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Åström, T., Östman, C., Nilsson, U., Sadiktsis, I. & Ruiz-Caldas, M.-X. (2025). Automated thermal desorption-gas chromatography/mass spectrometry for screening of hazardous chemicals in cotton and cotton blend garments – analytical challenges. Analytical and Bioanalytical Chemistry
Open this publication in new window or tab >>Automated thermal desorption-gas chromatography/mass spectrometry for screening of hazardous chemicals in cotton and cotton blend garments – analytical challenges
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2025 (English)In: Analytical and Bioanalytical Chemistry, ISSN 1618-2642, E-ISSN 1618-2650Article in journal (Refereed) Published
Abstract [en]

The global production of textiles involves large amounts of health-hazardous chemicals, constituting possible health risks since residues usually remain in the finished garments. An analytical method based on automated thermal desorption (ATD) coupled online to GC/MS for screening of several classes of toxic chemicals in synthetic garments was recently published by us. In the present study, the ATD-GC/MS methodology is further extended to cotton and cotton blend materials. 

Different textile materials with a high content of cotton were found to exhibit large variations in adsorption strength for many chemicals frequently detected in textiles. This was shown to influence the thermal desorption efficiency strongly in ATD-GC/MS. By using absolute response factors from appropriate internal standards spiked directly onto the textile samples, the effects of these differences could be minimized. In this way, accurate quantification was made possible regardless of textile composition, and quantification of native textile chemicals in garments made with the ATD-GC/MS method agreed well with an offline method based on solvent extraction and GC/MS analysis.

The ATD-GC/MS method has now been shown to be applicable for quantitative screening of around 75% of [UN1] [TÅ2] all the textiles on the retail market. The simplified quantification method makes it suitable for screening many samples. For all textile chemicals and fibre materials investigated, the method limits of detection, using only 20 mg of textile, is at least 100 times lower than the current EU regulation for quinoline and several toxic arylamines.

Keywords
Thermal desorption, Cotton analysis, Textile analysis, Quantification
National Category
Analytical Chemistry Textile, Rubber and Polymeric Materials
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-241995 (URN)10.1007/s00216-025-05993-y (DOI)001524906100001 ()2-s2.0-105010044742 (Scopus ID)
Funder
Mistra - The Swedish Foundation for Strategic Environmental Research, 2018/11
Available from: 2025-04-11 Created: 2025-04-11 Last updated: 2025-08-11
Carlsson, J., Dostberg, A., Åström, T., Matyjasiak, J., Kallin, A., Juric, S. & Nilsson, U. (2024). Health risks from exposure to chemicals in clothing - non-regulated halogenated aromatic compounds. Chemosphere, 363, Article ID 142930.
Open this publication in new window or tab >>Health risks from exposure to chemicals in clothing - non-regulated halogenated aromatic compounds
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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: 2025-04-11Bibliographically approved
Åström, T., Ruiz-Caldas, M.-X., Skedung, L., Chelcea, I., Nilsson, C., Mathew, A. P., . . . Nilsson, U. (2024). The fate of hazardous textile pollutants in an upcycling process for post-consumer garments. Cleaner Engineering and Technology, 22, Article ID 100794.
Open this publication in new window or tab >>The fate of hazardous textile pollutants in an upcycling process for post-consumer garments
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2024 (English)In: Cleaner Engineering and Technology, ISSN 2666-7908, Vol. 22, article id 100794Article in journal (Refereed) Published
Abstract [en]

