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 logPand 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.Graphical abstract
Skin allergy is a chronic condition that affects about 20% of the population of the western world. This disease is caused by small reactive compounds, haptens, able to penetrate into the epidermis and modify endogenous proteins, thereby triggering an immunogenic reaction. Phenyl isothiocyanate (PITC) and ethyl isothiocyanate (EITC) have been suggested to be responsible for allergic skin reactions to chloroprene rubber, the main constituent of wetsuits, orthopedic braces, and many types of sports gear. In the present work we have studied the reactivity of the isothiocyanates PITC, EITC, and tetramethylrhodamine-6-isothiocyanate (6-TRITC) toward peptides under aqueous conditions at physiological pH to gain information about the types of immunogenic complexes these compounds may form in the skin. We found that all three compounds reacted quickly with cysteine moieties. For PITC and 6-TRITC the cysteine adducts decomposed over time, while stable adducts with lysine were formed. These experimental findings were verified by DFT calculations. Our results may suggest that the latter are responsible for allergic reactions to isothiocyanates. The initial adduct formation with cysteine residues may still be of great importance as it prevents hydrolysis and facilitates the transport of isothiocyanates into epidermis where they can form stable immunogenic complexes with lysine-containing proteins.
Background: Colophonium (rosin) can cause allergic contact dermatitis, mainly due to autoxidation of abietic acid (AbA). Products containing ≥0.1% colophonium should be labeled with EUH208 — “Contains rosin; colophony. May produce an allergic reaction.” How should this be measured?Objective: To compare the results from different strategies for estimating colophonium levels in consumer products: (a) from AbA, and (b) the sum of all major resin acids. To investigate the ratio of 7‐oxodehydroabietic acid (7‐O‐DeA)/AbA as indication of autoxidation.Methods: Resin acids were extracted from consumer products, derivatized, and then separated by gas chromatography/mass spectrometry (GC/MS).Results: Resin acids were detected in 9 of 15 products. No product contained colophonium ≥0.1%. Estimation based on AbA resulted in underestimation of the colophonium levels in four of nine products. For three products, the obtained levels from this strategy were only one of two compared to when estimating from the sum of all resin acids. The ratio 7‐O‐DeA/AbA varied from 74% to 1.4%.Conclusions: We propose to measure colophonium based on the sum of all detectable major resin acids, including 7‐O‐DeA. The ratio of 7‐O‐DeA/AbA should be used as a marker of autoxidation, indicating an increased risk of sensitization. The presented analytical method is simple to use and suitable for further screening studies.
11 January 2011 in Analytical and Bioanalytical Chemistry
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