Thomas M. Peters

Airborne Monitoring to Distinguish Engineered Nanomaterials from Incidental Particles for Environmental Health and Safety

Two methods were used to distinguish airborne engineered nanomaterials from other airborne particles in a facility that produces nano-structured lithium titanate metal oxide powder. The first method involved off-line analysis of filter samples collected with conventional respirable samplers at each of seven locations (six near production processes and one outdoors). Throughout most of the facility and outdoors, respirable mass concentrations were low (<0.050 mg/m3) and were attributed to particles other than the nanomaterial (<10% by mass titanium determined with inductively coupled plasma atomic emission spectrometry). In contrast, in a single area with extensive material handling, mass concentrations were greatest (0.118 mg m−3) and contained up to 39% ± 11% lithium titanium, indicating the presence of airborne nanomaterial. Analysis of the filter samples collected in this area by transmission electron microscope and scanning electron microscope revealed that the airborne nanomaterial was associated only with spherical aggregates (clusters of fused 10–80 nm nanoparticles) that were larger than 200 nm. This analysis also showed that nanoparticles in this area were the smallest particles of a larger distribution of submicrometer chain agglomerates likely from welding in an adjacent area of the facility. The second method used two, hand-held, direct-reading, battery-operated instruments to obtain a time series of very fine particle number (<300 nm), respirable mass, and total mass concentration, which were then related to activities within the area of extensive material handling. This activity-based monitoring showed that very fine particle number concentrations (<300 nm) had no apparent correlation to worker activities, but that sharp peaks in the respirable and total mass concentration coincided with loading a hopper and replacing nanomaterial collection bags. These findings were consistent with those from the filter-based method in that they demonstrate that airborne nanoparticles in this facility are dominated by “incidental” sources (e.g., welding or grinding), and that the airborne “engineered” product is predominately composed of particles larger than several hundred nanometers. The methods presented here are applicable to any occupational or environmental setting in which one needs to distinguish incidental sources from engineered product.

Characterization and control of airborne particles emitted during production of epoxy/carbon nanotube nanocomposites.

This work characterized airborne particles generated from the weighing of bulk, multiwall carbon nanotubes (CNTs) and the manual sanding of epoxy test samples reinforced with CNTs. It also evaluated the effectiveness of three local exhaust ventilation (LEV) conditions (no LEV, custom fume hood, and biosafety cabinet) for control of particles generated during sanding of CNT-epoxy nanocomposites. Particle number and respirable mass concentrations were measured using an optical particle counter (OPC) and a condensation particle counter (CPC), and particle morphology was assessed by transmission electron microscopy. The ratios of the geometric mean (GM) concentrations measured during the process to that measured in the background (P/B ratios) were used as indices of the impact of the process and the LEVs on observed concentrations. Processing CNT-epoxy nanocomposites materials released respirable size airborne particles (P/B ratio: weighing = 1.79; sanding = 5.90) but generally no nanoparticles (P/B ratio ∼1). The particles generated during sanding were predominantly micron sized with protruding CNTs and very different from bulk CNTs that tended to remain in large (>1 μm) tangled clusters. Respirable mass concentrations in the operators breathing zone were lower when sanding was performed in the biological safety cabinet (GM = 0.20 μg/m3 compared with those with no LEV (GM = 2.68 μg/m3 or those when sanding was performed inside the fume hood (GM = 21.4 μg/m3; p-value < 0.0001). The poor performance of the custom fume hood used in this study may have been exacerbated by its lack of a front sash and rear baffles and its low face velocity (0.39 m/sec).

Concentration measurement and counting efficiency of the aerodynamic particle sizer 3321

The aerodynamic particle sizer (APS) model 3321 (TSI, Inc., St. Paul, MN) aims to resolve issues identi3ed with an earlier APS, model 3320. These issues include discrepancies between concentrations measured in summing and in correlated modes, and the creation of “anomalous”, large particles caused by recirculation within the detection region. In the present work, the number concentration of a laboratory aerosol was measured with the APS 3321 to be statistically the same in summing mode and in correlated mode for all particles except those in bin 1, i 0:523 � m. Further, anomalous large particles were not measured with the APS 3321. The counting e ciency of the APS 3321 was lower than that for the APS 3320 and ranged from 40% to 60% for particles from 0.8 to 4 � m, respectively. Thus, concentrations reported by the APS 3321 were lower than those measured by the impactor. However, because counting e ciencies were roughly constant with particle size and anomalous particles were absent, the shape of the size distribution was similar to that obtained using the impactor. ? 2003 Elsevier Science Ltd. All rights reserved.