The environmental impact is a strong incentive for the development of upcycling processes for textile waste. However, toxic chemicals may occur in both brand-new textiles and post-consumer garments, and the chemical transfer in such routes is important to investigate. The present study applied non-target screening and quantification with liquid chromatography/mass spectrometry to follow the fate of hazardous chemicals from post-consumer polycotton garments to a new material, cellulose nanocrystals, in a chemical upcycling utilizing strongly acidic conditions. The majority of hazardous chemicals detected within the process were found to be transferred to a residual of polyester material and not to the enriched cellulose. However, phthalates were found to be mainly attached to the cellulose nanocrystals. The detected total concentration, in this case, was below 5 μg/g, at least 200 times lower than the limit set by the European Union. This indicates the importance of monitoring and controlling the phthalate content in the starting material of the process, i.e., the post-consumer garments. The chemical release into the process waste effluent could be estimated based on water solubility data for chemicals under the applied conditions. Three compounds, the water-repellent substance perfluorooctanesulfonic acid and the dyes Crystal Violet and Victoria Pure Blue, were almost entirely transferred into the process waste effluent. Although the levels detected were very low in the present pilot process, their presence eventually indicates the need for wastewater purification at further upscaling, depending on the exposure and dose in relation to toxicological relevant thresholds.

Keywords
Cellulose nanocrystals, Chemical upcycling, Hazard ranking, Non-target screening, Polycotton, Textile chemicals
National Category
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-237678 (URN)10.1016/j.clet.2024.100794 (DOI)001301184100001 ()2-s2.0-85201782572 (Scopus ID)
Available from: 2025-01-10 Created: 2025-01-10 Last updated: 2025-10-03Bibliographically approved
Carlsson, J., Åström, T., Östman, C. & Nilsson, U. (2023). Solvent-free automated thermal desorption-gas chromatography/mass spectrometry for direct screening of hazardous compounds in consumer textiles. Analytical and Bioanalytical Chemistry, 415(19), 4675-4687
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: 2025-04-11Bibliographically approved
Clark, E., Nilsson, U., Samaran, Q. & Raison-Peyron, N. (2022). Allergic contact dermatitis from Cannabis sativa (hemp) seed oil. Contact Dermatitis, 87(3), 292-293
Open this publication in new window or tab >>Allergic contact dermatitis from Cannabis sativa (hemp) seed oil
2022 (English)In: Contact Dermatitis, ISSN 0105-1873, E-ISSN 1600-0536, Vol. 87, no 3, p. 292-293Article in journal, Editorial material (Other academic) Published
Keywords
allergic contact dermatitis, Cannabis sativa L, caryophyllene, CAS 89958-21-4, case report, cosmetics, hemp seed oil, plant, terpenes
National Category
Dermatology and Venereal Diseases
Identifiers
urn:nbn:se:su:diva-206330 (URN)10.1111/cod.14142 (DOI)000796873600001 ()35514096 (PubMedID)2-s2.0-85130231022 (Scopus ID)
Available from: 2022-06-21 Created: 2022-06-21 Last updated: 2022-09-24Bibliographically approved
Ruiz-Caldas, M.-X., Carlsson, J., Sadiktsis, I., Jaworski, A., Nilsson, U. & Mathew, A. P. (2022). Cellulose Nanocrystals from Postconsumer Cotton and Blended Fabrics: A Study on Their Properties, Chemical Composition, and Process Efficiency. ACS Sustainable Chemistry and Engineering, 10(11), 3787-3798
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
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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
Lim, H., Silvergren, S., Spinicci, S., Rad, F. M., Nilsson, U., Westerholm, R. & Johansson, C. (2022). Contribution of wood burning to exposures of PAHs and oxy-PAHs in Eastern Sweden. Atmospheric Chemistry And Physics, 22(17), 11359-11379
Open this publication in new window or tab >>Contribution of wood burning to exposures of PAHs and oxy-PAHs in Eastern Sweden
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2022 (English)In: Atmospheric Chemistry And Physics, ISSN 1680-7316, E-ISSN 1680-7324, Vol. 22, no 17, p. 11359-11379Article in journal (Refereed) Published
Abstract [en]

