Occupational and environmental aerosol exposure assessment: a scientific journey from the past, through the present and into the future

This paper reviews how aerosol exposure assessment, for people in both working and living environments, has evolved over the years. It charts the main scientific developments that led to progressively improved ways of thinking and methods to assess exposure to airborne particulate matter in a manner more relevant to human health. It has been a long scientific journey as one generation of pioneering contributors has handed off to the next. In the process a consistent rationale has emerged, producing aerosol sampling criteria--and in turn exposure standards--which have been increasingly relevant to actual human exposures. The journey continues as a new generation of scientists steps up to deal with the new challenges that are emerging. An appreciation of the history of what went before is essential to charting the most effective path looking forward.     

Assessing workplace chemical exposures: the role of exposure monitoring

Occupational exposure is the condition of being subjected through employment to a chemical, physical, or biological agent, or to a specific process, practice, behavior, or organization of work. Exposure to a chemical agent is typically the contact of that agent with the outer boundary of a subject, such as the respiratory system, skin, or digestive system. In occupational hygiene we are most concerned with exposure through the respiratory system, although, increasingly we are concerned with the results of dermal exposures, including those exposures to the skin that can be transferred to the mouth and digestive system. This presentation will detail methods available for assessing personal exposures to chemicals through monitoring. The results from monitoring can then be compared to established guidelines and regulations, although this is not the only rationale for making measurements. These monitoring methods are currently used around the world to establish the benchmark hazard from which risk to the worker can be predicted. The presentation will describe the general techniques for assessing exposures to the respiratory system from chemical gases and vapors, chemical dusts, and exposures to the skin from bulk chemicals or chemical contamination of surfaces. For respiratory exposures, direct-reading instruments are available for spot measurements, and for monitoring short-term fluctuations in concentration. However, most standards and regulations are based on time-integrated (time-weighted average) exposures, requiring longer-term integrative methods. Therefore, the specific focus of this review will be the methods available for full work-shift sampling. For gases and vapors this will include taking whole-air samples in canisters or polymer bags, or concentration of chemicals by absorption in liquids or adsorption on solid sorbents, with subsequent chemical analysis. Chemical concentration can take place by pumping air through the sorbing media, or by allowing molecules to diffuse to the sorbent surface. Transfer of the collected chemicals to the analytical instrumentation can be accomplished using solvent displacement and injection, or through the application of heat to bring the collected molecules back into the vapor phase. For particles, the particle size is important as this determines the site of deposition in the lungs, and so time-integrated sampling on filters using various types of size-selective samplers is preferred. Finally, some techniques that have been used to assess the potential for chemical contamination of the skin are presented. Biomonitoring is another tool that can be used to assess exposure, and the results are more relevant to dosimetric considerations than exposure. Biomonitoring is a complex subject worthy of a separate review, and will be considered only briefly here.     

Assessment of diesel particulate matter exposure in the workplace: freight terminals

A large study has been undertaken to assess the exposure to diesel exhaust within diesel trucking terminals. A critical component of this assessment is an analysis of the variation in carbonaceous particulate matter (PM) across trucking terminal locations; consistency in the primary sources can be effectively tracked by analyzing trends in elemental carbon (EC) and organic molecular marker concentrations. Ambient samples were collected at yard, dock and repair shop work stations in 7 terminals in the USA and 1 in Mexico. Concentrations of EC ranged from 0.2 to 12 microg m(-3) among the terminals, which corresponds to the range seen in the concentration of summed hopanes (0.5 to 20.5 ng m(-3)). However, when chemical mass balance (CMB) source apportionment results were presented as percent contribution to organic carbon (OC) concentrations, the contribution of mobile sources to OC are similar among the terminals in different cities. The average mobile source percent contribution to OC was 75.3 +/- 17.1% for truck repair shops, 65.4 +/- 20.4% for the docks and 38.4 +/- 9.5% for the terminal yard samples. A relatively consistent mobile source impact was present at all the terminals only when considering percentage of total OC concentrations, not in terms of absolute concentrations.     

