Advanced REACH Tool (ART): calibration of the mechanistic model

The mechanistic model of the Advanced Reach Tool (ART) provides a relative ranking of exposure levels from different scenarios. The objectives of the calibration described in this paper are threefold: to study whether the mechanistic model scores are accurately ranked in relation to exposure measurements; to enable the mechanistic model to estimate actual exposure levels rather than relative scores; and to provide a method of quantifying model uncertainty. Stringent data quality guidelines were applied to the collated data. Linear mixed effects models were used to evaluate the association between relative ART model scores and measurements. A random scenario and company component of variance were introduced to reflect the model uncertainty. Stratified analyses were conducted for different forms of exposure (abrasive dust, dust, vapours and mists). In total more than 2000 good quality measurements were available for the calibration of the mechanistic model. The calibration showed that after calibration the mechanistic model of ART was able to estimate geometric mean (GM) exposure levels with 90% confidence for a given scenario to lie within a factor between two and six of the measured GM depending upon the form of exposure.     

Statistical modeling of crystalline silica exposure by trade in the construction industry using a database compiled from the literature

A quantitative determinants-of-exposure analysis of respirable crystalline silica (RCS) levels in the construction industry was performed using a database compiled from an extensive literature review. Statistical models were developed to predict work-shift exposure levels by trade. Monte Carlo simulation was used to recreate exposures derived from summarized measurements which were combined with single measurements for analysis. Modeling was performed using Tobit models within a multimodel inference framework, with year, sampling duration, type of environment, project purpose, project type, sampling strategy and use of exposure controls as potential predictors. 1346 RCS measurements were included in the analysis, of which 318 were non-detects and 228 were simulated from summary statistics. The model containing all the variables explained 22% of total variability. Apart from trade, sampling duration, year and strategy were the most influential predictors of RCS levels. The use of exposure controls was associated with an average decrease of 19% in exposure levels compared to none, and increased concentrations were found for industrial, demolition and renovation projects. Predicted geometric means for year 1999 were the highest for drilling rig operators (0.238 mg m(-3)) and tunnel construction workers (0.224 mg m(-3)), while the estimated exceedance fraction of the ACGIH TLV by trade ranged from 47% to 91%. The predicted geometric means in this study indicated important overexposure compared to the TLV. However, the low proportion of variability explained by the models suggests that the construction trade is only a moderate predictor of work-shift exposure levels. The impact of the different tasks performed during a work shift should also be assessed to provide better management and control of RCS exposure levels on construction sites.     

Air formaldehyde and solvent concentrations during surface coating with acid-curing lacquers and paints in the woodworking and furniture industry

An investigation of contemporary exposure to formaldehyde and organic solvents has been carried out during surface coating with acid-curing lacquers and paints in the Norwegian woodworking and furniture industry over a period of 3 years. The investigation covered 27 factories of different sizes and with different types of production, and totally 557 parallel formaldehyde and solvent samples were collected. The formaldehyde concentration (geometric mean) was 0.15 ppm (range 0.01-1.48 ppm) with about 10% of the samples exceeding the Norwegian occupational exposure limit of 0.5 ppm. The solvent concentration as additive effect (geometric mean) was 0.13 (range 0.0004-5.08) and about 5% of the samples exceeded the Norwegian occupational exposure limit. The most frequently occurring solvents from acid-curing lacquers were n-butyl acetate, ethanol, ethyl acetate and 1-butanol, which were found in 88-98% of the samples. Toluene, n-butyl acetate and 1-butanol were the only solvents with maximum concentrations exceeding their respective occupational exposure limits. Curtain painting machine operators were exposed to the highest concentrations of both formaldehyde (geometric mean 0.51 ppm, range 0.08-1.48 ppm) and organic solvents (additive effect, geometric mean 1.18, range 0.02-5.08). Other painting application work tasks such as automatic and manual spray-painting, manual painting and dip painting, showed on average considerably lower concentrations of both formaldehyde (geometric means 0.07-0.16 ppm) and organic solvents (additive effect, geometric mean 0.02-0.18). Non-painting work tasks also displayed moderate concentrations of formaldehyde (geometric means 0.11-0.17 ppm) and organic solvents (additive effect, geometric mean 0.04-0.07).     

