Characterization of particle exposure during tunnel excavation by tunnel boring machines.

Tunnel boring machines (TBMs) are used to excavate tunnels in a manner where the rock is constantly penetrated with rotating cutter heads. Fine particles of the rock minerals are thereby generated. Workers on and in the vicinity of the TBM are exposed to particulate matter (PM) consisting of bedrock minerals including α-quartz. Exposure to respirable α-quartz remains a concern because of the respiratory diseases associated with this exposure. The particle size distribution of PM and α-quartz is of special importance because of its influence on adverse health effects, monitoring and control strategies as well as accurate quantification of α-quartz concentrations. The major aim of our study was therefore to investigate the particle size distribution of airborne PM and α-quartz generated during tunnel excavation using TBMs in an area dominated by gneiss, a metamorphic type of rock. Sioutas cascade impactors were used to collect personal samples on 3 separate days. The impactor fractionates the dust in 5 size fractions, from 10 µm down to below 0.25 µm. The filters were weighted, and the α-quartz concentrations were quantified using X-ray diffraction (XRD) analysis and the NIOSH 7500 method on the 5 size fractions. Other minerals were determined using Rietveld refinement XRD analysis. The size and elemental composition of individual particles were investigated by scanning electron microscopy. The majority of PM mass was collected on the first 3 stages (aerodynamic diameter = 10 to 0.5 µm) of the Sioutas cascade impactor. No observable differences were found for the size distribution of the collected PM and α-quartz for the 3 sampling days nor the various work tasks. However, the α-quartz proportion varied for the 3 sampling days demonstrating a dependence on geology. The collected α-quartz consisted of more particles with sizes below 1 µm than the calibration material, which most likely affected the accuracy of the measured respirable α-quartz concentrations. This potential systematic error is important to keep in mind when analyzing α-quartz from occupational samples. Knowledge of the particle size distribution is also important for control measures, which should target particle sizes that efficiently capture the respirable α-quartz concentration.

Job function as determinant of clinker exposure at workplaces during cement production.

OBJECTIVES: In the cement production industry, exposure to airborne particulate matter is associated with a decline in lung function and increased airway symptoms. Exposure to clinker-the major constituent of cement and supposedly the cause of the observed adverse health effects-was determined recently in 15 cement production plants located in 8 different countries (Estonia, Greece, Italy, Norway, Sweden, Switzerland, Spain, Turkey). It was shown that the median clinker abundance in the thoracic fraction varied between approximately 20% and 70% for individual plants. The present study complements the previous work by investigating the significance of job function as a determinant of clinker exposure. METHODS: The elemental composition (water and acid-soluble fractions separately) of 1,227 personal thoracic workplace samples was analyzed by positive matrix factorization (PMF) to determine the contribution of different sources to the composition of airborne particulate matter and to quantify the clinker content. RESULTS: Median thoracic mass air concentrations varied for individual job functions between 0.094 and 12 mg/m3 (estimated separately for different plants). The PMF 5-factor solution yielded median relative clinker abundances in the personal thoracic samples between 7.6% and 81% for individual job functions. Thoracic clinker air concentrations are highest for cleaning, production, and maintenance work, and lowest for administration and other work. Foremen and laboratory personnel show intermediate exposure levels. The plant was found to have a much higher contribution to the total variance of the thoracic clinker air concentrations than the job function. Thoracic clinker air concentrations (medians between 0.01 and 5.5 mg/m3) are strongly correlated with the thoracic mass air concentrations and to a lesser extent with the relative clinker abundance in an aerosol sample. CONCLUSIONS: Job function is an important predictor of exposure to clinker in the cement production industry. As clinker is suspected to be the causal agent for the observed adverse health effects among cement production workers, the clinker air concentration may be a better exposure metric than thoracic air mass concentration despite the strong correlation between the two. Reduction strategies should focus on the most exposed job categories cleaning, production, and maintenance work.

Content of clinker and other materials in personal thoracic aerosol samples from cement plants estimated by scanning electron microscopy and energy-dispersive X-ray microanalysis.

