Human exposure to carbon-based fibrous nanomaterials: A review.

In an emerging field of nanotechnologies, assessment of exposure to carbon nanotubes (CNT) and carbon nanofibers (CNF) is an integral component of occupational and environmental epidemiology, risk assessment and management, as well as regulatory actions. The current state of knowledge on exposure to carbon-based fibrous nanomaterials among workers, consumers and general population was studied in frame of the International Agency for Research on Cancer (IARC) Monographs-Volume 111 "Some Nanomaterials and Some Fibres". Completeness and reliability of available exposure data for use in epidemiology and risk assessment were assessed. Occupational exposure to CNT/CNF may be of concern at all stages of the material life-cycle from research through manufacture to use and disposal. Consumer and environmental exposures are only estimated by modeled data. The available information of the final steps of the life-cycle of these materials remains incomplete so far regarding amounts of handled materials and levels of exposure. The quality and amount of information available on the uses and applications of CNT/CNF should be improved to enable quantitative assessment of human exposure to these materials. For that, coordinated effort in producing surveys and exposure inventories based on harmonized strategy of material test, exposure measurement and reporting results is strongly encouraged.

Quantification of short and long asbestos fibers to assess asbestos exposure: a review of fiber size toxicity.

The fibrogenicity and carcinogenicity of asbestos fibers are dependent on several fiber parameters including fiber dimensions. Based on the WHO (World Health Organization) definition, the current regulations focalise on long asbestos fibers (LAF) (Length: L ≥ 5 µm, Diameter: D < 3 µm and L/D ratio > 3). However air samples contain short asbestos fibers (SAF) (L < 5 µm). In a recent study we found that several air samples collected in buildings with asbestos containing materials (ACM) were composed only of SAF, sometimes in a concentration of ≥10 fibers.L-1. This exhaustive review focuses on available information from peer-review publications on the size-dependent pathogenetic effects of asbestos fibers reported in experimental in vivo and in vitro studies. In the literature, the findings that SAF are less pathogenic than LAF are based on experiments where a cut-off of 5 µm was generally made to differentiate short from long asbestos fibers. Nevertheless, the value of 5 µm as the limit for length is not based on scientific evidence, but is a limit for comparative analyses. From this review, it is clear that the pathogenicity of SAF cannot be completely ruled out, especially in high exposure situations. Therefore, the presence of SAF in air samples appears as an indicator of the degradation of ACM and inclusion of their systematic search should be considered in the regulation. Measurement of these fibers in air samples will then make it possible to identify pollution and anticipate health risk.

Short, fine and WHO asbestos fibers in the lungs of quebec workers with an asbestos-related disease.

BACKGROUND: The possible role of short asbestos fibers in the development of asbestos-related diseases and availability of lung fiber burden data prompted this study on the relationships between fiber characteristics and asbestos-related diseases among compensated workers. METHODS: Data collected between 1988 and 2007 for compensation purposes were used; lung asbestos fibers content of 123 Quebec workers are described according to socio-demographic characteristics, job histories and diseases (asbestosis, mesothelioma, lung cancer). RESULTS: Most workers (85%) presented chrysotile fibers in their lungs, and respectively 76%, 64%, and 43% had tremolite, amosite, and crocidolite. Half of the total fibers were short, 30% were thin fibers and 20% corresponded to the World Health Organization definition of fibers (length ≥ 5 µm, diameter ≥ 0.2 and <3 µm). Chrysotile fibers were still observed in the lungs of workers 30 years or more after last exposure. CONCLUSION: Our findings stress the relevance of considering several dimensional criteria to characterize health risks associated with asbestos inhalation.

Assessment of the contribution of electron microscopy to nanoparticle characterization sampled with two cascade impactors.