Industrial point source CO<Subscript>2</Subscript> emission strength estimation with aircraft measurements and dispersion modelling

CO₂ remains the greenhouse gas that contributes most to anthropogenic global warming, and the evaluation of its emissions is of major interest to both research and regulatory purposes. Emission inventories generally provide quite reliable estimates of CO₂ emissions. However, because of intrinsic uncertainties associated with these estimates, it is of great importance to validate emission inventories against independent estimates. This paper describes an integrated approach combining aircraft measurements and a puff dispersion modelling framework by considering a CO₂ industrial point source, located in Biganos, France. CO₂ density measurements were obtained by applying the mass balance method, while CO₂ emission estimates were derived by implementing the CALMET/CALPUFF model chain. For the latter, three meteorological initializations were used: (i) WRF-modelled outputs initialized by ECMWF reanalyses; (ii) WRF-modelled outputs initialized by CFSR reanalyses and (iii) local in situ observations. Governmental inventorial data were used as reference for all applications. The strengths and weaknesses of the different approaches and how they affect emission estimation uncertainty were investigated. The mass balance based on aircraft measurements was quite succesful in capturing the point source emission strength (at worst with a 16% bias), while the accuracy of the dispersion modelling, markedly when using ECMWF initialization through the WRF model, was only slightly lower (estimation with an 18% bias). The analysis will help in highlighting some methodological best practices that can be used as guidelines for future experiments.     

Carbon disulfide at a Chinese viscose factory external and internal exposure assessment

This article presents the results of carbon disulfide exposure measurements in a Chinese viscose rayon factory. The objectives of the study were to identify the external exposure levels at a large factory and to investigate the 2-thiothiazolidine-4-carboxylic acid (TTCA) concentrations in the urine of the subjects who were exposed to carbon disulfide in the working place atmosphere. The metabolism of carbon disulfide in the exposed subjects was also studied in order to demonstrate the best points in time for the internal exposure sampling. The measurement of the amount of personal exposure to carbon disulfide in the air of the workplace was performed by GC-FPD; the presence of TTCA in the workers urine was analyzed by use of a modified HPLC method. The kinetics of TTCA excretion was studied by analyses at different time-points both during and after exposure to carbon disulfide in the subjects. A total of 155 personal samples were obtained. The carbon disulfide concentration in the staple viscose hall was 13.72 +/- 1.12 mg m-3 in terms of the geometric mean +/- geometric standard deviation, and was 20.05 +/- 1.33 mg m-3 in the filament spinning hall. The TTCA values in the subjects who worked in the staple spinning hall were 1.18 +/- 0.43 mg g-1 creatinine and 1.07 +/- 0.38 mg g-1 creatinine for subjects working in the filament spinning hall. The best time for TTCA sampling is at the end of the working shift, the TTCA excretion was stable for a period of 4-12 h after exposure of the subjects to the carbon disulfide. It might be that the Chinese have different anthropometric characteristics; a sampling bias may therefore appear among different races.     

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.     

Assessment of uncertainty of NO2 measurements by the chemiluminescence method and discussion of the quality objective of the NO2 European Directive

Hereafter, an assessment of the ability of the chemiluminescence method to measure ambient NO2 with an accuracy within 15%, as requested by the data quality objective of European directive 1999/30/CE, is presented. In general, uncertainty is evaluated using the response to reference materials or by means of inter-comparisons used to determine some statistics like repeatability, reproducibility and calibration bias. These are incomplete approaches and the method of the Guide to the Expression of Uncertainty in Measurement, advised by the Directive, should be preferred. In fact, even if it requires a large data set, it allows the relative influence of all possible sources of uncertainty to be studied. The extent of NO2 uncertainty is mainly dependent on the level of NO. It is decreased by NOx and the correlation between NOx and NO. Furthermore, the uncertainty budget reveals that the contribution of accuracy of calibration standard, linearity, converter efficiency and drift of the analyser between calibration checks to the overall uncertainty is less important than the contribution of interference, mainly humidity and PAN in rural areas. The relative expanded uncertainty of the NO2 hourly average exceeds 30% for NO2 concentrations lower than 40 microg m(-3). Nevertheless, the data quality objective of 15% is reached for 200 microg m(-3), the hourly limit value of the European directive. On the contrary, at the limit value on the annual average, 40 microg m(-3), the data quality objective is not met if NO is higher than 100 microg m(-3). However, the data quality objective could be reached by correcting the measurements with the bias due to interference.     