OBJECTIVES: To estimate the composition and exposure to clinker and other specific components in personal thoracic dust samples of cement production workers. METHODS: A procedure for the classification of airborne particles in cement production plants was developed based on classification trees. For this purpose, the chemical compositions of 27,217 particles in 29 material samples (clinker, limestone, gypsum, clay, quartz, bauxite, iron source, coal fly ash, and coal) were determined automatically by scanning electron microscopy (SEM) and energy-dispersive X-ray microanalysis (EDX). The concentrations of the major elements in cement (calcium, aluminium, silicon, iron, and sulphur) were used for the classifications. The split criteria of the classification trees obtained in the material samples were used to classify 44,176 particles in 34 personal thoracic aerosol samples. The contents of clinker and other materials were estimated, and the clinker contents were analysed statistically for differences between job types and job tasks. RESULTS: Between 64% and 88% of the particles from material samples were classified as actual materials. The material types with variable composition (clay, coal fly ash, and coal) were classified with the lowest consistency (64% to 67%), while materials with a more limited compositional variation (clinker, gypsum, and quartz) were classified more consistently (76% to 85%). The arithmetic mean (AM) of the clinker content in personal samples was 62.1%, the median was 55.3%, and 95% confidence interval (CI) was 42.6% to 68.1%. No significant differences were observed between job types. However, the clinker content in samples when workers handled materials with high clinker content was significantly higher than when materials with lower clinker content were handled, 85% versus 65% (P = 0.02). The limestone content was AM 14.8%, median 13.2% (95% CI 5.5 to 20.9), whereas the other materials were present with relative abundances of median ≤ 6.4%. DISCUSSION: Automated particle analysis by SEM-EDX followed by classification tree analysis quantified clinker with fairly high consistency when evaluated together with raw materials that are expected to be airborne in cement production plants. The clinker proportions for job types were similar. Tasks a priori ranked by assumed clinker content were significantly different and according to expectations, which supports the validity of the chosen methodology. CONCLUSIONS: The composition of personal samples of mineral aerosols in the cement production industry could be estimated by automated single particle analysis with SEM-EDX and classification by a classification tree procedure. Clinker was the major component in the thoracic aerosol that cement production workers were exposed to. Differences between job types were relatively small and not significant. The clinker content from tasks was in agreement with assumptions.

The variability of arsenic in blood and urine of humans.

BACKGROUND: Humans are exposed to inorganic and organic arsenic. The total arsenic (As) concentration in urine is a commonly used biomarker of exposure. However, little is known about variability of As in biological fluids and the diurnal variation of As excretion. OBJECTIVES: Main objectives were to assess the variability of As in urine, plasma (P-As), whole blood (B-As), and the blood cell fraction (C-As), and to assess diurnal variation of As excretion. METHODS: Six urine samples were collected at fixed times during 24 h on two different days around one week apart among 29 men and 31 women. Blood samples were collected when the morning urine samples were delivered. The intra-class correlation coefficient (ICC) was calculated as the ratio of the between-individuals variance to the total observed variance. RESULTS: Geometric mean (GM) 24 h urinary excretions of As (U-As24 h) were 41 and 39 µg/24 h on the two days of sampling. Concentrations of B-As, P-As and C-As were highly correlated with U-As24 h and As in first void morning urine. No statistically significant differences were observed for the urinary As excretion rate between the different sampling times. A high ICC was observed for As in the cellular blood fraction (0.803), while ICC for first morning urine corrected for creatine was low (0.316). CONCLUSIONS: The study suggests that C-As is the most reliable biomarker for use in exposure assessment of individual exposure. Morning urine samples have low reliability for such use. No apparent diurnal variation was observed in the urinary As excretion rate.

Chemical Composition of Thoracic Dust at Workplaces During Cement Production.