This study assessed the contribution of electron microscopy to the characterization of nanoparticles and compared the degree of variability in sizes observed within each stage when sampled by two cascade impactors: an Electrical Low Pressure Impactor (ELPI) and a Micro-Orifice Uniform Deposit Impactor (MOUDI). A TiO(2) nanoparticle (5 nm) suspension was aerosolized in an inhalation chamber. Nanoparticles sampled by the impactors were collected on aluminum substrates or TEM carbon-coated copper grids using templates, specifically designed in our laboratories, for scanning and transmission electron microscopy (SEM, TEM) analysis, respectively. Nanoparticles were characterized using both SEM and TEM. Three different types of diameters (inner, outer, and circular) were measured by image analysis based on count and volume, for each impactor stage. Electron microscopy, especially TEM, is well suited for the characterization of nanoparticles. The MOUDI, probably because of the rotation of its collection stages, which can minimize the resuspension of particles, gave more stable results and smaller geometric standard deviations per stage. Our data suggest that the best approach to estimate particle size by electron microscopy would rely on geometric means of measured circular diameters. Overall, the most reliable data were provided by the MOUDI and the TEM sampling technique on carbon-coated copper grids for this specific experiment. This study indicates interesting findings related to the assessment of impactors combined with electron microscopy for nanoparticle characterization. For future research, since cascade impactors are extensively used to characterize nano-aerosol exposure scenarios, high-performance field emission scanning electron microscopy (FESEM) should also be considered.

Occupational exposure to silica in construction workers: a literature-based exposure database.

We created an exposure database of respirable crystalline silica levels in the construction industry from the literature. We extracted silica and dust exposure levels in publications reporting silica exposure levels or quantitative evaluations of control effectiveness published in or after 1990. The database contains 6118 records (2858 of respirable crystalline silica) extracted from 115 sources, summarizing 11,845 measurements. Four hundred and eighty-eight records represent summarized exposure levels instead of individual values. For these records, the reported summary parameters were standardized into a geometric mean and a geometric standard deviation. Each record is associated with 80 characteristics, including information on trade, task, materials, tools, sampling strategy, analytical methods, and control measures. Although the database was constructed in French, 38 essential variables were standardized and translated into English. The data span the period 1974-2009, with 92% of the records corresponding to personal measurements. Thirteen standardized trades and 25 different standardized tasks are associated with at least five individual silica measurements. Trade-specific respirable crystalline silica geometric means vary from 0.01 (plumber) to 0.30 mg/m³ (tunnel construction skilled labor), while tasks vary from 0.01 (six categories, including sanding and electrical maintenance) to 1.59 mg/m³ (abrasive blasting). Despite limitations associated with the use of literature data, this database can be analyzed using meta-analytical and multivariate techniques and currently represents the most important source of exposure information about silica exposure in the construction industry. It is available on request to the research community.

Generating nano-aerosols from TiO2 (5 nm) nanoparticles showing different agglomeration states. Application to toxicological studies.

Agglomeration of nanoparticles (NP) is a key factor in the generation of aerosols from nano-powders and may represent an important parameter to consider in toxicological studies. For this reason, the characterization of NP aerosols (e.g., concentration, size, and structure of agglomerates) is a critical step in the determination of the relationship between exposure and effects. The aim of this study was to generate and characterize aerosols composed of TiO2 (5 nm) NP showing different agglomeration states. Two concentrations were tested: 2 and 7 mg/m³. Stable mass concentrations over 6 hr were successfully generated by a wet method using Collison and Delavan nebulizers that resulted in aerosols composed of smaller agglomerates (<100 nm), while aerosols composed of larger agglomerates (>100 nm) were obtained by dry generation techniques using either a Palas dust feeder or a Fluidized Bed. Particle size distributions in the aerosols were determined by an electrical low pressure impactor. Median number aerodynamic diameters corresponding to the aerosol with smaller and larger agglomerates were 30 and 185 nm, respectively, for the 2 mg/m³ concentration, and 31 and 194 nm for the 7 mg/m³ experiment. Image analysis by transmission electron microscopy showed the presence of compact or agglomerates with void spaces in the different nano-aerosols. These characterized nano-aerosols will be used in further experiments to study the influence of agglomerate size on NP toxicity.