Intercomparison of five PM10 monitoring devices and the implications for exposure measurement in epidemiological research

Five different instruments for the determination of the mass concentration of PM10 in air were compared side-by-side for up to 33 days in an undisturbed indoor environment: a tripod mounted BGI Inc. PQ100 gravimetric sampler with a US EPA certified Graseby Andersen PM10 inlet; an Airmetrics Minivol static gravimetric sampler; a Casella cyclone gravimetric personal sampler; an Institute of Occupational Medicine gravimetric PM10 personal sampler; and two TSI Inc. Dustrak real-time optical scattering personal samplers. For 24 h sampling of ambient PM10 concentrations around 10 microg m(-3), the estimated measurement uncertainty for the two gravimetric personal samplers was larger (approximately +/- 20%) compared with estimated measurement uncertainty for the PQ100/Graseby Andersen sampler (< +/- 5%). Measurement uncertainty for the Dustraks was lower (approximately +/- 15% on average) but calibration of the optical response against a reference PM10 method is essential since the Dustraks systematically over-read PM10 determined gravimetrically by a factor approximately 2.2. However, once calibrated, the Dustrak devices demonstrated excellent functionality in terms of ease of portability and real-time data acquisition. Estimated measurement uncertainty for PM10 concentrations determined with the Minivol were +/- 5%. The Minivol data correlated well with PQ100/Graseby Andersen data (r= 0.97, n = 18) but were, on average, 23% greater. The reason for the systematic discrepancy could not be traced. Intercomparison experiments such as these are essential for assessing measurement error and revealing systematic bias. Application of two Dustraks demonstrated the spatial and temporal variability of exposure to PM10 in different walking and transport microenvironments in the city of Edinburgh, UK. For example, very large exposures to PM10 were identified for the lower deck of a double-decker tour bus compared with the open upper deck of the same vehicle. The variability observed emphasises the need to determine truly personal exposure profiles of PM10 for quantifying exposure response relationships for epidemiological studies.     

Evaluation of the diffusion size classifier (meDiSC) for the real-time measurement of particle size and number concentration of nanoaerosols in the range 20-700 nm

In the frame of assessing exposure to nanostructured particles, the aim of this work is to study the performance of a new device devoted to the real-time measurement of nanostructured aerosol: the meDiSC (Diffusion Size Classifier, Matter Engineering, Switzerland). This instrument is based on unipolar diffusion charging of particles which are then collected successively in diffusion and filtration stages. From currents measured in these stages, the instrument is capable of determining aerosol mean size and number concentration. These data were compared to reference measurements regarding monodisperse aerosols in a range from 20 to 700 nm; the relative biases were found unsatisfying. This led us to investigate the principle of the instrument. Consequently, the charging law of the diffusion charger was experimentally established, as well as the calibration curve allowing the determination of the mean size of the particles. The latter analysis was completed by a model based on diffusion theory. Our results indicate the possibility to improve the range of size measurement up to 350 nm. Measured particle size and number concentration were also used to calculate geometric surface-area concentration; the experimental data were compared to a reference calculated surface-area concentration. The results demonstrate the possibility to evaluate this parameter within acceptable uncertainty. In a second step, the meDiSC was challenged with polydisperse aerosols. It was observed that meDiSC overestimates particle size by a factor 1.7, while particle number concentrations are found within ±40% of the reference. The model applied to polydisperse aerosols indicates that polydispersity little influences particle size up to 300 nm while geometric standard deviation remains below 1.7.     