Relationships Among Particle Number, Surface Area, and Respirable Mass Concentrations in Automotive Engine Manufacturing

This study investigated the relationships between particle number, surface area, and respirable mass concentration measured simultaneously in a foundry and an automotive engine machining and assembly center. Aerosol concentrations were measured throughout each plant with a condensation particle counter for number concentration, a diffusion charger for active surface area concentration, and an optical particle counter for respirable mass concentration. At selected locations, particle size distributions were characterized with the optical particle counter and an electrical low pressure impactor. Statistical analyses showed that active surface area concentration was correlated with ultrafine particle number concentration and weakly correlated with respirable mass concentration. Correlation between number and active surface area concentration was stronger during winter (R 2 = 0.6 for both plants) than in the summer (R 2 = 0.38 and 0.36 for the foundry and engine plant respectively). The stronger correlation in winter was attributed to use of direct-fire gas fired heaters that produced substantial numbers of ultrafine particles with a modal diameter between 0.007 and 0.023 μ m. These correlations support findings obtained through theoretical analysis. Such analysis predicts that active surface area increasingly underestimates geometric surface area with increasing particle size, particularly for particles larger than 100 nm. Thus, a stronger correlation between particle number concentration and active surface area concentration is expected in the presence of high concentrations of ultrafine particles. In general, active surface area concentration may be a concentration metric that is distinct from particle number concentration and respirable mass concentration. For future health effects or toxicological studies involving nano-materials or ultrafine aerosols, this finding needs to be considered, as exposure metrics may influence data interpretation.

Single-particle SEM-EDX analysis of iron-containing coarse particulate matter in an urban environment: sources and distribution of iron within Cleveland, Ohio.

The physicochemical properties of coarse-mode, iron-containing particles and their temporal and spatial distributions are poorly understood. Single-particle analysis combining X-ray elemental mapping and computer-controlled scanning electron microscopy (CCSEM-EDX) of passively collected particles was used to investigate the physicochemical properties of iron-containing particles in Cleveland, OH, in summer 2008 (Aug-Sept), summer 2009 (July-Aug), and winter 2010 (Feb-March). The most abundant classes of iron-containing particles were iron oxide fly ash, mineral dust, NaCl-containing agglomerates (likely from road salt), and Ca-S containing agglomerates (likely from slag, a byproduct of steel production, or gypsum in road salt). The mass concentrations of anthropogenic fly ash particles were highest in the Flats region (downtown) and decreased with distance away from this region. The concentrations of fly ash in the Flats region were consistent with interannual changes in steel production. These particles were observed to be highly spherical in the Flats region, but less so after transport away from downtown. This change in morphology may be attributed to atmospheric processing. Overall, this work demonstrates that the method of passive collection with single-particle analysis by electron microscopy is a powerful tool to study spatial and temporal gradients in components of coarse particles. These gradients may correlate with human health effects associated with exposure to coarse-mode particulate matter.

A Task-Specific Assessment of Swine Worker Exposure to Airborne Dust

A task-based analysis of personal airborne dust exposures was performed in two swine confinement facilities used to house sows and their litters. Airborne particulate levels were assessed during summer, winter, and spring. Personal aerosol measurements of workers were made with a photometer every 15 sec and corrected to compare with an integrated concentration measurement made with a co-located IOM inhalable dust sampler. Task type and time period were recorded by the workers over an 8-hr work shift. There was a significant difference in dust concentrations between seasons (p < 0.001), with winter months providing the highest levels (geometric mean = 3.76 mg/m 3 ). The application of a general linear model of log-transformed task concentrations relative to site, season, and task demonstrated significant differences (P < 0.001) among all three covariates. Tasks performed near moving animals, especially the weaning process, resulted in the greatest concentrations. These results indicate the need to evaluate the concentration levels for separate tasks during multi-task work shifts, such as swine rearing, to optimize efforts to minimize exposures by focusing on high-concentration tasks.

A Personal Nanoparticle Respiratory Deposition (NRD) Sampler

A lightweight (60 g), personal nanoparticle respiratory deposition (NRD) sampler was developed to selectively collect particles smaller than 300 nm similar to their typical deposition in the respiratory tract. The sampler operates at 2.5 Lpm and consists of a respirable cyclone fitted with an impactor and a diffusion stage containing mesh screens. The cut-point diameter of the impactor was determined to be 300 nm with a sharpness σ = 1.53. The diffusion stage screens collect particles with an efficiency that matches the deposition efficiency of particles smaller than 300 nm in the respiratory tract. Impactor separation performance was unaffected by loading at typical workplace levels (p-value = 0.26). With chemical analysis of the diffusion media, the NRD sampler can be used to directly assess exposures to nanoparticles of a specific composition apart from other airborne particles. The pressure drop of the NRD sampler is sufficiently low to permit its operation with conventional, belt-mounted sampling pumps.

