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The importance of aerosol mixing state and size-resolved composition on CCN concentration and the variation of the importance with atmospheric aging of aerosols

Aerosol microphysics, chemical composition, and CCN concentrations were measured at the T0 urban supersite in Mexico City during Megacity Initiative: Local and Global Research Observations (MILAGRO) in March 2006. The aerosol size distribution and composition often showed strong diurnal variation associated with traffic emissions and aging of aerosols through coagulation and local photochemical production of secondary aerosol species. CCN concentrations (NCCN) are derived using Köhler theory from the measured aerosol size distribution and various simplified aerosol mixing state and chemical composition, and are compared to concurrent measurements at five supersaturations ranging from 0.11% to 0.35%. The influence of assumed mixing state on calculated NCCN is examined using both aerosols observed during MILAGRO and representative aerosol types. The results indicate that while ambient aerosols often consist of particles with a wide range of compositions at a given size, NCCN may be derived within ~20% assuming an internal mixture (i.e., particles at a given size are mixtures of all participating species, and have the identical composition) if great majority of particles has an overall κ (hygroscopicity parameter) value greater than 0.1. For a non-hygroscopic particle with a diameter of 100 nm, a 3 nm coating of sulfate or nitrate is sufficient to increase its κ from 0 to 0.1. The measurements during MILAGRO suggest that the mixing of non-hygroscopic primary organic aerosol (POA) and black carbon (BC) particles with photochemically produced hygroscopic species and thereby the increase of their κ to 0.1 take place in a few hours during daytime. This rapid process suggests that during daytime, a few tens of kilometers away for POA and BC sources, NCCN may be derived with sufficient accuracy by assuming an internal mixture, and using bulk chemical composition. The rapid mixing also indicates that, at least for very active photochemical environments such as Mexico City, the timescale during daytime for the conversion of hydrophobic POA and BC to hydrophilic particles is substantially shorter than the 1–2 days used in some global models. The conversion time scale is substantially longer during night. Most POA and BC particles emitted during evening hours likely remain non-hygroscopic until efficiently internally mixed with secondary species in the next morning. The results also suggest that the assumed mixing state strongly impacts calculated NCCN only when POA and BC represent a large fraction of the total aerosol volume. One of the implications is that while physically unrealistic, external mixtures, which are used in many global models, may also sufficiently predict NCCN for aged aerosol, as the contribution of non-hygroscopic POA and BC to overall aerosol volume is often substantially reduced due to the condensation of secondary species.
First ground-based FTIR observations of methane in the inner tropics over several years

Total column concentrations of methane have been retrieved from ground-based solar absorption FTIR spectra in the near-infrared recorded in Paramaribo (Suriname). The methane FTIR observations are compared with TM5 model simulations and satellite observations from SCIAMACHY, and represent the first validation of SCIAMACHY retrievals in the inner tropics using ground-based remote sensing techniques. Apart from local biomass burning features, our methane FTIR observations agree well with TM5 model simulations. The comparison of the direct measured CH4/CO2 ratios by FTIR and satellite reveals that the satellite can hardly detect methane emissions of tropical biomass burning due to the used retrieval method.
Atmospheric transport of persistent semi-volatile organic chemicals to the Arctic and cold condensation in the mid-troposphere – Part 1: 2-D modeling in mean atmosphere

In the first part of this study for revisiting the cold condensation effect on global distribution of semi-volatile organic chemicals (SVOCs), the atmospheric transport of SVOCs to the Arctic in the mid-troposphere in a mean meridional atmospheric circulation over the Northern Hemisphere was simulated by a two-dimensional (2-D) atmospheric transport model. Results show that under the mean meridional atmospheric circulation the long-range atmospheric transport of SVOCs from warm latitudes to the Arctic occurs primarily in the mid-troposphere. Although major sources are in low and mid-latitude soils, the modeled air concentration of SVOCs in the mid-troposphere is of the same order as or higher than that near the surface, demonstrating that the mid-troposphere is an important pathway and reservoir of SVOCs. The cold condensation of the chemicals is also likely to take place in the mid-troposphere over a source region of SVOCs in warm low latitudes through interacting with clouds. We demonstrate that the temperature dependent vapour pressure and atmospheric degradation rate of SVOCs exhibit similarities between lower atmosphere over the Arctic and the mid-troposphere over a tropical region. Frequent occurrence of atmospheric ascending motion and convection over warm latitudes carry the chemicals to a higher altitude where some of these chemicals may partition onto solid or aqueous phase through interaction with atmospheric aerosols, cloud water droplets and ice particles, and become more persistent at lower temperatures. Stronger winds in the mid-troposphere then convey solid and aqueous phase chemicals to the Arctic where they sink by large-scale descending motion and wet deposition. Using calculated water droplet-air partitioning coefficient of several persistent organic semi-volatile chemicals under a mean air temperature profile from the equator to the North Pole we propose that clouds are likely important sorbing media for SVOCs and pathway of the cold condensation effect and poleward atmospheric transport. The role of deposition and atmospheric descending motion in the cold condensation effect over the Arctic is also discussed.
Technical Note: Evaluation of the WRF-Chem "Aerosol Chemical to Aerosol Optical Properties" Module using data from the MILAGRO campaign