6项环境监测分析方法标准中钴、铬、钼、钛的不确定度分析及其在达标判定中的应用

研究依据测定不确定度的基本理论和ISO 21748：2017《采用重复性、再现性和正确度评估测量不确定度的导则》，提出了基于中国环境监测分析方法标准多家实验室验证中已获得的数据计算合成标准不确定度的方法，将方法标准中规定的重复性、再现性等指标与合成标准不确定度进行了衔接。分析了近年发布的6项水质监测分析方法标准中钴、铬、钼、钛等4种金属元素的相对合成标准不确定度，结果表明：被测量的浓度是影响方法标准测量不确定度的重要因素。对于火焰原子吸收分光光度法（FAAS）和石墨炉原子吸收分光光度法（GAAS），样品浓度为方法标准测定下限3倍左右时，测定结果的相对标准不确定度可保持在15%以下；对于电感耦合等离子体发射光谱法（ICP-AES），样品浓度为方法标准测定下限3~5倍时，测定结果的相对标准不确定度为12%~17%；对于电感耦合等离子体质谱法（ICP-MS），钛元素浓度为测定下限3倍左右时，相对标准不确定度在15%以下，而钴、铬、钼的浓度在测定下限40~100倍以上时，相对标准不确定度在15%以下。6项方法标准可分别用于《地表水环境质量标准》（GB 3838—2002）以及22项水污染物排放标准钴、铬、钼、钛的达标监测。     

Passive sampling of glycol ethers and their acetates in indoor air

This study examined the performances of a thermal desorbable radial diffusive sampler for the weekly measurement of eight glycol ethers in indoor air and described the results of an application of this method carried out as part of HABIT'AIR Nord - Pas de Calais program for the air monitoring of these compounds in sixty homes located in northern France. The target compounds were the four glycol ethers banned from sale to the public in France since the 1990s (i.e. 2-methoxy ethanol, 2-ethoxy ethanol and their acetates) and four other glycol ethers derivatives of which the use have increased considerably (i.e. 1-methoxy-2-propanol, 2-butoxy ethanol and their acetates).A test program was carried out with the aim of validating the passive sampling method. It allowed the estimation of all the parameters of a method for each compound (calibration, analytical precision, desorption efficiency, sampling rate in standard conditions, detection limit and stability of sample before and after exposure), the examination of the influence of environmental factors on the sampling rate by some exposure chamber experiments and the assessment of the uncertainty of the measurements.The results of this evaluation demonstrated that the method has turned out to be suitable for six out of eight glycol ethers tested. The effect of the environmental factors on the sampling rates was the main source of measurement uncertainty. The measurements done in sixty homes revealed a relative abundance of 1-methoxy-2-propanol that was found in more than two thirds of homes at concentration levels of 4.5 microg m(-3) on average (a maximum value of 28 microg m(-3)). 1-methoxy-2-propanol acetate and 2-butoxy ethanol were also detected, but less frequently (in 19% of homes) and with the concentrations below 12 microg m(-3). The highest levels of these glycol ethers appear to be in relation to the emissions occurring at the time of cleaning tasks.     

Influence of environmental parameters on the accuracy of nitrogen dioxide passive diffusion tubes for ambient measurement

Two studies at three sites in the UK provided confirmation that systematic positive bias in NO2 diffusion tube measurement occurred because of changes to "within-tube" chemistry, rather than eddy diffusion at the mouth of the tube. In the first study in Cambridge, UK, sampler overestimation for 1 and 2 week exposures was compared to corresponding time-averaged monitor measurements (NO-NO2-NOx, O3) and weather variables. Noninearity between sampler and monitor NO2 measurements was interpreted in terms of spatial and temporal variations in relative and absolute availability of NO, NO2 and O3 at the site. A maximum overestimation occurred for an exposure mean NO2/NOx approximately 0.5. The separate contributions of reduced NO2 photolysis and eddy diffusion were compared in Study II using samplers of two materials, acrylic and quartz, and of different lengths (40, 55, 71 and 120 mm) at three sites: Norwich background, Cambridge intermediate, London kerbside. For compared sites, NO2 measured by acrylic samplers was significantly higher than for equivalent quartz samplers. For quartz samplers [NO2]mean was only just above the monitor at Norwich and London; sampler/monitor NO2 = 1.04 (P = 0.59) and 1.01(P = 0.76), respectively. For acrylic samplers the order of [NO2]mean was 40 mm > 120 mm > 71 mm > or = 55 mm. Excepting 40 mm samplers, this accords with a chemical bias where co-diffusing NO and 03 molecules in longer tubes have more time to react to form excess NO2. Bias in 40 mm samplers is discussed. Eddy diffusion is negligible for standard samplers because [NO2]mean was equivalent for 55 mm and 71 mm acrylic samplers and close to monitor NO2 for 71 mm quartz tubes. Both studies showed that sampler accuracy was dependent on location. Significantly, overestimation was greatest (approximately 3-4 ppb) where the NO2 annual mean was approximately 20 ppb, close to the UK and EU air quality standard of 21 ppb.     

