Emanuele Cauda

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.

A Multi-Cyclone Sampling Array for the Collection of Size-Segregated Occupational Aerosols

In this study a serial multi-cyclone sampling array capable of simultaneously sampling particles of multiple size fractions, from an occupational environment, for use in in vivo and in vitro toxicity studies and physical/chemical characterization, was developed and tested. This method is an improvement over current methods used to size-segregate occupational aerosols for characterization, due to its simplicity and its ability to collect sufficient masses of nano- and ultrafine sized particles for analysis. This method was evaluated in a chamber providing a uniform atmosphere of dust concentrations using crystalline silica particles. The multi-cyclone sampling array was used to segregate crystalline silica particles into four size fractions, from a chamber concentration of 10 mg/m3. The size distributions of the particles collected at each stage were confirmed, in the air, before and after each cyclone stage. Once collected, the particle size distribution of each size fraction was measured using light scattering techniques to further confirm the size distributions. As a final confirmation, scanning electron microscopy was used to collect images of each size fraction. The results presented here, using multiple measurement techniques, show that this multi-cyclone system was able to successfully collect distinct size-segregated particles at sufficient masses to perform toxicological evaluations and physical/chemical characterization.

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.

Calibration of high flow rate thoracic-size selective samplers

ABSTRACT High flow rate respirable size selective samplers, GK4.126 and FSP10 cyclones, were calibrated for thoracic-size selective sampling in two different laboratories. The National Institute for Occupational Safety and Health (NIOSH) utilized monodisperse ammonium fluorescein particles and scanning electron microscopy to determine the aerodynamic particle size of the monodisperse aerosol. Fluorescein intensity was measured to determine sampling efficiencies of the cyclones. The Health Safety and Laboratory (HSL) utilized a real time particle sizing instrument (Aerodynamic Particle Sizer) and polydisperse glass sphere particles and particle size distributions between the cyclone and reference sampler were compared. Sampling efficiency of the cyclones were compared to the thoracic convention defined by the American Conference of Governmental Industrial Hygienists (ACGIH)/Comité Européen de Normalisation (CEN)/International Standards Organization (ISO). The GK4.126 cyclone showed minimum bias compared to the thoracic convention at flow rates of 3.5 l min−1 (NIOSH) and 2.7–3.3 l min−1 (HSL) and the difference may be from the use of different test systems. In order to collect the most dust and reduce the limit of detection, HSL suggested using the upper end in range (3.3 l min−1). A flow rate of 3.4 l min−1 would be a reasonable compromise, pending confirmation in other laboratories. The FSP10 cyclone showed minimum bias at the flow rate of 4.0 l min−1 in the NIOSH laboratory test. The high flow rate thoracic-size selective samplers might be used for higher sample mass collection in order to meet analytical limits of quantification.

Emissions from a Diesel Engine using Fe-based Fuel Additives and a Sintered Metal Filtration System.

A series of laboratory tests were conducted to assess the effects of Fe-containing fuel additives on aerosols emitted by a diesel engine retrofitted with a sintered metal filter (SMF) system. Emission measurements performed upstream and downstream of the SMF system were compared, for cases when the engine was fueled with neat ultralow sulfur diesel (ULSD) and with ULSD treated with two formulations of additives containing Fe-based catalysts. The effects were assessed for four steady-state engine operating conditions and one transient cycle. The results showed that the SMF system reduced the average total number and surface area concentrations of aerosols by more than 100-fold. The total mass and elemental carbon results confirmed that the SMF system was indeed very effective in the removal of diesel aerosols. When added at the recommended concentrations (30 p.p.m. of iron), the tested additives had minor adverse impacts on the number, surface area, and mass concentrations of filter-out (FOut) aerosols. For one of the test cases, the additives may have contributed to measurable concentrations of engine-out (EOut) nucleation mode aerosols. The additives had only a minor impact on the concentration and size distribution of volatile and semi-volatile FOut aerosols. Metal analysis showed that the introduction of Fe with the additives substantially increased Fe concentration in the EOut, but the SMF system was effective in removal of Fe-containing aerosols. The FOut Fe concentrations for all three tested fuels were found to be much lower than the corresponding EOut Fe concentrations for the case of untreated ULSD fuel. The results support recommendations that these additives should not be used in diesel engines unless they are equipped with exhaust filtration systems. Since the tested SMF system was found to be very efficient in removing Fe introduced by the additives, the use of these additives should not result in a measurable increase in emissions of de novo generated Fe-containing aerosols. The findings from this study should promote a better understanding of the benefits and challenges of using sintered metal systems and fuel additives to control the exposure of underground miners and other workers to diesel aerosols and gases.

