Exposure to polycyclic aromatic hydrocarbons assessed by biomonitoring of firefighters during fire operations in Germany.

BACKGROUND: Firefighters are exposed to a variety of hazardous substances including carcinogens such as polycyclic aromatic hydrocarbons (PAH) during firefighting. In order to minimize the uptake of such substances into the body, firefighters wear personal protective equipment. Only few data exist from real-life firefighting missions and under common although highly variable exposure scenarios such as fighting fires in residential buildings, outdoor, and vehicle fires. The aim of this study is to assess the levels of 1-Hydroxypyrene (1-OHP) as marker for incorporated PAH during firefighting operations in Germany using biomonitoring methods. METHODS: We analyzed urine samples for 1-OHP from 77 firefighters who reported firefighting operations (with and without creatinine adjustment). Urine samples were collected before (baseline) and, where applicable, after firefighting operations at three time points subsequent (2-4, 6-8, and 12 h). RESULTS: Compared to the baseline measurements, mean 1-OHP concentrations after firefighting missions were doubled (0.14 vs. 0.31 µg/L urine, 0.13 µg/g vs. 0.27 µg/g creatinine) and this increase was observed 2-4 h after firefighting. Firefighting in residential buildings (N = 54) and of outdoor and vehicle fires (N = 17) occurred most frequently, whereas blazes, vegetation fires, and fires in underground facilities (N = 6) were rarely encountered. For residential building fires, a 3-fold increase in mean 1-OPH concentrations was observed, whereas no increase could be observed for outdoor and vehicle fires. The highest increase was observed for firefighters with interior attack missions (0.11 µg/L vs. 0.48 µg/L 1-OHP) despite the use of self-contained breathing apparatus (SCBA). During the suppression of outdoor or vehicle fires using SCBA, again, no increase was observed. Although PAH are taken up during certain firefighting missions, the 1-OHP levels almost entirely remained (in 64 of the 77 reported missions) within the normal range of the German general population, i.e., below the reference levels (95th percentiles) of smokers (0.73 µg/g creatinine) and non-smokers (0.30 µg/g creatine). CONCLUSION: Under study conditions, properly applied protective clothing and wearing of SCBA led to a significant reduction of PAH exposure levels. But there are individual situations in which PAH are increasingly incorporated since the incorporation depends on several factors and can be extremely variable. In contrast to many workplaces with high occupational exposure levels, firefighters are not exposed to PAH on a daily basis. Nevertheless, the possibility of an individual increased cancer risk for a particular firefighter cannot completely be ruled out.

Construction of an In Vitro Air-Liquid Interface Exposure System to Assess the Toxicological Impact of Gas and Particle Phase of Semi-Volatile Organic Compounds.

Anthropogenic activities and industrialization render continuous human exposure to semi-volatile organic compounds (SVOCs) inevitable. Occupational monitoring and safety implementations consider the inhalation exposure of SVOCs as critically relevant. Due to the inherent properties of SVOCs as gas/particle mixtures, risk assessment strategies should consider particle size-segregated SVOC association and the relevance of released gas phase fractions. We constructed an in vitro air-liquid interface (ALI) exposure system to study the distinct toxic effects of the gas and particle phases of the model SVOC dibutyl phthalate (DBP) in A549 human lung epithelial cells. Cytotoxicity was evaluated and genotoxic effects were measured by the alkaline and enzyme versions of the comet assay. Deposited doses were assessed by model calculations and chemical analysis using liquid chromatography tandem mass spectrometry. The novel ALI exposure system was successfully implemented and revealed the distinct genotoxic effects of the gas and particle phases of DBP. The empirical measurements of cellular deposition and the model calculations of the DBP particle phase were concordant.The model SVOC DBP showed that inferred oxidative DNA damage may be attributed to particle-related effects. While pure gas phase exposure may follow a distinct mechanism of genotoxicity, the contribution of the gas phase to total aerosol was comparably low.

Estimating cobalt exposure in respirable dust from cobalt in inhalable dust.