A proficiency testing scheme for aromatic hydrocarbons in air by the manual thermal desorption-GC method: a comparison of laboratory performance with the uncertainty requirements of the European Union Ambient Air Directive

The Workplace Analysis Scheme for Proficiency (WASP) is a proficiency testing scheme for the analysis of occupational hygiene and environmental air samples and is operated in the UK by the Health and Safety Laboratory. Since 1997, WASP has offered samples of benzene, toluene and m-xylene, at environmental levels on Tenax, and has about 35 laboratories participating, mostly from industry, local government and consultancy organisations in the UK. The results reported cover the first 10 rounds of the environmental analytes (1997-1999) and demonstrate the important role of proficiency testing in assessing the quality of laboratory performance. Estimates are obtained for within-laboratory precision and the total variability at each analyte level. The estimates of within-laboratory precision suggest that laboratories have more difficulty analysing toluene and m-xylene than benzene. Linear relationships for the reproducibility relative standard deviation (RSDT) with loading level are evident for the analytes at occupational levels. At environmental levels, the relationship between loading level and reproducibility is much less well defined. The standard deviation for the proficiency testing assessment for all three analytes at the environmental level is 14%, as derived from the benzene data. Expanded uncertainty estimates (k = 1.96), for the analysis of samples since the scheme started, are obtained from the average total variance, and are 27% for benzene, 39% for toluene and 36% for m-xylene. Although the linear trend of performance against round number was not significant at the 95% level of confidence (p = 0.23 for benzene, p = 0.3 for toluene and p = 0.32 for m-xylene), there was a general improvement in RSDT from 26-34% to about 8-13% 10 rounds later. Currently, for a laboratory to meet one of the data quality objectives in the Ambient Air Directive (indicative measurement of benzene, expanded uncertainty +/- 30% or less), it would have to achieve a level of analytical performance to satisfy the category 1 (best performance) limit of better than +/- 8.8%. In the last proficiency testing round, discussed in this paper, only 58% of laboratories obtained performance scores that indicated that they were able to consistently achieve this level of performance.     

Exposure to inhalable dust and endotoxin among Danish livestock farmers: results from the SUS cohort study

Studies on personal dust and endotoxin concentrations among animal farmers have been either small or limited to a few sectors in their investigations. The present study aimed to provide comparable information on the levels and variability of exposure to personal dust and endotoxin in different types of animal farmers. 507 personal inhalable dust samples were collected from 327 farmers employed in 54 pig, 26 dairy, 3 poultry, and 3 mink farms in Denmark. Measurements in pig and dairy farmers were full-shift and performed during summer and winter, while poultry and mink farmers were monitored during 4 well-defined production stages. The collected samples were measured for dust gravimetrically and analyzed for endotoxin by the Limulus amebocyte lysate assay. Simple statistics and random-effect analysis were used to describe the levels and the variability in measured dust and endotoxin exposure concentrations. Measured inhalable dust levels had an overall geometric mean of 2.5 mg m(-3) (range 相似文献   

A comparative study of respirable particulate microenvironmental concentrations and personal exposures

