Martin Harper

Impact of silanol surface density on the toxicity of silica aerosols measured by erythrocyte haemolysis.

Exposures to silica-containing dusts are associated with a risk of developing life-threatening lung diseases. However, the mechanism of silica toxicity is poorly understood. In this work the atomic structure of the surfaces of different silica polymorphs was determined, and a relationship with in vitro silica toxicity was examined. The density of geminal and single silanol groups was quantitatively estimated for different silica polymorphs using a novel molecular modeling method. An association was found between the reported haemolytic activity and modeled densities of surface geminal (but not single) silanol groups on several silica polymorphs. These findings suggest a new view of aerosol toxicity based on the estimation of surface site densities. The results can be used in the development of new toxicological assays for respirable particulates, including nanomaterials.

Performance of High Flow Rate Samplers for Respirable Particle Collection

The American Conference of Governmental Industrial hygienists (ACGIH) lowered the threshold limit value (TLV) for respirable crystalline silica (RCS) exposure from 0.05 to 0.025 mg m−3 in 2006. For a working environment with an airborne dust concentration near this lowered TLV, the sample collected with current standard respirable aerosol samplers might not provide enough RCS for quantitative analysis. Adopting high flow rate sampling devices for respirable dust containing silica may provide a sufficient amount of RCS to be above the limit of quantification even for samples collected for less than full shift. The performances of three high flow rate respirable samplers (CIP10-R, GK2.69, and FSP10) have been evaluated in this study. Eleven different sizes of monodisperse aerosols of ammonium fluorescein were generated with a vibrating orifice aerosol generator in a calm air chamber in order to determine the sampling efficiency of each sampler. Aluminum oxide particles generated by a fluidized bed aerosol generator were used to test (i) the uniformity of a modified calm air chamber, (ii) the effect of loading on the sampling efficiency, and (iii) the performance of dust collection compared to lower flow rate cyclones in common use in the USA (10-mm nylon and Higgins–Dewell cyclones). The coefficient of variation for eight simultaneous samples in the modified calm air chamber ranged from 1.9 to 6.1% for triplicate measures of three different aerosols. The 50% cutoff size (50dae) of the high flow rate samplers operated at the flow rates recommended by manufacturers were determined as 4.7, 4.1, and 4.8 μm for CIP10-R, GK2.69, and FSP10, respectively. The mass concentration ratio of the high flow rate samplers to the low flow rate cyclones decreased with decreasing mass median aerodynamic diameter (MMAD) and high flow rate samplers collected more dust than low flow rate samplers by a range of 2–11 times based on gravimetric analysis. Dust loading inside the high flow rate samplers does not appear to affect the particle separation in either FSP10 or GK2.69. The high flow rate samplers overestimated compared to the International Standards Organization/Comité Européen de Normalisation/ACGIH respirable convention [up to 40% at large MMAD (27.5 μm)] and could provide overestimated exposure data with the current flow rates. However, both cyclones appeared to be able to provide relatively unbiased assessments of RCS when their flow rates were adjusted.

Comparison of wood-dust aerosol size-distributions collected by air samplers

A method has been described previously for determining particle size distributions in the inhalable size range collected by personal samplers for wood dust. In this method, the particles collected by a sampler are removed, suspended, and re-deposited on a mixed cellulose-ester filter, and examined by optical microscopy to determine particle aerodynamic diameters. This method is particularly appropriate to wood-dust particles which are generally large and close to rectangular prisms in shape. The method was used to investigate the differences in total mass found previously in studies of side-by-side sample collection with different sampler types. Over 200 wood-dust samples were collected in three different wood-products industries, using the traditional 37 mm closed-face polystyrene/acrylonitrile cassette (CFC), the Institute of Occupational Medicine (IOM) inhalable sampler, and the Button sampler developed by the University of Cincinnati. Total mass concentration results from the samplers were found to be in approximately the same ratio as those from traditional long-term gravimetric samples, but about an order of magnitude higher. Investigation of the size distributions revealed several differences between the samplers. The wood dust particulate mass appears to be concentrated in the range 10-70 aerodynamic equivalent diameter (AED), but with a substantial mass contribution from particles larger than 100 microm AED in a significant number of samples. These ultra-large particles were found in 65% of the IOM samples, 42% of the CFC samples and 32% of the Button samples. Where present, particles of this size range dominated the total mass collected, contributing an average 53% (range 10-95%). However, significant differences were still found after removal of the ultra-large particles. In general, the IOM and CFC samplers appeared to operate in accordance with previous laboratory studies, such that they both collected similar quantities of particles at the smaller diameters, up to about 30-40 [micro sign]m AED, after which the CFC collection efficiency was reduced dramatically compared to the IOM. The Button sampler collected significantly less than the IOM at particle sizes between 10.1 and 50 microm AED. The collection efficiency of the Button sampler was significantly different from that of the CFC for particle sizes between 10.1 and 40 microm AED, and the total mass concentration given by the Button sampler was significantly less than that given by the CFC, even in the absence of ultra-large particles. The results are consistent with some relevant laboratory studies.