Cobalt is a commonly used element in metal industry. Exposure to workers occurs mainly by inhalation of cobalt-containing dust. For the evaluation of cobalt exposure, risk assessment and investigations on occupational diseases, measurements of cobalt in respirable dust are needed. Up to now, often only data for cobalt in inhalable dust are available, which is due to the earlier classification of the limit value in this fraction. Therefore, a possibility to convert cobalt concentrations mathematically from inhalable into respirable concentrations is desirable. In this study, 639 parallel measurements of cobalt concentrations in inhalable (cI(Co)) and respirable dust fractions (cR(Co)) were extracted from the non-public exposure database MEGA (Measurement data relating to workplace exposure to hazardous substances, maintained at the Institute for Occupational Safety and Health of the German Social Accident Insurance) and investigated by regression analysis. For the whole dataset regression shows high quality measures (correlation coefficient R = 0.888, adjusted coefficient of determination adj. R2 = 0.788 - R2 is adjusted to sample size). Further description of the data is achieved by splitting the dataset according to the type of sampling ('stationary' and 'personal') and three working activity groups, 'high temperature processing', 'filling/transport/storage', and 'machining/abrasive techniques' (0.845 ≤ R ≤ 0.876; 0.711 ≤ adj. R2 ≤ 0.762). As subgroups of 'high temperature processing' and 'machining/abrasive techniques' two further groups could be determined. These groups are called heuristic groups, since they have to be formed non-systematically by trial and error. These heuristic groups are 'welding' and 'grinding'. They are more selective on the included working activities with adj. R2 of 0.703 and 0.748 respectively. The resulting conversion functions of all groups are power functions with exponents between 0.704 and 0.794. For the estimation of cobalt in respirable dust in other studies, it is possible to use the conversion functions of the heuristic and working activity groups. Limitations of the possibility to use the conversion functions are discussed.

In vitro genotoxicity of dibutyl phthalate on A549 lung cells at air-liquid interface in exposure concentrations relevant at workplaces.

The ubiquitous use of phthalates in various materials and the knowledge about their potential adverse effects is of great concern for human health. Several studies have uncovered their role in carcinogenic events and suggest various phthalate-associated adverse health effects that include pulmonary diseases. However, only limited information on pulmonary toxicity is available considering inhalation of phthalates as the route of exposure. While in vitro studies are often based on submerged exposures, this study aimed to expose A549 alveolar epithelial cells at the air-liquid interface (ALI) to unravel the genotoxic and oxidative stress-inducing potential of dibutyl phthalate (DBP) with concentrations relevant at occupational settings. Within this scope, a computer modeling approach calculating alveolar deposition of DBP particles in the human lung was used to define in vitro ALI exposure conditions comparable to potential occupational DBP exposures. The deposited mass of DBP ranged from 0.03 to 20 ng/cm2 , which was comparable to results of a human lung particle deposition model using an 8 h workplace threshold limit value of 580 µg/m3 proposed by the Scientific Committee on Occupational Exposure Limits for the European Union. Comet and Micronucleus assay revealed that DBP induced genotoxicity at DNA and chromosome level in sub-cytotoxic conditions. Since genomic instability was accompanied by increased generation of the lipid peroxidation marker malondialdehyde, oxidative stress might play an important role in phthalate-induced genotoxicity. The results highlight the importance of adapting in vitro studies to exposure scenarios relevant at occupational settings and reconsidering occupational exposure limits for DBP.

Estimating nickel exposure in respirable dust from nickel in inhalable dust.