OBJECTIVES: Cement belongs to the most used building materials. Clinker is the major constituent of cement, and it is believed that the strong increase of pH after hydration of clinker minerals is responsible for the observed decline in lung function of cement production workers. Information on clinker exposure at workplaces in the cement production industry is scarse. The aims of this study are to determine the chemical composition of thoracic dust and to quantify workplace exposure to clinker in cement production. METHODS: The elemental composition of 1250 personal thoracic samples collected at workplaces in 15 plants located in 8 different countries (Estonia, Greece, Italy, Norway, Sweden, Switzerland, Spain, Turkey) was determined by inductively coupled plasma optical emission spectrometry (ICP-OES), separately for water- and acid-soluble fraction. Positive matrix factorization (PMF) was used to determine the contribution of different sources to the dust composition and to quantify the clinker content in 1227 of the thoracic samples. In addition, 107 material samples were analysed to facilitate interpretation of the factors obtained by PMF. RESULTS: The median thoracic mass concentrations varied for individual plants between 0.28 and 3.5 mg/m3. PMF with 8 water-soluble and 10 insoluble (i.e., acid-soluble) element concentrations yielded a five-factor solution: Ca, K, Na sulfates; silicates; insoluble clinker; soluble clinker-rich; and soluble Ca-rich. The clinker content of the samples was calculated as sum of the insoluble clinker and soluble clinker-rich factors. The median clinker fraction of all samples was 45% (range 0-95%), and varied between 20% and 70% for individual plants. DISCUSSION: The 5-factor solution of PMF was selected on the basis of several mathematical parameters recommended in the literature as well as the mineralogical interpretability of the factors. In addition, interpretation of the factors was supported by the measured apparent solubility of Al, K, Si, Fe, and to a lesser extent Ca in material samples. The total clinker content obtained in the present study is considerably lower than estimates based on the Ca concentrations in a sample, and somewhat lower than estimates based on Si concentrations after selective leaching with a methanol/maleic acid mixture. The clinker abundance in workplace dust of one plant investigated in the present contribution was also estimated in a recent study by electron microscopy, and the good agreement between both studies gives confidence in the results of PMF. CONCLUSIONS: The clinker fraction in personal thoracic samples could be quantified from the chemical composition by positive matrix factorization. Our results allow for further epidemiological analyses of health effects in the cement production industry. As these estimates are more accurate for clinker exposure than aerosol mass, stronger associations with respiratory effects are expected if clinker is the main cause of these effects.

Urinary iodine excretion and optimal time point for sampling when estimating 24-h urinary iodine.

Iodine deficiency may cause thyroid dysfunction. The iodine intake in a population is measured by urinary iodine concentration (UIC) in spot samples or 24-h urinary iodine excretion (24UIE). 24UIE is considered the gold standard and may be estimated using an equation including UIC, urinary creatinine concentration, sex and age (e24UIE). The aims of this study were to evaluate the preferable timing of UIC when using this equation and assess the variability of UIE. Sixty healthy non-smoking women (n 31) and men (n 29) were included in Gothenburg, Sweden. Twelve urine samples were collected at six fixed times on two separate days. Variability was calculated for UIC, 24UIE, e24UIE, iodine excretion per hour (iHr) and UIC adjusted for creatinine and specific gravity. Median 24UIE was 156 µg/24 h and the median UIC (all spot samples) was 104 µg/l. UIC (P < 0·001), 24UIE (P = 0·001) and e24UIE (P < 0·001) were significantly higher in men. e24UIE was relatively similar to 24UIE. However, when e24UIE was calculated from UIC in the first void, it was about 15 % lower than 24UIE (P < 0·001). iHr was lowest in the morning and highest in the afternoon. Median iHr was higher in men (7·4 v. 5·3 µg/h, P < 0·001). The variability of UIE was higher within individuals than between individuals. This study suggests that most time points for estimation of individual 24UIE are appropriate, but they should preferably not be collected in the first void.

Exhaust and non-exhaust contributions from road transport to PM10 at a Southern European traffic site.