A growing trend in developed countries is the use of wood as fuel for domestic heating due to measures taken to reduce the usage of fossil fuels. However, this imposed another issue with the environment and human health. That is, the emission from wood burning contributed to the increased level of atmospheric particulates and the wood smoke caused various respiratory diseases. The aim of this study was to investigate the impact of wood burning on the polycyclic aromatic hydrocarbons (PAHs) in air PM10 using known wood burning tracers, i.e. levoglucosan, mannosan and galactosan from the measurement at the urban background and residential areas in Sweden. A yearly measurement from three residential areas in Sweden showed a clear seasonal variation of PAHs during the cold season mainly from increased domestic heating and meteorology. Together, an increased sugar level assured the wood burning during the same period. The sugar ratio (levoglucosan(mannosan+galactosan)) was a good marker for wood burning source such as the wood type used for domestic heating and garden waste burning. On the Walpurgis Night, the urban background measurement demonstrated a dramatic increase in levoglucosan, benzo[a]pyrene (B[a]P) and oxygenated PAHs (OPAHs) concentrations from the increased wood burning. A significant correlation between levoglucosan and OPAHs was observed suggesting OPAHs to be an indicator of wood burning together with levoglucosan. The levoglucosan tracer method and modelling used in predicting the B[a]P concentration could not fully explain the measured levels in the cold season. The model showed that the local wood source contributed to 98 % of B[a]P emissions in the Stockholm area and 2 % from the local traffic. However, non-local sources were dominating in the urban background (60 %). A further risk assessment estimated that the airborne particulate PAHs caused 13.4 cancer cases per 0.1 million inhabitants in Stockholm County.

National Category
Earth and Related Environmental Sciences
Identifiers
urn:nbn:se:su:diva-209457 (URN)10.5194/acp-22-11359-2022 (DOI)000849846400001 ()
Available from: 2022-09-19 Created: 2022-09-19 Last updated: 2025-02-07Bibliographically approved
Zurita, J., Motwani, H. V., Ilag, L. L., Souliotis, V. L., Kyrtopoulos, S. A., Nilsson, U. & Törnqvist, M. (2022). Detection of Benzo[a]pyrene Diol Epoxide Adducts to Histidine and Lysine in Serum Albumin In Vivo by High-Resolution-Tandem Mass Spectrometry. Toxics, 10(1), Article ID 27.
Open this publication in new window or tab >>Detection of Benzo[a]pyrene Diol Epoxide Adducts to Histidine and Lysine in Serum Albumin In Vivo by High-Resolution-Tandem Mass Spectrometry
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2022 (English)In: Toxics, E-ISSN 2305-6304, Vol. 10, no 1, article id 27Article in journal (Refereed) Published
Abstract [en]

Electrophilic diol epoxide metabolites are involved in the carcinogenicity of benzo[a]pyrene, one of the widely studied polycyclic aromatic hydrocarbons (PAHs). The exposure of humans to this PAH can be assessed by measuring stable blood protein adducts, such as to histidine and lysine in serum albumin, from their reactive metabolites. In this respect, measurement of the adducts originating from the genotoxic (+)-anti-benzo[a]pyrene diol epoxide is of interest. However, these are difficult to measure at such low levels as are expected in humans generally exposed to benzo[a]pyrene from air pollution and the diet. The analytical methods detecting PAH-biomarkers still suffer from low selectivity and/or detectability to enable generation of data for calculation of in vivo doses of specific stereoisomers, for evaluation of risk factors and assessing risk from exposures to PAH. Here, we suggest an analytical methodology based on high-pressure liquid chromatography (HPLC) coupled to high-resolution tandem mass spectrometry (MS) to lower the detection limits as well as to increase the selectivity with improvements in both chromatographic separation and mass determination. Method development was performed using serum albumin alkylated in vitro by benzo[a]pyrene diol epoxide isomers. The (+)-anti-benzo[a]pyrene diol epoxide adducts could be chromatographically resolved by using an HPLC column with a pentafluorophenyl stationary phase. Interferences were further diminished by the high mass accuracy and resolving power of Orbitrap MS. The achieved method detection limit for the (+)-anti-benzo[a]pyrene diol epoxide adduct to histidine was approximately 4 amol/mg serum albumin. This adduct as well as the adducts to histidine from (−)-anti- and (+/−)-syn-benzo[a]pyrene diol epoxide were quantified in the samples from benzo[a]pyrene-exposed mice. Corresponding adducts to lysine were also quantified. In human serum albumin, the anti-benzo[a]pyrene diol epoxide adducts to histidine were detected in only two out of twelve samples and at a level of approximately 0.1 fmol/mg.

