Sampling and analysis of carbon in diesel exhaust particulates--an international comparison.

OBJECTIVES: The European Co-ordination on Diesel Soot Exposure (ECDSE) working group organised a laboratory inter-comparison which integrated both the sampling and the analytical determination. The aim was to gain more information on the performance of the methods for the determination of diesel particulate matter at workplaces and on their comparability, and to also confirm that the requirements of the European standard EN 482 are fulfilled for this analytical procedure. METHODS: Sampling was carried out in a diesel aerosol test chamber where participants used their own sampling devices. Overall, ten sampling exercises at two different concentration levels were performed and both personal air sampling systems and stationary samplers were used. The analytical determination was performed according to the laboratory's own standard procedure. RESULTS: There was good agreement between the laboratories for the determination of organic carbon (OC), elemental carbon (EC) and total carbon (TC). Almost all the results when expressed as a coefficient of variation were in the range +/-30% of the overall means. The results also showed that the coefficient of variation for OC was approximately twice the coefficient of variation for EC. This is not too critical, because existing occupational exposure levels (OELs) are based on the measurement of EC. CONCLUSIONS: The inter-comparison showed that existing analytical procedures for the determination of diesel particulate matter at workplaces fulfil the requirements of European standard EN 482. Both personal air samplers and stationary samplers give comparable results. The parameters for the analytical determination are not critical within the range of parameter values presented in this article. Additionally, it may be concluded that the diesel aerosol test chamber used in this exercise is well suited for producing an atmosphere containing a constant and reproducible level of diesel particulate matter.

Color vision and occupational toluene exposure.

We examined the relationship between acquired color vision loss and exposure to toluene and total hydrocarbons among 125 male workers. Seventy-two toluene-exposed printers were compared with 34 workers from the same photogravure plant with ambient background exposure, and with 19 workers from a bookbinding plant located in the same town (nonexposed). Environmental mean toluene exposure level at workstation was estimated from individual 8-h sampling. Historic exposure data from the last 30 years were used to construct two cumulative exposure indices, one for toluene and one for total hydrocarbons. Airborne toluene levels were overall lower than the current Threshold Limit Value (TLV) of 50 ppm. Color vision was assessed by the Lanthony D-15 desaturated panel. Color vision loss was quantitatively established by the Color Confusion Index (CCI) and classified by type of acquired dyschromatopsia according to Verriest's classification. CCI was positively related to current airborne toluene levels, and cumulative exposure indices for toluene and total hydrocarbons (.18< or =r< or =.35). Odds ratios of acquired dyschromatopsia were significant for current airborne toluene, toluene, and total hydrocarbon past exposure (1.27 [1.02-1.58], 1.21 [1.04-1.39], 1.15 [1.02-1.31], respectively). In conclusion, this study suggests that the Lanthony D-15 desaturated panel detects early neurotoxic effects among workers exposed to toluene.

Immunologic and renal markers among photogravure printers exposed to toluene.

OBJECTIVES: This study assessed immunologic and early renal effects of chronic toluene exposure. METHODS: In a longitudinal study of 92 printers and 74 referents, 145 subjects had pre- and poststudy samples of blood and urine taken for the following measurements: immunoglobulin E (IgE), antiglomerular basement membrane (anti-GBM) and antilaminin (anti-LAM) antibodies in blood; creatinine and beta2-microglobulin in blood and urine; and microalbumin, N-acetyl-b-D-glucosaminidase (NAG) and alanine-aminopeptidase in urine. Creatinine clearance was calculated according to the Cockroft-Gault formula. Eight-hour personal air samples were collected twice to assess present exposure to toluene. A job-exposure matrix was developed to estimate past cumulative exposure. Information about potential confounders was recorded by questionnaire. Multiple regression analysis was performed to study dose-effect relations adjusted for age and smoking. RESULTS: No subject was positive for anti-GBM antibodies, and only 12 were positive for anti-LAM. No relation was observed between the markers studied and present exposure to toluene except that creatinine clearance was higher among the exposed subjects than among the referents. A dose-response relation was observed between cumulative toluene exposure and both IgE and NAG excretion. No interaction was observed between hypertension and exposure, but the relationship with NAG did not persist when subjects with hypertension were excluded. Past or present exposure did not alter the 2-year trend of any marker studied. CONCLUSIONS: According to the results of this study, toluene at 50 ppm is not related to detectable renal dysfunction. The increased IgE levels associated with present and past exposure require further investigation.