It is a well - established fact that road traffic is one of the main contributors to ambient levels of airborne particulate matter (APM). This study was carried out at a traffic site in which the PM10 levels are monitored all year round. A trend analysis of these levels revealed that over a decade there was no discernible trend, with the PM10 concentrations normally hovering around the EU limit values. In 2018, one of these limit values was exceeded. The contribution of traffic at the site was therefore investigated through a chemical speciation of 209 PM10 samples collected throughout this year. The speciation data were used in a source apportionment exercise in which the output of the PMF model was further refined using the lesser-known, constraint weighted non - negative matrix factorization (CW - NMF) model. This technique enabled the isolation of two factors clearly related to traffic, which were labelled as "exhaust contribution" (responsible for 3.4% of the PM10), "tire/brake wear contribution" (contributing 17% of the PM10). Additionally, a factor including both traffic resuspended dust and crustal material was also isolated and labelled "road dust/crustal" factor. The two contributors to the factor jointly contribute 18% to the PM10 and the contribution of the traffic resuspended dust was estimated at 7.3%. The traffic resuspended component of this factor together with the "tire/brake wear contribution" jointly make up the non-exhaust contribution of traffic - derived dust. Consonant with what has been known for quite some time, the exhaust fraction is the minor component of traffic PM10. It is therefore, clear that policies aimed at controlling traffic derived PM10 pollution at the receptor will have a minimal effect unless the non - exhaust emissions are adequately controlled.

Physicochemical characterization of particulate matter in a cement production plant.

Employees working in cement production plants are exposed to airborne particulate matter (PM) which may lead to lung function impairments and airway symptoms. The PM consists of raw materials, clinker and additives which vary depending on cement blend. The aim of this work was to characterize the thoracic fraction of PM with regard to size, phase composition and mixing state. Both stationary and personal impactors were used to collect size-fractionated samples in a cement production plant in Norway. Stationary samples were measured with aerosol particle counters and collected with a 13-stage cascade impactor, which were stationed at three locations of the cement production plant: at the raw meal mill, clinker conveyor belt and cement mill. Sioutas cascade impactors, and thoracic and respirable dust samplers were used in parallel for personal sampling. Additionally, particles for electron microscopy were collected with the stationary cascade impactor for size-fractionated single particle characterization. Gravimetric measurements and element compositions of the samples from the stationary impactors show that the PM mass is dominated by calcium-rich particles of size >1 µm. The size distribution results of stationary and personal impactors were similar. Characterization of single particles reveals that limestone is the dominating material in the raw meal mill, whereas clinker and limestone dominate at the clinker conveyor belt and at the cement mill. The element composition of clinker PM did not change with particle size. The PM collected on impactor stages with aerodynamic diameter cut-offs below 0.56 µm was dominated by soot and volatile secondary particles at the three locations. The number of ultrafine particles of the cement related compounds was low. Air concentrations of PM in personal respirable and thoracic samples ranged from 0.14-10 mg m-3 to 0.37-9.5 mg m-3, respectively. Considerable local variations exist, both in composition and air concentration of the PM.

Variability of lead in urine and blood in healthy individuals.

BACKGROUND: Lead is a non-essential toxic trace element. Lead in blood (BPb) is the most common biomarker of lead exposure but lead in urine (UPb) has also been used. There is, however, limited data on the variability of UPb in the general population and the association with BPb. OBJECTIVES: Our aims were to assess variability of lead in repeated blood and urine samples. The diurnal variation of UPb was also examined as well as associations with BPb. METHODS: We established an openly available biobank including 60 healthy non-smoking individuals, 29 men and 31 women, 21-64 years of age (median 31 years), with repeated sampling of blood and urine. Timed urine samples were collected at six fixed time points in two 24 h periods, about one week apart, and adjusted for creatinine and specific gravity (SG). BPb and UPb were analyzed by inductively coupled plasma mass spectrometry. The within- and between-individual variabilities and intra-class correlation coefficients (ICCs; ratios of the between-individual to total observed variances) were calculated using mixed-effects models. RESULTS: The ICCs for UPb samples were mostly above 0.5, when adjusted for creatinine or SG, and higher for overnight samples compared with daytime samples. The highest ICCs were obtained for BPb (ICC = 0.97) and for urine samples corrected for dilution by SG or creatinine. The ICC was 0.66 for overnight samples adjusted for creatinine. High correlations with BPb were found for 24 h UPb (rs = 0.77) and overnight samples, e.g. rs = 0.74 when adjusted for SG. There was diurnal variation of UPb with lowest excretion rate in overnight samples. There was also a significant association between the Pb excretion rate and urinary flow rate. CONCLUSIONS: In addition to BPb, UPb adjusted for creatinine or SG seems to be a useful biomarker for exposure assessment in epidemiological studies.