Personal monitoring (PM) for respirable suspended particulate matter (RSP) of thirty subjects was performed as part of an air pollution health effects study conducted in Houston, Texas. Parallel RSP measurements were performed in the study subjects' homes and two fixed site monitoring stations. The participants' daytime activities were independently recorded by study techicians. These data were used to characterize RSP concentrations in each microenvironment visited by the participants. Four estimates of daytime exposure to RSP were calculated based on two different microenvironmental models, and home and fixed site mean daytime RSP concentrations. These estimates were compared to mean daytime personal exposure from PM. Hourly estimates of exposure were calculated from a microenvironmental model and mean hourly home RSP concentrations and compared to hourly PM data. The results of the study indicate that, as in the case of NO₂, it is important to characterize indoor microenvironmental RSP concentrations according to location, sources, and concurrent activities, both qualitatively and quantitatively. Stratification of concentrations according to sources present and self-reported activity can lead to misclassification of exposures. For RSP and, probably, other pollutants with indoor sources and with short exposure integration times, adequate measures of exposure can only be obtained with very detailed and complex microenvironmental models or comprehensive personal monitoring.     

Assessing uncertainty in annual nitrogen,phosphorus, and suspended sediment load estimates in three agricultural streams using a 21-year dataset

Accurate estimation of constituent loads is important for studies of ecosystem mass balance or total maximum daily loads. In response, there has been an effort to develop methods to increase both accuracy and precision of constituent load estimates. The relationship between constituent concentration and stream discharge is often complicated, potentially leading to high uncertainty in load estimates for certain constituents, especially at longer-term (annual) scales. We used the loadflex R package to compare uncertainty in annual load estimates from concentration vs. discharge relationships in constituents of interest in agricultural systems, including ammonium as nitrogen (NH₄-N), nitrate as nitrogen (NO₃-N), soluble reactive phosphorus (SRP), and suspended sediments (SS). We predicted that uncertainty would be greatest in NO₃-N and SS due to complex relationships between constituent concentration and discharge. We also predicted lower uncertainty with a composite method compared to regression or interpolation methods. Contrary to predictions, we observed the lowest uncertainty in annual NO₃-N load estimates (relative error 1.5–23%); however, uncertainty was greatest in SS load estimates, consistent with predictions (relative error 19–96%). For all constituents, we also generally observed reductions in uncertainty by up to 34% using the composite method compared to regression and interpolation approaches, as predicted. These results highlight differences in uncertainty among different constituents and will aid in model selection for future studies requiring accurate and precise estimates of constituent load.     

Interlaboratory evaluation of an extraction and fluorescence method for the determination of trace beryllium in soils

Analytical methods for the determination of trace beryllium in soils are needed so that anthropogenic sources of this element can be distinguished from native (background) levels of beryllium. In this work, a collaborative interlaboratory evaluation of a new extraction and fluorescence-based procedure for determining beryllium in soil samples was carried out to fulfil method validation requirements for ASTM International voluntary consensus standard test methods. A Canadian reference material, CCRMP Till-1 soil, with a background beryllium concentration of 2.4 microg g(-1), was selected for study. This certified reference material (CRM) was spiked and homogenized with varying levels of beryllium oxide in order to give batches of material with beryllium concentrations of 4.36 +/- 0.69, 11.5 +/- 0.7, 124 +/- 7 and 246 +/- 16 microg g(-1) (+/- values are standard deviations). In the interlaboratory study (ILS), which was carried out in accordance with an applicable ASTM International standard practice (ASTM E691), samples of these spiked soils were subjected to extraction in dilute ammonium bifluoride at approximately 90 degrees C for 40 h. Fluorescence measurement of the extracted beryllium was carried out via detection using the high quantum yield fluorophore, hydroxybenzoquinoline sulfonate (HBQS). Interlaboratory precision estimates from six participating laboratories ranged from 0.048 to 0.103 (relative standard deviations) for the five different beryllium concentrations. Pooled bias estimates resulting from this ILS were between -0.049 and 0.177 for the various beryllium levels. These figures of merit support promulgation of the analytical procedure as an ASTM International standard test method.     

