To study the associations between exposure to vapours and aerosols of bitumen and genotoxic effects, a cross-sectional and cross-shift study was conducted in 320 exposed workers and 118 non-exposed construction workers. Ambient air measurements were carried out to assess external exposure to vapours and aerosols of bitumen. Hydroxylated metabolites of naphthalene, phenanthrene and pyrene were measured in urine, whereas (+)-anti-benzo[a]pyrene-7,8-diol-9,10-epoxide ((+)-anti-BPDE), 8-oxo-7,8-dihydro-2'-deoxyguanosine (8oxodGuo) and DNA strand breaks were determined in blood. Significantly higher levels of 8-oxodGuo adducts and DNA strand breaks were found in both pre- and post-shift blood samples of exposed workers compared to those of the referents. No differences between exposed workers and referents were observed for (+)-anti-BPDE. Moreover, no positive associations between DNA damage and magnitude of airborne exposure to vapours and aerosols of bitumen could be observed in our study. Additionally, no relevant association between the urinary metabolites of PAH and the DNA damage in blood was observed. Overall, our results indicate increased oxidative DNA damage in workers exposed to vapours and aerosols of bitumen compared to non-exposed referents at the group level. However, increased DNA strand breaks in bitumen workers were still within the range of those found in non-exposed and healthy persons as reported earlier. Due to the lack of an association between oxidative DNA damage and exposure levels at the workplaces under study, the observed increase in genotoxic effects in bitumen workers cannot be attributed to vapours and aerosols of bitumen.
Historically, workplace exposure to the volatile inorganic acids hydrochloric acid (HCl) and nitric acid (HNO(3)) has been determined mostly by collection on silica gel sorbent tubes and analysis of the corresponding anions by ion chromatography (IC). However, HCl and HNO(3) can be present in workplace air in the form of mist as well as vapor, so it is important to sample the inhalable fraction of airborne particles. As sorbent tubes exhibit a low sampling efficiency for inhalable particles, a more suitable method was required. This is the first of two articles on "Evaluation of Sampling Methods for Measuring Exposure to Volatile Inorganic Acids in Workplace Air" and describes collaborative sampling exercises carried out to evaluate an alternative method for sampling HCl and HNO(3) using sodium carbonate-impregnated filters. The second article describes sampling capacity and breakthrough tests. The method was found to perform well and a quartz fiber filter impregnated with 500 μL of 1 M Na(2)CO(3) (10% (m/v) Na(2)CO(3)) was found to have sufficient sampling capacity for use in workplace air measurement. A pre-filter is required to remove particulate chlorides and nitrates that when present would otherwise result in a positive interference. A GSP sampler fitted with a plastic cone, a closed face cassette, or a plastic IOM sampler were all found to be suitable for mounting the pre-filter and sampling filter(s), but care has to be taken with the IOM sampler to ensure that the sampler is tightly closed to avoid leaks. HCl and HNO(3) can react with co-sampled particulate matter on the pre-filter, e.g., zinc oxide, leading to low results, and stronger acids can react with particulate chlorides and nitrates removed by the pre-filter to liberate HCl and HNO(3), which are subsequently collected on the sampling filter, leading to high results. However, although there is this potential for both positive and negative interferences in the measurement, these are unavoidable. The method studied has now been published in ISO 21438-2:2009.