Particle characterisation and bioaccessibility of manganese in particulate matter in silico- and ferromanganese smelters.

The aim of this study was to characterise particulate matter (PM) collected in the furnace area during SiMn and high carbon (HC)-FeMn production in terms of single particle analysis and to determine the bioaccessibility of Mn in the PM in a simulated lung fluid. Airborne PM was collected with Sioutas cascade impactors and respirable cyclones in the breathing zone of tappers and crane operators. Stationary samples were collected from the furnace area with a nanoMOUDI cascade impactor and an ESPnano electrostatic particle collector. Individual particles were characterised by scanning and transmission electron microscopy. Bioaccessibility of Mn was studied in terms of the dissolution of Mn in Gamble solution (24 hours leaching at 37 °C) relative to total Mn. Slag particles, alloy fragments, Mn and Fe oxides as well as carbonaceous particles were observed in the size fraction > 1 µm aerodynamic diameter (dae). Thermally generated condensation particles dominated the dae size range of 0.18-1 µm collected from the tapping fumes, while carbonaceous particles dominated the fraction below 0.18 µm. Condensation generated particles from the furnace area of HC-FeMn production were coated with an amorphous Si-O rich surface layer which seemed to hold primary particles together as aggregates. In the same size range, the particles from the furnace area of SiMn production were dominated by spherical condensation particles rich in Si, Mn and O, but without a Si-O rich surface layer. Instead, the Mn oxides were enclosed in an amorphous Si-O rich matrix. The bioaccessibility of Mn was low to moderate (<30%), but higher for SiMn furnace workers (highest median = 23%) than HC-FeMn furnace workers (highest median = 12%). This difference in bioaccessibility was significant for PM with dae up to 2.5 µm, and most pronounced in the dae size range between 0.25 and 1.0 µm. Also, a significantly higher bioaccessibility of Mn was found for PM larger than dae of 0.5 µm collected among crane operators compared to tappers in the HC-FeMn smelter.

Normal variability of 22 elements in 24-hour urine samples - Results from a biobank from healthy non-smoking adults.

BACKGROUND: Urine is often used for biomonitoring the exposure to elements. However, most studies report concentrations in spot urine samples, which may not accurately mirror the "gold standard" of complete 24-h (24 h) urine samples. There are relatively few data published for 24 h samples, and little information on the within- and between person variability. OBJECTIVES: The present study aimed at assessing variability within and between individuals in 24 h excretion for a number of elements in adults from the general population and the typical 24 h excretion of these elements. In addition, we assessed concentrations adjusted for creatinine and specific gravity (SG), and associations between elements. METHODS: 60 healthy non-smokers (31 women and 29 men) from Sweden, aged 21-64 years, collected all urine during 24 h (split into six separate samples) on two occasions, about one week apart. Concentrations of As, Br, Cd, Co, Cr, Cu, Fe, Hg, Li, Mn, Mo, Ni, P, Pb, S, Sb, Se, Sn, U, V, W, and Zn in urine were analyzed by inductively coupled plasma sector-field mass spectrometry (ICP-SF-MS) and 24 h excretion rates were calculated for each day. The ratio of between-individual variance and the total variance, the intra-class correlation (ICC) was calculated based on natural log-transformed 24 h excretion. Correlation coefficients were calculated between excretion rates (mass/24 h), and concentrations adjusted for creatinine and SG. RESULTS: Geometric means (GM), and 90-percentiles are presented for each element. The 24 h excretion was higher in men than in women for most elements, and the difference was statistically significant for Cr, Cu, Fe, Li, P, Pb, S, Se, U, V, and Zn. However, for Cd and Co, the excretion was higher in women. Variability between days was low for Cd, Co, Hg, Pb, Sn, Se, V, and Zn (ICC 0.75-0.90), highest for Cr (ICC = 0.3) and Sb (ICC = 0.18), and moderate for the other elements. Spearman's rank correlation coefficients were about 0.8-0.9 for 17 elements, and 0.3-0.7 for Br, Cu, P, S, Se. Excretion of P and S were highly correlated, and also associated with excretion of most of the other elements, especially Cu, Se, V, and Zn. A high correlation was also found between As and Hg, between Mo and W, as well as between Cr, Fe and Mn. CONCLUSIONS: These data present normal variability of 24 h excretion of a number of elements, and can also be used as updated reference levels for elements with no or limited previous literature available. Information on variability within- and between individuals is important to know when designing studies with urine levels of elements used as exposure biomarker in studies of associations with health outcomes.

