Arthur L. Miller

Morphological and Elemental Classification of Freshly Emitted Soot Particles and Atmospheric Ultrafine Particles using the TEM/EDS

The Transmission Electron Microscopy (TEM) and Energy Dispersive Spectroscopy (EDS) were used to determine morphology and elemental composition of a variety of freshly emitted soot particles (acetylene flame, candle flame, kerosene flame, diesel exhaust, electric arc, plastic burning, styrofoam burning, wood burning [white oak and pine bark], and rice straw burning), which can be possible candidate soot in the ambient atmosphere, and ultrafine particles sampled in urban, industrial, and coastal sites during ultrafine particle formation events (combustion and photochemical events). By using mobility-classified non-refractory ((NH 4 ) 2 SO 4 ) and refractory (Polystyrene latex (PSL) and salt (NaCl)) particles, limitation of the TEM was tested. Data showed that the TEM method can be used to examine shapes of both volatile particles such as (NH 4 ) 2 SO 4 (100 nm) at low, but not high magnification (refer to low and high beam intensity, respectively), and non-volatile particles like NaCl (100 nm) and PSL (84 nm) at either low or high magnification. Distinct differences in morphological properties such as primary particle diameter, fractal dimension, and microstructure were observed among the different types of fresh soot particles. The atmospheric ultrafine particles were classified as agglomerates, sulfate mixtures (spherical), metallic oxides (spherical and polygonal), C-rich refractory (not agglomerated), C-rich non-refractory (not agglomerated), Si-rich (spherical), Na-rich (porous), or P-containing (non-spherical) particles. At the urban Gwangju site, a higher fraction of fresh and aged agglomerates was observed than at other sites. The C-rich non-refractory and sulfate mixtures were often observed in the photochemical event. The C-rich refractory particles were abundant at the Gwangju and Yeosu sites. The coastal Taean site had few agglomerates due to limited anthropogenic combustion source.

A Handheld Electrostatic Precipitator for Sampling Airborne Particles and Nanoparticles

Researchers at NIOSH are developing methods for characterizing ultrafine aerosols in workplaces. One method includes the detailed analysis of collected particles using electron microscopy (EM). In order to collect samples for EM at remote workplaces including mining and manufacturing facilities, researchers have developed a handheld electrostatic precipitator (ESP) particle sampler capable of collecting airborne particles including nanoscale materials, for subsequent EM analysis. The handheld ESP has been tested in the laboratory and is currently undergoing beta testing in the field. Gross collection efficiencies were measured with a CPC and net efficiencies by EM analysis of collected samples. Using laboratory-generated NaCl aerosols in the 30–400 nm size range at a flow rate of 55 cc/min and ESP operating voltages between 5.6–6.8 kV, both gross and net efficiencies were measured and showed a similar correlation with voltage, with maximum efficiency of approximately 86% at 6.4 kV. EM images from samples were also used to estimate particle size distributions of the original aerosols and the size-dependent deposition was evaluated for upstream versus downstream locations on the sample media. Results suggest that the number concentration and particle size distribution of sampled aerosols may potentially be estimated from a single ESP sample, but that the accuracy and repeatability of such quantification need to be investigated and refined. NIOSH is planning to license the ESP sampler for commercial manufacturing.

Characterizing Exposures to Airborne Metals and Nanoparticle Emissions in a Refinery

An air quality survey was conducted at a precious metals refinery in order to evaluate worker exposures to airborne metals and to provide detailed characterization of the aerosols. Two areas within the refinery were characterized: a furnace room and an electro-refining area. In line with standard survey practices, both personal and area air filter samples were collected on 37-mm filters and analyzed for metals by inductively coupled plasma-atomic emission spectroscopy. In addition to the standard sampling, measurements were conducted using other tools, designed to provide enhanced characterization of the workplace aerosols. The number concentration and number-weighted particle size distribution of airborne particles were measured with a fast mobility particle sizer (FMPS). Custom-designed software was used to correlate particle concentration data with spatial location data to generate contour maps of particle number concentrations in the work areas. Short-term samples were collected in areas of localized high concentrations and analyzed using transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS) to determine particle morphology and elemental chemistry. Analysis of filter samples indicated that all of the workers were exposed to levels of silver above the Occupational Safety and Health Administration permissible exposure limit of 0.01 mg m(-3) even though the localized ventilation was functioning. Measurements with the FMPS indicated that particle number concentrations near the furnace increased up to 1000-fold above the baseline during the pouring of molten metal. Spatial mapping revealed localized elevated particle concentrations near the furnaces and plumes of particles rising into the stairwells and traveling to the upper work areas. Results of TEM/EDS analyses confirmed the high number of nanoparticles measured by the FMPS and indicated the aerosols were rich in metals including silver, lead, antimony, selenium, and zinc. Results of the survey were used to deduce appropriate strategies for mitigation of worker exposure to airborne metals.