Analytical Performance Criteria: Concerning Sampler Wall Deposits in the Chemical Analysis of Airborne Metals

The findings and conclusions in this report are those of the author and do not necessarily represent the views of the National Institute for Occupational Safety and Health. A question has arisen as to what constitutes the actual sample collected by an aerosol sampler. In the past, the sampler was considered to be simply a filter holder, with the sample being the material that is collected on the filter. More recent considerations of particle size-selective sampling suggest that the sample should include the entire aspiration of particles into the sampler no matter where they come to rest inside the sampler. The following is a discussion of the issues and the current state of the art.

Wood Dust Sampling: Field Evaluation of Personal Samplers When Large Particles Are Present

Recent recommendations for wood dust sampling include sampling according to the inhalable convention of International Organization for Standardization (ISO) 7708 (1995) Air quality—particle size fraction definitions for health-related sampling. However, a specific sampling device is not mandated, and while several samplers have laboratory performance approaching theoretical for an ‘inhalable’ sampler, the best choice of sampler for wood dust is not clear. A side-by-side field study was considered the most practical test of samplers as laboratory performance tests consider overall performance based on a wider range of particle sizes than are commonly encountered in the wood products industry. Seven companies in the wood products industry of the Southeast USA (MS, KY, AL, and WV) participated in this study. The products included hardwood flooring, engineered hardwood flooring, door skins, shutter blinds, kitchen cabinets, plywood, and veneer. The samplers selected were 37-mm closed-face cassette with ACCU-CAP™, Button, CIP10-I, GSP, and Institute of Occupational Medicine. Approximately 30 of each possible pairwise combination of samplers were collected as personal sample sets. Paired samplers of the same type were used to calculate environmental variance that was then used to determine the number of pairs of samples necessary to detect any difference at a specified level of confidence. Total valid sample number was 888 (444 valid pairs). The mass concentration of wood dust ranged from 0.02 to 195 mg m−3. Geometric mean (geometric standard deviation) and arithmetic mean (standard deviation) of wood dust were 0.98 mg m−3 (3.06) and 2.12 mg m−3 (7.74), respectively. One percent of the samples exceeded 15 mg m−3, 6% exceeded 5 mg m−3, and 48% exceeded 1 mg m−3. The number of collected pairs is generally appropriate to detect a 35% difference when outliers (negative mass loadings) are removed. Statistical evaluation of the nonsimilar sampler pair results produced a finding of no significant difference between any pairing of sampler type. A practical consideration for sampling in the USA is that the ACCU-CAP™ is similar to the sampler currently used by the Occupational Safety and Health Administration for purposes of demonstrating compliance with its permissible exposure limit for wood dust, which is the same as for Particles Not Otherwise Regulated, also known as inert dust or nuisance dust (Method PV2121).

Differentiating non-asbestiform amphibole and amphibole asbestos by size characteristics.

Mining or processing asbestos minerals can liberate isolated fibers or fiber bundles regulated as airborne asbestos fibers. Coarsely crystalline amphibole minerals are more common than asbestos in many geologic environments, and disturbance can result in the release of prismatic or acicular single crystals or cleavage fragments resembling asbestos fibers or fiber bundles but that are not currently regulated as asbestos. Bulk samples of six coarsely crystalline amphiboles and their five asbestos analogs were processed to maximize the number of particles meeting the criterion for counting under the current U.S. National Institute for Occupational Safety and Health Method 7400 “A” counting rules (> 5 μm long with an aspect ratio ≥ 3:1) and also within the respirable width range, i.e. < 3 μm width. The length distributions of the particles produced showed substantial overlap between cleavage fragments and asbestos fibers. Available data sets generally confirmed the relevance of the size distributions of particles generated from reference materials to airborne particles. The length criterion in the current ASTM International standard D7200-06 causes a large proportion (e.g., 40% grunerite and 39% tremolite) of the non-asbestiform particles to be considered potential asbestos. An alternative procedure may be to use a distinction based on width alone as some, but not the majority of, cleavage fragments were thinner than 1 μm (e.g., 9% of actinolite and 20% of grunerite particles), and not many amphibole asbestos particles were wider (e.g., 5% of crocidolite and 18% of amosite particles). This proposal would need further testing. This research should not be considered as addressing any controversy with regard to the toxicity of non-asbestiform amphibole particles of similar dimensions to asbestos particles.