Investigating the plausibility of a PMF source apportionment solution derived using a small dataset: A case study from a receptor in a rural site in Apulia - South East Italy.

Results of a methodological study on the use of Positive Matrix Factorization (PMF) with smaller datasets are being reported in this work. This study is based on 29 PM10 and 33 PM2.5 samples from a receptor in a rural setup in Apulia (Southern Italy). Running PMF on the two size fractions separately resulted in the model not functioning correctly. We therefore, augmented the size of the dataset by aggregating the PM10 and PM2.5 data. The 5-factor solution obtained for the aggregated data was fairly rotationally stable, and was further refined by the rotational tools included in USEPA PMF version 5. These refinements include the imposition of constraints on the solution, based on our knowledge of the chemical composition of the aerosol sources affecting the receptor. Additionally, the uncertainties associated with this solution were fully characterised using the improved error estimation techniques in this version of PMF. Five factors in all, were isolated by PMF: ammonium sulfate, marine aerosol, mixed carbonaceous aerosol, crustal/Saharan dust and total traffic. The results obtained by PMF were further tested inter alia, by comparing them to those obtained by two other receptor modelling techniques: Constrained Weighted Non-negative Matrix Factorization (CW - NMF) and Chemical Mass Balance (CMB). The results of these tests suggest that the solution obtained by PMF, is valid, indicating that for this particular airshed PMF managed to extract most of the information about the aerosol sources affecting the receptor - even from a dataset with a limited number of samples.

On the bio-accessibility of 14 elements in welding fumes.

The bio-accessibility of 14 elements in welding fume particulate matter was investigated in 325 personal air samples collected during welding in two shipyards and one factory producing heavy machinery. The apparent solubility in a synthetic lung lining fluid (Hatch's solution) was used as proxy for the bio-accessibility. The Hatch solubility of the different elements was highly variable with a median < 1% for Al, Fe, Pb, Ti, between 4 and 6% for Co, Cr, Ni, V, W, between 13 and 27% for Cd, Cu, Mn, Zn, and 41% for Mo. For many elements, the solubility varied over a wide range of several tens of percent. The welding techniques used influenced the solubility of Co, Cr, Cu, Mn and V significantly. The plants investigated (i.e., the welded materials and used electrodes) had a significant influence on the solubility of Co, Cr, Cu, Mn, Mo, V and W. According to principal component analysis (PCA), the variation in solubility can be described by four components, which explain 69% of the variance. The first principal component mostly comprises elements that can predominantly occur as divalent cations, the second principal component elements often forming oxyanions. The principal components are independent of the absolute value of the Hatch solubility. The results of PCA indicate that the co-variation of Hatch solubility is mainly controlled by the most soluble compounds in contrast to the absolute value of apparent solubility, which is strongly influenced by the distribution of the elements between compounds with different equilibrium solubilities. The observed large variability and the significant differences between welding techniques and plants clearly show that the bio-accessibility cannot be obtained from the literature but has to be studied experimentally at each location of interest.

Comparison of operator- and computer-controlled scanning electron microscopy of particles from different atmospheric aerosol types.