Mass, surface area and number metrics in diesel occupational exposure assessment

While diesel aerosol exposure assessment has traditionally been based on the mass concentration metric, recent studies have suggested that particle number and surface area concentrations may be more health-relevant. In this study, we evaluated the exposures of three occupational groups-bus drivers, parking garage attendants, and bus mechanics-using the mass concentration of elemental carbon (EC) as well as surface area and number concentrations. These occupational groups are exposed to mixtures of diesel and gasoline exhaust on a regular basis in various ratios. The three groups had significantly different exposures to workshift TWA EC with the highest levels observed in the bus garage mechanics and the lowest levels in the parking ramp booth attendants. In terms of surface area, parking ramp attendants had significantly greater exposures than bus garage mechanics, who in turn had significantly greater exposures than bus drivers. In terms of number concentrations, the exposures of garage mechanics exceeded those of ramp booth attendants by a factor of 5-6. Depending on the exposure metric chosen, the three occupational groups had quite different exposure rankings. This illustrates the importance of the choice of exposure metric in epidemiological studies. If these three occupational groups were part of an epidemiological study, depending on the metric used, they may or may not be part of the same similarly exposed group (SEG). The exposure rankings (e.g., low, medium, or high) of the three groups also changes with the metric used. If the incorrect metric is used, significant misclassification errors may occur.     

Application of recent advances in aerosol sampling science towards the development of improved sampling devices: the way ahead

This paper reviews the framework that underpins the development of a new generation of personal samplers capable of operating at much lower flowrates that those of the current generation and so capable of being used for exposure assessment not only for 'traditional' occupational populations (i.e., industrial workers) but also for people exposed to aerosols in the ambient atmosphere (including children). The opportunity for this new generation of samplers stems from the availability of very light and compact low-flowrate pumps. The development and deployment of such instruments presents: (a) physical challenges in terms of how to collect particle size fractions in a manner which is consistent with the new particle size-selective sampling criteria, and (b) analytical challenges in terms of how to quantitate the much smaller amounts of collected material that need to be analysed. The paper lays out the physical and analytical scenarios, and points the way forward to how such challenges can be overcome. Work is already in progress in several countries to develop prototype instruments for applications like those described.     

Performance of methods for measurement of exposure to inorganic acids in workplace air

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.     

The exposure commitment method in environmental pollutant assessment

The exposure commitment method is a time independent approach to pollutant assessment. The exposure commitment is a measure of the intensity and duration of a pollutant's presence in an environmental reservoir. The method is a particularly convenient means of comparing contributions to intake and exposure from various pathways and in expressing source-receptor relationships. The concepts and definitions of the method are presented and application shown for the transfer of lead and cadmium from general atmospheric sources to man.     

SPME-based air sampling method for inhalation exposure assessment studies: case study on perchlorethylene exposure in dry cleaning

Exposure to perchlorethylene, especially for dry cleaning workers and for people living near dry cleaning shops, could lead to several diseases and disorders. This study examines the value of solid-phase microextraction (SPME) for sampling perchlorethylene in the atmosphere of dry cleaning shops. Carboxen/polydimethylsiloxane (CAR/PDMS) in 0.5-cm retracted mode was selected. There were no significant differences between sampling rates at different temperatures (range of 20 to 30 °C) and air velocities (2 to 50 cm/s). On the opposite, relative humidity (RH) had a significant effect on sampling rates. Method reproducibility was realized in the laboratory and field conditions and was 6.2 % and 7 to 11 %, respectively. Repeatability was also determined as 8.9 %. Comparison of the results according to the American Industrial Hygiene Association exposure assessment strategy showed the SPME sampler yields more conservative results in comparison with traditional standard method.     

