Evaluation of PVC and PTFE filters for direct-on-filter crystalline silica quantification by FTIR.

Direct-on-Filter (DoF) analysis of respirable crystalline silica (RCS) by Fourier Transform Infrared (FTIR) spectroscopy is a useful tool for assessing exposure risks. With the RCS exposure limits becoming lower, it is important to characterize and reduce measurement uncertainties. This study systematically evaluated two filter types (i.e., polyvinyl chloride [PVC] and polytetrafluoroethylene [PTFE]) for RCS measurements by DoF FTIR spectroscopy, including the filter-to-filter and day-to-day variability of blank filter FTIR reference spectra, particle deposition patterns, filtration efficiencies, and pressure drops. For PVC filters sampled at a flow rate of 2.5 L/min for 8 h, the RCS limit of detection (LOD) was 7.4 µg/m3 when a designated laboratory reference filter was used to correct the absorption by the filter media. When the spectrum of the pre-sample filter (blank filter before dust sampling) was used for correction, the LOD could be up to 5.9 µg/m3. The PVC absorption increased linearly with reference filter mass, providing a means to correct the absorption differences between the pre-sample and reference filters. For PTFE, the LODs were 12 and 1.2 µg/m3 when a designated laboratory blank or the pre-sample filter spectrum was used for blank correction, respectively, indicating that using the pre-sample blank spectrum will reduce RCS quantification uncertainty. Both filter types exhibited a consistent radially symmetric deposition pattern when particles were collected using 3-piece cassettes, indicating that RCS can be quantified from a single measurement at the filter center. The most penetrating aerodynamic diameters were around 0.1 µm with filtration efficiencies ≥ 98.8% across the measured particle size range with low-pressure drops (0.2-0.3 kPa) at a flow rate of 2.5 L/min. This study concludes that either the PVC or the PTFE filters are suitable for RCS analysis by DoF FTIR, but proper methods are needed to account for the variability of blank absorption among different filters.

Development of a Multispectral Albedometer and Deployment on an Unmanned Aircraft for Evaluating Satellite Retrieved Surface Reflectance over Nevada's Black Rock Desert.

Bright surfaces across the western U.S. lead to uncertainties in satellite derived aerosol optical depth (AOD) where AOD is typically overestimated. With this in mind, a compact and portable instrument was developed to measure surface albedo on an unmanned aircraft system (UAS). This spectral albedometer uses two Hamamatsu micro-spectrometers (range: 340⁻780 nm) for measuring incident and reflected solar radiation at the surface. The instrument was deployed on 5 October 2017 in Nevada's Black Rock Desert (BRD) to investigate a region of known high surface reflectance for comparison with albedo products from satellites. It was found that satellite retrievals underestimate surface reflectance compared to the UAS mounted albedometer. To highlight the importance of surface reflectance on the AOD from satellite retrieval algorithms, a 1-D radiative transfer model was used. The simple model was used to determine the sensitivity of AOD with respect to the change in albedo and indicates a large sensitivity of AOD retrievals to surface reflectance for certain combinations of surface albedo and aerosol optical properties. This demonstrates the need to increase the number of surface albedo measurements and an intensive evaluation of albedo satellite retrievals to improve satellite-derived AOD. The portable instrument is suitable for other applications as well.

Longitudinal Spin Relaxation of Optically Pumped Rubidium Atoms in Solid Parahydrogen.

We have grown crystals of solid parahydrogen using a single closed-cycle cryostat. We have doped the crystals with rubidium atoms at densities on the order of 10^{17} cm^{-3} and used optical pumping to polarize the spin state of the implanted atoms. The optical spectrum of the rubidium atoms shows larger broadening than previous work in which the rubidium was implanted in solid argon or neon. However, the optical pumping behavior is significantly improved, with both a larger optical pumping signal and a longer longitudinal relaxation time. The spin relaxation time shows a strong dependence on orthohydrogen impurity levels in the crystal, as well as the applied magnetic field. Current performance is comparable to state-of-the-art solid state systems at comparable spin densities, with potential for improvement at higher parahydrogen purities.

Concentrations of mobile source air pollutants in urban microenvironments.