Assessment of biological chromium among stainless steel and mild steel welders in relation to welding processes.

Air and biological monitoring were used for assessing external and internal chromium exposure among 116 stainless steel welders (SS welders) using manual metal arc (MMA), metal inert gas (MIG) and tungsten inert gas (TIG) welding processes (MMA: n = 57; MIG: n = 37; TIG: n = 22) and 30 mild steel welders (MS welders) using MMA and MIG welding processes (MMA: n = 14; MIG: n = 16). The levels of atmospheric total chromium were evaluated after personal air monitoring. The mean values for the different groups of SS welders were 201 micrograms/m3 (MMA) and 185 micrograms/m3 (MIG), 52 micrograms/m3 (TIG) and for MS welders 8.1 micrograms/m3 (MMA) and 7.3 micrograms/m3 (MIG). The curve of cumulative frequency distribution from biological monitoring among SS welders showed chromium geometric mean concentrations in whole blood of 3.6 micrograms/l (95th percentile = 19.9), in plasma of 3.3 micrograms/l (95th percentile = 21.0) and in urine samples of 6.2 micrograms/l (95th percentile = 58.0). Among MS welders, mean values in whole blood and plasma were rather more scattered (1.8 micrograms/l, 95th percentile = 9.3 and 1.3 micrograms/l, 95th percentile = 8.4, respectively) and in urine the value was 2.4 micrograms/l (95th percentile = 13.3). The analysis of variance of chromium concentrations in plasma previously showed a metal effect (F = 29.7, P < 0.001), a process effect (F = 22.2, P < 0.0001) but no metal-process interaction (F = 1.3, P = 0.25). Concerning urinary chromium concentration, the analysis of variance also showed a metal effect (F = 30, P < 0.0001), a process effect (F = 72, P < 0.0001) as well as a metal-process interaction (F = 13.2, P = 0.0004). Throughout the study we noted any significant differences between smokers and non-smokers among welders. Taking in account the relationships between chromium concentrations in whole, plasma or urine and the different welding process. MMA-SS is definitely different from other processes because the biological values are clearly higher. These higher levels are due to the very significant concentrations of total soluble chromium, mainly hexavalent chromium, in welding fumes.

International round robin tests on the measurement of carbon in diesel exhaust particulates.

OBJECT: Diesel soot has been recognized as probably carcinogenic to humans. Elemental carbon (also called black carbon) in soot is considered at the moment as the most significant surrogate to be measured for assessing the exposure to this pollutant. Its analysis is done by combustion in an oven and determination of the CO2 formed, after elimination of the organic fraction of the soot by heating and/or by solvent extraction. The analysis allows determination of both fractions of the soot: "elemental carbon" (EC) and organic carbon (OC). The sum of EC and OC is called TC (total carbon). METHOD: An informal European coordination group organized two round robin tests on filter samples collected from diluted diesel emissions. The first round (RRT1) was performed on 13 different samples analyzed by ten laboratories. The range of loading was 2.5 to 150 micrograms/cm2 of EC. No evaluation of the precision within laboratories could be made since each laboratory gave only one result per sample. Therefore a second round (RRT2) was organized with two samples and a blank filter sent in several portions to 11 laboratories. It should be stressed that each laboratory used its own method and that no standardization was planned at this stage. RESULTS: Results of RRT1 showed that the coefficient of variation between laboratories decreased with higher loading and was around 10% to 15% for EC above about 20 micrograms/cm2. Dispersion of the results varied and it appeared that the way OC is removed from the soot is probably the most important factor of influence. The correlation between the laboratories was good as a whole but some systematic differences could be detected. Besides the different techniques to remove the organic carbon, the pretreatment of the filter by HCl (either as a vapor or as a solution) to remove the inorganic carbonates (potential interference sources), is probably also a significant factor of influence in the dispersion of the results between laboratories. It is not yet clear from these results whether the "environmental" laboratories give different results from the "occupational" laboratories, but it is clear that their objectives differ since for the "environmentalists", EC is not a specific marker of diesel emmissions, in contrast to the "occupationalists". CONCLUSION: It can be concluded that, although significant differences exist between laboratories they can be attributed mainly to the narrow distribution of the results within a single laboratory, and that the overall agreement of the results for EC and TC is fairly good. These results obtained with pure diesel engine emissions, should be complemented by field samples, but they have already achieved relevant findings in the performance of the procedures used to assess exposure to diesel soot.