Silica exposure during construction activities: statistical modeling of task-based measurements from the literature.

Many construction activities can put workers at risk of breathing silica containing dusts, and there is an important body of literature documenting exposure levels using a task-based strategy. In this study, statistical modeling was used to analyze a data set containing 1466 task-based, personal respirable crystalline silica (RCS) measurements gathered from 46 sources to estimate exposure levels during construction tasks and the effects of determinants of exposure. Monte-Carlo simulation was used to recreate individual exposures from summary parameters, and the statistical modeling involved multimodel inference with Tobit models containing combinations of the following exposure variables: sampling year, sampling duration, construction sector, project type, workspace, ventilation, and controls. Exposure levels by task were predicted based on the median reported duration by activity, the year 1998, absence of source control methods, and an equal distribution of the other determinants of exposure. The model containing all the variables explained 60% of the variability and was identified as the best approximating model. Of the 27 tasks contained in the data set, abrasive blasting, masonry chipping, scabbling concrete, tuck pointing, and tunnel boring had estimated geometric means above 0.1mg m(-3) based on the exposure scenario developed. Water-fed tools and local exhaust ventilation were associated with a reduction of 71 and 69% in exposure levels compared with no controls, respectively. The predictive model developed can be used to estimate RCS concentrations for many construction activities in a wide range of circumstances.

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.

An International comparison of the crystallinity of calibration materials for the analysis of respirable alpha-quartz using X-ray diffraction and a comparison with results from the infrared KBr disc method.

It is important that analytical results, produced to demonstrate compliance with exposure limits are comparable, to ensure controls are monitored to similar standards. Correcting a measurement result of respirable alpha-quartz for the percentage of crystalline material in the calibration dust is good analytical practice and significant changes in the values assigned to calibration materials will affect the interpretation of results by an analyst or occupational hygiene professional. The reissue of the certification for the quartz reference material NIST 1878a in 2005 and differences in comparative values obtained by other work created uncertainty about the values of crystallinity assigned to national calibration dusts for alpha-quartz. Members of an International Organization for Standardization working group for silica measurement ISO/TC146/SC2/WG7 collaborated to investigate the comparability of results by X-ray diffraction (XRD) and to reach a consensus. This paper lists the values recommended by the working group for use with XRD analysis. The values for crystallinity obtained for some of the materials (NIST 1878, Min-U-Sil5 and A9950) were 6-7% lower than the original certification or estimates reported in other comparisons. Crystallinity values obtained by XRD gave a good correlation with BET surface area measurements (r2 = 0.91) but not with mean aerodynamic particle size (r2 = 0.31). Subsamples of two of the materials (A9950 Respirable and Quin 1 Respirable) with smaller particle size distribution than their parent material did not show any significant change in their values for crystallinity, suggesting that the area XRD measurement of these materials within the particle size range collected is more dependent on how the quartz is formed geologically or how it is processed for use. A comparison of results from laboratories using the infrared (IR) and KBr disc method showed that this method is more dependent than XRD on differences in the particle size within the respirable size range, whereas the XRD values were more consistent between the different measurement values obtained on each material. It was not possible to assign a value for percentage purity to each material for users of IR analysis. This work suggests that differences are likely to exist between the results from XRD and IR analysis when measuring 'real' workplace samples and highlights the importance of matching the particle size of the calibration material to the particle size of the workplace dust for measurements of crystalline quartz.

Physical and chemical characterization of beryllium particles from several workplaces in Québec, Canada--part B: time-of-flight secondary-ion mass spectroscopy.

