A theoretical model chemistry designed to achieve high accuracy for enthalpies of formation of atoms and small molecules is described. This approach is entirely independent of experimental data and contains no empirical scaling factors, and includes a treatment of electron correlation up to the full coupled-cluster singles, doubles, triples and quadruples approach. Energies are further augmented by anharmonic zero-point vibrational energies, a scalar relativistic correction, first-order spin-orbit coupling, and the diagonal Born-Oppenheimer correction. The accuracy of the approach is assessed by several means. Enthalpies of formation (at 0 K) calculated for a test suite of 31 atoms and molecules via direct calculation of the corresponding elemental formation reactions are within 1 kJ mol(-1) to experiment in all cases. Given the quite different bonding environments in the product and reactant sides of these reactions, the results strongly indicate that even greater accuracy may be expected in reactions that preserve (either exactly or approximately) the number and types of chemical bonds.

Abstract. An Aerodyne high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed during the Carbonaceous Aerosols and Radiative Effects Study (CARES) that took place in northern California in June 2010. We present results obtained at Cool (denoted as the T1 site of the project) in 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 this study, the average mass loading of submicrometer particles (PM 1 ) was 3.0 µg m −3 , dominated by organics (80 %) and sulfate (9.9 %). The organic aerosol (OA) had a nominal formula of C 1 H 1.38 N 0.004 O 0.44 , thus an average organic mass-to-carbon (OM/OC) ratio of 1.70. Two distinct oxygenated OA factors were identified via Positive matrix factorization (PMF) of the high-resolution mass spectra of organics. The more oxidized MO-OOA (O/C = 0.54) was interpreted as a surrogate for secondary OA (SOA) influenced by biogenic emissions whereas the less oxidized LO-OOA (O/C = 0.42) was found to represent SOA formed in photochemically processed urban emissions. LO-OOA correlated strongly with ozone and MO-OOA correlated well with two 1st generation isoprene oxidation products (methacrolein and methyl vinyl ketone), indicating that both SOAs were relatively fresh. A hydrocarbon like OA (HOA) factor was also identified, representing primary emissions mainly due to local traffic. On average, SOA (= MO-OOA + LO-OOA) accounted for 91 % of the total OA mass and 72 % of the PM 1 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 PM 1 mass loading was considerably higher in urban plumes than in air masses dominated by biogenic SOA. The change in OA mass relative to CO ( OA/ CO) varied in the range of 5-196 µg m −3 ppm −1 , reflecting large variability in SOA production. The highest OA/ CO 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 m −3 ppm −1 on average, was much higher than when urban plumes arrived in a low BVOC Published by Copernicus Publications on behalf of the European Geosciences Union. 8132A. Setyan et al.: Characterization of submicron particles environment (∼36 µg m −3 ppm −1 ) or during other periods dominated by biogenic SOA (35 µg m −3 ppm −1 ). These results demonstrate that SOA formation is enhanced when anthropogenic emissions interact with biogenic precursors.

Abstract. Transport of aerosols in pollution plumes from the mainland Asian continent was observed in situ at Jeju, South Korea during the Cheju Asian Brown Cloud Plume-Asian Monsoon Experiment (CAPMEX) field campaign throughout August and September 2008 using a 3-laser photoacoustic spectrometer (PASS-3), chemical filter analysis, and size distributions. The PASS-3 directly measures the effects of morphology (e.g. coatings) on light absorption that traditional filter-based instruments are unable to address. Transport of mixed sulfate, carbonaceous, and nitrate aerosols from various Asian pollution plumes to Jeju accounted for 74% of the deployment days, showing large variations in their measured chemical and optical properties. Analysis of eight distinct episodes, spanning wide ranges of chemical composition, optical properties, and source regions, reveals that episodes with higher organic carbon (OC)/sulfate (SO 2− 4 ) and nitrate (NO pollution episodes by using the observed particle size distributions and the measured optical properties. The smallest mean particle diameter corresponds to the high OC/SO episode. Idealized analysis indicates increased absorption at 781 nm by factors greater than 3 relative to denuded black carbon in the laboratory. We hypothesize that coatings of black carbon cores are the mechanism of this enhancement. This implies that climate warming and atmospheric heating rates from black carbon particles can be significantly larger than have been estimated previously. The results of this study demonstrate ways in which atmospheric processing and mixing can amplify particle light absorption for carbonaceous aerosol, significantly at short wavelength, underscoring the need to understand and predict chemical composition effects on optical properties to accurately estimate the climate radiative forcing by mixed carbonaceous aerosols.