Keywords
polycyclic aromatic hydrocarbons, metabolism, liquid chromatography-mass spectrometry, protein adducts, human exposure
National Category
Earth and Related Environmental Sciences Chemical Sciences Pharmacology and Toxicology
Identifiers
urn:nbn:se:su:diva-202029 (URN)10.3390/toxics10010027 (DOI)000746177400001 ()35051069 (PubMedID)
Available from: 2022-02-10 Created: 2022-02-10 Last updated: 2025-01-31Bibliographically approved
Carlsson, J., Åström, T., Östman, C. & Nilsson, U. (2022). Disperse azo dyes, arylamines and halogenated dinitrobenzene compounds in synthetic garments on the Swedish market. Contact Dermatitis, 87(4), 315-324
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: 2025-04-11Bibliographically approved
Carlsson, J., Iadaresta, F., Eklund, J., Avagyan, R., Östman, C. & Nilsson, U. (2021). Suspect and non-target screening of chemicals in clothing textiles by reversed-phase liquid chromatography/hybrid quadrupole-Orbitrap mass spectrometry. Analytical and Bioanalytical Chemistry, 414(3), 1403-1413
Open this publication in new window or tab >>Suspect and non-target screening of chemicals in clothing textiles by reversed-phase liquid chromatography/hybrid quadrupole-Orbitrap mass spectrometry
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2021 (English)In: Analytical and Bioanalytical Chemistry, ISSN 1618-2642, E-ISSN 1618-2650, Vol. 414, no 3, p. 1403-1413Article in journal (Refereed) Published
Abstract [en]

The global manufacturing of clothing is usually composed of multistep processes, which include a large number of chemicals. However, there is generally no information regarding the chemical content remaining in the finished clothes. Clothes in close and prolonged skin contact may thus be a significant source of daily human exposure to hazardous compounds depending on their ability to migrate from the textiles and be absorbed by the skin. In the present study, twenty-four imported garments on the Swedish market were investigated with respect to their content of organic compounds, using a screening workflow. Reversed-phase liquid chromatography coupled to electrospray ionization/high-resolution mass spectrometry was used for both suspect and non-target screening. The most frequently detected compound was benzothiazole followed by quinoline. Nitroanilines with suspected mutagenic and possible skin sensitization properties, and quinoline, a carcinogenic compound, were among the compounds occurring at the highest concentrations. In some garments, the level of quinoline was estimated to be close to or higher than 50,000 ng/g, the limit set by the REACH regulation. Other detected compounds were acridine, benzotriazoles, benzothiazoles, phthalates, nitrophenols, and organophosphates. Several of the identified compounds have logP and molecular weight values enabling skin uptake. This pilot study indicates which chemicals and compound classes should be prioritized for future quantitative surveys and control of the chemical content in clothing as well as research on skin transfer, skin absorption, and systemic exposure. The results also show that the current control and prevention from chemicals in imported garments on the Swedish market is insufficient.

Keywords
Textile chemicals, Suspect screening, Non-target screening, LC/MS, High-resolution MS, Orbitrap MS
National Category
Chemical Sciences Earth and Related Environmental Sciences
Identifiers
urn:nbn:se:su:diva-199511 (URN)10.1007/s00216-021-03766-x (DOI)000719180700001 ()34786606 (PubMedID)
Available from: 2021-12-13 Created: 2021-12-13 Last updated: 2025-01-31Bibliographically approved
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Identifiers
ORCID iD: ORCID iD iconorcid.org/0000-0002-2981-3617

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