Respirable size-selective sampler for end-of-shift quartz measurement: Development and performance

ABSTRACT Aims of this study were to develop a respirable size-selective sampler for direct-on-filter (DoF) quartz measurement at the end-of-shift (EoS) using a portable Fourier transform infrared (FTIR) spectrometer and to determine its size-selective sampling performance. A new miniaturized sampler has been designed to have an effective particle deposition diameter close to the portable FTIR beam diameter (6 mm). The new sampler (named the EoS cyclone) was constructed using a 3D printer. The sampling efficiency of the EoS cyclone was determined using polydisperse glass sphere particles and a time-of-flight direct reading instrument. Respirable dust mass concentration and quartz absorbance levels of samples collected with the EoS cyclone were compared to those collected with the 10-mm nylon cyclone. The EoS cyclone operated at a flow rate of 1.2 l min−1 showed minimum bias compared to the international standard respirable convention. The use of the EoS cyclone induced respirable dust mass concentration results similar but significantly larger (5%) than those obtained from samples collected with 10-mm nylon cyclones. The sensitivity of the DoF-FTIR analysis in estimating quartz was found increased more than 10 times when the samples were collected with the EoS cyclone. The average particle deposition diameter was 8.8 mm in 60 samples. The newly developed user friendly EoS cyclone may provide a better sampling strategy in quartz exposure assessment with faster feedback.

Characterizing Particle Size Distributions of Crystalline Silica in Gold Mine Dust

Dust containing crystalline silica is common in mining environments in the U.S. and around the world. The exposure to respirable crystalline silica remains an important occupational issue and it can lead to the development of silicosis and other respiratory diseases. Little has been done with regard to the characterization of the crystalline silica content of specific particle sizes of mine-generated dust. Such characterization could improve monitoring techniques and control technologies for crystalline silica, decreasing worker exposure to silica and preventing future incidence of silicosis. Three gold mine dust samples were aerosolized in a laboratory chamber. Particle size-specific samples were collected for gravimetric analysis and for quantification of silica using the Microorifice Uniform Deposit Impactor (MOUDI). Dust size distributions were characterized via aerodynamic and scanning mobility particle sizers (APS, SMPS) and gravimetrically via the MOUDI. Silica size distributions were constructed using gravimetric data from the MOUDI and proportional silica content corresponding to each size range of particles collected by the MOUDI, as determined via X-ray diffraction and infrared spectroscopic quantification of silica. Results indicate that silica does not comprise a uniform proportion of total dust across all particle sizes and that the size distributions of a given dust and its silica component are similar but not equivalent. Additional research characterizing the silica content of dusts from a variety of mine types and other occupational environments is necessary in order to ascertain trends that could be beneficial in developing better monitoring and control strategies.

Evaluation of Diffuse Reflection Infrared Spectrometry for End-of-Shift Measurement of α-quartz in Coal Dust Samples

The inhalation of toxic substances is a major threat to the health of miners, and dust containing respirable crystalline silica (α-quartz) is of particular concern, due to the recent rise in cases of coal workers’ pneumoconiosis and silicosis in some U.S. mining regions. Currently, there is no field-portable instrument that can measure airborne α-quartz and give miners timely feedback on their exposure. The U.S. National Institute for Occupational Safety and Health (NIOSH) is therefore conducting studies to investigate technologies capable of end-of-shift or real-time measurement of airborne quartz. The present study focuses on the potential application of Fourier transform infrared (FT-IR) spectrometry conducted in the diffuse reflection (DR) mode as a technique for measuring α-quartz in respirable mine dust. A DR accessory was used to analyze lab-generated respirable samples of Min-U-Sil 5 (which contains more than 90% α-quartz) and coal dust, at mass loadings in the ranges of 100–600 μg and 600–5300 μg, respectively. The dust samples were deposited onto three different types of filters, borosilicate fiberglass, nylon, and polyvinyl chloride (PVC). The reflectance, R, was calculated by the ratio of a blank filter and a filter with deposited mine dust. Results suggest that for coal and pure quartz dusts deposited on 37 mm PVC filters, measurements of -log R correlate linearly with known amounts of quartz on filters, with R2 values of approximately 0.99 and 0.94, respectively, for samples loaded up to ∼4000 μg. Additional tests were conducted to measure quartz in coal dusts deposited onto the borosilicate fiberglass and nylon filter media used in the NIOSH-developed Personal Dust Monitor (PDM). The nylon filter was shown to be amenable to DR analysis, but quantification of quartz is more accurate when the filter is “free,” as opposed to being mounted in the PDM filter holder. The borosilicate fiberglass filters were shown to produce excessive interference, making quartz quantification impossible. It was concluded that, while the DR/FT-IR method is potentially useful for on-filter measurement of quartz in dust samples, the use of PVC filters produced the most accurate results.