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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 µg/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 µg/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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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-M® 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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

In two previous papers, the authors have shown that benzothiazole, benzotriazole, quinoline, and several of their derivatives are widespread in clothing textile articles. A number of these compounds exhibit allergenic and irritating properties and, due to their octanol-water partition coefficient, are prone to be absorbed by the skin. Moreover, they are slightly soluble in water, which could make washing of clothes a route of emission into the environment. In the present study, the washout effect of benzothiazole, benzotriazole, quinoline, and some of their derivatives has been investigated. Twenty-seven textile samples were analyzed before, as well as after five and ten times of washing. The most abundant analyte was found to be benzothiazole, which was detected in 85 % of the samples with an average concentration of 0.53 μg/g (median 0.44 μg/g), followed by quinoline, detected in 81 % of the samples with an average concentration of 2.42 μg/g (median 0.21 μg/g). The average decrease in concentration for benzothiazoles was 50 % after ten times washing, while it was around 20 % for quinolines. The average emission to household wastewater of benzothiazoles and quinolines during one washing (5 kg of clothes made from polyester materials) was calculated to 0.5 and 0.24 g, respectively. These results strongly indicate that laundering of clothing textiles can be an important source of release of these compounds to household wastewater and in the end to aquatic environments. It also demonstrates a potential source of human exposure to these chemicals since considerable amounts of the compounds remain in the clothes even after ten times of washing. [ABSTRACT FROM AUTHOR]

Biofilms in the oral cavity can be visualized by fluorescence and a common assumption is that the endogenously produced porphyrins in certain bacteria give rise to this fluorescence. Porphyrin content in oral bacteria has been sparingly investigated, and non-selective detection techniques such as utilizing the Soret fluorescence band of porphyrins are often used. In the present study, a quantitative and selective method for the determination of porphyrins in oral bacteria has been developed and validated using high performance liquid chromatography-tandem mass spectrometry. Lysis of bacteria using Tris-EDTA buffer together with ultrasonication showed high microbial killing efficiency ≥99.98 %, and sample clean-up using C-solid phase extraction resulted in low matrix effects ≤14 % for all analytes. Using this method, the porphyrin content was determined in the two oral pathogens Aggregatibacter actinomycetemcomitans and Porphyromonas gingivalis, as well as for baker's yeast, Saccharomyces cerevisiae. Uroporphyrin, 7-carboxylporphyrin, 6-carboxylporphyrin, coproporphyrin, and protoporphyrin IX were identified in the investigated microorganisms, and it was shown that the porphyrin profile differs between the two bacteria, as well as for S. cerevisiae. To our knowledge, this is the first time the porphyrin profile has been determined for the bacterium A. actinomycetemcomitans. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Textiles play an important role in our daily life, and textile production is one of the oldest industries. In the manufacturing chain from natural and/or synthetic fibers to the final clothing products, the use of many different chemicals is ubiquitous. A lot of research has focused on chemicals in textile wastewater, but the knowledge of the actual content of harmful chemicals in clothes sold on the retail market is limited. In this paper, we have focused on eight benzothiazole and benzotriazole derivatives, compounds rated as high production volume chemicals. Twenty-six clothing samples of various textile materials and colors manufactured in 14 different countries were analyzed in textile clothing using liquid chromatography tandem mass spectrometry. Among the investigated textile products, 11 clothes were for babies, toddlers, and children. Eight of the 11 compounds included in the investigation were detected in the textiles. Benzothiazole was present in 23 of 26 investigated garments in concentrations ranging from 0.45 to 51 μg/g textile. The garment with the highest concentration of benzothiazole contained a total amount of 8.3 mg of the chemical. The third highest concentration of benzothiazole (22 μg/g) was detected in a baby body made from 'organic cotton' equipped with the 'Nordic Ecolabel' ('Svanenmärkt'). It was also found that concentrations of benzothiazoles in general were much higher than those for benzotriazoles. This study implicates that clothing textiles can be a possible route for human exposure to harmful chemicals by skin contact, as well as being a potential source of environmental pollutants via laundering and release to household wastewater. [ABSTRACT FROM AUTHOR]

A production process in which the use of various types of chemicals seems to be ubiquitous makes the textile industry a growing problem regarding both public health as well as the environment. Among several substances used at each stage, the present study focuses on the quinolines, a class of compounds involved in the manufacture of dyes, some of which are skin irritants and/or classified as probable human carcinogens. A method was developed for the determination of quinoline derivatives in textile materials comprising ultrasound-assisted solvent extraction, solid phase extraction cleanup, and final analysis by gas chromatography/mass spectrometry. Quinoline and ten quinoline derivatives were determined in 31 textile samples. The clothing samples, diverse in color, material, brand, country of manufacture, and price, and intended for a broad market, were purchased from different shops in Stockholm, Sweden. Quinoline, a possible human carcinogen, was found to be the most abundant compound present in almost all of the samples investigated, reaching a level of 1.9 mg in a single garment, and it was found that quinoline and its derivatives were mainly correlated to polyester material. This study points out the importance of screening textiles with nontarget analysis to investigate the presence of chemicals in an unbiased manner. Focus should be primarily on clothing worn close to the body. [ABSTRACT FROM AUTHOR]