The conversion of dust components is of high importance for retrospective evaluations of exposure levels, of occupational diseases or the time trend of occupational dust exposure. For this purpose, possibilities to convert nickel concentrations from inhalable to respirable dust are discussed in this study. Therefore, 551 parallel measurements of nickel concentrations in inhalable and respirable dust fractions were extracted from the exposure database MEGA (maintained at the Institute for Occupational Safety and Health of the German Social Accident Insurance) and investigated by linear regression analysis of ln-transformed concentrations. Inhalable dust is the most important predictor variable, showing an adjusted coefficient of determination (adj. R2) of 0.767 (R2 adjusted to sample size). Since multilinear regression analysis, cannot be applied, further description of data is gained by splitting the whole dataset into working activity groups (e. g. 'high temperature processing', adj. R2 = 0.628,' filling/transport/storage' adj. R2 = 0.741, 'machining/abrasive techniques', adj. R2 = 0.777). From these groups, four task restrictive subgroups, so-called 'heuristic groups', can be derived by pooling similar working tasks with similar regression coefficients and enhanced quality measures (adj. R2 between 0.724 and 0.924): 'welding (grinding time fraction [GTF] < 5%)', 'welding (grinding time fraction [GTF] > 5%)', 'high temperature cutting' and 'grinding'. For the working activity group 'high temperature processing' and the heuristic group 'welding' the determination of the grinding time fraction and its inclusion or exclusion from a dataset has a huge impact on the description of data and whether a transformation of nickel concentrations using the natural logarithm (ln) is necessary or not. In case of GTF < 5%, the conversions functions are linear, all other conversion functions are power functions with exponents between 0.713 and 0.986. It is possible to develop conversion functions for estimating the nickel concentration in the respirable dust fraction (cR(Ni)) out of the nickel concentration in the inhalable dust fraction (cI(Ni)). For the estimation of Nickel in respirable dust other studies, it is recommend to use the conversion functions of the heuristic trial and error groups. Limitations of the possibility to use the conversion functions are discussed.

Naphthalene: irritative and inflammatory effects on the airways.

OBJECTIVE: This cross-sectional study determined whether acute sensory irritative or (sub)chronic inflammatory effects of the eyes, nose or respiratory tract are observed in employees who are exposed to naphthalene at the workplace. METHODS: Thirtynine healthy and non-smoking male employees with either moderate (n = 22) or high (n = 17) exposure to naphthalene were compared to 22 male employees from the same plants with no or only rare exposure to naphthalene. (Sub)clinical endpoint measures included nasal endoscopy, smell sensitivity, self-reported work-related complaints and the intensity of naphthalene odor and irritation. In addition, cellular and soluble mediators in blood, nasal lavage fluid (NALF) and induced sputum (IS) were analysed. All measurements were carried out pre-shift on Monday and post-shift on Thursday. Personal air monitoring revealed naphthalene shift concentrations up to 11.6 mg/m3 with short-term peak concentrations up to 145.8 mg/m3 and 1- and 2-naphthol levels (sum) in post-shift urine up to 10.1 mg/L. RESULTS: Acute sensory irritating effects at the eyes and upper airways were reported to occur when directly handling naphthalene (e.g., sieving pure naphthalene). Generally, naphthalene odor was described as intense and unpleasant. Habituation effects or olfactory fatigue were not observed. Endoscopic examination revealed mild inflammatory effects at the nasal mucosa of exposed employees in terms of reddening and swelling and abnormal mucus production. No consistent pattern of cellular and soluble mediators in blood, NALF or IS was observed which would indicate a chronic or acute inflammatory effect of naphthalene in exposed workers. CONCLUSIONS: The results suggest that exposure to naphthalene induces acute sensory irritative effects in exposed workers. No (sub)chronic inflammatory effects on the nasal epithelium or the respiratory tract could be observed under the study conditions described here.

(Mono-) Exposure to Naphthalene in the Abrasives Industry: Air Monitoring and Biological Monitoring.

Exposure to the bicyclic aromatic hydrocarbon naphthalene occurs in most cases along with other polycyclic aromatic hydrocarbons. Here we report from an investigation of 63 healthy, non-smoking male employees in the abrasives industry where naphthalene is the only relevant chemical exposure. Exposure assessment was performed using a combination of Air and Biological Monitoring over nearly a whole working week (Mo.-Th.). Air measurements were carried out during the shift on Thursday with the GGP mini-sampling system, combining particle and vapour sampling at low flow rates. In urine spot samples, the metabolites 1- and 2-naphthol were measured Mo.-Th. pre- and post-shift (for the reference group only Mo. pre- and Th. post-shift). With regard to naphthalene concentrations measured in air and concentrations of its metabolites (1- and 2-naphthol) in urine, study participants could be divided into a high and a low exposure group, and a reference group. The naphthalene concentration in air was in the range of 0.1-11.6 mg m-3, and naphthol concentrations (sum of 1- and 2-naphthol) in post-shift urine were in the range of <1 to 10 127 µg l-1. Naphthalene concentrations in air and naphthol concentrations in urine were closely correlated, indicating mainly airborne exposure at the investigated workplaces. As expected from toxicokinetic data, internal body burden increased slightly during a working week and did not completely decline over a work-free weekend to background concentrations observed in occupationally not exposed persons. Taking into account the observed increase in pre- and post-shift values during the working week, urine sampling for Biological Monitoring at workplaces should be carried out after several preceding shifts. Our data allow the derivation of biological limit values for the sum of 1- and 2-naphthol in urine corresponding to occupational exposure limits for naphthalene in air.

