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Textile Related Chemicals: Analytical Approaches Towards the Assessment of Human and Environmental Exposures
Stockholm University, Faculty of Science, Department of Environmental Science and Analytical Chemistry.ORCID iD: 0000-0002-9537-5512
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The textile manufacturing chain involves an extensive use of chemicals as early as fabric-production. To confer special features to textile materials, more chemicals are required in subsequent steps. Furthermore, potentially harmful substances can end up in clothes as transformation products. Compounds that are not covalently bonded to the fabrics have high probability to be released on the skin or into the environment when the clothes are worn or laundered.

In order to remove interfering compounds from solvent extracts of investigated textiles, a cleanup step based on solid phase extraction using graphitic carbon black was developed resulting in effective dye removal. In a pilot screening, nitroanilines were detected up to 0.57 mg/g, which was 2-3 order of magnitude higher than measured quinolines.

Human exposure to chemicals can occur through skin contact. Benzothiazole was chosen as model compound for in-vitro experiments. Its permeation was experimentally determined in order to estimate dermal exposure. Carcinogenic and non-carcinogenic risks, associated to wearing t-shirt containing BT, according to international standards, were found to be below the acceptable exposure levels.

It has been shown that chemical concentrations decreased during domestic washing. A procedure was developed for enrichment and clean-up of textile related compounds from water samples. The method was applied to three wastewater treatment plant effluents located in Stockholm. Tolyltriazole, 1-benzotriazole, and UV-P were detected within the range of 53-1148 ng/L.

Suspect and non-target screening methodology was developed do detect and identify substances in textile materials. The occurrence of thirteen suspect compounds, belonging to quinolines, nitroanilines, benzotriazoles, benzothiazoles and phthalates, was confirmed through suspect analysis approach. Furthermore, using a non-target screening approach, compounds not included in the suspect list such as nitrophenols, organophosphate and acridine were identified.

In order to remove interfering compounds from the textile extracts, a cleanup step based on solid phase extraction using graphitic carbon black was developed resulting in effective dye removal. In a pilot screening, nitroanilines were detected up to 0.57 mg/g, which was 2-3 times higher than measured quinolines.

Human exposure to chemicals can occur through skin contact. Benzothiazole was chosen as model compound for in-vitro experiments. Its permeation was experimentally determined in order to estimate dermal exposure. Carcinogenic and non-carcinogenic risks, associated to wearing t-shirt containing BT, according to international standards, were found to be below the acceptable exposure levels.

It has been shown that chemical concentrations decreased during domestic washing. A procedure was developed for enrichment and clean-up of textile related compounds from water samples. The method was applied to three wastewater treatment plant effluents located in Stockholm. Tolyltriazole, 1-benzotriazole, and UV-P were detected within the range of 53-1148 ng/L.  

Suspect and non-target screening methodology was developed do detect and identify substances in textile materials. The occurrence of thirteen suspect compounds, belonging to quinolines, nitroanilines, benzotriazoles, benzothiazoles and phthalates, was confirmed through suspect approach. Furthermore, using a non-target screening approach, compounds not included in suspect list such as nitrophenols, organophosphate and acridine were identified.

Place, publisher, year, edition, pages
Stockholm: Department of Environmental Science and Analytical Chemistry, Stockholm University , 2019. , p. 75
Keywords [en]
graphitized carbon black- GCB, franz cell, diffusion cell, risk assessment, screening, textile
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
URN: urn:nbn:se:su:diva-175503ISBN: 978-91-7797-877-0 (print)ISBN: 978-91-7797-878-7 (electronic)OAI: oai:DiVA.org:su-175503DiVA, id: diva2:1368246
Public defence
2019-12-20, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Manuscript.

