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To quantify the fine-scale spatial variations and local source impacts of urban ultrafine particle (UFP) concentrations, we conducted 3-6 weeks of continuous measurements of particle number (a proxy for UFP) and other air pollutant (CO, NO2, and PM2.5) concentrations at 32 sites in Pittsburgh, Pennsylvania during the winters of 2017 and 2018. Sites were selected to span a range of urban land use attributes, including urban background, near local and arterial roads, traffic intersections, urban street canyon, near-highway, near large industrial source, and restaurant density. The spatial variations in urban particle number concentrations varied by about a factor of three. Particle number concentrations are 2-3 times more spatially heterogeneous than PM2.5 mass. The observed order of spatial heterogeneity is UFP > NO2 > CO > PM2.5. On average, particle number concentrations near local roads with a cluster of restaurants and near arterial roads are roughly two times higher than the urban background. Particle number concentrations in the urban street canyon, downwind of a major highway, and near large industrial sources are 2-4 times higher than background concentrations. While traffic is known as an important contributor to particle number concentrations, restaurants and industrial emissions also contribute significantly to spatial variations in Pittsburgh. Particle size distribution measurements using a mobile laboratory show that the local spatial variations in particle number concentrations are dictated by concentrations of particles smaller than 50 nm. A large fraction of urban residents (e.g., ~50%) in Pittsburgh live near local sources and are therefore exposed to 50%-300% higher particle number concentrations than urban background location. These locally emitted particles may have greater health effects than background particles.

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Emissions from solid-fuel cookstoves have been linked to indoor and outdoor air pollution, climate forcing, and human disease. Although task-based laboratory protocols, such as the Water Boiling Test (WBT), overestimate the ability of improved stoves to lower emissions, WBT emissions data are commonly used to benchmark cookstove performance, estimate indoor and outdoor air pollution concentrations, estimate impacts of stove intervention projects, and select stoves for large-scale control trials. Multiple-firepower testing has been proposed as an alternative to the WBT and is the basis for a new standardized protocol (ISO 19867-1:2018); however, data are needed to assess the value of this approach. In this work, we (a) developed a Firepower Sweep Test [FST], (b) compared emissions from the FST, WBT, and in-home cooking, and (c) quantified the relationship between firepower and emissions using correlation analysis and linear model selection. Twenty-three stove-fuel combinations were evaluated. The FST reproduced the range of PM2.5 and CO emissions observed in the field, including high emissions events not typically observed under the WBT. Firepower was modestly correlated with emissions, although the relationship varied between stove-fuel combinations. Our results justify incorporating multiple-firepower testing into laboratory-based protocols but demonstrate that firepower alone cannot explain the observed variability in cookstove emissions.

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Characterizing intracity variations of atmospheric particulate matter has mostly relied on fixed-site monitoring and quantifying variability in terms of different bulk aerosol species. In this study, we performed ground-based mobile measurements using a single-particle mass spectrometer to study spatial patterns of source-specific particles and the evolution of particle mixing state in 21 areas in the metropolitan area of Pittsburgh, PA. We selected sampling areas based on traffic density and restaurant density with each area ranging from 0.2 to 2 km2. Organics dominate particle composition in all of the areas we sampled while the sources of organics differ. The contribution of particles from traffic and restaurant cooking varies greatly on the neighborhood scale. We also investigate how primary and aged components in particles mix across the urban scale. Lastly we quantify and map the particle mixing state for all areas we sampled and discuss the overall pattern of mixing state evolution and its implications. We find that in the upwind and downwind of the urban areas, particles are more internally mixed while in the city center, particle mixing state shows large spatial heterogeneity that is mostly driven by emissions. This study is to our knowledge, the first study to perform fine spatial scale mapping of particle mixing state using ground-based mobile measurement and single-particle mass spectrometry.

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Organic aerosols provide a measure of complexity in the urban atmosphere. This is because the aerosols start as an external mixture, with many populations from varied local sources, that all interact with each other, with background aerosols, and with condensing vapors from secondary organic aerosol formation. The externally mixed particle populations start to evolve immediately after emission because the organic molecules constituting the particles also form thermodynamic mixtures - solutions - in which a large fraction of the constituents are semi-volatile. The external mixtures are thus well out of thermodynamic equilibrium, with very different activities for many constituents, and yet also have the capacity to relax toward equilibrium via gas-phase exchange of semi-volatile vapors. Here we describe experiments employing quantitative single-particle mass spectrometry designed to explore the extent to which various primary organic aerosol particle populations can interact with each other or with secondary organic aerosols representative of background aerosol populations. These methods allow us to determine when these populations will and when they will not mix with each other, and then to constrain the timescales for that mixing.