Development of a Personal Aerosol Sampler for Monitoring the Particle-Vapour Fractionation of SVOCs in Workplaces.

Semi-volatile organic compounds (SVOCs), partitioned between particulates and vapours of an aerosol, require special attention. The toxicological effects caused by the inhalation of such aerosols may depend on the concentration and in which phase the organic compounds are found. A personal denuder-gas-particle separation aerosol sampler was developed to provide information about the partitioning of aerosols from organic compounds. The sampler was tested in a series of controlled laboratory experiments, which confirmed the capability and accuracy of the sampler to measure gas-particle mixtures. An average difference of 14.8 ± 4.8% was found between sampler and reference laboratory instruments. The obtained results showed that our sampler enables a more accurate measurement of the SVOC aerosols' gas-particle fractionation, compared with that of conventional samplers.

Estimating Respirable Dust Exposure from Inhalable Dust Exposure.

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.

Piezoelectric Micro-dosing System for Spiking Quality Samples in Occupational Hygiene Laboratories.

Quality control is crucially important in the arena of chemical analysis. Reference materials are essential for calibration and quality control processes, and for verification of the accuracy and reliability of the analytical results obtained. Owing to the complexity of their manufacture, reference materials for chemical agents occurring at workplaces are expensive and available only on a limited scale and for a small number of substances. Therefore, their cost-effective and fast production is an important aim. The Institute for Occupational Health and Safety (IFA) of the German Social Accident Insurance (DGUV) currently pursues different strategies for the production of reference materials. One strategy entails the use of a piezoelectric micro-dispensing system for non-contact spiking of extremely small quantities of substances with high reproducibility. The dispensing system is coupled to a semi-automated assembly unit for loading high numbers of samples. It is used for spiking phosphoric and sulphuric acid onto quartz fibre filters. Comparison of the results obtained on different days shows higher variability than results observed on the same day. However, after daily adjustment of the number of droplets to the current droplet volume, highly reproducible series with an adequate number of samples (>500) could be realized. The results of the internal quality control were verified in an interlaboratory comparison. Furthermore, storage stability was investigated systematically over a period of 2 years. The samples produced are suitable for use as reference materials for both inorganic acids.

Comparison of Microwave-Assisted Digestion and Consensus Open-Vessel Digestion Procedures for Evaluation of Metalliferous Airborne Particulate Matter.

Metal occupational exposure limits mainly focus on total content of the respective metals of interest. The methods applied for trace metal analysis in occupational health and safety laboratories are usually standardized to pragmatic consensus digestion schemes, ensuring comparability of results. The objective of the present study entailed the evaluation of a recently developed HNO3-only microwave-assisted digestion procedure by comparison with the German consensus hot-block digestion and other national digestion schemes. An inter-laboratory comparison test with participation of nine national occupational health and safety laboratories from Europe and North America was organized. For adequate emulation of what workers are at risk of inhaling four different industrial metal processing workplace dusts (electronic recycling, high-speed steel grinding, cylinder head cleaning, and battery combustion ash) were homogenized and sieved to the particle size < 100 µm diameter at IFA. The participants were asked to process air sample-typical amounts according to the German hot-plate technique, the IFA microwave-assisted digestion scheme as well as their national or in-house conventional digestion method for airborne dust and analyze for Cd, Co, Cr, Co, Fe, Mg, Ni, Pb, and Zn. Recoveries (relative to consensus open-vessel digestion) obtained for the new IFA microwave-assisted digestion were between 88 and 114% and relative reproducibility standard deviations were <10% for most metals of interest. The in-house digestion procedures applied varied widely but (whether microwave, hot block, or open vessel) yielded comparable results for the predominantly elemental alloy type dusts supplied. Results become more diverse for the combustion dust, especially if a combination of microwave-assisted digestion procedures with high temperatures and hydrofluoric acid is applied. ISO 15202-2 is currently being revised; this digestion procedure will be included as a possible variant in annex 2.