Exposure of contractors to chemical pollutants during the maintenance shut-down of a chemical plant.

The exposure of employees of different contracting firms to chemical pollutants was assessed during the five-week biennial maintenance shut-down of an isocyanate (TDI) synthesis plant. This assessment was mainly based on personal sampling, but work-related constraints occasionally required that area samples be used instead. Many tasks were carried out during the shut-down procedure (dismantling of reactors, installation of insulation, refection of kilns, cleaning, painting, electricity, etc.), thereby causing the employees of the contracting firms to be exposed to different kinds of pollutants, including products used or manufactured in the process (solvents, TDI and its synthesis intermediates), and products specific to the contractors' activity (welding fumes, crystalline silica, mineral fibers of heat insulation). The highest level of exposure (mainly to TDI) was found for the mechanical engineering activities undertaken during the dismantling of reactors and for cleaning activities. It was demonstrated that there was much variability in day-to-day exposure levels, and occasionally in the exposure levels encountered during a given shift. Cases of concomitant exposure to TDI (mainly short-term exposures) and other pollutants due to simultaneous activities from different tasks in the same area (co-activity) were also observed. Both the need for, and limitations of personal protective equipment (mainly respiratory) are stressed. Special emphasis is put on the responsibility of the owner of the facilities in helping the contractors in the organization of a health and safety policy.

Effect of different exposure compounds on urinary kinetics of aluminium and fluoride in industrially exposed workers.

OBJECTIVE: To conduct a field study to obtain information on the urinary concentrations of aluminium (Al) and fluoride (F-) depending on the different compounds exposed to in the aluminum industry. METHODS: 16 workers from one plant that produced aluminium fluoride (AlF3), and from two plants that produced aluminium electrolytically by two different processes participated in the study for one working week. Pollutants were monitored by eight hour personal sampling every day, and urine samples were collected during the week. Al and F- were analysed in both atmospheric and urine samples by atomic absorption spectrometry and an ion selective electrode. RESULTS: The principal results show different characteristics of kinetic curves of Al and F- excretion in workers with different exposures. Some characteristics of excretory peaks were linked to specific exposures--for instance, after exposure to AlF3 there was one delayed Al peak associated with one delayed F- peak about eight hours after the end of the daily shift, and after mixed exposure to HF and AlF3, two F- peaks were noted, one fast peak at the end of the shift and another delayed peak at 10 hours synchronised with an Al peak. In one of the electrolysis plants, the exposure to Al and F- compounds led to the simultaneous excretion of Al and F- peaks, either as a single peak or two individual ones depending on the type of technology used on site (open or enclosed potlines). The average estimated half life of Al was 7.5 hours, and of F- about nine hours. Quantitative relations between excretion and exposure showed an association between the F- atmospheric limit value of 2.5 mg/m3 with a urinary F- concentration of 6.4 mg/g creatinine at the end of the shift, a peak of 7.4 mg/g creatinine, and 7.4 mg excreted a day. For Al, the exposure to 1.36 mg/m3 during the shift corresponded to a urinary concentration at the end of the shift of 200 microgram/g creatinine. Daily excretion of 200 micrograms corresponded to an exposure to 0.28 mg/m3. CONCLUSION: Particular differences in the behaviour of Al and F- in urine depended upon the original molecular form in the pollutant. These results reinforce the principle that, in biological monitoring, the sampling strategy and the choice of limit value should be dependent on kinetic data that take the exposure compound of the element in question into account.

Exposure to metallic catalyst dust: manufacturing and handling of catalysts in the chemical industry.

The exposure of workers to metallic catalyst dust was assessed in manufacturing and reprocessing industries, and during catalyst handling in the chemical industry. The level of exposure was found to be generally low during the manufacturing and reprocessing activities taking place in permanent installations, and extremely variable during catalyst handling performed by workers of sub-contracting specialized firms. The difficulties in treating the occupational hygiene problems of these workers are pointed out.

[Exposure of urban bus drivers to traffic pollution]. / Exposition des conducteurs de bus urbains aux polluants de la circulation automobile.