Environmental and Biological Assessment of Exposure to Benzene in Petroleum Workers

Occupational exposure to benzene was measured in two gasoline marketing terminals and five major refineries in Singapore. A total of 280 workers were monitored over two years. This assessment was carried out with two primary objectives: (1) To find out the extent of occupational exposure to benzene in the petroleum industry in Singapore, (2) To identify suitable biomarkers for monitoring of low levels of benzene exposure. The exposure was measured in five different categories of petroleum and petrochemical workers, i.e., truck drivers, despatch assistant, process operators, oil movements operators and laboratory technicians. The results revealed wide variations in exposure, from 0.01 to 13.6 ppm for personal time weighted average (TWA) exposure over the whole workshift. The exposure of truck drivers appeared to be the highest, with geometric mean (GM) of 1.98 ppm (ranged from 0.25 to 13.6 ppm). The average benzene exposure for process operators was relative low with a GM of 0.04 ppm. Lowest benzene exposure was found in the laboratory technicians, with a GM of 0.02 ppm. As cigarette smoking is known to affect metabolism of benzene, data analyses on the relationships with environmental exposure were conducted only on the 190 nonsmokers. The results showed that urinary trans, trans-muconic acid (ttMA), unmetabolized benzene in urine (UBZ) and benzene in blood (BBZ) were better biomarkers for low level benzene exposure as compared to urinary phenolic metabolites in urine, such as hydroquinone, phenol and catechol.     

Comparison of tanker drivers' occupational exposures before and after the installation of a vapour recovery system

The purpose of this study was to compare tanker drivers' occupational exposure level before and after the installation of vapour recovery facilities at 14 service stations. Road tanker drivers are exposed when handling volatile petrol liquid in bulk in the distribution chain. The drivers' exposure was studied during the unloading operation as the bulk petrol flowed into underground storage tanks, displacing vapours in the tank space and causing emission to the environment and the drivers' work area. The exposures were measured again when the dual point Stage I vapour recovery systems were installed for recycling vapours. Short-term measurements were carried out in the drivers' breathing zones by drawing polluted air through a charcoal tube during unloading. The samples were analysed in the laboratory by gas chromatography for C3-C11 aliphatic hydrocarbons, tert-butyl methyl ether (MTBE), tert-amyl methyl ether (MTAE), benzene, toluene and xylene. The road tanker loads delivered consisted of oxygenated and reformulated petrol (E95 and E98 brands), which contained on average 13% oxygenates. Before the installation of the vapour recovery system, the geometric mean (GM) concentration of aliphatic hydrocarbons was 65 mg m-3 (range 6-645 mg m-3) in the drivers' breathing zones. After the installation at the same service stations, the corresponding exposure level was 8.3 mg m-3 (range < 1-79 mg m-3). The GM of the MTBE concentrations was 8.6 mg m-3 (range 1-67 mg m-3) without vapour recovery and 1.5 mg m-3 (range < 0.1-10 mg m-3) with vapour recovery. The differences between the aliphatic hydrocarbons and the MTBE exposure levels during the unloading of the road tankers without and with vapour recovery were statistically significant (p < 0.05).     

Laboratory and field comparison of measurements obtained using the available diffusive samplers for ozone and nitrogen dioxide in ambient air

This study presents an evaluation of the extent of differences between measurements performed by O(3) and NO(2) diffusive samplers and by the reference methods for diffusive samplers commercially available. The tests were performed in an exposure chamber under extreme conditions of controlling factors and under field conditions. For NO(2), the results of the laboratory experiments showed that most of the diffusive samplers were affected by extreme exposure conditions. The agreement between the samplers and the reference method was better for the field tests than for the laboratory ones. The estimate of the uptake rate for the exposure conditions using a model equation improved the agreement between the diffusive samplers and the reference methods. The agreement between O(3) measured by the diffusive samplers and by the reference method was satisfactory for 1-week exposure. For 8-hour exposures, the diffusive samplers with high uptake rates quantified better the O(3) concentration than the samplers with low uptake rates. As for NO(2), the results of the O(3) field tests were in better agreement with the reference method than the ones of the laboratory tests. The field tests showed that the majority of diffusive samplers fulfils the 25% uncertainty requirement of the NO(2) European Directive and the 30% uncertainty requirement of the O(3) European Directive for 1-week exposure.