Validity of different biomonitoring parameters in human urine for the assessment of occupational exposure to naphthalene.

Up to date, information on the validity of human biomonitoring (HBM) parameters of naphthalene exposure is poor. This study was performed to reveal the relation between occupational exposure to naphthalene and biological exposure markers. Therefore, ten lowly and highly exposed workers from the abrasives industry were selected to characterise a broad exposure range. Naphthalene in air was determined by personal air monitoring during one shift. For biological monitoring, pre- and post-shift urine samples collected on 2 days of a working week were analysed for 1,2-dihydroxynaphthalene (1,2-DHN), 1- and 2-naphthol, 1- and 2-naphthylmercapturic acid (NMA). The naphthalene concentration in air was in the range of 0.5 to 11.6 mg/m3. The biomarkers in urine showed post-shift concentration in the range of 114-51,809 µg/L for 1,2-DHN, 0.8-666 µg/L for 1-NMA, 2-2698 µg/L for 1-naphthol and 4-1135 µg/L for 2-naphthol, respectively. 2-NMA was not detected. The urinary levels increased significantly from pre- to post-shift for all analysed parameters and an accumulation over the working week was observed. Significant positive correlations were observed between 1,2-DHN, 1-NMA, 1- and 2-naphthol in post-shift urine samples and personal exposure to naphthalene in the air. 1-NMA and 1,2-DHN, 1- and 2-naphthol have been demonstrated as suitable biomarkers for naphthalene exposure monitoring. Of the determined biomarkers, 1,2-DHN is by far the metabolite with the highest concentration in the urine samples.

Sampling and Analysis of Bitumen Fumes: Comparison of German and French Methods to Determine a Conversion Formula.

Bitumen is classed as possibly carcinogenic to humans according to the International Agency for Research on Cancer. Data on individual exposure to bitumen fumes is therefore required to highlight the exposing situations and develop methods to prevent them. The Institute for Occupational Safety and Health of the German Social Accident Insurance (IFA) and the French National Research and Safety Institute for the Prevention of Occupational Accidents and Diseases (INRS) have both developed methods to measure individual exposure. The objective of this study was to determine a conversion factor to allow interconversion of data acquired by the two methods. To develop this conversion factor, comparative laboratory and workplace tests were performed according to both the IFA method (No. 6305) and the INRS method (MetroPol M-2). The amounts of organic material collected on the filters and XAD-2 beds were compared. The results revealed differences between the sampling and analytical methods that could be linked to sampler design, extraction solvent, and the detection method used. The total quantification returned by the two methods-the sum of the masses quantified on filter and XAD-2 bed for each sampler-were correlated in both controlled and real-life tests. A conversion equation was therefore determined, based on field tests: CIFA = 1.76 CINRS ± 0.39 (R2 = 0.99) that is applicable to total quantification data. This formula can be applied to data acquired by the two institutes to increase the number of data points available on exposure to bitumen fumes in various conditions, and thus increase the statistical power of studies into occupational prevention.

Carbonaceous Monolithic Multi-Channel Denuders as Vapour-Particle Partitioning Tools for the Occupational Sampling of Semi-Volatile Organic Compounds.

Denuders are gas-particle partitioning tools and can be used in combination with filters and adsorbers for phase-separated collection of hazardous semi-volatile organic compound (SVOC) aerosols. Here, we investigated the suitability of carbonaceous monolithic multi-channel denuders for this approach. Particle transmission efficiency through the denuders was investigated using particles of polystyrene latex (PSL) and droplets of n-hexadecane and diethylene glycol. The time-dependent vapour collection efficiency was analysed for n-hexadecane and diethylene glycol vapours and also compared to calculated predictions. Our measurements showed an averaged transmission efficiency of 97 ± 4.4% for PSL particles with diameters of 0.51, 0.99, 1.93, and 3.00 µm. Measurements with one denuder and 1.08, 1.98, and 2.97 µm particles consisting of n-hexadecane or diethylene glycol resulted in an averaged transmission efficiency of 99 ± 6.5%. Regarding the vapour collection efficiency at a flow rate of 5 l min-1, n-hexadecane vapour could be adsorbed to a similar extent (91 ± 1.4% for one denuder, 98 ± 0.3% for two denuders) as diethylene glycol vapour (93 ± 1.8% for one denuder, 97 ± 0.9% for two denuders). The comparison between experimental and theoretical vapour collection efficiencies revealed differences around 2.8% for n-hexadecane and around 12.3% for diethylene glycol. The results show that the tested denuders can be used as vapour collection tools for SVOCs, and can be integrated in currently used personal air samplers for separated vapour and particle collection.