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The Marcellus Shale is the largest natural gas deposit in the U.S. and rapid development of this resource has raised concerns about regional air pollution. A field campaign was conducted in the southwestern Pennsylvania region of the Marcellus Shale to investigate the impact of unconventional natural gas (UNG) production operations on regional air quality. Whole air samples were collected throughout an 8050 km(2) grid surrounding Pittsburgh and analyzed for methane, carbon dioxide, and C1-C10 volatile organic compounds (VOCs). Elevated mixing ratios of methane and C2-C8 alkanes were observed in areas with the highest density of UNG wells. Source apportionment was used to identify characteristic emission ratios for UNG sources, and results indicated that UNG emissions were responsible for the majority of mixing ratios of C2-C8 alkanes, but accounted for a small proportion of alkene and aromatic compounds. The VOC emissions from UNG operations accounted for 17 ± 19% of the regional kinetic hydroxyl radical reactivity of nonbiogenic VOCs suggesting that natural gas emissions may affect compliance with federal ozone standards. A first approximation of methane emissions from the study area of 10.0 ± 5.2 kg s(-1) provides a baseline for determining the efficacy of regulatory emission control efforts.

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We used a mobile measurement platform to characterize a suite of air pollutants (black carbon (BC), particle-bound polycyclic aromatic hydrocarbons (PB-PAH), benzene, and toluene) in the city of Pittsburgh and surrounding areas. More than 270 h of data were collected from forty-two sites which were selected based on analysis in the geographic information system (GIS). Mobile measurements were performed during three different times of day (mornings, afternoons/evenings, and overnight) in both winter (November 2011 to February 2012) and summer (June 2012 to August 2012). Pollutant concentrations were elevated in river valleys by 9% (benzene) to 30% (PB-PAH) relative to upland areas. Traffic had strong impacts on measured pollutants. PB-PAH and BC concentrations at high traffic sites were a factor of 2 and 30% higher than at low traffic sites, respectively. Pollutant concentrations were highest in the morning sessions due to a combination of traffic and meteorological conditions. The highly time-resolved data indicated that elevated pollutant concentrations at high traffic sites were due to short duration plume events associated with high emitting vehicles. High emitting vehicles contributed up to 70% of the near road PB-PAH and 30% of BC; emissions from these vehicles drove substantial spatial variations in BC and PB-PAH concentrations. Many high emitting vehicles were presumably diesel trucks or buses, because plumes were strongly correlated with truck traffic volume. In contrast, PB-PAH and BC in the nonplume background air was weakly correlated with traffic, and their spatial patterns were more influenced by terrain and point source emissions. The spatial variability in contributions of high emitting vehicles suggests that the effect of potential control strategies vary for different pollutants and environments.

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Experimental results from laboratory emission testing have indicated that particulate emission measurements are sensitive to the dilution process of exhaust using fabricated dilution systems. In this paper, we first categorize the dilution parameters into two groups: (1) aerodynamics (e.g., mixing types, mixing enhancers, dilution ratios, residence time); and (2) mixture properties (e.g., temperature, relative humidity, particle size distributions of both raw exhaust and dilution gas). Then we employ the Comprehensive Turbulent Aerosol Dynamics and Gas Chemistry (CTAG) model to investigate the effects of those parameters on a set of particulate emission measurements comparing two dilution tunnels, i.e., a T-mixing lab dilution tunnel and a portable field dilution tunnel with a type of coaxial mixing. The turbulent flow fields and aerosol dynamics of particles are simulated inside two dilution tunnels. Particle size distributions under various dilution conditions predicted by CTAG are evaluated against the experimental data. It is found that in the area adjacent to the injection of exhaust, turbulence plays a crucial role in mixing the exhaust with the dilution air, and the strength of nucleation dominates the level of particle number concentrations. Further downstream, nucleation terminates and the growth of particles by condensation and coagulation continues. Sensitivity studies reveal that a potential unifying parameter for aerodynamics, i.e., the dilution rate of exhaust, plays an important role in new particle formation. The T-mixing lab tunnel tends to favor the nucleation due to a larger dilution rate of the exhaust than the coaxial mixing field tunnel. Our study indicates that numerical simulation tools can be potentially utilized to develop strategies to reduce the uncertainties associated with dilution samplings of emission sources.