A review of workplace aerosol sampling procedures and their relevance to the assessment of beryllium exposures

Standardized conventions governing the fractions of airborne particles that can penetrate the human head airways, the thoracic airways and the alveolar spaces have been internationally (although not universally) adopted. Several agencies involved in setting limit values for occupational exposure concentrations have taken these conventions into account when considering the appropriate standard for specific chemicals, in order to ensure the standards are biologically relevant. A convention is selected based on the characteristic health effects, and forms the basis of measurement against the limiting concentration value. In order to assess exposure for comparison to this metric or any other purposes, it is necessary to choose a sampler whose performance matches the convention, and protocols have been developed and used to test sampler performance. Several aerosol sampling devices are available, nominally at least, for each of the conventions. Some considerations important to the sampling of airborne particles containing beryllium with regard to the sampling conventions, the test protocols and sampler performance are discussed.     

Manganese air exposure assessment and biological monitoring in the manganese alloy production industry

One hundred workers carried personal air sampling equipment during three days to assess exposure to inhalable and respirable Mn. A novel four-step chemical fractionation procedure developed for the speciation of Mn in workroom aerosols was applied for selected aerosol filters. Blood and urine samples were analysed for Mn. The geometric mean (GM) concentrations of inhalable (n = 265) and respirable (n = 167) Mn determined in all filters were 254 microg m(-3) and 28 microg m(-3) respectively. Only 10.6% (95% CI 8.9-12.5) respirable Mn was found in the inhalable fraction when inhalable and respirable samples collected in parallel were considered (n = 153 pairs). There was a high correlation (Pearson's r = 0.70; p < 0.001) between respirable and inhalable Mn. The largest amounts of Mn in the inhalable aerosol fraction were found as Mn0 and Mn2+ (47.4%), whereas 28% was practically "insoluble". The associations between B-Mn and aerosol concentrations of Mn were weak, but an association was found between U-Mn and respirable Mn; Pearson's r being 0.38 between "soluble" respirable Mn and U-Mn. No significant association was found between the "insoluble" components (probably SiMn) and Mn in biological samples.     

Health impact assessment of air pollution using a dynamic exposure profile: Implications for exposure and health impact estimates

In both ambient air pollution epidemiology and health impact assessment an accurate assessment of the population exposure is crucial. Although considerable advances have been made in assessing human exposure outdoors, the assessments often do not consider the impact of individual travel behavior on such exposures.Population-based exposures to NO₂ and O₃ using only home addresses were compared with models that integrate all time-activity patterns—including time in commute—for Flanders and Brussels. The exposure estimates were used to estimate the air pollution impact on years of life lost due to respiratory mortality.Health impact of NO₂ using an exposure that integrates time-activity information was on average 1.2% higher than when assuming that people are always at their home address. For ozone the overall estimated health impact was 0.8% lower. Local differences could be much larger, with estimates that differ up to 12% from the exposure using residential addresses only. Depending on age and gender, deviations from the population average were seen.Our results showed modest differences on a regional level. At the local level, however, time-activity patterns indicated larger differences in exposure and health impact estimates, mainly for people living in more rural areas. These results suggest that for local analyses the dynamic approach can contribute to an improved assessment of the health impact of various types of pollution and to the understanding of exposure differences between population groups.     

Sampling over time: developing a cost effective and precise exposure assessment program

Studies requiring ambient exposure assessments invariably ask: How often should measurements be taken? Answer to such questions is dictated by budgetary considerations as well as spatial and temporal variability in the data. For example, do we obtain measurements during all seasons, all months within seasons, weeks within months and days within weeks? On one hand, we can obtain a one-time snapshot sample and regard it as representing the "true" mean exposure. On the other hand, we may obtain a large number of measurements over time and then average these in order to represent this "true" mean exposure. The former estimate is the least expensive but may also be the least precise while the latter, may be very precise but prohibitively costly. In this paper, we demonstrate how a pilot study can be undertaken with a potentially promising and feasible sampling plan for the full-scale study. By applying the statistical methodology of variance component analysis (VCA) to the pilot study data and exploiting mathematical relationship between the variance of the overall mean exposure and posited variance components, we can develop a sampling design with decreased sampling costs and/or increased precision of the mean exposure. Our approach was applied to determine sampling design choices for an on-going study that aimed at assessing ambient particulate matter exposure. We conclude that a pilot study followed by the VCA analysis may often lead to sampling design choices that offer considerable cost savings and, at the same time, promise to provide relatively precise estimates of the mean exposure for the subsequent full-scale study.     

