Evaluation of a non-dispersive infrared spectrometer for quantifying organic and elemental carbon in diesel particulate matter.

Diesel particulate matter (DPM) is a common and well-known health hazard in the mining environment. The regulatory method for monitoring both the organic and elemental carbon (OC, EC) portions of DPM is a laboratory-based thermal-optical method with a typical turnaround time of one week. In order to evaluate exposure levels and take corrective action prior to overexposure, a portable real-time device capable of quantifying both OC and EC is needed. To that end, researchers from the National Institute for Occupational Safety and Health (NIOSH) designed and tested the feasibility of a device based on bandpass optical filters that target key infrared wavelengths associated with DPM and its spectroscopic baseline. The resulting device, referred to here as a non-dispersive infrared (NDIR) spectrometer could serve as the basis of a cost-effective, field-portable alternative to the laboratory thermal-optical method. The limits of quantification (LOD) indicate that the NDIR spectrometer can quantify EC, OC, and TC provided they are present at 20, 37, and 46 µg/m3 or more, respectively. In the event that the NDIR spectrometer is integrated with a sampler and filter tape the LOD is estimated to be reduced to 13, 7, and 10 µg/m3 for EC, OC, and TC, respectively. These LOD estimates assume a face velocity of 59 cm/s and a sampling time of 30 min.

Quantifying elemental and organic carbon in diesel particulate matter by mid-infrared spectrometry.

A method for the quantification of airborne organic carbon (OC) and elemental carbon (EC) within aerosolized diesel particulate matter (DPM) is described in this article. DPM is a known carcinogen encountered in many industrial workplaces (notably mining) and in the ambient atmosphere. The method described here collects DPM particles onto a quartz fiber filter, after which reflection-mode infrared spectra are measured on a mid-infrared Fourier transform (FT-IR) spectrometer. Several infrared absorption bands are investigated for their efficacy in quantifying OC and EC. The thermo-optical (T-O) method is used to calibrate a linear regression model to predict OC and EC from the infrared spectra. The calibrated model, generated from laboratory DPM samples, is then utilized to quantify OC and EC in mine samples obtained from two metal mine locations under a variety of operating conditions. The feasibility of further improving these results by partial least squares (PLS) regression was investigated. A single calibration that is broadly applicable would be considered an improvement over currently available portable instruments, which require aerosol-specific calibration.

Evaluation of an improved prototype mini-baghouse to control the release of respirable crystalline silica from sand movers.

The OSHA final rule on respirable crystalline silica (RCS) will require hydraulic fracturing companies to implement engineering controls to limit workers' exposure to RCS. RCS is generated by pneumatic transfer of quartz-containing sand during hydraulic fracturing operations. Chronic inhalation of RCS can lead to serious disease, including silicosis and lung cancer. NIOSH research identified at least seven sources where RCS aerosols were generated at hydraulic fracturing sites. NIOSH researchers developed an engineering control to address one of the largest sources of RCS aerosol generation, RCS escaping from thief hatches on the top of sand movers. The control, the NIOSH Mini-Baghouse Retrofit Assembly (NMBRA), mounts on the thief hatches. Unlike most commercially available engineering controls, the NMBRA has no moving parts and requires no power source. This article details the results of an evaluation of generation 3 of the NMBRA at a sand mine in Arkansas from May 19-21, 2015. During the evaluation, 168 area air samples were collected at 12 locations on and around a sand mover with and without the NMBRA installed. Analytical results for respirable dust and RCS indicated the use of the NMBRA effectively reduced concentrations of both respirable dust and RCS downwind of the thief hatches. Reductions of airborne respirable dust were estimated at 99+%; reductions in airborne RCS ranged from 98-99%. Analysis of bulk samples of the dust showed the likely presence of freshly fractured quartz, a particularly hazardous form of RCS. Use of an improved filter fabric and a larger area of filter cloth led to substantial improvements in filtration and pressures during these trials, as compared to the generation 2 NMBRA. Planned future design enhancements, including a weather cover, will increase the performance and durability of the NMBRA. Future trials are planned to evaluate the long-term operability of the technology.

Simultaneously reducing CO2 and particulate exposures via fractional recirculation of vehicle cabin air.