Human exposures to criteria and hazardous air pollutants (HAPs) in urban areas vary greatly due to temporal-spatial variations in emissions, changing meteorology, varying proximity to sources, as well as due to building, vehicle, and other environmental characteristics that influence the amounts of ambient pollutants that penetrate or infiltrate into these microenvironments. Consequently, the exposure estimates derived from central-site ambient measurements are uncertain and tend to underestimate actual exposures. The Exposure Classification Project (ECP) was conducted to measure pollutant concentrations for common urban microenvironments (MEs) for use in evaluating the results of regulatory human exposure models. Nearly 500 sets of measurements were made in three Los Angeles County communities during fall 2008, winter 2009, and summer 2009. MEs included in-vehicle, near-road, outdoor and indoor locations accessible to the general public. Contemporaneous 1- to 15-min average personal breathing zone concentrations of carbon monoxide (CO), carbon dioxide (CO2), volatile organic compounds (VOCs), nitric oxide (NO), nitrogen oxides (NO(x)), particulate matter (< 2.5 microm diameter; PM2.5) mass, ultrafine particle (UFP; < 100 nm diameter) number black carbon (BC), speciated HAPs (e.g, benzene, toluene, ethylbenzene, xylenes [BTEX], 1,3-butadiene), and ozone (O3) were measured continuously. In-vehicle and inside/outside measurements were made in various passenger vehicle types and in public buildings to estimate penetration or infiltration factors. A large fraction of the observed pollutant concentrations for on-road MEs, especially near diesel trucks, was unrelated to ambient measurements at nearby monitors. Comparisons of ME concentrations estimated using the median ME/ambient ratio versus regression slopes and intercepts indicate that the regression approach may be more accurate for on-road MEs. Ranges in the ME/ambient ratios among ME categories were generally greater than differences among the three communities for the same ME category, suggesting that the ME proximity factors may be more broadly applicable to urban MEs. Implications: Estimates of population exposure to air pollutants extrapolated from ambient measurements at ambient fixed site monitors or exposure surrogates are prone to uncertainty. This study measured concentrations of mobile source air toxics (MSAT) and related criteria pollutants within in-vehicle, outdoor near-road, and indoor urban MEs to provide multipollutant ME measurements that can be used to calibrate regulatory exposure models.

Influence of photolysis on multispectral photoacoustic measurement of nitrogen dioxide concentration.

Multispectral photoacoustic instruments are commonly used to measure aerosol and nitrogen dioxide (NO2) light absorption coefficients to determine the radiation budget of the atmosphere. Here a new photoacoustic system is developed to explore the effect of photolysis on the measured signal in a multispectral photoacoustic spectrometer In this system, a 405-nm laser is used primarily as light source for photolysis. Additionally, a well-overlapped 532-nm laser, modulated at the resonant frequency of the photoacoustic instrument, is used to probe the NO2 concentration. As a result, the photolysis effect at 405 nm can be observed by the photoacoustic instrument through the 532-nm laser. This work determines an 11% reduction of the photoacoustic signal caused by the photolysis effect for typical conditions, which needs to be taken into account when calibrating multispectral photoacoustic spectrometers with NO2.

Spatial variations of particulate matter and air toxics in communities adjacent to the Port of Oakland.

The Bay Area Air Quality Management District (BAAQMD) sponsored the West Oakland Monitoring Study (WOMS) to provide supplemental air quality monitoring that will be used by the BAAQMD to evaluate local-scale dispersion modeling of diesel emissions and other toxic air contaminants for the area within and around the Port of Oakland. The WOMS was conducted during two seasonal periods of 4 weeks in summer 2009 and winter 2009/2010. Monitoring data showed spatial patterns of pollutant concentrations that were generally consistent with proximity to vehicle traffic. Concentrations of directly emitted pollutants were highest on heavily traveled roads with consistently lower concentrations away from the roadways. Pollutants that have higher emission rates from diesel trucks (nitric oxide, black carbon) tended to exhibit sharper gradients than pollutants that are largely associated with gasoline vehicles, such as carbon monoxide and volatile organic compounds, including benzene, toluene, ethylbenzene, and xylenes (BTEX). BTEX concentrations in West Oakland were similar to those measured at the three air toxics monitoring network sites in the Bay Area (San Francisco, Fremont, and San Jose). Aldehyde levels were higher in Fremont and San Jose than in West Oakland, reflecting greater contributions from photo-oxidation of hydrocarbons downwind of the Bay Area. A 2005 modeling-based health risk assessment of diesel particulate matter concentrations is consistent with aerosol carbon concentrations measured during the WOMS after adjusting for recent mitigation measures and improved estimates of heavy-duty truck traffic volumes.

Photoacoustic measurements of black carbon light absorption coefficients in Irbid city, Jordan.