Estimating sampling frequency in pollen exposure assessment over time

A time series model was fitted to the pollen concentration data collected in the Greater Cincinnati area for the Cincinnati Childhood Allergy and Air Pollution Study (CCAAPS). A traditional time series analysis and temporal variogram approach were applied to the regularly spaced databases (collected in 2003) and irregularly spaced ones (collected in 2002), respectively. The aim was to evaluate the effect of the sampling frequency on the sampling precision in terms of inverse of standard error of the overall level of mean value across time. The presence of high autocorrelation in the data was confirmed and indicated some degree of temporal redundancy in the pollen concentration data. Therefore, it was suggested that sampling frequency could be reduced from once a day to once every several days without a major loss of sampling precision of the overall mean over time. Considering the trade-offs between sampling frequency and the possibility of sampling bias increasing with larger sampling interval, we recommend that the sampling interval should take values from 3 to 5 days for the pollen monitoring program, if the goal is to track the long-term average.     

Spatial variability of air pollutants in the city of Taranto, Italy and its potential impact on exposure assessment

Epidemiological studies typically use monitored air pollution data from a single station or as averaged data from several stations to estimate population exposure. In industrialized urban areas, this approach may present critical issues due to the spatial complexities of air pollutants which are emitted by different sources. This study focused on the city of Taranto, which is one of the most highly industrialized cities in southern Italy. Epidemiological studies have revealed several critical situations in this area, in terms of mortality excess and short-term health effects of air pollution. The aims of this paper are to study the variability of air pollutants in the city of Taranto and to interpret the results in relation to the applicability of the data in assessing population exposure. Meteorological and pollution data (SO2, NO2, PM10), measured simultaneously and continuously during the period 2006–2010 in five air quality stations, were analyzed. Relative and absolute spatial concentration variations were investigated by means of statistical indexes. Results show significant differences among stations. The highest correlation between stations was observed for PM10 concentrations, while critical values were found for NO2. The worst values were observed for the SO2 series. The high values of 90th percentile of differences between pairs of monitoring sites for the three pollutants index suggest that mean concentrations differ by large amounts from site to site. The overall analysis supports the hypothesis that various parts of the city are differently affected by the different emission sources, depending on meteorological conditions. In particular, analysis revealed that the influence of the industrial site may be primarily identified with the series of SO2 data which exhibit higher mean concentration values and positive correlations with wind intensity when the monitoring station is downwind from the industrial site. Results suggest evaluating the population exposure to air pollutants in industrialized cities by taking into account the possible zones of influence of different emission sources. More research is needed to identify an indicator, which ought to be a synthesis of several pollutants, and take into account the meteorological variables.     

An analytical model for the assessment of pesticide exposure levels in soils and groundwater

The movement and degradation of pesticide residues in soils and groundwater are complex processes affected by soil physical, (bio)chemical, and hydrogeological properties, climatic conditions, and agricultural practices. This work presents a physically-based analytical model suitable for long-term predictions of pesticide concentrations in groundwater. The primary interest is to investigate the impact of soil environment, related physical and (bio)chemical processes, especially, volatilization, crop uptake, and agricultural practices on long-term vulnerability of groundwater to contamination by pesticides. The soil is separated into root and intermediate vadose zones, each with uniform properties. Transport in each soil zone is modeled on the basis of complete mixing, by spatial averaging the related point multiphase-transport partial differential equation (i.e., linear-reservoir models). Transport in the aquifer, however, is modeled by a two-dimensional advection-dispersion transport equation, considering adsorption and first-order decay rate. Vaporization in the soil is accounted for by assuming liquid-vapor phase partitioning using Henry's law, and vapor flux (volatilization) from the soil surface is modeled by diffusion through an air boundary layer. Sorption of liquid-phase solutes by crops is described by a linear relationship which is valid for first-order (passive) crop uptake. The model is applied to five pesticides (atrazine, bromacil, chlordane, heptachlor, and lindane), and the potential for pesticide contamination of groundwater is investigated for sandy and clayey soils. Simulation results show that groundwater contamination can be substantially reduced for clayey soil environments, where bio(chemical) degradation and volatilization are most efficient as natural loss pathways for the pesticides. Also, uptake by cross can be a significant mechanism for attenuating exposure levels in ground-water especially in a sandy soil environment, and for relatively persisting pesticides. Further, simulations indicate that changing agricultural practices can have a profound effect on vulnerability of groundwater to mobile and relatively persisting pesticides.     