Abstract. We describe the synoptic and regional-scale meteorological conditions that affected the transport and mixing of trace gases and aerosols in the vicinity of Sacramento, California during June 2010 when the Carbonaceous Aerosol and Radiative Effects Study (CARES) was conducted. The meteorological measurements collected by various instruments deployed during the campaign and the performance of the chemistry version of the Weather Research and Forecasting model (WRF-Chem) are both discussed. WRF-Chem was run daily during the campaign to forecast the spatial and temporal variation of carbon monoxide emitted from 20 anthropogenic source regions in California to guide aircraft sampling. The model is shown to reproduce the overall circulations and boundary-layer characteristics in the region, although errors in the upslope wind speed and boundary-layer depth contribute to differences in the observed and simulated carbon monoxide. Thermally-driven upslope flows that transported pollutants from Sacramento over the foothills of the Sierra Nevada occurred every afternoon, except during three periods when the passage of mid-tropospheric troughs disrupted the regional-scale flow patterns. The meteorological conditions after the passage of the third trough were the most favorable for photochemistry and likely formation of secondary organic aerosols. Meteorological measurements and model forecasts indicate that the Sacramento pollutant plume was likely transported over a downwind site that collected trace gas and aerosol measurements during 23 time periods; however, direct transport occurred during only eight of these periods. The model also showed that emissions from the San Francisco Bay area transported by intrusions of marine air contributed a large fraction of the carbon monoxide in the vicinity of Sacramento, suggesting that this source likely affects local chemistry. Contributions from other sources of pollutants, such as those in the Sacramento Valley and San Joaquin Valley, were relatively low. Aerosol layering in the free troposphere was observed during the morning by an airborne Lidar. WRF-Chem forecasts showed that mountain venting processes contributed to aged pollutants aloft in the valley atmosphere that are then entrained into the growing boundary layer the subsequent day.

Published by Copernicus Publications on behalf of the European Geosciences Union. R. A. Zaveri et al.: Overview of the 2010 CARESAbstract. Substantial uncertainties still exist in the scientific understanding of the possible interactions between urban and natural (biogenic) emissions in the production and transformation of atmospheric aerosol and the resulting impact on climate change. The US Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) program's Carbonaceous Aerosol and Radiative Effects Study (CARES) carried out in June 2010 in Central Valley, California, was a comprehensive effort designed to improve this understanding. The primary objective of the field study was to investigate the evolution of secondary organic and black carbon aerosols and their climate-related properties in the Sacramento urban plume as it was routinely transported into the forested Sierra Nevada foothills area. Urban aerosols and trace gases experienced significant physical and chemical transformations as they mixed with the reactive biogenic hydrocarbons emitted from the forest. Two heavily-instrumented ground sites -one within the Sacramento urban area and another about 40 km to the northeast in the foothills area -were set up to characterize the evolution of meteorological variables, trace gases, aerosol precursors, aerosol size, composition, and climaterelated properties in freshly polluted and "aged" urban air. On selected days, the DOE G-1 aircraft was deployed to make similar measurements upwind and across the evolving Sacramento plume in the morning and again in the afternoon. The NASA B-200 aircraft, carrying remote sensing instruments, was also deployed to characterize the vertical and horizontal distribution of aerosols and aerosol optical properties within and around the plume. This overview provides: (a) the scientific background and motivation for the study, (b) the operational and logistical information pertinent to the execution of the study, (c) an overview of key observations and initial findings from the aircraft and ground-based sampling platforms, and (d) a roadmap of planned data analyses and focused modeling efforts that will facilitate the integration of new knowledge into improved representations of key aerosol processes and properties in climate models.