There is a need to recognize air pollution levels by particles, especially in developing countries such as Jordan where data are scarce due to the absence of routine monitoring of ambient air quality. This study aims at studying the air quality in different locations at Irbid, Jordan through the measurement and analysis of the time series of black carbon light absorption coefficients (B (abs)). Black carbon light absorption coefficients were measured with a photoacoustic instrument at a wavelength of 870 nm. The measurements were conducted during July 2007 at six sites in Irbid city, Jordan. Comparisons of black carbon concentrations at various locations were conducted to understand where values tend to be largest. The average value of B (abs) of all sites was 40.4 Mm(-1). The largest value of B (abs) was 61.2 Mm(-1) at Palestine Street which is located at a very crowded street in a highly populated region in the city center. The lowest value was 14.1 Mm(-1) at Thirtieth Street which is located at a main street in an open plain region in the east of the city. The black carbon light absorption coefficients fluctuate above a background level (transported black carbon from the neighboring states), which are almost identical at all sampling sites. The light absorption coefficients will be used as a benchmark in later years as combustion efficiencies and population patterns change.

Particle optics in the Rayleigh regime.

Light scattering and absorption by particles suspended in the atmosphere modifies the transfer of solar energy in the atmosphere, thereby influencing global and regional climate change and atmospheric visibility. Of particular interest are the optical properties of particles in the Rayleigh regime, where particles are small compared with the wavelength of the scattered or absorbed light, because these particles experience little gravitational settlement and may have long atmospheric lifetimes. Optical properties of particles in the Rayleigh regime are commonly derived from electromagnetic theory using Maxwell's equations and appropriate boundary conditions. The size dependence of particle scattering and absorption are derived here from the most basic principles for coherent processes such as Rayleigh scattering (i.e., add amplitudes if in phase) and incoherent processes such as absorption (i.e., add cross sections), at the same time yielding understanding of the upper particle size limit for the Rayleigh regime. The wavelength dependence of Rayleigh scattering and absorption are also obtained by adding a basic scale invariance for particle optics. Simple consequences for particle single-scattering albedo ("whiteness") and the optical measurement of particle mass densities are explained. These alternative derivations complement the conventional understanding obtained from electromagnetic theory.

Variations in speciated emissions from spark-ignition and compression-ignition motor vehicles in California's south coast air basin.

The U.S. Department of Energy Gasoline/Diesel PM Split Study examined the sources of uncertainties in using an organic compound-based chemical mass balance receptor model to quantify the contributions of spark-ignition (SI) and compression-ignition (CI) engine exhaust to ambient fine particulate matter (PM2.5). This paper presents the chemical composition profiles of SI and CI engine exhaust from the vehicle-testing portion of the study. Chemical analysis of source samples consisted of gravimetric mass, elements, ions, organic carbon (OC), and elemental carbon (EC) by the Interagency Monitoring of Protected Visual Environments (IMPROVE) and Speciation Trends Network (STN) thermal/optical methods, polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes, alkanes, and polar organic compounds. More than half of the mass of carbonaceous particles emitted by heavy-duty diesel trucks was EC (IMPROVE) and emissions from SI vehicles contained predominantly OC. Although total carbon (TC) by the IMPROVE and STN protocols agreed well for all of the samples, the STN/IMPROVE ratios for EC from SI exhaust decreased with decreasing sample loading. SI vehicles, whether low or high emitters, emitted greater amounts of high-molecular-weight particulate PAHs (benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and coronene) than did CI vehicles. Diesel emissions contained higher abundances of two- to four-ring semivolatile PAHs. Diacids were emitted by CI vehicles but are also prevalent in secondary organic aerosols, so they cannot be considered unique tracers. Hopanes and steranes were present in lubricating oil with similar composition for both gasoline and diesel vehicles and were negligible in gasoline or diesel fuels. CI vehicles emitted greater total amounts of hopanes and steranes on a mass per mile basis, but abundances were comparable to SI exhaust normalized to TC emissions within measurement uncertainty. The combustion-produced high-molecular-weight PAHs were found in used gasoline motor oil but not in fresh oil and are negligible in used diesel engine oil. The contributions of lubrication oils to abundances of these PAHs in the exhaust were large in some cases and were variable with the age and consumption rate of the oil. These factors contributed to the observed variations in their abundances to total carbon or PM2.5 among the SI composition profiles.

Scattering cross-section emission factors for visibility and radiative transfer applications: military vehicles traveling on unpaved roads.

