Biomarkers in hydrolysed urine, plasma and erythrocytes among workers exposed to thermal degradation products from toluene diisocyanate foam.
ABSTRACT Blood and urine samples were collected from six workers and two volunteers exposed to thermal degradation products from toluene diisocyanate (TDI)-based polyurethane (PUR) before and during the summer vacation. Air samples were collected on filters impregnated with 9-(N-methylaminomethyl)anthracene. The concentrations of the amines corresponding to 2,4- and 2,6-TDI, i.e., 2,4- and 2,6-toluenediamine (TDA), were determined in urine (U-TDA), plasma (P-TDA) and erythrocytes (E-TDA) after acid hydrolysis as pentafluoropropionic anhydride derivatives by GC-MS. Among the workers urinary elimination phases were seen. The estimated medians of the urinary half-lives were for the slow phase 18 d for 2,4-TDA and 19 d for 2,6-TDA. P-2,4-TDA ranged between 2.5 and 19 ng ml-1 and P-2,6-TDA between 4.4 and 30 ng ml-1. The estimated median of the half-lives in plasma were 7.8 d for 2,4-TDA and 9.6 d for 2,6-TDA. E-2,4-TDA ranged between 0.5 and 6.6 ng g-1 and E-2,6-TDA between 1.2 and 14 ng g-1. A significant linear relationship was found between the mean P-TDA and the mean E-TDA. Linear relationships were observed between the mean daily U-TDA and P-TDA and E-TDA. Virtually linear relationships were obtained for P-TDA and E-TDA and the TDI air levels. Proteins from lysed erythrocytes were separated and fractionated by gel filtration. 'TDI'-modified proteins were found in six out of a total of 80 fractions (fractions 51-56). These co-eluted completely with the haemoglobin (UV, 415 nm). Fractions 51-56 contained 89% of the applied amounts of 2,4-TDA and 81% of 2,6-TDA.
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ABSTRACT: Exposure to isocyanates is known to have respiratory effects in workers and therefore it is essential to monitor the occupational exposure. An earlier study of a continuous foaming plant using toluene diisocyanate (TDI) showed that the exposure to isocyanates can be high. Since then several preventive actions were implemented at the plant. The aim of this study was to observe the effect of these actions measured by air and biological monitoring. Four workers were monitored in the year 2000 and six in 2005, with air measurements during the continuous foaming process, and with measurements of biomarkers in one plasma sample each year and with two urinary samples being collected in the year 2000 and one in 2005. The median TDI air concentrations in 2005 were approximately 20% of the 2000 levels and the median levels of biomarkers in 2005 were approximately 10% of the 2000 levels. According to our measurements the preventive action had a real effect to decrease the exposure to TDI. As the workers both before and after the preventive actions used personal protective equipment, the use of biomarkers was necessary to assess the real gain in the preventive actions.Annals of Occupational Hygiene 05/2008; 52(3):187-94. · 2.16 Impact Factor
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ABSTRACT: PURPOSE: Exposure to diisocyanates is a known occupational hazard. One method for monitoring occupational exposure is by analyzing biomarkers in hydrolyzed urine and plasma. The half-life of the biomarkers in plasma is about 3 weeks, and the urinary elimination is divided into one fast (hours) and one slow phases (weeks). Polymorphism in glutathione S-transferase enzymes (GST) is earlier shown to modify the metabolism. The aim of the study was to assess whether biomarkers of exposure in urine collected after two non-exposed days correlate with levels in plasma and whether they can be used as a measure for long-term exposure to aromatic diisocyanates and further whether polymorphisms in GST influenced the correlations. METHODS: Biomarkers of exposure was analyzed in urine and blood samples collected from 24 workers, exposed to at least one of toluene-, methylenediphenyl- or naphthalene diisocyanate, on a Monday morning after at least two unexposed days. Moreover, genotype was determined for 19 of the workers. RESULTS: The corresponding specific gravity-adjusted biomarkers in urine and plasma levels for the different diisocyanates correlated well (r between 0.689 and 0.988). When taking all samples together, the correlation coefficient was 0.926. Polymorphism in the GSTM1 genotype seemed to modify the association. CONCLUSION: Urine collected after two unexposed days can possibly be used as long-term biomarker of exposure for aromatic diisocyanates.International Archives of Occupational and Environmental Health 04/2013; · 2.10 Impact Factor
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ABSTRACT: Urinary 1,6-hexamethylene diamine (HDA) may serve as a biomarker for systemic exposure to 1,6-hexamethylene diisocyanate (HDI) in occupationally exposed populations. However, the quantitative relationships between dermal and inhalation exposure to HDI and urine HDA levels have not been established. We measured acid-hydrolyzed urine HDA levels along with dermal and breathing-zone levels of HDI in 48 automotive spray painters. These measurements were conducted over the course of an entire workday for up to three separate workdays that were spaced approximately 1 month apart. One urine sample was collected before the start of work with HDI-containing paints and subsequent samples were collected during the workday. HDA levels varied throughout the day and ranged from nondetectable to 65.9 microg l(-1) with a geometric mean and geometric standard deviation of 0.10 microg l(-1) +/- 6.68. Dermal exposure and inhalation exposure levels, adjusted for the type of respirator worn, were both significant predictors of urine HDA levels in the linear mixed models. Creatinine was a significant covariate when used as an independent variable along with dermal and respirator-adjusted inhalation exposure. Consequently, exposure assessment models must account for the water content of a urine sample. These findings indicate that HDA exhibits a biphasic elimination pattern, with a half-life of 2.9 h for the fast elimination phase. Our results also indicate that urine HDA level is significantly associated with systemic HDI exposure through both the skin and the lungs. We conclude that urinary HDA may be used as a biomarker of exposure to HDI, but biological monitoring should be tailored to reliably capture the intermittent exposure pattern typical in this industry.Annals of Occupational Hygiene 08/2010; 54(6):678-91. · 2.16 Impact Factor