Multi-channel silicone rubber traps as denuders for gas-particle partitioning of aerosols from semi-volatile organic compounds.

During many measurements it is important to account for possible changes in the gas-particle distribution of aerosols containing semi-volatile organic compounds (SVOCs). If denuders are combined with currently used personal air samplers, a simultaneous differential sampling of the gas and particle phase is possible. Here we analysed the transmission efficiency of denuders based on multi-channel silicone rubber traps (setup: 9 cm long glass liner (ID 4 mm), containing 22 parallel silicone rubber tubes (55 mm long, ID 0.3 mm, OD 0.5 mm)) with polystyrene latex (PSL) particles for different scenarios. n-Hexadecane, dimethyl phthalate and diethylene glycol gases were used to measure the time-dependent gas phase collection efficiency of a denuder. Additionally, the evaporation of n-hexadecane aerosol particles passing through the denuders was investigated. Our results showed high transmission efficiencies from 91 to 100% (variation coefficients 3.69-9.65%) for the denuders operated vertically at a flow rate of 0.5 l min-1. With regard to the gas phase collection efficiency, nonpolar n-hexadecane gas was trapped with higher efficiency (87% after 22 h) than dimethyl phthalate gas (27% after 22 h), while for highly polar diethylene glycol the gas phase collection efficiency was 50% after 2 h. Regarding the evaporation of aerosol particles, smaller particles and lower flow rates led to higher particle volume reduction inside the denuders. In conclusion, the tested denuders are suitable for determining the gas-particle partitioning of SVOC aerosols of nonpolar substances and show above 90% transmission for all tested particle sizes.

Implantation of a MitraClip between two previously implanted MitraClips to treat recurrent severe mitral regurgitation.

We first describe the implantation of a MitraClip (Abbott Vascular, Abbott Park, IL, USA) between 2 previously implanted MitraClips to treat recurrent mitral regurgitation (MR). An 82-year-old male patient presented with dyspnea New York Heart Association NYHA class III due to recurrent severe MR 18 months after primarily successful implantation of 2 MitraClips. The initial procedure was performed to treat severe MR due to prolapse and flail of the anterior leaflet and resulted in mild MR after implantation of 2 MitraClips. Concomitant diseases were persistent atrial fibrillation, moderate tricuspid valve regurgitation, and chronic kidney disease stage 3. Thus, the patient was not considered a suitable candidate for surgical treatment. Using fluoroscopic guidance, 2D- and 3D-transesophageal echocardiographies, we succeeded in placing a third clip between the previously implanted clips and reduced the severe MR to mild MR without increase in the mean gradient. No periprocedural complications were observed. Six months after the procedure the patient presented with mild MR and NYHA class I. .

Metabolites of the PAH diol epoxide pathway and other urinary biomarkers of phenanthrene and pyrene in workers with and without exposure to bitumen fumes.

PURPOSE: This study investigates the diol epoxide pathway of phenanthrene (PHE) together with phenolic metabolites of PHE and pyrene (PYR) in workers with and without exposure to bitumen fumes. METHODS: The metabolite concentrations were determined in urine samples collected from 91 mastic asphalt workers and 42 construction workers as reference group before and after shift. During shift, vapours and aerosols of bitumen were measured according to a German protocol in the workers' breathing zone. RESULTS: The median concentration of vapours and aerosols of bitumen in mastic asphalt workers was 6.3 mg/m3. Metabolite concentrations were highest in post-shift urines of smokers with bitumen exposure and showed an increase during shift. The Spearman correlations between the creatinine-adjusted concentrations of metabolites and vapours and aerosols of bitumen in non-smokers were weak (e.g. sum of Di-OH-PYR: 0.28) or negligible (e.g. 1,2-PHE-diol: 0.08; PHE-tetrol: 0.12). Metabolites from the diol epoxide pathway of PHE were excreted in higher concentrations than phenolic metabolites (post-shift, non-smoking asphalt workers: 1,2-PHE-diol 2.59 µg/g crea vs. sum of all OH-PHE 1.87 µg/g crea). 1,2-PHE-diol was weakly correlated with PHE-tetrol (Spearman coefficient 0.30), an endpoint of the diol epoxide pathway. By contrast, we found a close correlation between the sum of 1,6-DiOH-PYR and 1,8-DiOH-PYR with 1-OH-PYR (Spearman coefficient 0.76). CONCLUSIONS: 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.

