[1] A new fully coupled meteorology-chemistry-aerosol model is used to simulate the urban-to regional-scale variations in trace gases, particulates, and aerosol direct radiative forcing in the vicinity of Houston over a 5 day summer period. Model performance is evaluated using a wide range of meteorological, chemistry, and particulate measurements obtained during the 2000 Texas Air Quality Study. The predicted trace gas and particulate distributions were qualitatively similar to the surface and aircraft measurements with considerable spatial variations resulting from urban, power plant, and industrial sources of primary pollutants. Sulfate, organic carbon, and other inorganics were the largest constituents of the predicted particulates. The predicted shortwave radiation was 30 to 40 W m À2 closer to the observations when the aerosol optical properties were incorporated into the shortwave radiation scheme; however, the predicted hourly aerosol radiative forcing was still underestimated by 10 to 50 W m À2 . The predicted aerosol radiative forcing was larger over Houston and the industrial ship channel than over the rural areas, consistent with surface measurements. The differences between the observed and simulated aerosol radiative forcing resulted from transport errors, relative humidity errors in the upper convective boundary layer that affect aerosol water content, secondary organic aerosols that were not yet included in the model, and uncertainties in the primary particulate emission rates. The current model was run in a predictive mode and demonstrates the challenges of accurately simulating all of the meteorological, chemical, and aerosol parameters over urban to regional scales that can affect aerosol radiative forcing.Citation: Fast, J. D., W. I. Gustafson Jr., R. C. Easter, R. A. Zaveri, J. C. Barnard, E. G. Chapman, G. A. Grell, and S. E. Peckham (2006), Evolution of ozone, particulates, and aerosol direct radiative forcing in the vicinity of Houston using a fully coupled meteorology-chemistry-aerosol model,

Abstract. The local and regional influence of elevated point sources on summertime aerosol forcing and cloud-aerosol interactions in northeastern North America was investigated using the WRF-Chem community model. The direct effects of aerosols on incoming solar radiation were simulated using existing modules to relate aerosol sizes and chemical composition to aerosol optical properties. Indirect effects were simulated by adding a prognostic treatment of cloud droplet number and adding modules that activate aerosol particles to form cloud droplets, simulate aqueous-phase chemistry, and tie a two-moment treatment of cloud water (cloud water mass and cloud droplet number) to precipitation and an existing radiation scheme. Fully interactive feedbacks thus were created within the modified model, with aerosols affecting cloud droplet number and cloud radiative properties, and clouds altering aerosol size and composition via aqueous processes, wet scavenging, and gas-phase-related photolytic processes. Comparisons of a baseline simulation with observations show that the model captured the general temporal cycle of aerosol optical depths (AODs) and produced clouds of comparable thickness to observations at approximately the proper times and places. The model overpredicted SO 2 mixing ratios and PM 2.5 mass, but reproduced the range of observed SO 2 to sulfate aerosol ratios, suggesting that atmospheric oxidation processes leading to aerosol sulfate formation are captured in the model. The baseline simulation was compared to a sensitivity simulation in which all emissions at model levels above the surface layer were set to zero, thus removing stack emissions. Instantaneous, site-specific differences for aerosol and cloud related properties between the two simulations could be quite large, as removing abovesurface emission sources influenced when and where clouds formed within the modeling domain. When summed spaCorrespondence to: E. G. Chapman (elaine.chapman@pnl.gov) tially over the finest resolution model domain (the extent of which corresponds to the typical size of a single global climate model grid cell) and temporally over a three day analysis period, total rainfall in the sensitivity simulation increased by 31% over that in the baseline simulation. Fewer optically thin clouds, arbitrarily defined as a cloud exhibiting an optical depth less than 1, formed in the sensitivity simulation. Domain-averaged AODs dropped from 0.46 in the baseline simulation to 0.38 in the sensitivity simulation. The overall net effect of additional aerosols attributable to primary particulates and aerosol precursors from point source emissions above the surface was a domain-averaged reduction of 5 W m −2 in mean daytime downwelling shortwave radiation.

Saharan dust storms have often been observed from space, but the full impact on the Earth's radiation balance has been difficult to assess, due to limited observations from the surface. We present the first simultaneous observations from space and from a comprehensive new mobile facility in Niamey, Niger, of a major dust storm in March 2006. The results indicate major perturbations to the radiation balance both at the top of the atmosphere and at the surface. Combining the satellite and surface data, we also estimate the impact on the radiation balance of the atmosphere itself. Using independent data from the mobile facility, we derive the optical properties of the dust and input these and other information into two radiation models to simulate the radiative fluxes. We show that the radiation models underestimate the observed absorption of solar radiation in the dusty atmosphere.

Many clouds important to the Earth's energy balance contain small amounts of liquid water, yet despite many improvements, large differences in retrievals of their liquid water amount and particle size still must be resolved.

Abstract.A comparison between observed aerosol optical properties from the MILAGRO field campaign, which took place in the Mexico City Metropolitan Area (MCMA) during March 2006, and values simulated by the Weather Research and Forecasting (WRF-Chem) model, reveals large differences. To help identify the source of the discrepancies, data from the MILAGRO campaign are used to evaluate the "aerosol chemical to aerosol optical properties" module implemented in the full chemistry version of the WRF-Chem model. The evaluation uses measurements of aerosol size distributions and chemical properties obtained at the MILAGRO T1 site. These observations are fed to the module, which makes predictions of various aerosol optical properties, including the scattering coefficient, B scat ; the absorption coefficient, B abs ; and the single-scattering albedo, 0 ; all as a function of time. Values simulated by the module are compared with independent measurements obtained from a photoacoustic spectrometer (PAS) at a wavelength of 870 nm. Because of line losses and other factors, only "fine mode" aerosols with aerodynamic diameters less than 2.5 µm are considered here. Over a 10-day period, the simulations of hour-by-hour variations of B scat are not satisfactory, but simulations of B abs and 0 are considerably better. When averaged over the 10-day period, the computed and observed optical properties agree within the uncertainty limits of the measurements and simulations. ues of 0 simulated by the full WRF-Chem model thus cannot be attributed to the "aerosol chemistry to optics" module. The discrepancy is more likely due, in part, to poor characterization of emissions near the T1 site, particularly black carbon emissions.

