Project at a Glance
Title: Extended analysis of the CARES aerosol chemistry data to characterize sources and processes of organic aerosol in the Sacramento Valley of California
Principal Investigator / Author(s): Zhang, Qi
Contractor: UC Davis
Contract Number: 10-305
Research Program Area: Atmospheric Processes
Topic Areas: Chemistry & Reactivity, Field Studies
This report explores the characteristics, sources, and processes of submicrometer particles in northern California via integrated analyses of atmospheric observation data obtained during the Carbonaceous Aerosols and Radiative Effects Study (CARES) that took place in northern California in June 2010. We focus on reporting aerosol chemistry, physical properties, and diurnal and temporal variations at Cool (denoted as the T1 site of the project) at the foothills of the Sierra Nevada Mountains, where intense biogenic emissions are periodically mixed with urban outflow transported by daytime southwesterly winds from the Sacramento metropolitan area. During CARES, the average mass loading of submicrometer particles (PM1) was 3.0 µg m-3, dominated by organics (80%) and sulfate (9.9%). The organic aerosol (OA) had a nominal formula of C1H1.38N0.004O0.44, thus an average organic mass-to-carbon (OM/OC) ratio of 1.70. Three OA types were identified by PMF analysis of the high resolution mass spectra: two different OOA components (90% of total organics) and a HOA (10%). The more oxidized MO-OOA (O/C = 0.54) was identified as biogenically influenced SOA, while the less oxidized LO-OOA (O/C = 0.42) corresponded to anthropogenically influenced SOA (e.g., from the Sacramento area). The HOA factor corresponded mainly to primary emissions from local traffic. On average, SOA (= MO-OOA + LO-OOA) accounted for 91% of the total OA mass and 72% of the PM1 mass observed at Cool. Twenty three periods of urban plumes from T0 (Sacramento) to T1 (Cool) were identified using the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem). The average PM1 mass loading was considerably higher in urban plumes than in air masses dominated by biogenic SOA. The change in OA mass relative to CO (ΔOA/ΔCO) varied in the range of 5-196 µg/m3/ppm, reflecting large variability in SOA production. The highest ΔOA/ΔCO was reached when air masses were dominated by anthropogenic emissions in the presence of a high concentration of biogenic volatile organic compounds (BVOCs). This ratio, which was 97 µg/m3/ppm on average, was much higher than when urban plumes arrived in a low BVOC environment (~36 µg/m3/ppm) or during other periods dominated by biogenic SOA (35 µg/m3/ppm). These results demonstrate that SOA formation is enhanced when anthropogenic emissions interact with biogenic precursors.
During CARES, regional new particle events (NPE) were observed on most days over the Sacramento and western Sierra Foothills area. Simultaneous particle measurements at both the T0 (Sacramento, urban site) and the T1 (Cool, rural site located ~40 km northeast of Sacramento) sites of CARES indicate that the NPE usually occurred in the morning with the appearance of an ultrafine mode centered at ~15 nm (in mobility diameter, Dm, measured by a scanning mobility particle sizer operating in the range 10-858 nm) followed by the growth of this mode to ~50 nm in the afternoon. These events were generally associated with southwesterly winds bringing urban plumes from Sacramento to the T1 site. The growth rate was on average higher at T0 (7.1±2.7 nm/hr) than at T1 (6.2±2.5 nm/hr), likely due to stronger anthropogenic influences at T0. Using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), we investigated the evolution of the size-resolved chemical composition of new particles at T1. Our results indicate that the growth of new particles was driven primarily by the condensation of oxygenated organic species and, to a lesser extent, ammonium sulfate. New particles appear to be fully neutralized during growth, consistent with high NH3 concentration in the region. Nitrogen-containing organic ions (i.e., CHN+, CH4N+, C2H3N+, and C2H4N+) that are indicative of the presence of alkyl-amine species in submicrometer particles enhanced significantly during the NPE days, suggesting that amines might have played a role in these events. Our results also indicate that the bulk composition of the ultrafine mode organics during NPE was very similar to that of anthropogenically-influenced secondary organic aerosol (SOA) observed in transported urban plumes. In addition, the concentrations of species representative of urban emissions (e.g., black carbon, CO, NOx, and toluene) were significantly higher whereas the photo-oxidation products of biogenic VOC and the biogenically-influenced SOA also increased moderately during the NPE days compared to the non-event days. These results indicate that the frequently occurring NPE over the Sacramento and Sierra Nevada regions were mainly driven by urban plumes from Sacramento and that the interaction of regional biogenic emissions with the urban plumes has enhanced the new particle growth. This finding has important implication for quantifying the climate impacts of NPE on global scale.
For questions regarding this research project, including available data and progress status, contact: Heather Choi at (916) 322-3893
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