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A series of smog chamber experiments were performed to investigate the effects of fuel composition on secondary particulate matter (PM) formation from dilute exhaust from a T63 gas-turbine engine. Tests were performed at idle and cruise loads with the engine fueled on conventional military jet fuel (JP-8), Fischer-Tropsch synthetic jet fuel (FT), and a 50/50 blend of the two fuels. Emissions were sampled into a portable smog chamber and exposed to sunlight or artificial UV light to initiate photo-oxidation. Similar to previous studies, neat FT fuel and a 50/50 FT/JP-8 blend reduced the primary particulate matter emissions compared to neat JP-8. After only one hour of photo-oxidation at typical atmospheric OH levels, the secondary PM production in dilute exhaust exceeded primary PM emissions, except when operating the engine at high load on FT fuel. Therefore, accounting for secondary PM production should be considered when assessing the contribution of gas-turbine engine emissions to ambient PM levels. FT fuel substantially reduced secondary PM formation in dilute exhaust compared to neat JP-8 at both idle and cruise loads. At idle load, the secondary PM formation was reduced by a factor of 20 with the use of neat FT fuel, and a factor of 2 with the use of the blend fuel. At cruise load, the use of FT fuel resulted in no measured formation of secondary PM. In every experiment, the secondary PM was dominated by organics with minor contributions from sulfate when the engine was operated on JP-8 fuel. At both loads, FT fuel produces less secondary organic aerosol than JP-8 because of differences in the composition of the fuels and the resultant emissions. This work indicates that fuel reformulation may be a viable strategy to reduce the contribution of emissions from combustion systems to secondary organic aerosol production and ultimately ambient PM levels.

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Experimental measurements of gas-particle partitioning and organic aerosol mass in diluted diesel and wood combustion exhaust are interpreted using a two-component absorptive-partitioning model. The model parameters are determined by fitting the experimental data. The changes in partitioning with dilution of both wood smoke and diesel exhaust can be described by two lumped compounds in roughly equal abundance with effective saturation concentrations of approximately 1600 microg m(-3) and approximately 20 microg m(-3). The model is used to investigate gas-particle partitioning of emissions across a wide range of atmospheric conditions. Under the highly dilute conditions found in the atmosphere, the partitioning of the emissions is strongly influenced by the ambient temperature and the background organic aerosol concentration. The model predicts large changes in primary organic aerosol mass with varying atmospheric conditions, indicating that it is not possible to specify a single value for the organic aerosol emissions. Since atmospheric conditions vary in both space and time, air quality models need to treat primary organic aerosol emissions as semivolatile. Dilution samplers provide useful information about organic aerosol emissions; however, the measurements can be biased relative to atmospheric conditions and constraining predictions of absorptive-partitioning models requires emissions data across the entire range of atmospherically relevant concentrations.

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Experiments were conducted to examine the effects of dilution on fine particle mass emissions from a diesel engine and wood stove. Filter measurements were made simultaneously using three dilution sampling systems operating at dilution ratios ranging from 20:1 to 510:1. Denuders and backup filters were used to quantify organic sampling artifacts. For the diesel engine operating at low load and wood combustion, large decreases in fine particle mass emissions were observed with increases in dilution. For example, the PM2.5 mass emission rate from a diesel engine operating at low load decreased by 50% when the dilution ratio was increased from 20:1 to 350:1. Measurements of organic and elemental carbon indicate that the changes in fine particle mass with dilution are caused by changes in partitioning of semivolatile organic compounds. At low levels of dilution semivolatile species largely occur in the particle phase, but increasing dilution reduces the concentration of semivolatile species, shifting this material to the gas phase in order to maintain phase equilibrium. Emissions of elemental carbon do not vary with dilution. Organic sampling artifacts are shown to vary with dilution because of the combination of changes in partitioning coupled with adsorption of gas-phase organics by quartz filters. The fine particle mass emissions from the diesel engine operating at medium load did not vary with dilution because of the lower emissions of semivolatile material and higher emissions of elemental carbon. To measure partitioning of semivolatile materials under atmospheric conditions, partitioning theory indicates that dilution samplers need to be operated such that the diluted exhaust achieves atmospheric levels of dilution. Too little dilution can potentially overestimate the fine particle mass emissions, and too much dilution (with clean air) can underestimate them.

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