Using irradiance data from a Multi-Filter Rotating Shadowband Radiometer (MFRSR) and an actinic flux spectroradiometer (SR), we derive aerosol single scattering albedo, 0,λ , as a function of wavelength, λ. We find that in the near-UV spectral range (250 to 400 nm) 0,λ is much lower compared to 0,λ at 500 nm indicating enhanced absorption in the near-UV range. Absorption by elemental carbon, dust, or gas cannot account for this enhanced absorption leaving the organic carbon component of the aerosol (OA) as the most likely absorber. We use data from a surface deployed Aerodyne Aerosol Mass Spectrometer (AMS) along with the inferred 0,λ to estimate the Mass Absorption Cross section (MAC) for the organic aerosol. We find that the MAC is about 10.5 m 2 /g at 300 nm and falls close to zero at about 500 nm; values that are roughly consistent with other estimates of organic aerosol MAC. These MAC values can be considered as "radiatively correct", because when used in radiative transfer calculations, the calculated irradiances/actinic fluxes match those measured at the wavelengths considered here. For an illustrative case study described here, we estimate that the light absorption by the "brown" (organic) carbonaceous aerosol can add about 40% to the light absorption of black carbon in Mexico City. This contribution will vary depending on the relative abundance of organic aerosol relative to black carbon. Furthermore, our analysis indicates that organic aerosol would slow down photochemistry by selectively scavenging the light reaching the ground at those wavelengths that drive photochemical Correspondence to: J. C. Barnard (james.barnard@pnl.gov) reactions. Finally, satellite retrievals of trace gases that are used to infer emissions currently assume that the MAC of organic carbon is zero. For trace gases that are retrieved using wavelengths shorter then 420 nm (i.e. SO 2 , HCHO, halogenoxides, NO 2 ), the assumption of non-zero MAC values will induce an upward correction to the inferred emissions. This assumption will be particularly relevant in polluted urban atmospheres and areas of biomass burning where organic aerosols are particularly abundant.

[1] The recently developed particle-resolved aerosol box model PartMC-MOSAIC (Particle Monte Carlo model-Model for Simulating Aerosol Interactions and Chemistry) was used to rigorously simulate the evolution of aerosol mixing state and the associated optical and cloud condensation nuclei (CCN) activation properties in an idealized urban plume. The model explicitly resolved the size and composition of individual particles from a number of sources and tracked their evolution due to condensation, evaporation, coagulation, emission, and dilution. The ensemble black carbon (BC)-specific absorption cross section increased by 40% over the course of 2 days due to BC aging by condensation and coagulation. Threefold and fourfold enhancements in CCN/CN ratios were predicted to occur within 6 h for 0.2% and 0.5% supersaturations (S), respectively. The particle-resolved results were used to evaluate the errors in the optical and CCN activation properties that would be predicted by a conventional sectional framework that assumes monodisperse, internally mixed particles within each bin. This assumption artificially increased the ensemble BC-specific absorption by 14-30% and decreased the single scattering albedo (SSA) by 0.03-0.07, while the bin resolution had a negligible effect. In contrast, the errors in CCN/CN ratios were sensitive to the bin resolution for a chosen supersaturation. For S = 0.2%, the CCN/CN ratio predicted using 100 internally mixed bins was up to 25% higher than the particle-resolved results, while it was up to 125% higher using 10 internally mixed bins. Neglecting coagulation overpredicted aerosol water content and number concentrations (<0.2 mm), causing errors in SSA from −0.02 to 0.035 and overprediction of CCN concentrations by 25-80% at S = 0.5%.Citation: Zaveri, R. A., J. C. Barnard, R. C. Easter, N. Riemer, and M. West (2010), Particle-resolved simulation of aerosol size, composition, mixing state, and the associated optical and cloud condensation nuclei activation properties in an evolving urban plume,

Abstract. This study was part of the Megacities Initiative: Local and Global Research Observations (MILAGRO) field campaign conducted in Mexico City metropolitan area during spring 2006. The physical and chemical transformations of particles aged in the outflow from Mexico City were investigated for the transport event of 22 March 2006. A detailed chemical analysis of individual particles was performed using a combination of complementary microscopy and micro-spectroscopy techniques. The applied techniques included scanning transmission X-ray microscopy (STXM) coupled with near edge X-ray absorption fine structure spectroscopy (NEXAFS) and computer controlled scanning electron microscopy with an energy dispersive X-ray analyzer (CCSEM/EDX). As the aerosol plume evolves from the city center, the organic mass per particle increases and the fraction of carbon-carbon double bonds (associated with elemental carbon) decreases. Organic functional groups enhanced with particle age include: carboxylic acids, alkyl groups, and oxygen bonded alkyl groups. At the city center (T0) the most prevalent aerosol type contained inorganic species (composed of sulfur, nitrogen, oxygen, and potassium) coated with organic material. At the T1 and T2 sites, located northeast of T0 (∼29 km and ∼65 km, respectively), the fraction of homogenously mixed organic particles increased in both Correspondence to: M. K. Gilles (mkgilles@lbl.gov) size and number. These observations illustrate the evolution of the physical mixing state and organic bonding in individual particles in a photochemically active environment.