Lipidor AB, Solna, Sweden, co-financed this PhD study by 20%  ​

Available from: 2019-11-27 Created: 2019-11-06 Last updated: 2019-11-20Bibliographically approved
List of papers
1. Determination of aniline and quinoline compounds in textiles
Open this publication in new window or tab >>Determination of aniline and quinoline compounds in textiles
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2016 (English)In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1471, p. 11-18Article in journal (Refereed) Published
Abstract [en]

A simple method for simultaneous determination of twenty-one analytes, belonging to two classes of compounds, aromatic amines and quinolines, is presented. Several of the analytes considered in this study frequently occur in textiles goods on the open market and have been related to allergic contact dermatitis and/or are proven or suspected carcinogens. The method includes an efficient clean-up step using graphitized carbon black (GCB) that simplifies and improves the robustness of the subsequent GC-MS analysis. Briefly, after solvent extraction of the textile sample, the extract is passed through a GCB SPE cartridge that selectively retain dyes and other interfering compounds present in the matrix, producing a clean extract, suitable for GC-MS analysis, is obtained. The method was evaluated by spiking blank textiles with the selected analytes. Method quantification limits (MQL) ranged from 5 to 720 ng/g depending on the analyte. The linear range of the calibration curves ranged over two order magnitude with coefficients of determination (R-2) higher than 0.99. Recoveries ranged from 70 to 92% with RSDs 1.7-14%. The effectiveness of the method was tested on a variety of textile materials samples from different origin. In a pilot explorative survey, 2,6-dichloro-4-nitroaniline was detected in all the analysed clothing samples in concentrations ranging from 1.0 to 576 mu g/g 2,4-dinitroaniline was detected in four of the seven samples with a highest concentration of 305 mu g/g Quinoline was detected in all samples in concentrations ranging from 0.06 to 6.2 mu g/g. (C) 2016 Elsevier B.V. All rights reserved.

Keywords
Aromatic amines, Anilines, Quinolines, Graphitized carbon black column, chromatography, Clothing textiles, Allergenic compounds
National Category
Analytical Chemistry Biological Sciences
Identifiers
urn:nbn:se:su:diva-136748 (URN)10.1016/j.chroma.2016.09.068 (DOI)000387520400002 ()
Available from: 2016-12-14 Created: 2016-12-14 Last updated: 2019-11-06Bibliographically approved
2. Chemicals from textiles to skin: an in vitro permeation study of benzothiazole
Open this publication in new window or tab >>Chemicals from textiles to skin: an in vitro permeation study of benzothiazole
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2018 (English)In: Environmental science and pollution research international, ISSN 0944-1344, E-ISSN 1614-7499, Vol. 25, no 25, p. 24629-24638Article in journal (Refereed) Published
Abstract [en]

Despite the possible impact on human health, few studies have been conducted to assess the penetration and accumulation of contaminants in the skin after a prolonged contact with textile materials. In previous studies, we have shown that benzothiazole and its derivatives, as well as other potentially hazardous chemicals, often are present as textile contaminants in clothes available on the retail market. Since benzothiazole is a common contaminant in clothes, these can be a possible route for human chemical exposure, both systemic and onto the skin. To investigate this potential exposure, Franz-type and flow-through cells were used for the permeation studies together with a Strat-MA (R) artificial membranes. Experiments were performed using solutions of benzothiazole, as well as contaminated textile samples in the donor chamber. Benzothiazole was demonstrated to penetrate through, as well as being accumulated in the membrane mimicking the skin. After 24 h, up to 62% of benzothiazole was found in the acceptor cell, while up to 37% was found absorbed in the skin mimicking membrane. It also was shown that there was release and permeation from contaminated fabrics. The results indicate that benzothiazole can be released from textile materials, penetrate through the skin, and further enter the human body. This will possibly also apply to other chemical contaminants in textiles, and the results of this study indicate that the presence of these textile contaminants entails potential health risks. A rough risk assessment was made for clothing textiles according to Environmental Protection Agency (EPA) and European regulations for carcinogenic and non-carcinogenic compounds, using literature data for benzothiazole.

