Decomposition Products of the Initiator Bis(2,4-dichlorobenzoyl)peroxide in the Silicone Industry: Human Biomonitoring in Plasma and Urine of Workers.

Bis(2,4-dichlorobenzoyl)peroxide (2,4-DCBP) is used as an initiator for silicone rubber production. During hot curing, 2,4-DCBP decomposes into 2,4-dichlorobenzoic acid, 1,3-dichlorobenzene, and the polychlorinated biphenyl (PCB) congeners PCB-47, PCB-51, and PCB-68. The extent of occupational exposure to these decomposition products has not been investigated yet. We determined for the first time the corresponding internal exposure of employees (n = 104) of a German silicone rubber facility by human biomonitoring in plasma and urine. Collected samples were investigated by gas chromatography/mass spectrometry for levels of PCBs in plasma and by liquid chromatography/tandem mass spectrometry for urinary post-shift levels of 2,4-dichlorobenzoic acid (2,4-DCBA) and the metabolites 3,5-dichlorocatechol (3,5-DCK), 2,4-dichlorophenol (2,4-DCP), and 3,5-dichlorophenol (3,5-DCP). PCB-47 and PCB-68 levels correlated significantly and were found in >97% of all samples with maximum values of 4.43 and 0.77 µg/L, respectively. 2,4-DCBA, 3,5-DCK, 2,4-DCP, and 3,5-DCP were quantified in >80% of all urine samples with maximum levels of 1.46; 26.92; 7.68; and 0.39 mg/L, respectively. There is a considerable uptake of decomposition products of 2,4-DCBP in workers of a silicone rubber facility, affecting employees in all work areas. Individual levels depended on the work task. Considering the carcinogenic potential of PCBs, the workers' additional exposure to PCB-47 and PCB-68 might be of concern.

Plasma polychlorinated biphenyls (PCB) levels of workers in a transformer recycling company, their family members, and employees of surrounding companies.

In spring 2010, high internal exposures (up to 236 µg/L plasma) for the sum of indicator polychlorinated biphenyls (PCB) were discovered in workers in a transformer recycling company in Germany, where PCB-contaminated material was not handled according to proper occupational hygiene. The release of PCB from this company raised growing concerns regarding possible adverse human health effects correlated with this exposure. This provided a basis for a large biological monitoring study in order to examine the internal exposure to PCB in individuals working in that recycling company, their family members, and relatives, as well as subjects working or living in the surroundings of this company. Blood samples from 116 individuals (formerly) employed in the transformer recycling company and 45 direct relatives of these persons were obtained. Further, blood samples of 190 subjects working in close vicinity of the recycling plant, 277 persons working in the larger area, and 41 residents of the area were investigated. Plasma samples were analyzed for the 6 indicator PCB (PCB 28, 52, 101, 138, 153, 180) and 12 dioxin-like PCB using gas chromatography/mass spectroscopy (GC/MS; limit of detection [LOD] at 0.01 µg/L). Median concentrations (maximum) for the sum of the 6 indicator PCB in blood of the employees, their relatives, individuals working in close vicinity, persons working in the larger area, and the residents were 3.68 (236.3), 1.86 (22.8), 1.34 (22.9), 1.19 (6.42), and 0.85 (7.22) µg/L plasma, respectively. The (former) employees of the transformer recycling plant partly showed the highest plasma PCB levels determined thus far in Germany. Even family members displayed highly elevated levels of PCB in blood due to contaminations of their homes by laundering of contaminated clothes. Vicinity to the recycling plant including reported contact with possibly contaminated scrap was the main contributor to the PCB levels of the workers of the surrounding companies. Residents of the area did not show significantly elevated blood PCB levels compared to the general population. Our biomonitoring results served as a basis for individual risk communication and successful risk management.

Current data on the background burden to the persistent organochlorine pollutants HCB, p,p'-DDE as well as PCB 138, PCB 153 and PCB 180 in plasma of the general population in Germany.

Despite their long-term ban, persistent organochlorine compounds like hexachlorobenzene (HCB), p,p'-dichlorodiphenylethylene (DDE) as well as polychlorinated biphenyls (PCBs) are still of environmental concern. For the evaluation of potential occupational or environmental exposures to these substances, it is essential to know the current background burden of the general population. As representative and up-to-date information is missing for Germany, we have analysed a large dataset generated in studies on potential exposure to lower chlorinated PCBs to fill this gap for the levels of HCB, DDE as well as PCB 138, PCB 153 and PCB 180. We have investigated n=2750 plasma samples of persons of the general population living in North Rhine-Westfalia and Hesse aged 6-65 years and sampled between September 2010 and March 2014. For evaluation of the age-dependent accumulation in the general population we have generated seven age groups in the collective. Our laboratory used a validated and quality controlled procedure using GC/MS for quantification of the organochlorine compounds in plasma (LOQ: 0.01µg/L). The median (95th percentile) levels for ∑ PCB 138+PCB 153+PCB 180 were 0.14 (0.73); 0.30 (0.82); 0.38 (0.88); 0.50 (1.14); 0.92; 1.58 (3.54) and 2.41 (4.82)µg/L plasma in the age groups 6-10 years (n=102), 11-17 years (n=499), 18-25 years (n=157), 26-35 years (n=710), 36-45 years (n=400), 46-55 years (n=525) and 56-65 years (n=357), respectively. Similarly, the median (95th percentile) levels of p,p'-DDE were 0.18 (1.24); 0.18 (0.74); 0.24 (0.85); 0.30 (1.20); 0.45 (1.74); 0.64 (3.25) and 0.94 (4.7)µg/L plasma. Finally, the median (95th percentile) of HCB in plasma in these age groups was 0.05 (0.10); 0.06 (0.11); 0.08 (0.15); 0.08 (0.15); 0.11 (0.22); 0.14 (0.42) and 0.20 (0.68)µg/L plasma. Our results prove an overall substantial reduction in the body burden to organochlorine compounds in Germany compared to earlier studies. However, 15% and 3.6% of the examined collective exceeded the HBM-I- and HBM-II-values for PCBs established by the German Human Biomonitoring Commission. Due to a large sample size and a collection period from 2010 to 2014, our data might be suitable for the evaluation of additional exposures to these POPs and may serve as reference values.

A biomarker approach to estimate the daily intake of benzene in non-smoking and smoking individuals in Germany.

Owing to its carcinogenic properties, benzene is one of the most important environmental air pollutants. We have applied a simple pharmacokinetic model to estimate the individual daily exposure of persons of the general population to benzene using their urinary excretion of S-phenylmercapturic acid as biomarker of exposure. On the basis of a non-representative convenience sample of the general population, spontaneous urine samples of 43 non-smoking persons, 13 persons with exposure to environmental tobacco smoke (ETS) (as determined by urinary cotinine) and 72 smokers were analyzed for S-phenylmercapturic acid, and benzene exposure was back calculated on the basis of the results. The pharmacokinetic model was based either on estimated daily urinary volume or creatinine excretion. Median daily exposure of non-smokers was calculated to be 47 microg/day (volume-based model) and 63 microg benzene/day (creatinine-based model). ETS-exposed persons had a slightly higher median daily exposure of 65 microg/day (volume-based model) and 72 microg benzene/day (creatinine-based model). The daily exposure of smokers was significantly higher with median values of 491 microg benzene/day (volume-based model) and 693 microg benzene/day (creatinine-based model). Our biomarker-based model gave plausible results for daily benzene exposure that were in good agreement with exposure estimations published earlier. As it is purely based on the determination of individual internal dose, our model provides a powerful tool for the risk assessment of environmental benzene.