Two measurement campaigns aimed at measuring the air pollutant emissions of vehicles (carbon monoxide, nitrogen oxides, lead, benzo[a]pyrene and formaldehyde) have been carried out using on-board sampling or analysis equipment in public buses in two major French towns. The study had a double objective: (i) to assess the occupational exposure through pollutant measurements in the breathing zone of the drivers at their working posts, (ii) to compare the quality of the air sampled outside, either at the bus front (current position of the ventilation air intake), or on the vehicle roof. Carbon monoxide measurements were performed with several Ecolyser (electrochemical detection) standardized with a Mahiak Unor 6N infra-red non-dispersive analyser and nitrogen mono- and dioxide with AC 30 M Environment S.A. analysers (chemiluminescent detection), with a data-logger recording the '5-min weighted average concentrations'. Lead on dust was sampled on cellulose acetate or quartz filters and analysed by atomic absorption, benzo[a]pyrene (as a tracer of polynuclear hydrocarbons) on quartz filters and by HPLC/UV fluorescence detector and formaldehyde (as a tracer of aldehydes) on 2,4-DNPH-impregnated silicagel tubes by HPLC/UV. Recording and sampling were performed for 18 single and return routes in the center of Paris (for 1.5-2 h each) and for 25 routes in the center of Bordeaux (for 35-60 min). The results clearly indicate that the occupational exposures of urban bus drivers for the six pollutants are lower than the exposure limit values in the working place (French Labour Department or A.C.G.I.H. standards). In particular, levels for benzopyrene, associated with carcinogenic hazard, do not increase 5% of the standard from Russian origin (150 ng/m3). On the contrary, concentrations reached the levels recommended by international air quality standards (OMS, US or European standards) for carbon monoxide, nitrogen dioxide and lead. When CO mean concentration values by bus lines in the driver's breathing zone are compared with the measurement results provided for the same sample days by the Air-Parif control network (in Paris), or the Gertrude traffic management system (in Bordeaux), it may be assumed that they are at the level of the most polluted surveillance stations. The CO concentrations are significantly lower in the outdoor air coming from the roof than in that coming from the front of the bus, so that better indoor air quality at the driving post can be found with air intake from an upper than a lower part.

Decreased serum ceruloplasmin concentration in aluminum welders exposed to ozone.

During an epidemiological survey on arc welders, serum copper and ceruloplasmin were determined in two groups of workers. One group consisted of aluminum welders who were divided into two groups: 13 welders working inside aluminum tanks (confined atmosphere) and 8 welders engaged in the production of vans for dump trucks (nonconfined atmosphere). The reference group consisted of 26 workers of the same plant who were not exposed to welding fumes. Ozone, the major pollutant in aluminum arc welding, was thought to be the principal factor in the significant decrease (P less than 0.01) of mean ceruloplasmin in confined welders. This decrease in the level of ceruloplasmin was still within the reference values and was not linked to age or to tobacco consumption. We found a linear relationship between ceruloplasmin concentration and the cumulated worktime along the week. This effect could be a sign in the serum of a lung reaction against oxidant activity in this type occupational exposure.

Lung function and clinical findings in a cross-sectional study of arc welders. An epidemiological study.

An epidemiological, cross-sectional study was conducted in order to assess non-neoplasic effects on the lung due to chronic exposure to arc welding fumes and gases. The study involved 346 arc welders and 214 control workers from a factory producing industrial vehicles. These workers (welders and controls) had never been exposed to asbestos. Respiratory impairments were evaluated by using a standardized questionnaire, a clinical examination, chest radiophotography and several lung function tests (spirometry, bronchial challenge test to acetylcholine, CO transfer tests according to the breath-holding and the steady-state methods, N2 washout test). The only significant differences between the welders overall compared to the controls were a slightly higher bronchial hyper-reactivity to acetylcholine and a lower lung diffusing capacity for CO in the welders. However, non-specific, radiologic abnormalities (reticulation, micronodulation) and obstructive signs were more frequent in the most exposed welders (welding inside tanks) than in welders working in well ventilated workplaces. The nature of the metal welded (mild-steel, stainless steel, aluminium) did not seem to have an influence on respiratory impairments. In the mild-steel welders, respiratory symptoms (dyspnoea, recurrent bronchitis) and obstructive signs were more frequent in the welders using a manual process than in the welders involved with the semi-automatic process (MIG). For all the workers (welders and controls), smoking had a markedly adverse effect on respiratory symptoms and lung function. Moreover, smoking seemed to interact with welding since CO lung transfer was more impaired in smoking welders than in smoking controls.