The levels of 22 phthalate diesters (phthalates) and organophosphate triesters (organophosphates) have been investigated in standard reference material 2585 (SRM 2585) 'organic contaminants in house dust.' Ultrasonic-assisted solvent extraction and solid-phase extraction on a Florisil adsorbent were used as the extraction and cleanup steps combined with analysis using gas chromatography-tandem mass spectrometry in positive ion chemical ionization mode. Seven phthalates were detected in the concentration range 1-570 μg/g. Di(2-ethylhexyl) phthalate was the major phthalate present at 570 μg/g. Ten organophosphates were detected in SRM 2585. Tris(2-butoxyethyl) phosphate was the predominant organophosphate at 82 μg/g, and nine organophosphates were determined at concentrations ranging from 0.19 to 2.3 μg/g. Five organophosphates were below the method detection limit, of which two were in level with the procedural blank. The applied extraction and cleanup method was evaluated for the analysis of SRM 2585. The extraction yield was ≥99%, except for tris(2-chloroethyl) phosphate (97%) and diethyl phthalate (98.5%). The problem of calibration curvature is addressed, and it is shown that the use of deuterated standards improves the analysis. The concentrations of ten organophosphate esters were determined in SRM 2585, and seven of these were compared with existing data. To our knowledge, this is the first report of the levels of the seven phthalates esters in SRM 2585 'organic contaminants in house dust.' [ABSTRACT FROM AUTHOR]

An extensive study has been conducted on the prevalence of organophosphorous flame retardants/plasticizers and phthalate ester plasticizers in indoor air. The targeted substances were measured in 45 multi-storey apartment buildings in Stockholm, Sweden. The apartment buildings were classified as high or low risk with regard to the reporting of sick building symptoms (SBS) within the project Healthy Sustainable Houses in Stockholm (3H). Air samples were taken from two to four apartments per building (in total 169 apartments) to facilitate comparison within and between buildings. Association with building characteristics has been examined as well as association with specific sources by combining chemical analysis and exploratory uni- and multivariate data analysis. The study contributes to the overall perspective of levels of organophosphate and phthalate ester in indoor air enabling comparison with other studies. The results indicated little or no difference in the concentrations of the target substances between the two risk classifications of the buildings. The differences between the apartments sampled within (intra) buildings were greater than the differences between (inter) buildings. The concentrations measured in air ranged up to 1200 ng m−3for organophosphate esters and up to 11 000 ng m−3for phthalate esters. Results in terms of sources were discerned e.g.PVC flooring is a major source of benzylbutyl phthalate in indoor air. [ABSTRACT FROM AUTHOR]

The monitoring of radioactive xenon isotopes is one of the principal methods for the detection of nuclear explosions in order to identify clandestine nuclear testing. In this work, a miniaturized, multiple-oven, six-column, preparative gas chromatograph was constructed in order to isolate trace quantities of radioactive xenon isotopes from ambient air, utilizing nitrogen as the carrier gas. The multidimensional chromatograph comprised preparative stainless steel columns packed with molecular sieves, activated carbon, and synthetic carbon adsorbents (e.g., Anasorb®-747 and Carbosphere®). A combination of purification techniques-ambient adsorption, thermal desorption, back-flushing, thermal focusing, and heart cutting-was selectively optimized to produce a well-defined xenon peak that facilitated reproducible heart cutting and accurate quantification. The chromatographic purification of a sample requires approximately 4 h and provides complete separation of xenon from potentially interfering components (such as water vapor, methane, carbon dioxide, and radon) with recovery and accuracy close to 100%. The preparative enrichment process isolates and concentrates a highly purified xenon gas fraction that is suitable for subsequent ultra-low-level γ-, ß/γ-spectroscopic or high-resolution mass spectrometric measurement (e.g., to monitor the gaseous fission products of nuclear explosions at remote locations). The Xenon Processing Unit is a free-standing, relatively lightweight, and transportable system that can be interfaced to a variety of sampling and detection systems. It has a relatively inexpensive, rugged, and compact modular (19-inch rack) design that provides easy access to all parts for maintenance and has a low power requirement. [ABSTRACT FROM AUTHOR]

Organophosphate esters (OPEs), utilized as flame retarding agents and/or plasticizers, are almost ubiquitous in environmental compartments, and biota and foods could be contaminated by bioaccumulation or during the treatment processes. A multiresidue method is proposed for the determination of 13 OPEs in fish tissues: analytes were simultaneously extracted and purified using the matrix solid phase dispersion technique and then determined by gas chromatography with nitrogen–phosphorus detection. The main parameters affecting extraction yield and selectivity, such as the type of dispersant material, clean-up co-sorbent, rinse and elution solvents, were evaluated to obtain lipid-free extracts and quantitative recoveries for OPEs. Under optimal conditions, 0.5 g of samples was dispersed with 2 g Florisil and 1 g anhydrous sodium sulphate and transferred to a solid phase extraction cartridge containing 1 g alumina. The lipids were removed using 5 mL n-hexane/dichloromethane (1:1) and analytes were recovered with 10 mL n-hexane/acetone (6:4) and directly analysed. The method developed provided recoveries between 70 and 110% for different kinds of fish, and the day-to-day variability was between 1 and 9%. This procedure constitutes the first analytical method for the analysis of OPEs in a food matrix and it is applicable to analyse a large number of samples to evaluate the occurrence and sources of OPEs in biota and foods. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