Individual aerosol particles from an urban background site in Mainz (Germany), a traffic hotspot site in Essen (Germany), the free troposphere in the Swiss Alps (high altitude research station Jungfraujoch), a rural background/marine site on Cyprus (Cyprus Atmospheric Observatory) and a rural background site in the forested area of Odenwald (Germany) were characterised with two different scanning electron microscopy techniques, operator controlled (opSEM) and computer controlled (ccSEM). For all samples, about 500 particles were investigated by opSEM, and between 1103 and 6940 particles by ccSEM. Large systematic differences (in some cases a factor up to ~ 20) in the abundance of the various particle groups are observed in the results of the two techniques. These differences are dependent on particle type and size. With ccSEM, information on the mixing state of particles (e.g., presence of heterogeneous inclusions, surface coatings or gradients in chemical composition) cannot be obtained, and particle groups which are recognised by their complex morphology (e.g., soot and fly ash particles) are classified into other particle groups. In addition, highly volatile particles (i.e., particles which evaporate under electron bombardment within seconds) will be overlooked by ccSEM. If these limitations of ccSEM are not considered, normalising the particle group abundances to 100% (a popular practise in many publications) may lead to drastic misinterpretation of the real aerosol composition. OpSEM is indispensable when detailed information of particle composition is required, although it suffers from a much higher expenditure of time. In conclusion, both techniques might be used for single particle characterisation as long as drawbacks of each are considered.

Elemental Carbon and Nitrogen Dioxide as Markers of Exposure to Diesel Exhaust in Selected Norwegian Industries.

Elemental carbon (EC) and nitrogen dioxide (NO2) in air as markers for diesel exhaust (DE) emission exposure were measured in selected work environments in Norway where diesel-powered engines are in use. Two hundred and ninety personal full-shift air samples were collected in primary aluminium production, underground and open-pit mining, road tunnel finishing, transport of ore, and among airport baggage handlers. EC was determined in the samples by a thermo-optical method, while NO2 was determined by ion chromatography. Highest EC air concentrations (geometric mean, GM) were found in aluminium smelters (GM = 45.5 µg m-3) followed by road tunnel finishing (GM = 37.8 µg m-3) and underground mining activities (GM = 18.9 µg m-3). Low EC air concentrations were measured for baggage handling at an international airport (GM = 2.7 µg m-3) and in an open-pit mine (GM = 1.2 µg m-3). Air concentrations of NO2 were similar in road tunnel finishing (GM = 128 µg m-3) and underground mining (GM = 108 µg m-3). Lower NO2 values were observed in open-pit mining (GM = 50 µg m-3), at the airport (GM = 37 µg m-3), and in the aluminium smelters (GM = 27 µg m-3). Highly significant (P < 0.001) positive correlations between NO2 and EC air concentrations in underground mining (r = 0.54) and road tunnel finishing (r = 0.71) indicate a common source of these pollutants. NO2 and EC were also correlated (P < 0.01) positively at the airport. However, due to the complex air chemistry and a potential contribution of various sources, the correlation between EC and NO2 cannot be regarded as unambiguous hint for a common source. The association between EC and NO2 was not of statistical significance in open-pit mining. In the aluminium smelters, EC and NO2 were negatively correlated, although not reaching statistical significance. The substantial differences in NO2/EC ratios across the investigated industries, ranging from around 0.2 in the primary aluminium production to around 25 during spring at the airport, clearly show that exposure to DE cannot be estimated based on NO2 concentrations, at least for outdoor environments. Results in the primary aluminium production suggest that the measured EC concentrations are related to DE emissions, although the NO2 concentrations were low. Further studies are required to assess the magnitude of exposure in primary aluminium production.

Size distribution and single particle characterization of airborne particulate matter collected in a silicon carbide plant.

The global SiC market is projected to grow in the coming years, and research on potential health effects as well as epidemiological studies is therefore of importance. A detailed characterization in terms of the phase composition, morphology and mixing state of airborne PM is still missing, though highly necessary to identify sources and to understand the risk factors in this industry. Particles in the size range of 10 nm to 10 µm were collected with a 13-stage NanoMOUDI impactor in the Acheson Furnace Hall as well as in processing departments during two sampling campaigns. Particle mass concentrations, including the fraction of ultrafine particles (UFPs), were lower in the processing departments in comparison to those in the Acheson Furnace Hall. The particle number size distribution measured with a scanning mobility particle sizer confirmed the low amount of UFPs in the processing departments compared to the furnace hall. Significant differences in the particle mass concentration and distribution were observed in the Acheson Furnace Hall during the two sampling campaigns. The PM size distribution depends upon the sampling location, on the cycle of the nearby furnaces and on special incidents occurring during a furnace run. Scanning and transmission electron microscopy (SEM and TEM) showed that the size range of 0.32-10 µm (aerodynamic diameter) is dominated by carbon (C)-rich particles, which were identified as petroleum coke, graphite, soot and amorphous spherical C-rich particles. Soot was further classified into three types based on the primary particle size, morphology and composition. Diesel-powered vehicles, pyrolysis of petroleum coke and incomplete combustion of volatile components from this pyrolysis are suggested as sources of different soot particle types. Amorphous spherical C-rich particles were also sub-classified based on their morphology and composition as tar balls (TBs) and C-spherical type 2. The amount of SiC fibers and crystalline SiO2 was found to be low. In the size fraction below 0.32 µm (aerodynamic diameter), sulphur (S)-rich particles dominate. This knowledge of the particle size distribution, and chemical and physical properties of the PM occurring in the SiC production is fundamental for an appropriate risk assessment, and these findings should have implications for future epidemiological studies and for the mitigation of worker exposure.