BGIA has organised round robins for the analysis of samples of inorganic acids in workplace air for a number of years. Test samples of the volatile acids HCl and HNO(3) are collected from a standard atmosphere and samples of the non-volatile acids H(3)PO(4) and H(2)SO(4) are prepared by spiking filters with acid solution. The last two round robins have also covered the sampling of volatile acids, with up to 15 "active" participants able to visit the test facility in Dresden and take samples themselves. For other "passive" participants, BGIA takes samples from the same atmosphere. The acid concentrations generated lie between 0,1 and 1 times the German limit values for HCl and HNO(3). The results for the last round robin showed no significant difference between the performance of the "active" and "passive" participants. The participant means were in good agreement with the theoretical concentrations and the quality control measurements. For "active" participants RSDs were between 7% and 14% and for all participants between 8% and 16%. The round robin for the non-volatile acids showed similar results. The participant means were again in excellent agreement with the quality control measurements and RSDs were between 12% and 15%. The BGIA round robins have demonstrated the proficiency of laboratories measuring exposure to inorganic acids in air. However, concerns remain about the performance of published methods. It has shown that the sampling efficiency of sorbent tubes falls off with increasing particle size and hence silica gel tube methods may give low results for acid mists. Another issue with silica gel tubes is that a substantial proportion of the sample can be collected on the glass wool plugs that retain the sorbent. This can be up to 50% for HCl and 100% for HNO(3). Hence, low results may be obtained if the glass wool plugs are discarded. Similarly, methods for volatile inorganic acids that use a pre-filter to remove particulates usually overlook the fact that the acids can react with co-particulate matter on the pre-filter. Low recoveries in the range 30%-50% have been found when sampling HCl through filters loaded with potential interferents. Finally, particulate salts interfere with filter sampling methods for non-volatile inorganic acids. A two-part International Standard is in preparation for inorganic acids by ion chromatography and the issues discussed above are being taken into consideration during its development.
In the sector of occupational safety and health only a limited amount of studies are concerned with the conversion of inhalable to respirable dust. This conversion is of high importance for retrospective evaluations of exposure levels or of occupational diseases. For this reason a possibility to convert inhalable into respirable dust is discussed in this study. To determine conversion functions from inhalable to respirable dust fractions, 15 120 parallel measurements in the exposure database MEGA (maintained at the Institute for Occupational Safety and Health of the German Social Accident Insurance) are investigated by regression analysis. For this purpose, the whole data set is split into the influencing factors working activity and material. Inhalable dust is the most important predictor variable and shows an adjusted coefficient of determination of 0.585 (R2 adjusted to sample size). Further improvement of the model is gained, when the data set is split into six working activities and three material groups (e.g. high temperature processing, adj. R2 = 0.668). The combination of these two variables leads to a group of data concerned with high temperature processing with metal, which gives rise to a better description than the whole data set (adj. R2 = 0.706). Although it is not possible to refine these groups further systematically, seven improved groups are formed by trial and error, with adj. R2 between 0.733 and 0.835: soldering, casting (metalworking), welding, high temperature cutting, blasting, chiseling/embossing, and wire drawing. The conversion functions for the seven groups are appropriate candidates for data reconstruction and retrospective exposure assessment. However, this is restricted to a careful analysis of the working conditions. All conversion functions are power functions with exponents between 0.454 and 0.946. Thus, the present data do not support the assumption that respirable and inhalable dust are linearly correlated in general.
The chemical complexity of emissions from bitumen applications is a challenge in the assessment of exposure. Personal sampling of vapours and aerosols of bitumen was organized in 320 bitumen-exposed workers and 69 non-exposed construction workers during 2001-2008. Area sampling was conducted at 44 construction sites. Area and personal sampling of vapours and aerosols of bitumen showed similar concentrations between 5 and 10 mg/m(3), while area sampling yielded higher concentrations above the former occupational exposure limit (OEL) of 10 mg/m(3). The median concentration of personal bitumen exposure was 3.46 mg/m(3) (inter-quartile range 1.80-5.90 mg/m(3)). Only few workers were exposed above the former OEL. The specificity of the method measuring C-H stretch vibration is limited. This accounts for a median background level of 0.20 mg/m³ in non-exposed workers which is likely due to ubiquitous aliphatic hydrocarbons. Further, area measurements of polycyclic aromatic hydrocarbons (PAHs) were taken at 25 construction sites. U.S. EPA PAHs were determined with GC/MS, with the result of a median concentration of 2.47 μg/m(3) at 15 mastic asphalt worksites associated with vapours and aerosols of bitumen, with a Spearman correlation coefficient of 0.45 (95% CI -0.13 to 0.78). PAH exposure at mastic-asphalt works was higher than at reference worksites (median 0.21 μg/m(3)), but about one order of magnitude lower compared to coke-oven works. For a comparison of concentrations of vapours and aerosols of bitumen and PAHs in asphalt works, differences in sampling and analytical methods must to be taken into account.