Emission factors for particulate matter (PM) are generally reported as mass emission factors (PM mass emitted per time or activity) as appropriate for air quality standards based on mass concentration. However, for visibility and radiative transfer applications, scattering, absorption, and extinction coefficients are the parameters of interest, with visibility standards based on extinction coefficients. These coefficients (dimension of inverse distance) equal cross-section concentrations, and, therefore, cross-section emission factors are appropriate. Scattering cross-section emission factors were determined for dust entrainment by nine vehicles, ranging from light passenger vehicles to heavy military vehicles, traveling on an unpaved road. Each vehicle made multiple passes at multiple speeds while scattering and absorption coefficients, wind velocity and dust plume profiles, and additional parameters were measured downwind of the road. Light absorption of the entrained PM was negligible, and the light extinction was primarily caused by scattering. The resulting scattering cross-section emission factors per vehicle kilometer traveled (vkt) range from 12.5 m2/vkt for a slow (16 km/ hr), light (1176 kg) vehicle to 3724 m2/vkt for a fast (64 km/hr), heavy (17,727 kg) vehicle and generally increase with vehicle speed and mass. The increase is approximately linear with speed, yielding emission factors per vkt and speed ranging from 4.2 m2/(vkt km/hr) to 53 m2/(vkt km/hr). These emission factors depend approximately linearly on vehicle mass within the groups of light (vehicle mass < or =3100 kg) and heavy (vehicle mass >8000 kg) vehicles yielding emission factors per vkt, speed, and mass of 0.0056 m2/(vkt km/hr kg) and 0.0024 m2/(vkt km/hr kg), respectively. Comparison of the scattering cross-section and PM mass emission factors yields average mass scattering efficiencies of 1.5 m2/g for the light vehicles and of 0.8 m2/g for the heavy vehicles indicating that the heavy vehicles entrain larger particles than the light vehicles.

Low fractal dimension cluster-dilute soot aggregates from a premixed flame.

Using a novel morphology segregation technique, we observed minority populations ( approximately 3%) of submicron-sized, cluster-dilute fractal-like aggregates, formed in the soot-formation window (fuel-to-air equivalence ratio of 2.0-3.5) of a premixed flame, to have mass fractal dimensions between 1.2 and 1.51. Our observations disagree with previous observations of a universal mass fractal dimension of approximately 1.8 for fractal-like aerosol aggregates formed in the dilute-limit via three-dimensional diffusion-limited cluster aggregation processes. A hypothesis is presented to explain this observation. Subject to verification of this hypothesis, it may be possible to control the fractal dimension and associated properties of aggregates in the cluster-dilute limit through application of a static electric field during the aggregation process.

Light scattering and absorption by fractal-like carbonaceous chain aggregates: comparison of theories and experiment.

This study compares the optical coefficients of size-selected soot particles measured at a wavelength of 870 nm with those predicted by three theories, namely, Rayleigh-Debye-Gans (RDG) approximation, volume-equivalent Mie theory, and integral equation formulation for scattering (IEFS). Soot particles, produced by a premixed ethene flame, were size-selected using two differential mobility analyzers in series, and their scattering and absorption coefficients were measured with nephelometry and photoacoustic spectroscopy. Scanning electron microscopy and image processing techniques were used for the parameterization of the structural properties of the fractal-like soot aggregates. The aggregate structural parameters were used to evaluate the predictions of the optical coefficients based on the three light-scattering and absorption theories. Our results show that the RDG approximation agrees within 10% with the experimental results and the exact electromagnetic calculations of the IEFS theory. Volume-equivalent Mie theory overpredicts the experimental scattering coefficient by a factor of approximately 3.2. The optical coefficients predicted by the RDG approximation showed pronounced sensitivity to changes in monomer mean diameter, the count median diameter of the aggregates, and the geometric standard deviation of the aggregate number size distribution.

Emissions from laboratory combustion of wildland fuels: emission factors and source profiles.