A method has been developed for determination of polycyclic aromatic hydrocarbons (PAH) in particulate matter from ambient air and diesel exhaust emissions. It is reproducible and accurate and, compared with similar methods for analysis of individual PAH components in complex matrices, it is relatively fast and simple. Single PAH components can be determined in samples of particulate matter from ambient air and diesel exhaust emissions with LOD of approximately 1 pg/sample. Further, sample throughput is high, because more than 20 samples can be extracted and prepared for analysis in one working (8-h) day. The particulate matter is subjected to ultrasound-assisted extraction, a technique that is shown to extract PAH from particulate material with efficiencies fully comparable with those of Soxhlet extraction. An aliphatic/PAH-enriched fraction is obtained by solid-phase extraction before isolation, separation, and identification/quantification of PAH by on-line liquid chromatography-gas chromatography-mass spectrometry. The method was validated by analysis of US National Institute of Standards and Technology (NIST) Standard Reference Materials (SRM) 1649a, Urban Dust, and 2975, Diesel Particulate Matter. Results from the method are in good agreement with the NIST-certified PAH concentrations and with NIST reference PAH concentrations. [ABSTRACT FROM AUTHOR]

Certain human biotransformation enzymes have been implicated in the formation and scavenging of the ultimate reactive metabolites, the diolepoxides, from polycyclic aromatic hydrocarbons (PAHs). In the present study, performed on aluminum smelter workers, we have analyzed airborne PAH, the pyrene metabolite 1-hydroxypyrene (1-OHP) in urine, and genotypes for biotransformation enzymes involved in PAH metabolism. The aim was to evaluate the correlation between external exposure and biomarkers of exposure and to investigate to what extent genetic polymorphism in metabolic enzymes can explain interindividual variation in urinary 1-OHP levels. DNA was prepared from blood samples from 98 potroom workers and 55 controls and altogether eight polymorphisms in the CYP1A1, mEH, GSTM1, GSTP1 and GSTT1 genes were analyzed. The 1-OHP excretion was found to correlate significantly (P ≤ 0.005) to the exposure. The interindividual difference in excretion of 1-OHP was vast (>100-fold) and univariate and multivariate regression analyses were used to find the variables that could determine differences in excretion. The variation could, to some degree, be explained by differences in exposure to airborne particulate-associated PAHs, the use of personal respiratory protection devices, smoking habits and genetic polymorphisms in the cytochrome P450 1A1, GSTM1 and GSTT1 enzymes. The part of the variance that could be explained by differences in biotransformation genotypes seemed to be of the same order of magnitude as the variance explained by differences in exposure. In the control group as well as in the occupationally exposed group, the highest 1-OHP levels were observed in individuals carrying the CYP1A1 Ile/Val genotype who were also of the GSTM1 null genotype. The results show that urinary 1-OHP is a sensitive indicator of recent human exposure to PAHs and that it may also to some extent reflect the interindividual variation in susceptibility to PAHs. [ABSTRACT FROM PUBLISHER]

The authors examined the hypothesized association between the body burden of polyclorinated biphenyls (PCB) in women and the risk of low birth weight for their infants. In Sweden, a main exposure route for PCBs and other persistent organochlorine compounds is through the consumption of fatty fish from the Baltic Sea (on the Swedish east coast). A previous comparison between a cohort of consumers of large quantities of fish from the Swedish east coast and a reference population, together with a following analysis based on questionnaire data from a case-control study within the east coast cohort, supported the hypothesized association. In 1995, blood samples were collected from the wives and ex-wives of fishermen from the Swedish east coast (n = 192) who had given birth during the period 1973–1991. Cases (n = 57), i.e., infants with low birth weight (1, 500–2,750 g), were matched with controls (n = 135; birth weight, 3,250–4,500 g) on gender, parity, and calendar year of birth. The concentration of 2,2′, 4,4′, 5,5′-hexachlorobiphenyl (CB-153) in plasma was analyzed: it has been suggested that CB-153 is a relevant biomarker of exposure to PCBs. The concentration of CB-153 in the plasma of mothers during the year of childbirth was “estimated” using some alternative plausible kinetic models. For two alternative estimated exposure datasets, which were focused on separately, an increase in the risk of a low birth weight was observed at a CB-153 concentration of 300 and 400 ng/g lipid weight, respectively (adjusted odds ratios of 2.1 (9% confidence interval (CI) 1.0–4.7) and 2.3 (95% CI 0.9–5.9)). The present results strengthen the findings reported previously for this study population. Am J Epidemiol 1998; 147:493–502. [ABSTRACT FROM AUTHOR]