Most urinary PAH metabolites were higher after shift in bitumen-exposed workers, although the association with bitumen was weak or negligible likely due to the small PAH content. The additional metabolites of PHE and PYR complete the picture of the complex metabolic pathways. Nevertheless, none of the PAH metabolites can be considered to be a specific biomarker for bitumen exposure.
A newly recommended Institute of Occupational Medicine (IOM) sampler, optimized for the inhalable fraction, was compared with 'total particulate' samplers currently used by five laboratories in different countries for the analysis of bitumen fumes. Using a laboratory fume generator, all samplers were uniformly exposed to bitumen fumes from typical USA bitumen (commercial Pen 65). The results show that, for laboratory-generated bitumen fumes, benzene-extractable inhalable particulate data for the IOM sampler are consistent with benzene soluble matter data from the other samplers. Direct comparison of the IOM sampler with the 37 mm closed-face cassette (USA sampler) using an identical protocol in a single laboratory gave a ratio of 1.05:1 (USA:IOM). Similarly, for total particulate matter, the standard previously recommended by the American Conference of Governmental Industrial Hygienists (ACGIH), an average value of approximately 1 between the IOM and the five samplers was obtained. For unadulterated bitumen fumes, the geometry of the cassettes does not appear to affect entry of the particles into the sampler. Field studies may show differences in results as other factors, e.g. wind and its effect on sampling efficiency, and also particulates originating from sources other than bitumen, such as dust, are involved. These will require thorough investigation prior to the assessment of the impact of the new sampler and prior to any reconsideration of occupational exposure limits taking into account practical feasibility. Other tests were conducted on the bitumen fume samples including total organic matter, simulated distillation and polycyclic aromatic compound analysis. These additional tests were performed on the fume collected on the filter plus the volatile portion that passed through the filter and was captured on various adsorbent materials. Protocols for sample collection and analysis varied in different countries with results reflective of these differences, suggesting the need for standardization.
Data concerning the irritative effects of current exposure to fumes of bitumen on the airways in humans are limited. To assess the effects of fumes of bitumen on the airways a crossshift study was conducted with monitoring of inflammatory process in upper and lower airways of workers exposed to fumes of bitumen and a reference group. All workers were examined immediately before and after shift. At both time points, spirometry was performed and nasal lavage fluid (NALF), induced sputum and spot urine were collected. Cellular composition and inflammatory mediator profile of the NALF and sputum samples were analyzed. Personal air sampling in each mastic asphalt worker's breathing zone was carried out to measure exposure to fumes of bitumen. The present cross-shift study with 202 mastic asphalt workers exposed to fumes of bitumen and 55 roadside construction workers as the reference group showed that fumes of bitumen released under high processing temperatures by mastic asphalt handling can exert acute and (sub-)chronic irritative effects on the upper and lower airway assessed with nasal lavage and induced sputum analysis. Airborne personal exposure to fumes of bitumen was associated with significant cross-shift declines in lung function parameters. Pre-shift lung function parameters (forced expiratory volume in 1 s [FEV 1 ] and forced vital capacity [FVC]) were significantly higher in the exposure group that pointed to a "healthy worker effect." Possible carryover effects could be observed in elevated pre-shift levels of several inflammation parameters in exposed workers indicating a (sub)chronic inflammation in these groups. Elevated interleukin-8 and protein levels in bitumen-exposed workers in sputum samples were found, but not in the nasal lavage fluid. The results emphasize irritative effects on the upper and lower airways under high exposure to fumes of bitumen. A more detailed analysis will be provided when all workers will be enrolled in that study.
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