Combustion of wildland fuels represents a major source of particulate matter (PM) and light-absorbing elemental carbon (EC) on a national and global scale, but the emission factors and source profiles have not been well characterized with respect to different fuels and combustion phases. These uncertainties limit the accuracy of current emission inventories, smoke forecasts, and source apportionments. This study investigates the evolution of gaseous and particulate emission and combustion efficiency by burning wildland fuels in a laboratory combustion facility. Emission factors for carbon dioxide (CO2), carbon monoxide (CO), total hydrocarbon (THC), nitrogen oxides (NO(x)), PM, light extinction and absorption cross sections, and spectral scattering cross sections specific to flaming and smoldering phases are reported. Emission factors are generally reproducible within +/- 20% during the flaming phase, which, despite its short duration, dominates the carbon emission (mostly in the form of CO2) and the production of light absorption and EC. Higher and more variable emission factors for CO, THC, and PM are found during the smoldering phase, especially for fuels containing substantial moisture. Organic carbon (OC) and EC mass account for a majority (i.e., > 60%) of PM mass; other important elements include potassium, chlorine, and sulfur. Thermal analysis separates the EC into subfractions based on analysis temperature demonstrating that high-temperature EC (EC2; at 700 degrees C) varies from 1% to 70% of PM among biomass burns, compared to 75% in kerosene soot. Despite this, the conversion factor between EC and light absorption emissions is rather consistent across fuels and burns, ranging from 7.8 to 9.6 m2/g EC. Findings from this study should be considered in the development of PM and EC emission inventories for visibility and radiative forcing assessments.

Structural and fractal properties of particles emitted from spark ignition engines.

Size, morphology, and microstructure of particles emitted from one light-duty passenger vehicle (Buick Century; model year 1990; PM (particulate matter) mass emission rate 3.1 mg/km) and two light-duty trucks (Chevrolet C2; model year 1973; PM mass emission rate 282 mg/km, and Chevrolet El Camino; model year 1976; PM mass emission rate 31 mg/km), running California's unified driving cycles (UDC) on a chassis dynamometer, were studied using scanning electron microscopy (SEM). SEM images yielded particle properties including three-dimensional density fractal dimensions, monomer and agglomerate number size distributions, and three different shape descriptors, namely aspect ratio, root form factor, and roundness. The density fractal dimension of the particles was between 1.7 and 1.78, while the number size distribution of the particles placed the majority of the particles in the accumulation mode (0.1-0.3 microm). The shape descriptors were found to decrease with increasing particle size. Partial melting of particles, a rare and previously unreported phenomenon, was observed upon exposure of particles emitted during phase 2 of the UDC to the low accelerating voltage electron beam of the SEM. The rate of melting was quantified for individual particles, establishing a near linear relationship between the melting rate and the organic carbon 1 to elemental carbon ratio.

Toward an ideal integrating nephelometer.

The Integrating Sphere Integrating Nephelometer is a novel and unique reciprocal nephelometer that uses an integrating sphere with attached truncation-reduction tubes to contain the sample volume and to integrate the scattered light. Its main advantage compared with current integrating nephelometers is a sevenfold reduction in truncation angle, which reduces errors in measured scattering from large particles. Additional features include improved sampling efficiency for large particles and a well-defined operating wavelength.

Equivalence of elemental carbon by thermal/optical reflectance and transmittance with different temperature protocols.

Charring of organic carbon (OC) during thermal/optical analysis is monitored by the change in a laser signal either reflected from or transmitted through a filter punch. Elemental carbon (EC) in suspended particulate matter collected on quartz-fiber filters is defined as the carbon that evolves after the detected optical signal attains the value it had prior to commencement of heating, with the rest of the carbon classified as organic carbon (OC). Heretofore, operational definitions of EC were believed to be caused by different temperature protocols rather than by the method of monitoring charring. This work demonstrates that thermal/ optical reflectance (TOR) corrections yield equivalent OC/ EC splits for widely divergent temperature protocols. EC results determined by simultaneous thermal/optical transmittance (TOT) corrections are 30% lower than TOR for the same temperature protocol and 70-80% lower than TOR for a protocol with higher heating temperatures and shorter residence times. This is true for 58 urban samples from Fresno, CA, as well as for 30 samples from the nonurban IMPROVE network that are individually dominated by wildfire, vehicle exhaust, secondary organic aerosol, and calcium carbonate contributions. Visual examination of filter darkening at different temperature stages shows that substantial charring takes place within the filter, possibly due to adsorbed organic gases or diffusion of vaporized particles. The filter transmittance is more influenced by the within-filter char, whereas the filter reflectance is dominated by charring of the near-surface deposit that appears to evolve first when oxygen is added to helium in the analysis atmosphere for these samples. The amounts of charred OC (POC) and EC are also estimated from incremental absorbance. Small amounts of POC are found to dominate the incremental absorbance. EC estimated from absorbance are found to agree better with EC from the reflectance charring correction than with EC from the transmittance charring correction.