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, Bscat; the absorption coefficient, Babs; and the single-scattering albedo, ϖ0; 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 Bscat are not satisfactory, but simulations of Babs and ϖ0 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. Specifically, the observed and calculated values are, respectively: (1) Bscat, 34.1±5.1 Mm−1 versus 30.4±3.4 Mm−1; (2) Babs, 9.7±1.0 Mm−1 versus 11.7±1.2 Mm−1; and (3) ϖ0, 0.78±0.05 and 0.74±0.03. The discrepancies in values of ϖ0 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.
The contribution of marine organics to the air quality of the western United States

The contribution of marine organic emissions to the air quality in coastal areas of the western United States is studied using the latest version of the US Environmental Protection Agency (EPA) regional-scale Community Multiscale Air Quality (CMAQv4.7) modeling system. Emissions of marine isoprene, monoterpenes, and primary organic matter (POM) from the ocean are implemented into the model to provide a comprehensive view of the connection between ocean biology and atmospheric chemistry and air pollution. Model simulations show that marine organics can increase the concentration of PM2.5 by 0.1–0.3 μg m−3 (up to 5%) in some coastal cities such as San Francisco, CA. This increase in the PM2.5 concentration is primarily attributed to the POM emissions, with small contributions from the marine isoprene and monoterpenes. When marine organic emissions are included, organic carbon (OC) concentrations over the remote ocean are increased by up to 50% (25% in coastal areas), values consistent with recent observational findings. This study is the first to quantify the air quality impacts from marine POM and monoterpenes for the United States, and it highlights the need for inclusion of marine organic emissions in air quality models.
Atmospheric transport of persistent semi-volatile organic chemicals to the Arctic and cold condensation in the mid-troposphere – Part 2: 3-D modeling of episodic atmospheric transport

Two 3-dimensional global atmospheric transport models for persistent organic pollutants (POPs) have been employed to investigate the association between the large-scale atmospheric motions and poleward transports of persistent semi-volatile organic chemicals (SVOCs). We examine the modeled daily air concentration of α- and γ-hexachlorocyclohexane (HCH) over a period from 1997 through 1999 during which a number of episodic atmospheric transport events were detected in this modeling study. These events provide modeling evidence for improving the interpretation on the cold condensation effect and poleward atmospheric transport of SVOCs in the mid-troposphere. Two episodic transport events of γ-HCH (lindane) to the high Arctic (80–90° N), one from Asian and another from Eurasian sources, are reported in this paper. Both events suggest that the episodic atmospheric transports occurring in the mid-troposphere (e.g. from 3000 m to 5500 m height) are driven by atmospheric horizontal and vertical motions. The association of the transport events with atmospheric circulation is briefly discussed. Strong southerly winds, forced by the evolution of two semi-permanent high pressure systems over mid-high latitudes in the Northern Hemisphere, play an important role in the long-range transport (LRT) of HCHs to the high latitudes from its sources. Being consistent with the cold condensation effect and poleward atmospheric transport in a mean meridional atmospheric circulation simulated by a 2-D atmospheric transport model, as reported by the first part of this study, this modeling study indicates that cold condensation is likely occurring more intensively in the mid-troposphere where rapid declining air temperature results in condensed phase of the chemical over and near its source regions and where stronger winds convey the chemical more rapidly to the polar region during the episodic poleward atmospheric transport events.
Single particle characterization of black carbon aerosols at a tropospheric alpine site in Switzerland