Comparison and Combination of Aerosol Size Distributions Measured with a Low Pressure Impactor, Differential Mobility Particle Sizer, Electrical Aerosol Analyzer, and Aerodynamic Particle Sizer

Data from a different mobility particle sizer (DMPS) or an electrical aerosol analyzer (EAA) has been combined with data from an aerodynamic particle sizer (APS) and converted to obtain aerosol mass distribution parameters on a near real-time basis. A low pressure impactor (LPI), a direct and independent measure of this mass distribution, provided information for comparison. The number distribution of particles within the electrical measurement range was obtained with the DMPS and EAA. Data from the APS for particles greater than that size were used to complete the number distribution. Two methods of obtaining mass distribution parameters from this number data were attempted. The first was to convert the number data, channel by channel, to mass data and then fit a log-normal function to this new mass distribution. The second method was to fit a log-normal function to the combined number distribution and then use the Hatch-Choate equations to obtain mass parameters. Both the DMPS / APS and the EAA / APS sy...

Satellite Remote Sensing for Developing Time and Space Resolved Estimates of Ambient Particulate in Cleveland, OH.

This article empirically demonstrates the use of fine resolution satellite-based aerosol optical depth (AOD) to develop time and space resolved estimates of ambient particulate matter (PM) ≤2.5 μm and ≤10 μm in aerodynamic diameters (PM2.5 and PM10, respectively). AOD was computed at three different spatial resolutions, i.e., 2 km (means 2 km × 2 km area at nadir), 5 km, and 10 km, by using the data from MODerate Resolution Imaging Spectroradiometer (MODIS), aboard the Terra and Aqua satellites. Multiresolution AOD from MODIS (AODMODIS) was compared with the in situ measurements of AOD by NASAs AErosol RObotic NETwork (AERONET) sunphotometer (AODAERONET) at Bondville, IL, to demonstrate the advantages of the fine resolution AODMODIS over the 10-km AODMODIS, especially for air quality prediction. An instrumental regression that corrects AODMODIS for meteorological conditions was used for developing a PM predictive model. The 2-km AODMODIS aggregated within 0.025° and 15-min intervals shows the best association with the in situ measurements of AODAERONET. The 2-km AODMODIS seems more promising to estimate time and space resolved estimates of ambient PM than the 10-km AODMODIS, because of better location precision and a significantly greater number of data points across geographic space and time. Utilizing the collocated AODMODIS and PM data in Cleveland, OH, a regression model was developed for predicting PM for all AODMODIS data points. Our analysis suggests that the slope of the 2-km AODMODIS (instrumented on meteorological conditions) is close to unity with the PM monitored on the ground. These results should be interpreted with caution, because the slope of AODMODIS ranges from 0.52 to 1.72 in the site-specific models. In the cross validation of the overall model, the root mean square error (RMSE) of PM10 was smaller (2.04 μg/m3 in overall model) than that of PM2.5 (2.5 μg/m3). The predicted PM in the AODMODIS data (∼2.34 million data points) was utilized to develop a systematic grid of daily PM at 5-km spatial resolution with the aid of spatiotemporal Kriging.

Characterization and Mapping of Very Fine Particles in an Engine Machining and Assembly Facility

Very fine particle number and mass concentrations were mapped in an engine machining and assembly facility in the winter and summer. A condensation particle counter (CPC) was used to measure particle number concentrations in the 0.01 μ m to 1 μ m range, and an optical particle counter (OPC) was used to measure particle number concentrations in 15 channels between 0.3 μ m and 20 μ m. The OPC measurements were used to estimate the respirable mass concentration. Very fine particle number concentrations were estimated by subtracting the OPC particle number concentrations from 0.3 μ m to 1 μ m from the CPC number concentrations. At specific locations during the summer visit, an electrical low pressure impactor was used to measure particle size distribution from 0.07 μ m to 10 μ m in 12 channels. The geometric mean ratio of respirable mass concentration estimated from the OPC to the gravimetrically measured mass concentration was 0.66 with a geometric standard deviation of 1.5. Very fine particle number concentrations in winter were substantially greater where direct-fire natural gas heaters were operated (7.5 × 105 particles/cm3) than where steam was used for heat (3 × 105 particles/cm3). During summer when heaters were off, the very fine particle number concentrations were below 105 particles/cm3, regardless of location. Elevated very fine particle number concentrations were associated with machining operations with poor enclosures. Whereas respirable mass concentrations did not vary noticeably with season, they were greater in areas with poorly fitting enclosures (0.12 mg/m3) than in areas where state-of-the-art enclosures were used (0.03 mg/m3). These differences were attributed to metalworking fluid mist that escaped from poorly fitting enclosures. Particles generated from direct-fire natural gas heater operation were very small, with a number size distribution modal diameter of less than 0.023 μ m. Aerosols generated by machining operations had number size distributions modes in the 0.023 μ m to 0.1 μ m range. However, multiple modes in the mass size distributions estimated from OPC measurements occurred in the 2–20 μ m range. Although elevated, very fine particle concentrations and respirable mass concentrations were both associated with poorly enclosed machining operations; the operation of the direct-fire natural gas heaters resulted in the greatest very fine particle concentrations without elevating the respirable mass concentration. These results suggest that respirable mass concentration may not be an adequate indicator for very fine particle exposure.