Prior studies demonstrate that air recirculation can reduce exposure to nanoparticles in vehicle cabins. However when people occupy confined spaces, air recirculation can lead to carbon dioxide (CO2) accumulation which can potentially lead to deleterious effects on cognitive function. This study proposes a fractional air recirculation system for reducing nanoparticle concentration while simultaneously suppressing CO2 levels in the cabin. Several recirculation scenarios were tested using a custom-programmed HVAC (heat, ventilation, air conditioning) unit that varied the recirculation door angle in the test vehicle. Operating the recirculation system with a standard cabin filter reduced particle concentrations to 1000 particles/cm3, although CO2 levels rose to 3000 ppm. When as little as 25% fresh air was introduced (75% recirculation), CO2 levels dropped to 1000 ppm, while particle concentrations remained below 5000 particles/cm3. We found that nanoparticles were removed selectively during recirculation and demonstrated the trade-off between cabin CO2 concentration and cabin particle concentration using fractional air recirculation. Data showed significant increases in CO2 levels during 100% recirculation. For various fan speeds, recirculation fractions of 50-75% maintained lower CO2 levels in the cabin, while still reducing particulate levels. We recommend fractional recirculation as a simple method to reduce occupants' exposures to particulate matter and CO2 in vehicles. A design with several fractional recirculation settings could allow air exchange adequate for reducing both particulate and CO2 exposures. Developing this technology could lead to reductions in airborne nanoparticle exposure, while also mitigating safety risks from CO2 accumulation.

Direct-on-Filter α-Quartz Estimation in Respirable Coal Mine Dust Using Transmission Fourier Transform Infrared Spectrometry and Partial Least Squares Regression.

In order to help reduce silicosis in miners, the National Institute for Occupational Health and Safety (NIOSH) is developing field-portable methods for measuring airborne respirable crystalline silica (RCS), specifically the polymorph α-quartz, in mine dusts. In this study we demonstrate the feasibility of end-of-shift measurement of α-quartz using a direct-on-filter (DoF) method to analyze coal mine dust samples deposited onto polyvinyl chloride filters. The DoF method is potentially amenable for on-site analyses, but deviates from the current regulatory determination of RCS for coal mines by eliminating two sample preparation steps: ashing the sampling filter and redepositing the ash prior to quantification by Fourier transform infrared (FT-IR) spectrometry. In this study, the FT-IR spectra of 66 coal dust samples from active mines were used, and the RCS was quantified by using: (1) an ordinary least squares (OLS) calibration approach that utilizes standard silica material as done in the Mine Safety and Health Administration's P7 method; and (2) a partial least squares (PLS) regression approach. Both were capable of accounting for kaolinite, which can confound the IR analysis of silica. The OLS method utilized analytical standards for silica calibration and kaolin correction, resulting in a good linear correlation with P7 results and minimal bias but with the accuracy limited by the presence of kaolinite. The PLS approach also produced predictions well-correlated to the P7 method, as well as better accuracy in RCS prediction, and no bias due to variable kaolinite mass. Besides decreased sensitivity to mineral or substrate confounders, PLS has the advantage that the analyst is not required to correct for the presence of kaolinite or background interferences related to the substrate, making the method potentially viable for automated RCS prediction in the field. This study demonstrated the efficacy of FT-IR transmission spectrometry for silica determination in coal mine dusts, using both OLS and PLS analyses, when kaolinite was present.

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

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.

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 R(2) 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.

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

The 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.

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 LOD's were 11.8, 0.032, and 108 µg Ti per filter, for XRF, LIBS, and FTIR, respectively and the LOQ's 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.

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.

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 µg/cm(2) and 0.05 µg/cm(2), respectively (corresponding to 0.16 µg/cm(2) and 0.20 µg/cm(2) 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.

Toward Developing a New Occupational Exposure Metric Approach for Characterization of Diesel Aerosols.

The extensive use of diesel-powered equipment in mines makes the exposure to diesel aerosols a serious occupational issue. The exposure metric currently used in U.S. underground noncoal mines is based on the measurement of total carbon (TC) and elemental carbon (EC) mass concentration in the air. Recent toxicological evidence suggests that the measurement of mass concentration is not sufficient to correlate ultrafine aerosol exposure with health effects. This urges the evaluation of alternative measurements. In this study, the current exposure metric and two additional metrics, the surface area and the total number concentration, were evaluated by conducting simultaneous measurements of diesel ultrafine aerosols in a laboratory setting. The results showed that the surface area and total number concentration of the particles per unit of mass varied substantially with the engine operating condition. The specific surface area (SSA) and specific number concentration (SNC) normalized with TC varied two and five times, respectively. This implies that miners, whose exposure is measured only as TC, might be exposed to an unknown variable number concentration of diesel particles and commensurate particle surface area. Taken separately, mass, surface area, and number concentration did not completely characterize the aerosols. A comprehensive assessment of diesel aerosol exposure should include all of these elements, but the use of laboratory instruments in underground mines is generally impracticable. The article proposes a new approach to solve this problem. Using SSA and SNC calculated from field-type measurements, the evaluation of additional physical properties can be obtained by using the proposed approach.