Quantifying silica in filter-deposited mine dusts using infrared spectra and partial least squares regression

AbstractThe feasibility of measuring airborne crystalline silica (α-quartz) in noncoal mine dusts using a direct-on-filter method of analysis is demonstrated. Respirable α-quartz was quantified by applying a partial least squares (PLS) regression to the infrared transmission spectra of mine-dust samples deposited on porous polymeric filters. This direct-on-filter method deviates from the current regulatory determination of respirable α-quartz by refraining from ashing the sampling filter and redepositing the analyte prior to quantification using either infrared spectrometry for coal mines or x-ray diffraction (XRD) from noncoal mines. Since XRD is not field portable, this study evaluated the efficacy of Fourier transform infrared spectrometry for silica determination in noncoal mine dusts. PLS regressions were performed using select regions of the spectra from nonashed samples with important wavenumbers selected using a novel modification to the Monte Carlo unimportant variable elimination procedure. Wavenumber selection helped to improve PLS prediction, reduce the number of required PLS factors, and identify additional silica bands distinct from those currently used in regulatory enforcement. PLS regression appeared robust against the influence of residual filter and extraneous mineral absorptions while outperforming ordinary least squares calibration. These results support the quantification of respirable silica in noncoal mines using field-portable infrared spectrometers. FigurePartial least squares predicted (Yfit) vs. observed (Yobs) reparable silica using infrared absorbance from the α-quartz doublet region of filter-deposited mine dust sample spectra. predictive features selected via backward Monte Carlo unimportant variable elimination (lower right hand corner) are also shown

Deposition Uniformity of Coal Dust on Filters and Its Effect on the Accuracy of FTIR Analyses for Silica

Miners are exposed to silica-bearing dust which can lead to silicosis, a potentially fatal lung disease. Currently, airborne silica is measured by collecting filter samples and sending them to a laboratory for analysis. Since this may take weeks, a field method is needed to inform decisions aimed at reducing exposures. This study investigates a field-portable Fourier transform infrared (FTIR) method for end-of-shift (EOS) measurement of silica on filter samples. Since the method entails localized analyses, spatial uniformity of dust deposition can affect accuracy and repeatability. The study, therefore, assesses the influence of radial deposition uniformity on the accuracy of the method. Using laboratory-generated Minusil and coal dusts and three different types of sampling systems, multiple sets of filter samples were prepared. All samples were collected in pairs to create parallel sets for training and validation. Silica was measured by FTIR at nine locations across the face of each filter and the data analyzed using a multiple regression analysis technique that compared various models for predicting silica mass on the filters using different numbers of “analysis shots.” It was shown that deposition uniformity is independent of particle type (kaolin vs. silica), which suggests the role of aerodynamic separation is negligible. Results also reflected the correlation between the location and number of shots versus the predictive accuracy of the models. The coefficient of variation (CV) for the models when predicting mass of validation samples was 4%–51% depending on the number of points analyzed and the type of sampler used, which affected the uniformity of radial deposition on the filters. It was shown that using a single shot at the center of the filter yielded predictivity adequate for a field method, (93% return, CV approximately 15%) for samples collected with 3-piece cassettes. Copyright 2013 American Association for Aerosol Research

Evaluation of Laser-Induced Breakdown Spectroscopy (LIBS) for Measurement of Silica on Filter Samples of Coal Dust

Airborne silica dust (quartz) is common in coal mines and represents a respiratory hazard that can lead to silicosis, a potentially fatal lung disease. With an eye toward developing a portable monitoring device for rapid analysis of silica dust, laser-induced breakdown spectroscopy (LIBS) was used to quantify quartz in coal dust samples collected on filter media. Pure silica (Min-U-Sil™ 5), Georgia kaolin, and Pittsburgh-4 and Illinois-6 coal dusts were deposited separately and at multiple mass loadings onto 37-mm polyvinylchloride (PVC) filters. LIBS-generated silicon emission was monitored at 288.16 nm, and non-silica contributions to that signal from kaolinite were removed by simultaneously detecting aluminum. Measurements of the four samples were used to calculate limits of detection (LOD) for silicon and aluminum of approximately 0.08 lg/cm2 and 0.05 μg/cm2, respectively (corresponding to 0.16 μg/cm2 and 0. 20 μg/cm2 for silica and kaolinite, respectively). Relative errors of prediction are around 10%. Results demonstrate that LIBS can dependably quantify silica on filter samples of coal dust and confirm that accurate quantification can be achieved for very lightly loaded samples, which supports the potential application of LIBS for rapid, in-field monitoring.

Comparison of field portable measurements of ultrafine TiO2: X-ray fluorescence, laser-induced breakdown spectroscopy, and Fourier-transform infrared spectroscopy

Laboratory measurements of ultrafine titanium dioxide (TiO2) particulate matter loaded on filters were made using three field portable methods (X-ray fluorescence (XRF), laser-induced breakdown spectroscopy (LIBS), and Fourier-transform infrared (FTIR) spectroscopy) to assess their potential for determining end-of-shift exposure. Ultrafine TiO2 particles were aerosolized and collected onto 37 mm polycarbonate track-etched (PCTE) filters in the range of 3 to 578 μg titanium (Ti). Limit of detection (LOD), limit of quantification (LOQ), and calibration fit were determined for each measurement method. The LODs were 11.8, 0.032, and 108 μg Ti per filter, for XRF, LIBS, and FTIR, respectively and the LOQs were 39.2, 0.11, and 361 μg Ti per filter, respectively. The XRF calibration curve was linear over the widest dynamic range, up to the maximum loading tested (578 μg Ti per filter). LIBS was more sensitive but, due to the sample preparation method, the highest loaded filter measurable was 252 μg Ti per filter. XRF and LIBS had good predictability measured by regressing the predicted mass to the gravimetric mass on the filter. XRF and LIBS produced overestimations of 4% and 2%, respectively, with coefficients of determination (R(2)) of 0.995 and 0.998. FTIR measurements were less dependable due to interference from the PCTE filter media and overestimated mass by 2% with an R(2) of 0.831.

