectrometry for direct screening of hazardous compounds in consumer textiles
2023 (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.

Keywords
ATD-GC/MS, Textiles, Arylamines, Quinoline, Halogenated nitroaromatic compounds, Skin sensitizer
National Category
Biological Sciences Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-221113 (URN)10.1007/s00216-023-04780-x (DOI)001015527200001 ()37338566 (PubMedID)2-s2.0-85162231222 (Scopus ID)
Available from: 2023-09-19 Created: 2023-09-19 Last updated: 2024-06-12Bibliographically approved
3. Health risks from exposure to chemicals in clothing - non-regulated halogenated aromatic compounds
Open this publication in new window or tab >>Health risks from exposure to chemicals in clothing - non-regulated halogenated aromatic compounds
Show others...
2024 (English)In: Chemosphere, ISSN 0045-6535, E-ISSN 1879-1298, Vol. 363, article id 142930Article in journal (Refereed) Published
Abstract [en]

The objective of the present study was to investigate some commonly detected halogenated textile pollutants for their bioavailability and hazardous properties. Release into artificial sweat and skin absorption in vitro were examined as well as mutagenic effects by Ames test, and skin-sensitizing properties from a peptide reactivity assay combined with a cell test.

All investigated compounds were shown to migrate from the textile into sweat and be absorbed by the skin, although to a different extent. The experimental values for migration were found to be up to 390 times higher compared to literature values. Two of the studied compounds, 2,5-dinitrochlorobenzene and 3,5-dinitrobromobenzene, both exhibited mutagenic effects in the Ames test, while both 2,5-dinitrochlorobenzene and 2,6-dichlorobenzene-1,4-diamine were classified as skin sensitizers. The allergenic reactivity of the latter was found to be due to an oxidized transformation product.

Risks for the induction of skin allergy and other non-carcinogenic effects from dermal exposure to the individual compounds were found low, even when considering clothing with the highest reported levels. However, the complex mixtures of chemicals often present in garments may still constitute a health risk, especially when considering the many hours of daily exposure. It is important to further study the toxicity of other frequently occurring chemicals as well as the synergistic effects of chemicals that co-occur in clothing.

Keywords
Halogenated pollutants, dermal exposure, skin sensitization, mutagenicity, risk assessment, textile chemicals
National Category
Analytical Chemistry
Research subject
Analytical Chemistry; Toxicology
Identifiers
urn:nbn:se:su:diva-230783 (URN)10.1016/j.chemosphere.2024.142930 (DOI)39053776 (PubMedID)2-s2.0-85199943488 (Scopus ID)
Available from: 2024-06-12 Created: 2024-06-12 Last updated: 2024-08-12Bibliographically approved
4. Cellulose Nanocrystals from Postconsumer Cotton and Blended Fabrics: A Study on Their Properties, Chemical Composition, and Process Efficiency
Open this publication in new window or tab >>Cellulose Nanocrystals from Postconsumer Cotton and Blended Fabrics: A Study on Their Properties, Chemical Composition, and Process Efficiency
Show others...
2022 (English)In: ACS Sustainable Chemistry and Engineering, E-ISSN 2168-0485, Vol. 10, no 11, p. 3787-3798Article in journal (Refereed) Published
Abstract [en]

From manufacturing to disposal, the textile industry faces multiple challenges to achieve sustainability and reduce its environmental impact. This work investigates the properties and composition of cellulose nanocrystals (CNCs) extracted from clothing waste made of cotton fibers. We isolated CNCs from cotton, polyester/cotton, and acrylic/cotton waste fabrics through acid hydrolysis with sulfuric acid. A yield of 51-62 wt S4, ( co tt on basis) was obtained, and nearly all the polyester and acrylic libers contained in the initial fabrics were recovered in a convenient shape that could allow easier recycling. CNCs extracted from the selected fabrics showed high purity, similar structural, physical, and chemical characteristics, and their properties were comparable to those extracted from virgin sources, although their surface chemistry and elemental composition slightly differed. The chemical components in the waste fabrics and the extracted CNCs were evaluated through a nontarget chromatographic-mass spectrometric screening strategy. Both the recycled textiles and the CNCs contained hundreds of compounds common in postconsumer textiles, including some with health and environmental concerns. However, our initial findings show that their concentrations in the CNCs are negligible. Our results provide insights into the challenges associated with the use of cotton waste textiles for the extraction of cellulose nanoparticles, and into the potential applications of the extracted nanomaterials.

Keywords
textile waste, acid hydrolysis, cellulose nanocrystals, nontarget screening, polyester/cotton, acrylic/cotton, Green & Sustainable Science & Technology
National Category
Chemical Sciences Chemical Engineering
Identifiers
urn:nbn:se:su:diva-204544 (URN)10.1021/acssuschemeng.2c00797 (DOI)000778745000039 ()2-s2.0-85126764053 (Scopus ID)
Available from: 2022-05-10 Created: 2022-05-10 Last updated: 2024-07-04Bibliographically approved

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