The Need for an International Sampling Convention for Inhalable Dust in Calm Air

Column Editor Kevin Ashley

Quartz Measurement in Coal Dust with High-Flow Rate Samplers: Laboratory Study

A laboratory study was performed to measure quartz in coal dust using high-flow rate samplers (CIP10-R, GK2.69 cyclone, and FSP10 cyclone) and low-flow rate samplers [10-mm nylon and Higgins-Dewell type (BGI4L) cyclones] and to determine whether an increased mass collection from high-flow rate samplers would affect the subsequent quartz measurement by Fourier transform infrared (FTIR) and X-ray diffraction (XRD) analytical procedures. Two different sizes of coal dusts, mass median aerodynamic diameter 4.48 μm (Coal Dust A) and 2.33 μm (Coal Dust B), were aerosolized in a calm air chamber. The mass of coal dust collected by the samplers was measured gravimetrically, while the mass of quartz collected by the samplers was determined by FTIR (NIOSH Manual of Analytical Method 7603) and XRD (NIOSH Manual of Analytical Method 7500) after one of two different indirect preparations. Comparisons between high-flow rate samplers and low-flow rate samplers were made by calculating mass concentration ratios of coal dusts, net mass ratios of coal dusts, and quartz net mass. Mass concentrations of coal dust from the FSP10 cyclone were significantly higher than those from other samplers and mass concentrations of coal dust from 10-mm nylon cyclone were significantly lower than those from other samplers, while the CIP10-R, GK2.69, and BGI4L samplers did not show significant difference in the comparison of mass concentration of coal dusts. The BGI4L cyclone showed larger mass concentration of ∼9% compared to the 10-mm nylon cyclone. All cyclones provided dust mass concentrations that can be used in complying with the International Standard Organization standard for the determination of respirable dust concentration. The amount of coal dust collected from the high-flow rate samplers was found to be higher with a factor of 2-8 compared to the low-flow rate samplers but not in direct proportion of increased flow rates. The high-flow rate samplers collected more quartz compared to low-flow rate samplers in the range of 2-10. There was no significant difference between the per cent (%) quartz in coal dust between the FTIR and XRD analyses. The findings of this study indicated that the increased mass of quartz collected with high-flow rate samplers would provide precise analytical results (i.e. significantly above the limit of detection and/or limit of quantification) compared to the mass collected with low-flow rate samplers, especially in environments with low concentrations of quartz or where short sampling times are desired.

Airborne endotoxin in woodworking (joinery) shops

Symptoms such as shortness of breath and cough have been noted in woodworking facilities even where wood dust itself is well-controlled. Suspicion has fallen on other possible contaminants in the workplace atmosphere, including bacterial endotoxin. A few studies have indicated potentially high endotoxin exposure with exposure to fresh wood in sawmills and in the production of fiberboard and chipboard, but fewer studies have been carried out on exposure to endotoxin in dry wood work, for example in joineries. A study of the endotoxin content of airborne wood dust samples from US woodworking facilities is presented, from the re-analysis of samples which previously had been taken to establish mass collection relationships between the IOM sampler, the closed-face 37 mm plastic cassette (CFC) sampler and the Button sampler. Endotoxin was strongly correlated with total dust, but the endotoxin content of a few fresh wood samples was found to be up to ten times higher per unit of wood dust than for dried-wood samples, and this difference was significant. No long-term time-weighted average sample exceeded the recommended limit value of 50 EU m(-3) (EU, endotoxin units)used in the Netherlands, although a number of the IOM samples came close (seven samples or 44% exceeded 20 EU m(-3)) and one short-term (48 minute) sample registered a high value of 73 EU m(-3). The geometric mean concentration from the IOM samples (11 EU m(-3)) is within the range of geometric means found from Australian joineries (3.7-60, combined: 24 EU m(-3)). In contrast, the corresponding values from the CFC (3.6 EU m(-3)), and the Button sampler (2.1 EU m(-3)) were much lower and no samples exceeded 20 EU m(-3). Endotoxin is likely only to be a significant problem in working with dried woods when associated with very high dust levels, where the wood dust itself is likely to be a cause for concern. The results from the few samples in this study where fresh wood was being worked were similar to results from other studies involving fresh woods. The agreement between these studies is encouraging given the difficulties of endotoxin analysis and the wide variation often expected between different laboratories.

Evaluation of COSHH Essentials: Methylene Chloride, Isopropanol, and Acetone Exposures in a Small Printing Plant

The current study evaluated the Control of Substances Hazardous to Health (COSHH) Essentials model for short-term task-based exposures and full-shift exposures using measured concentrations of three volatile organic chemicals at a small printing plant. A total of 188 exposure measurements of isopropanol and 187 measurements of acetone were collected and each measurement took approximately 60 min. Historically, collected time-weighted average concentrations (seven results) were evaluated for methylene chloride. The COSHH Essentials model recommended general ventilation control for both isopropanol and acetone. There was good agreement between the task-based exposure measurements and the COSHH Essentials predicted exposure range (PER) for cleaning and print preparation with isopropanol and for cleaning with acetone. For the other tasks and for full-shift exposures, agreement between the exposure measurements and the PER was either moderate or poor. However, for both isopropanol and acetone, our findings suggested that the COSHH Essentials model worked reasonably well because the probabilities of short-term exposure measurements exceeding short-term occupational exposure limits (OELs) or full-shift exposures exceeding the corresponding full-shift OELs were <0.05 under the recommended control strategy. For methylene chloride, the COSHH Essentials recommended containment control but a follow-up study was not able to be performed because it had already been replaced with a less hazardous substance (acetone). This was considered a more acceptable alternative to increasing the level of control.