The Nanoparticle Information Library (NIL): a prototype for linking and sharing emerging data.

I ndustrial hygienists and other health protection professionals face significant challenges in understanding and controlling a myriad of potential factors that may influence the toxicity, exposure, and ultimately the health risks of producing, handling, and using engineered nanomaterials. As an early step to foster information exchange and understanding nanoparticles and their properties, the National Institute for Occupational Safety and Health (NIOSH) has created an Internetbased Nanoparticle Information Library (NIL). The NIL supports the NIOSH mission to identify and prevent potential adverse effects from nanoparticles by communicating information about health and safety issues that may be associated with nanoparticle manufacturing, handling, or exposure. The current prototype version of the NIL can be accessed at www.cdc.gov/niosh/ topics/nanotech. As illustrated in a representative view of the NIL homepage (Figure 1), the NIL is part of the broader, Internet-based NIOSH Safety and Health Topic page on nanotechnology. The topic page includes information on NIOSH research for nanotechnology safety and health, as well as documents for public comment such as Approaches to Safe Nanotechnology: A Dialogue with NIOSH. As described in the following paragraphs, the NIL provides an online forum for contributing nanoparticle information; access to profiles of the scientists, engineers, and researchers who have contributed information to the NIL; search capabilities for nanoparticle properties and information; access to health and safety information from complimentary databases; a news and information feature that highlights current NIL progress and future developments; and opportunities to provide constructive feedback and comments.

Promoting early exposure monitoring for respirable crystalline silica: Taking the laboratory to the mine site

ABSTRACT The exposure to respirable crystalline silica (RCS) in the mining industry is a recognized occupational hazard. The assessment and monitoring of the exposure to RCS is limited by two main factors: (1) variability of the silica percent in the mining dust and (2) lengthy off-site laboratory analysis of collected samples. The monitoring of respirable dust via traditional or real-time techniques is not adequate. A solution for on-site quantification of RCS in dust samples is being investigated by the Office of Mine Safety and Health Research, a division of the National Institute for Occupational Safety and Health. The use of portable Fourier transform infrared analyzers in conjunction with a direct-on-filter analysis approach is proposed. The progress made so far, the necessary steps in progress, and the application of the monitoring solution to a small data set is presented. When developed, the solution will allow operators to estimate RCS immediately after sampling, resulting in timelier monitoring of RCS for self-assessment of compliance at the end of the shift, more effective engineering monitoring, and better evaluation of control technologies.

The development and testing of a prototype mini-baghouse to control the release of respirable crystalline silica from sand movers.

ABSTRACT Inhalation of respirable crystalline silica (RCS) is a significant risk to worker health during well completions operations (which include hydraulic fracturing) at conventional and unconventional oil and gas extraction sites. RCS is generated by pneumatic transfer of quartz-containing sand during hydraulic fracturing operations. National Institute for Occupational Safety and Health (NIOSH) researchers identified concentrations of RCS at hydraulic fracturing sites that exceed 10 times the Occupational Safety and Health Administration (OSHA) Permissible Exposure Limit (PEL) and up to 50 times the NIOSH Recommended Exposure Limit (REL). NIOSH research identified at least seven point sources of dust release at contemporary oil and gas extraction sites where RCS aerosols were generated.  NIOSH researchers recommend the use of engineering controls wherever they can be implemented to limit the RCS released. A control developed to address one of the largest sources of RCS aerosol generation is the NIOSH mini-baghouse assembly, mounted on the thief hatches on top of the sand mover. This article details the results of a trial of the NIOSH mini-baghouse at a sand mine in Arkansas from November 18–21, 2013.  During the trial, area air samples were collected at 12 locations on and around a sand mover with and without the mini-baghouse control installed. Analytical results for respirable dust and RCS indicate the use of the mini-baghouse effectively reduced both respirable dust and RCS downwind of the thief hatches. Reduction of airborne respirable dust ranged from 85–98%; reductions in airborne RCS ranged from 79–99%. A bulk sample of dust collected by the baghouse assembly showed the likely presence of freshly fractured quartz, a particularly hazardous form of RCS.  Planned future design enhancements will increase the performance and durability of the mini-baghouse, including an improved bag clamp mechanism and upgraded filter fabric with a modified air-to-cloth ratio. Future trials are planned to determine additional respirable dust and RCS concentration reductions achieved through these design changes.