The refractory black carbon (rBC) mass, size distribution (190–720 nm) and mixing state in sub-micron aerosols were characterized from late February to March 2007 using a single particle incandescence method at the high alpine research station Jungfraujoch (JFJ), Switzerland (46.33° N, 7.59° E, 3580 m a.s.l.). JFJ is a ground based location, which is at times exposed to continental free tropospheric air. A median mass absorption coefficient (MAC) of 10.2±3.2 m2 g−1 at λ=630 nm was derived by comparing single particle incandescence measurements of black carbon mass with continuous measurements of absorption coefficient. This value is comparable with other estimates at this location. The aerosols measured at the site were mostly well mixed and aged during transportation via the free troposphere. Pollutant sources were traced by air mass back trajectories, trace gases concentrations and the mass loading of rBC. In southeasterly wind directions, mixed or convective weather types provided the potential to vent polluted boundary layer air from the southern Alpine area and industrial northern Italy, delivering enhanced rBC mass loading and CN concentrations to the JFJ. The aerosol loadings at this site were also significantly influenced by precipitation, which led to the removal of rBC from the atmosphere. Precipitation events were shown to remove about 65% of the rBC mass from the free tropospheric background reducing the mean loading from 13±5 ng m−3 to 6±2 ng m−3(corrected to standard temperature and pressure). Overall, 40±15% of the observed rBC particles within the detectable size range were mixed with large amounts of non-refractory materials present as a thick coating. The growth of particle size into the accumulation mode was positively linked with the degree of rBC mixing, suggesting the important role of condensable materials in increasing particle size and leading to enhanced internal mixing of these materials with rBC. It is the first time that BC mass, size distribution and mixing state are reported in the free troposphere over Europe. These ground based measurements also provide the first temporal study of rBC in the European free troposphere quantitatively measured by single particle methods. At the present time there is only limited information of BC and its mixing state in the free troposphere, especially above Europe. The results reported in this paper provide an important constraint on modelled representation of BC.
The contribution of anthropogenic aerosols to aerosol light-scattering and CCN activity in the California coastal zone

Aircraft-based measurements of aerosol light-scattering coefficient, cloud condensation nuclei (CCN) measured directly or by proxy, and aerosol chemical composition are reported for three different years in the region of the large stratocumulus deck off the California coast. Receptor modeling is used to differentiate the contributions of the main aerosol sources to the light scattering and CCN activity. The contribution of anthropogenic sources to the two climatically important aerosol parameters (for direct and indirect forcing) varied from year to year but, on average, was found to be 67% in the case of CCN concentration and 57% in the case of light-scattering coefficient.
Combining visible and infrared radiometry and lidar data to test simulations in clear and ice cloud conditions

Measurements taken during the 2003 Pacific THORPEX Observing System Test (P-TOST) by the MODIS Airborne Simulator (MAS), the Scanning High-resolution Interferometer Sounder (S-HIS) and the Cloud Physics Lidar (CPL) are compared to simulations performed with a line-by-line and multiple scattering modeling methodology (LBLMS). Formerly used for infrared hyper-spectral data analysis, LBLMS has been extended to the visible and near infrared with the inclusion of surface bi-directional reflectance properties. A number of scenes are evaluated: two clear scenes, one with nadir geometry and one cross-track encompassing sun glint, and three cloudy scenes, all with nadir geometry. CPL data is used to estimate the particulate optical depth at 532 nm for the clear and cloudy scenes and cloud upper and lower boundaries. Cloud optical depth is retrieved from S-HIS infrared window radiances, and it agrees with CPL values, to within natural variability. MAS data are simulated convolving high resolution radiances. The paper discusses the results of the comparisons for the clear and cloudy cases. LBLMS clear simulations agree with MAS data to within 20% in the shortwave (SW) and near infrared (NIR) spectrum and within 2 K in the infrared (IR) range. It is shown that cloudy sky simulations using cloud parameters retrieved from IR radiances systematically underestimate the measured radiance in the SW and NIR by nearly 50%, although the IR retrieved optical thickness agree with same measured by CPL. MODIS radiances measured from Terra are also compared to LBLMS simulations in cloudy conditions, using retrieved cloud optical depth and effective radius from MODIS, to understand the origin for the observed discrepancies. It is shown that the simulations agree, to within natural variability, with measurements in selected MODIS SW bands. The impact of the assumed particles size distribution and vertical profile of ice content on results is evaluated. Sensitivity is much smaller than differences between measured and simulated radiances in the SW and NIR. The paper dwells on a possible explanation of these contradictory results, involving the phase function of ice particles in the shortwave.
NO2 photolysis frequencies in street canyons

Photolysis frequencies for NO2 are modeled for the conditions in urban streets, which are taken into account as canyons with variable height and width. The effect of a street canyon is presented with absolute values and as a ratio RJ of the photolysis frequency within the street compared to that with free horizon. This allows further use of the existing photolysis parameterizations. Values are presented for variable solar elevation and azimuth angles, varying atmospheric conditions and different street properties. The NO2 photolysis frequency in a street depends strongly on the relative width of the street and its orientation towards the sun. Averaged over atmospheric conditions and street orientation, the NO2 photolysis frequency is reduced in comparison with the values for free horizon: to less than 20% for narrow skyscraper streets, to about 40% for typical urban streets, and only to about 80% for garden streets. A parameterization with the global solar irradiance is given for the averaged RJ values.