Keywords
Benzothiazole, Permeation study, Textiles, Clothes, Franz cell, Flow-through diffusion cell, Strat-M (R), Dermal exposure, Risk assessment
National Category
Earth and Related Environmental Sciences
Identifiers
urn:nbn:se:su:diva-160231 (URN)10.1007/s11356-018-2448-6 (DOI)000443012600010 ()29911295 (PubMedID)
Available from: 2018-09-20 Created: 2018-09-20 Last updated: 2019-11-06Bibliographically approved
3. Determination of Textile Related Compounds (Benzothiazole, Benzotriazole, Nitroaniline, Quinoline and some Derivatives) in Wastewater
Open this publication in new window or tab >>Determination of Textile Related Compounds (Benzothiazole, Benzotriazole, Nitroaniline, Quinoline and some Derivatives) in Wastewater
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

Manufacturing of textile consumer goods involve a multitude of chemicals during the entire production chain. In order to investigate the release of harmful compounds from the end products, a sensitive and robust multicomponent procedure for the analysis of three classes of textile related chemicals in aqueous matrices has been developed. The method involves solid phase extraction (SPE) using a graphitized carbon black (GCB) sorbent, followed by GC-MS or LC-MS/MS analysis. The described method can be used to monitor thirty-two selected compounds in waste water. Several of these analytes are regulated by the European Union (REACH) due to their carcinogenic and/or mutagenic properties. After sampling on SPE, three different compound classes are desorbed and analyzed using different chromatographic conditions. The use of GCB provided quantitative and reproducible recoveries of the selected compounds and a cleanup of the wastewater sample. The procedure was evaluated using wastewater sample matrices. Finally, the method was applied in a pilot study to investigate the occurrence of these classes of analytes in the effluent of three different wastewater treatment plants in the Stockholm area. 

Keywords
Textile chemicals, wastewater, LC/MS, GC/MS, SPE, GCB
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-175507 (URN)
Available from: 2019-11-06 Created: 2019-11-06 Last updated: 2019-11-06Bibliographically approved
4. Strategies Towards Suspect and Non-target Screening of Chemicals in Clothing Textiles by Reverse Phase Liquid Chromatography–hybrid Linear Ion Trap Orbitrap Mass Spectrometry
Open this publication in new window or tab >>Strategies Towards Suspect and Non-target Screening of Chemicals in Clothing Textiles by Reverse Phase Liquid Chromatography–hybrid Linear Ion Trap Orbitrap Mass Spectrometry
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

Textile industry uses a large number of various chemicals in the multi-step production chain. Some of these chemicals are intentionally used to give specific features to textile materials (softness, color, improve fastness, flame resistant etc.). Some other are unintentionally added, such us transformation products (e.g. dye degradation production), impurities of other used compounds and/or biocides. Due to the large number of cloths manufacturing steps, starting from fabric production to clothes trade, information regarding the chemicals used are not always available. Clothes are in close and prolonged contact with the skin, making possible a human exposure to chemicals present in textile material. Furthermore, chemicals, if not removed from wastewater treatment plants, can be released in the environment through the laundry of textile materials. In the present study, reverse phase liquid chromatography coupled to high resolution mass spectrometry was used for screening of suspect and unknown compounds in twenty-four textile samples. Strategies towards suspect and non-target screening are discussed considering the experimental conditions and the subsequent data treatment. Suspect compounds belonging to benzotriazoles, benzothiazoles, nitroanilines, quinolines and phthalates were confirmed in the analyzed samples. The method was able also to successfully identify compounds not included in the suspect list, such as nitrophenols, acridine, and phosphates.

Keywords
Textile chemicals, suspect screening, non target screening, orbitrap, strategies
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-175508 (URN)
Note

Available from: 2019-11-06 Created: 2019-11-06 Last updated: 2019-11-06Bibliographically approved

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23456786 of 8
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