The problems associated with detecting and characterizing beryllium (Be) particles in industrial samples from Québec were addressed in the companion article (Rouleau et al., 2005). The present study is a continuation of the work aimed at redefining the current occupational exposure level for beryllium. The goals were to determine the principal chemical forms and the principal physical characteristics of Be particles sampled in four Québec industries. Bulk particle chemistry was determined using inductively coupled plasma-mass spectroscopy (ICP-MS) and flame atomic absorption spectrophotometry (FAAS). Time-of-flight secondary-ion mass spectroscopy (TOF-SIMS) was used to characterize particle surface chemistry and physical particle size. The dust samples collected had Be concentrations varying from 58 to 146 microg/g. Results showed that numerous fine Be particles or aggregates were evenly dispersed throughout the samples. Thus, Be does not appear to be concentrated in large particles. However, it was not possible to confirm if these fine particles were combined to specific compounds, chemically or physically, or independent Be particles. Most of the particles containing Be were fine, with diameters less than 10 microm, which is important from an occupational health and safety standpoint. TOF-SIMS should be considered as an appropriate technique for qualitative characterization of Be particles, and a valuable complement to the recognized quantitative methods ICP-MS and FAAS.

Physical and chemical characterization of beryllium particles from several workplaces in Québec, Canada--part A: determining methods for the analysis of low levels of beryllium.

Chemical and physical characterizations of beryllium (Be) particles found in settled dust samples from four industries based in Québec were attempted using a variety of analytical methods. Bulk particle chemistry was determined using inductively coupled plasma-mass spectrometry (ICP-MS), graphite furnace atomic absorption spectrometry (GFAAS), and instrumental neutron activation analysis (INAA). Time-of-flight secondary-ion mass spectrometry (TOF-SIMS), transmission electron microscopy, scanning electron microscopy, energy-dispersive spectroscopy, x-ray diffraction (XRD), electron energy loss spectrometry (EELS), and Auger microscopy were used to characterize physicochemical properties of particles. These analyses were deemed important based on the hypotheses that (1) different chemical forms of Be do not present the same risks, and (2) different morphologies lead to different risks. Standards were used to prove the adequacy of XRD, EELS, and Auger microscopy prior to the analyses of industrial samples. However, low concentrations of Be in samples were a limiting factor for most methods; few detected Be in industrial samples. Only ICP-MS, GFAAS, and TOF-SIMS were able to detect Be in industrial samples analyzed in this study. Characterization of settled dust samples showed high number of Be particles, even for Be concentrations below 100 ppm. Furthermore, Be seems to be present as fine particles of Be metal, possibly mechanically agglomerated or aggregated to larger particles or compounds such as cryolite. Other major elements detected with INAA present in the samples were limited to Na, Al, Ca, and F. It was concluded that TOF-SIMS is a valid method for characterizing particles containing approximately 0.01% Be.

Assessment of exposure to quartz, cristobalite and silicon carbide fibres (whiskers) in a silicon carbide plant.

The main objective of the present paper is to report on the concentration of silicon carbide (SiC) fibres, crystalline silica and respirable dust in a Canadian SiC production plant and to compare the results with earlier investigations. The second objective is to tentatively explain the differences in concentration of the fibrogenic substances between different countries. The assessment of SiC fibres, dusts, respirable quartz and cristobalite was performed according to standard procedures. The highest 8 h time-weighted average concentrations of fibres were found among the crusher and backhoe attendants and the carboselectors with an arithmetic mean of 0.63 fibres ml(-1) for the former group and 0.51 fibres ml(-1) for the latter group. The results of respirable SiC fibres in the Canadian plant were lower than in the Norwegian and Italian industries. Most of the 8 h time-weighted average concentrations for quartz were less than or around the limit of detection of 0.01 mg m(-3). The maximum 8 h time-weighted average concentration for quartz was found among the carboselectors (0.157 mg m(-3)), followed by the labourers (0.032 mg m(-3)). Similarly, most of the 8 h time-weighted average cristobalite measurements were less than the limit of detection of 0.01 mg m(-3) except for the carboselectors where it was found to be 0.044 mg m(-3). The assessment of the Italian occupational settings exposure demonstrated elevated quartz concentrations, while cristobalite was absent. The authors have concluded that the investigations that were performed in the last two decades in this field by researchers from different countries seem to support that SiC fibres (whiskers) constitute a major airborne health hazard.