Katharine Moore

Emissions of Particulate Trace Elements, Metals and Organic Species from Gasoline, Diesel, and Biodiesel Passenger Vehicles and Their Relation to Oxidative Potential

Three light-duty passenger vehicles were tested in five configurations in a chassis dynamometer study to determine the chemical and oxidative potential of the particulate exhaust emissions. The first vehicle was a diesel Honda with a three-stage oxidation system. Its main catalyst was replaced with a diesel particulate filter (DPF) and tested as a second configuration. The second vehicle was a gasoline-fuelled Toyota Corolla with a three-way catalytic converter. The last vehicle was an older Volkswagen Golf, tested using petro-diesel in its original configuration, and biodiesel with an oxidation catalyst as an alternative configuration. Particulate matter (PM) was collected on filters and subsequently analyzed using various chemical and toxicological assays. The production of reactive oxygen species (ROS), quantified by the dithiothreitol (DTT) and macrophage-ROS assays, was used to measure the PM-induced oxidative potential. The results showed that the Golf vehicle in both configurations had the highest emissions of organic species (PAHs, hopanes, steranes, and organic acids). The DPF-equipped diesel Accord car emitted PM with the lowest amounts of organic species and the lowest oxidative potential. Correlation analyses showed that soluble Fe is strongly associated with particulate ROS activity (R = 0.99), while PAHs and hopanes were highly associated with DTT consumption rates (R = 0.94 and 0.91, respectively). In particular, tracers of lube oil emissions, namely Zn, P, Ca, and hopanes, were strongly correlated with distance-based DTT consumption rates (R = 0.96, 0.92, 0.83, and 0.91, respectively), suggesting that incomplete combustion of lube oil might be important driving factors of the overall PM-induced oxidative stress.

Spatial and Temporal Variability of Coarse (PM10−2.5) Particulate Matter Concentrations in the Los Angeles Area

Recent epidemiological and toxicological studies suggest that coarse particulate matter (CPM, particles smaller than 10 and larger than 2.5 μm in diameter, PM 10−2.5 ) concentrations may be associated with adverse health outcomes at levels similar to or larger than those associated with PM 2.5 concentrations. CPM may consist of several, mechanically generated, potentially toxic components, including re-suspended road dust, industrial materials, trace metals, and bio-aerosols. In an effort to better understand and quantify the linkage between sources, composition and the toxicity of coarse PM, 10 sampling sites were set-up in the Los Angeles area. Sites within this diverse monitoring network were selected to encompass urban, rural, coastal, inland, near-freeway, community-based, upwind pollutant “source” and downwind pollutant “receptor” sites to fully characterize the range of likely conditions. At each location, a 24 h time-integrated coarse PM sample was collected once per week for one year in order to assess the seasonal and spatial patterns in coarse PM concentrations. Annual geometric mean CPM mass concentrations varied from <5.0 μg/m 3 to approximately 12 μg/m 3 . Concentrations were 2–4 times higher in the summer than the winter. CPM correlations between sites in close proximity to each other tended to be high (r 2 > 0.80), but were poor between urban center and inland sites. The coefficients of divergence (COD) were also calculated across all site pairs to quantify CPM mass concentration spatial heterogeneity. The CODs (most monthly median values >0.2) suggest modest heterogeneity overall, but the CODs calculated between the urban core site pairs were homogeneous.

Intra-Community Variability in Total Particle Number Concentrations in the San Pedro Harbor Area (Los Angeles, California)

Recent evidence links elevated ultrafine particle (UFP) concentrations with adverse health effects, but exposure assessments based upon PM 2.5 mass concentrations may be misleading. In order to better understand and quantify intra-community variability in UFP concentrations, a dense network of 14 monitoring sites was set-up in Los Angeles in two clusters—San Pedro/Wilmington and West Long Beach—in communities surrounding the Ports of Los Angeles and Long Beach. The network measured total particle number concentrations greater than 7 nm in diameter. In this range, UFP comprise approximately 90% of the total. Port-related activities—particularly goods movement associated with high volumes of heavy-duty diesel vehicle (HDDV) traffic—represent significant UFP sources. The field study was conducted from mid-February through mid-December 2007 to assess diurnal, seasonal, and spatial patterns and intra-community variability in total particle number concentrations. For sites within a few km of each other, simultaneous particle number concentrations can vary up to a factor of 10 (< 10,000 cm−3 up to 90,000 cm−3 for hourly averages calculated by month). The median hourly correlation coefficient (r) across all sites was modest and varied from 0.3 to 0.56. Specific site locations, particularly proximity to roadways used for goods movement, strongly affect observations. Clear diurnal and seasonal patterns are evident in the data. A diurnal pattern associated with high HDDV volumes and goods movement was identified. Coefficients of Divergence calculated for the site pairs suggest moderate heterogeneity overall (median study COD ≈ 0.35). The intra-urban variability observed in this study is comparable to and exceeds the inter-urban variability observed in a previous study in Los Angeles. UFP concentrations can vary considerably on short spatial scales in source-rich environments strongly influencing the accuracy of exposure assessments.

Field Validation of the New Miniature Versatile Aerosol Concentration Enrichment System (mVACES)

Recently a new compact aerosol concentration enrichment system was developed at the University of Southern California, specifically intended to provide particle-laden air at flow rates and pressures suitable for interfacing with on-line continuous aerosol instrumentation for chemical analysis such as mass spectrometers. The re-design and engineering of the miniature Versatile Aerosol Concentration Enrichment System (mVACES) and primarily laboratory-based validation of the individual components and overall system has been previously reported (Geller et al. 2005). From September to December 2005, a field performance validation study of the mVACES was conducted in Los Angeles, California at a mixed urban site influenced by both freeway traffic and construction. A variety of continuous and semi-continuous physical and chemical composition measurements were performed to assess the performance of the mVACES compared to accepted methods for validation. Near-ideal performance for aerosol concentration enhancement by the mVACES was observed for mass and number distribution with minimal evidence for distortion of the size distribution. Similarly, near-ideal concentration enhancement factors were observed for both inorganic and organic species suggesting that the mVACES works equally well across the range of externally mixed urban aerosol. The data suggest that aerosol concentration enhancements up to an ideal factor of 20 in a delivered flow on the order of 1.5 liters min–1 are readily achievable in an urban environment for the ambient conditions studied.

Inter- and Intra-Community Variability in Continuous Coarse Particulate Matter (PM10-2.5) Concentrations in the Los Angeles Area

Continuous coarse particulate matter (CPM, PM 10−2.5 ) concentrations were measured hourly at three different sites in the Los Angeles area from April 2008 through May 2009 as part of a larger study of the characteristics and toxicology of CPM. Mean hourly concentrations calculated seasonally ranged from less than 5 μg m –3 to near 70 μg m –3 at the three sites depending upon the CPM source variability and prevailing meteorology. Different diurnal concentration profiles were observed at each site. Correlation analysis indicates that CPM concentrations can generally be explained by wind-induced road dust re-suspension, particularly in drier seasons. CPM concentrations between the sites were not appreciably correlated and metrics used to assess variability between the sites—the coefficients of divergence—indicated that CPM concentrations were heterogeneous. The relative CPM contribution to observed PM 10 concentrations varied by season and between sites. Additional concurrent CPM data available within a few km of the three sites indicate that intra-community variability can be on the same order as that observed for inter-community variability, although a similar analysis using PM 10 data yielded reduced heterogeneity. The results indicate that accurate exposure assessment to CPM in the Los Angeles area requires measurements of CPM concentrations at different sites with higher temporal resolution than a single daily mean value.