Evaluating portable infrared spectrometers for measuring the silica content of coal dust.

Miners face a variety of respiratory hazards while on the job, including exposure to silica dust which can lead to silicosis, a potentially fatal lung disease. Currently, field-collected filter samples of silica are sent for laboratory analysis and the results take weeks to be reported. Since the mining workplace is constantly moving into new and often different geological strata with changing silica levels, more timely data on silica levels in mining workplaces could help reduce exposures. Improvements in infrared (IR) spectroscopy open the prospect for end-of-shift silica measurements at mine sites. Two field-portable IR spectrometers were evaluated for their ability to quantify the mass of silica on filter samples loaded with known amounts of either silica or silica-bearing coal dust (silica content ranging from 10-200 µg/filter). Analyses included a scheme to correct for the presence of kaolin, which is a confounder for IR analysis of silica. IR measurements of the samples were compared to parallel measurements derived using the laboratory-based U.S. Mine Safety and Health Administration P7 analytical method. Linear correlations between Fourier transform infrared (FTIR) and P7 data yielded slopes in the range of 0.90-0.97 with minimal bias. Data from a variable filter array spectrometer did not correlate as well, mainly due to poor wavelength resolution compared to the FTIR instrument. This work has shown that FTIR spectrometry has the potential to reasonably estimate the silica exposure of miners if employed in an end-of-shift method.

Role of lubrication oil in particulate emissions from a hydrogen-powered internal combustion engine.

Recent studies suggest that trace metals emitted by internal combustion engines are derived mainly from combustion of lubrication oil. This hypothesis was examined by investigation of the formation of particulate matter emitted from an internal combustion engine in the absence of fuel-derived soot. Emissions from a modified CAT 3304 diesel engine fueled with hydrogen gas were characterized. The role of organic carbon and metals from lubrication oil on particle formation was investigated under selected engine conditions. The engine produced exhaust aerosol with log normal-size distributions and particle concentrations between 10(5) and 10(7) cm(-3) with geometric mean diameters from 18 to 31 nm. The particles contained organic carbon, little or no elemental carbon, and a much larger percentage of metals than particles from diesel engines. The maximum total carbon emission rate was estimated at 1.08 g h(-1), which is much lower than the emission rate of the original diesel engine. There was also evidence that less volatile elements, such as iron, self-nucleated to form nanoparticles, some of which survive the coagulation process.

Real-time estimation of elemental carbon emitted from a diesel engine.

New Mining Safety and Health Administration (MSHA) regulations limit the mass concentration of airborne diesel particulate matter (DPM) or, more specifically, the concentration of elemental carbon (EC), in underground mines. The mine operators are responding by introducing a variety of controls to reduce DPM in the mines, potentially including the evaluation of new maintenance procedures to reduce underground mine vehicle emissions. There is currently a lack of an inexpensive and dependable method to directly measure the DPM concentration emitted from the vehicle tailpipe. To that end, this work demonstrated a simple field portable method for estimating the mass concentration of elemental carbon exiting the tailpipe of a diesel engine using a direct reading photometer. Simultaneous measurements of tailpipe exhaust were made with a Thermo Electron Personal DataRAM 1200 photometer (particulate mass concentration based on light scattering) and by analyzing PM2.5 and PM1.0 samples collected on quartz fiber filters using the National Institute of Occupational Safety and Health (NIOSH) method 5040 (mass concentration of EC via thermal-optical method). Results indicate surprisingly good correlation (R2 = 0.97) of the two methods when the data are adjusted for relative humidity (RH) and corrected using an empirically generated calibration factor. Although preliminary, it may be possible to implement this method in maintenance shops to monitor emission trends and to compare emissions of various vehicles in a fleet. Such data will be useful for fleet planning to meet new air quality standards.