Background: Textile chemicals may constitute a hazardous exposure and lead to skin sensitization or other health problems. Children, due to their thinner, less developed skin, are more susceptible to this exposure. Objectives: To investigate the occurrence and levels of 50 textile chemicals in childrens skin-close clothing. Further, to investigate the washout effect of these textile chemicals and their tendencies to migrate from the textile fibres into artificial sweat. Methods: Screening of 60 children's clothes purchased on the Swedish retail market was performed using coupled automated thermal desorption-gas chromatography/mass spectrometry (ATD-GC/MS). Results: Among the most frequently occurring chemicals were non-regulated quinolines, halogenated arylamines, phthalates, and nitrobenzenes. The highest concentrations were found for benzyl benzoate, 1400 mu g/g, and 2-bromo-4,6-dinitroaniline, 300 mu g/g. The highest number and levels of chemicals were detected in garments made of 100% polyester, while the fewest and lowest levels were determined in light-coloured cotton. Laundry experiments revealed that cotton garments had the greatest washout effect, whereas most of the chemical content remained in 100% polyester garments even after 10 laundry cycles. Conclusions: Results indicate a lower exposure from the investigated cotton garments, especially after laundry. On the other hand, cotton exhibited threefold greater chemical migration into artificial sweat than polyester. The strong dependence on fibre material is important to consider when estimating the bioaccessible chemical exposure from garments and related health risks.

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.

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.

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.

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.

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.

One of the main threats to the achievements in modern medicine is antimicrobial resistance. Molecular targeting of bacterial acquisition mechanisms of heme has been suggested to be an alternative to antibiotics. In the present study, HPLC-MS/MS combined with a simple clean-up based on liquid-liquid extraction has been developed and evaluated for simultaneous determination of heme and porphyrin heme precursors in microorganisms. Experimental design was used to optimize the extraction parameters, to obtain a method with high recovery, low matrix effects, and high precision. The effects of additives in the culture medium on the biosynthesis of heme were studied using Escherichia coli as a model microorganism. 5-Aminolaevulinic acid and hemin increased the heme concentration in E. coli by a factor of 1.5 and 4.5, respectively. Addition of 5-aminolaevulinic acid bypassed the E. coli negative feedback control of heme biosynthesis, which led to high amounts of intracellular porphyrins. The high heme concentration obtained when hemin was used as a culture additive shows that E. coli has an uptake of heme from its surroundings. In contrast, addition of cobalt protoporphyrin IX to the growth medium reduced the amount of heme in E. coli, demonstrating this compound’s ability to mimic real heme and inhibit the heme acquisition mechanisms.

Background: Increasing antibiotic resistance among pathogens has raised the demands for new treatment methods such as antimicrobial photodynamic therapy (aPDT) and phototherapy (PT). Experiments for investigating the effects of these methods are often performed in vitro, but the procedures for cultivation of microbes vary between different studies. The aim of this study has been to elucidate how the profile of endogenously produced porphyrins differs by changing the variables of bacteria culturing conditions.

Methods: Two oral pathogens, Aggregatibacter actinomycetemcomitans and Porphyromonasgingivalis, were selected as model organisms. The contents of porphyrins and heme in the bacteria were analysed with liquid chromatography-tandem mass spectrometry when bacteria was cultivated for different lengths of time (3-9 days), upon passaging as well as when growth medium were supplemented with or without horse blood.

Results: Both porphyrin and heme content in A. actinomycetemcomitans are highly affected by the age of the culture, and that the porphyrin profiles changes during cultivation. When cultivated colonies of A. actinomycetemcomitans were passaged onto a new, fresh growth medium a large change in porphyrin content occurred. Additional porphyrins were detected; uroporphyrin and 7-carboxylporphyrin, and the total porphyrin content increased up to 28 times, When P. gingivalis was grown on blood containing medium higher concentrations of protoporphyrin IX (2.5 times) and heme (5.4 times) were quantified compared to bacteria grown without blood.

Conclusions: This study demonstrate that there is a need for more standardized culturing protocols when performing aPDT and PT experiments in vitro to avoid large variations in porphyrin profiles and concentrations, the aPDT/PT target compounds, depending on the culturing conditions.

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.

In this study, the occurrence of nine phthalate diesters (phthalates) and 14 organophosphorus flame retardants (PFRs) was investigated in 62 house dust samples collected from 19 buildings in Stockholm area during the year 2008. Eight phthalates were detected in almost all samples, with median concentrations ranging from 0.47 mu g/g to 449 mu g/g with di(2-ethylhexyl)phthalate being the most abundant compound. Twelve PFRs were detected with median concentrations ranging from 0.19 mu g/g to 11 mu g/g. Within this class of compounds, the most abundant were tris(2-chloroisopropyl) and tris(2-butoxyethyl) phosphate. Both classes of compounds were also measured in the air of the apartments, but no correlation between air and dust concentrations could be found. Based on these measurements, exposure, via house dust ingestion and air inhalation, was calculated for adults and toddlers, and compared to published limit values in order to estimate potential health risks. In an extreme exposure scenario for toddlers, di(2-ethylhexyl) phthalate, tris (2-chloroethyl) phosphate, tris(2-butoxyethyl) phosphate, and tributyl phosphate were close to the reference dose for chronic oral exposure or the tolerable daily intake. Standard Reference Material SRM 2585 was used as a quality control sample, and the levels of diisononyl and diisodecyl phthalates were determined in this material.