Indoor air pollution levels in public buildings in Thailand and exposure assessment

Levels of pollutants including PM2.5 and PM2.5 composition (black carbon and water soluble ions), SO(2), NO(2), CO, CO(2), and BTEX (benzene, toluene, ethylbenzene, xylene) were monitored for indoor and outdoor air at a university campus and a shopping center, both located in the Northern suburb of Bangkok. Sampling was done during December 2005-February 2006 on both weekdays and weekends. At the university, indoor monitoring was done in two different air conditioned classrooms which shows the I/O ratios for all pollutants to be below 0.5-0.8 during the weekends. However, on weekdays the ratios for CO(2) and most detected BTEX were above 1.0. The concept of classroom occupancy was defined using a function of the student number in a lecture hour and the number of lecture hours per day. Classroom 2, which had a higher occupancy than classroom 1, was characterized by higher concentrations of most pollutants. PM2.5 was an exception and was higher in classroom 1 (37 microg/m(3), weekdays) as compared to classroom 2 (26 microg/m(3), weekdays) which was likely linked to the dust resuspension from the carpeted floor in the former. Monitoring was also done in the shopping mall at three different sites. Indoor pollutants levels and the I/O ratios at the shopping mall were higher than at the university. Levels of all pollutants measured at the car park, except for toluene and CO(2), were the highest. I/O ratios of the pollutants at the mall were above 1.0, which indicates the relatively higher influence of the indoor sources. However, the black carbon content in PM2.5 outdoor is higher than indoor, which suggest the important contribution from outdoor combustion sources such as the traffic. Major sources of outdoor air pollution in the areas were briefly discussed. Exposure modeling was applied using the time activity and measured pollutant concentrations to assess the exposure of different groups of people in the study areas. High exposure to PM2.5, especially for the people working in the mall, should be of health effect concern.     

Modelling of occupational respirable crystalline silica exposure for quantitative exposure assessment in community-based case-control studies

We describe an empirical model for exposure to respirable crystalline silica (RCS) to create a quantitative job-exposure matrix (JEM) for community-based studies. Personal measurements of exposure to RCS from Europe and Canada were obtained for exposure modelling. A mixed-effects model was elaborated, with region/country and job titles as random effect terms. The fixed effect terms included year of measurement, measurement strategy (representative or worst-case), sampling duration (minutes) and a priori exposure intensity rating for each job from an independently developed JEM (none, low, high). 23,640 personal RCS exposure measurements, covering a time period from 1976 to 2009, were available for modelling. The model indicated an overall downward time trend in RCS exposure levels of -6% per year. Exposure levels were higher in the UK and Canada, and lower in Northern Europe and Germany. Worst-case sampling was associated with higher reported exposure levels and an increase in sampling duration was associated with lower reported exposure levels. Highest predicted RCS exposure levels in the reference year (1998) were for chimney bricklayers (geometric mean 0.11 mg m(-3)), monument carvers and other stone cutters and carvers (0.10 mg m(-3)). The resulting model enables us to predict time-, job-, and region/country-specific exposure levels of RCS. These predictions will be used in the SYNERGY study, an ongoing pooled multinational community-based case-control study on lung cancer.