Characterization of air contaminants emitted during laser cutting of carbon fiber-reinforced composite materials.

The emission of ultrafine carbonaceous particles during the laser cutting of fiber-reinforced polymer (CFRP) composite materials was investigated. The study was based on characterization of air contaminants emitted during laser cutting of an epoxy-based CFRP material with respect to particle size distribution, particle morphology, and chemical composition. Results indicate that about 90% of the total particulate mass is present as fine particulate matter with an aerodynamic cut-off diameter of 0.25 µm, and considerable amounts of ultrafine carbonaceous particulate matter dominated by organic carbon are emitted during high-power laser cutting of CFRP.

Estimation of the contributions of the sources driving PM2.5 levels in a Central Mediterranean coastal town.

Receptor modelling techniques are widely used in order to identify the main natural and anthropogenic processes driving aerosol levels at a receptor. In this work, Positive Matrix Factorization (PMF) was used to apportion PM2.5 levels at a traffic site (Msida) located in a coastal town. 180 filters collected throughout a yearly sampling campaign conducted in 2016, were chemically characterized by light absorbance analysis, x-ray fluorescence and ion chromatography in order to determine the concentrations of black carbon, 17 elements and 5 ions, respectively. The resulting chemical data base was used in conjunction with PMF in order to identify the 7 components affecting the PM2.5 levels at the receptor site. Six of these sources are considered to be typical of the atmospheric composition of coastal traffic sites: traffic (27.3%), ammonium sulfate (23.6%), Saharan dust (15%), aged sea salt (12.7%), shipping (5%) and fresh sea salt (4.6%). This is the first time that such a study was carried out in Malta and helps in understanding the aerosol pollution climate of the Central Mediterranean, which is still relatively understudied when compared to the Eastern and Western Mediterranean. Furthermore, we have isolated a factor exclusive to Malta: the fireworks component, which is responsible for 2.9% of the PM2.5 and which has health implications due to its chemical composition. The results of this work should also serve to guide the policy makers in achieving the necessary emission reductions in order to achieve the WHO guideline for PM2.5 by 2020.

Phase identification of individual crystalline particles by combining EDX and EBSD: application to workplace aerosols.

This paper discusses the combined use of electron backscatter diffraction (EBSD) and energy dispersive X-ray microanalysis (EDX) to identify unknown phases in particulate matter from different workplace aerosols. Particles of α-silicon carbide (α-SiC), manganese oxide (MnO) and α-quartz (α-SiO2) were used to test the method. Phase identification of spherical manganese oxide particles from ferromanganese production, with diameter less than 200 nm, was unambiguous, and phases of both MnO and Mn3O4 were identified in the same agglomerate. The same phases were identified by selected area electron diffraction (SAED) in transmission electron microscopy (TEM). The method was also used to identify the phases of different SiC fibres, and both ß-SiC and α-SiC fibres were found. Our results clearly demonstrate that EBSD combined with EDX can be successfully applied to the characterisation of workplace aerosols. Graphical abstract Secondary electron image of an agglomerate of manganese oxide particles collected at a ferromanganese smelter (a). EDX spectrum of the particle highlighted by an arrow (b). Indexed patterns after dynamic background subtraction from three particles shown with numbers in a