An evaluation of the "GGP" personal samplers under semi-volatile aerosols: sampling losses and their implication on occupational risk assessment.

Semi-volatile (SV) aerosols still represent an important challenge to occupational hygienists due to toxicological and sampling issues. Particularly problematic is the sampling of hazardous SV that are present in both particulate and vapour phases at a workplace. In this study we investigate the potential evaporation losses of SV aerosols when using off-line filter-adsorber personal samplers. Furthermore, we provide experimental data showing the extent of the evaporation loss that can bias the workplace risk assessment. An experimental apparatus consisting of an aerosol generator, a flow tube and an aerosol monitoring and sampling system was set up inside a temperature controlled chamber. Aerosols from three n-alkanes were generated, diluted with nitrogen and sampled using on-line and off-line filter-adsorber methods. Parallel measurements using the on-line and off-line methods were conducted to quantify the bias induced by filter sampling. Additionally, two mineral oils of different volatility were spiked on filters and monitored for evaporation depending on the samplers flow rate. No significant differences between the on-line and off-line methods were detected for the sum of particles and vapour. The filter-adsorber method however tended to underestimate up to 100% of the particle mass, especially for the more volatile compounds and lower concentrations. The off-line sampling method systematically returned lower particle and higher vapour values, an indication for particle evaporation losses. We conclude that using only filter sampling for the assessment of semi-volatiles may considerably underestimate the presence of the particulate phase due to evaporation. Thus, this underestimation can have a negative impact on the occupational risk assessment if the evaporated particle mass is no longer quantified.

Development and field testing of a miniaturized sampling system for simultaneous sampling of vapours and droplets.

The sampling of semi volatiles (SV) in workplaces may lead to different results as measurements may be affected by sampling bias. The new European Standard EN 13936 defines "semi-volatiles" as substances with vapour pressures in the range between 0.001 and 100 Pa at room temperature. EN 13936 regulates the basic requirements for SV compounds that can occur as vapour and particle at the same time. Vapour and particles shall not be sampled separately and particles have to be sampled as inhalable fraction. Following EN 13936, the Institute for Occupational Safety and Health (Institut für Arbeitsschutz - IFA) has developed a miniaturized droplet-vapour sampler (GGP-Mini) which is designed to sample the inhalable aerosol fraction at low flow rates. The GGP-Mini uses 13 mm filters for particle sampling combined with adsorption tubes for vapour sampling. Laboratory tests were performed on 11 polar and non-polar compounds in a boiling point range from 188 °C to 318 °C. The substances were spiked directly on the filter followed by aspiration of 40 litres of air. Substances with boiling points below 230 °C were almost completely evaporated. Substances with boiling points above 230 °C up to 300 °C were found on both filter and charcoal tube. Lower-volatile compounds remained almost completely on the filter. For polar substances, the atmospheric humidity had a considerable influence upon the distribution of the liquid and vaporous components. A strong influence of the sampling temperature was found in the range from 0 °C to 50 °C. Droplet-vapour mixtures of n-hexadecane and diethylene glycol with droplet sizes between 1 µm and 4 µm were generated in a flow tube to verify the laboratory results. The aerosol concentrations were analysed on-line with a particle sizer and a flame ionisation detector, while parallel off-line samples were taken with the GGP-Mini. Evaporation losses from filters could be studied by comparing the on-line with off-line measurements. All sampling simulations, both spiking and tests on a droplet aerosol, have shown that the distribution between vapour and droplets is not constant and influenced e. g. by volatility, concentration, temperature and humidity. Only the sum of vapour and droplets constitutes a reproducible result.