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Sulfur dioxide (SO2) is a major atmospheric pollutant with a strong anthropogenic component mostly produced by the combustion of fossil fuel and other industrial activities. As a precursor of sulfate aerosols that affect climate, air quality, and human health, this gas needs to be monitored on a global scale. Global climate and chemistry models including aerosol processes along with their radiative effects are important tools for climate and air quality research. Validation of these models against in-situ and satellite measurements is essential to ascertain the credibility of these models and to guide model improvements. In this study the Goddard Chemistry, Aerosol, Radiation, and Transport (GOCART) module running on-line inside the Goddard Earth Observing System version 5 (GEOS-5) model is used to simulate aerosol and SO2 concentrations. Data taken in November 2010 over Frostburg, Maryland during an SO2 field campaign involving ground instrumentation and aircraft are used to evaluate GEOS-5 simulated SO2 concentrations. Preliminary data analysis indicated the model overestimated surface SO2 concentration, which motivated the examination of mixing processes in the model and the specification of SO2 anthropogenic emission rates. As a result of this analysis, a revision of anthropogenic emission inventories in GEOS-5 was implemented, and the vertical placement of SO2 sources was updated. Results show that these revisions improve the model agreement with observations locally and in regions outside the area of this field campaign. In particular, we use the ground-based measurements collected by the United States Environmental Protection Agency (US EPA) for the year 2010 to evaluate the revised model simulations over North America.

Partitioning of mineral dust, pollution, smoke, and mixtures using remote sensing techniques can help improve accuracy of satellite retrievals and assessments of the aerosol radiative impact on climate. Spectral aerosol optical depth (tau) and single scattering albedo (omega (sub 0) ) from Aerosol Robotic Network (AERONET) measurements are used to form absorption [i.e., omega (sub 0) and absorption Angstrom exponent (alpha(sub abs))] and size [i.e., extinction Angstrom exponent (alpha(sub ext)) and fine mode fraction of tau] relationships to infer dominant aerosol types. Using the long-term AERONET data set (1999-2010), 19 sites are grouped by aerosol type based on known source regions to: (1) determine the average omega (sub 0) and alpha(sub abs) at each site (expanding upon previous work); (2) perform a sensitivity study on alpha(sub abs) by varying the spectral omega (sub 0); and (3) test the ability of each absorption and size relationship to distinguish aerosol types. The spectral omega (sub 0) averages indicate slightly more aerosol absorption (i.e., a 0.0 < delta omega (sub 0) <= 0.02 decrease) than in previous work and optical mixtures of pollution and smoke with dust show stronger absorption than dust alone. Frequency distributions of alpha(sub abs) show significant overlap among aerosol type categories and at least 10% of the alpha(sub abs) retrievals in each category are below 1.0. Perturbing the spectral omega (sub 0) by +/- 0.03 induces significant alpha(sub abs) changes from the unperturbed value by at least approx. +/- 0.6 for Dust, approx. +/-0.2 for Mixed, and approx. +/-0.1 for Urban/Industrial and Biomass Burning. The omega (sub 0)440nm and alpha(sub ext) 440-870nm relationship shows the best separation among aerosol type clusters, providing a simple technique for determining aerosol type from surface- and future space-based instrumentation.

Aerosols are generated in the atmosphere through anthropogenic and natural mechanisms. These sources have signatures in the aerosol optical and microphysical properties that can be used to identify the aerosol type/mixture. Spectral aerosol absorption information (absorption Angstrom exponent; AAE) used in conjunction with the particle size parameterization (extinction Angstrom exponent; EAE) can only identify the dominant absorbing aerosol type in the sample volume (e.g., black carbon vs. iron oxides in dust). This AAE/EAE relationship can be expanded to also identify non-absorbing aerosol types/mixtures by applying an absorption weighting. This new relationship provides improved aerosol type distinction when the magnitude of absorption is not equal (e.g, black carbon vs. sulfates). The Aerosol Robotic Network (AERONET) data provide spectral aerosol optical depth and single scattering albedo - key parameters used to determine EAE and AAE. The proposed aerosol type/mixture relationship is demonstrated using the long-term data archive acquired at AERONET sites within various source regions. The preliminary analysis has found that dust, sulfate, organic carbon, and black carbon aerosol types/mixtures can be determined from this AAE/EAE relationship when applying the absorption weighting for each available wavelength (Le., 440, 675, 870nm). Large, non-spherical dust particles absorb in the shorter wavelengths and the application of 440nm wavelength absorption weighting produced the best particle type definition. Sulfate particles scatter light efficiently and organic carbon particles are small near the source and aggregate over time to form larger less absorbing particles. Both sulfates and organic carbon showed generally better definition using the 870nm wavelength absorption weighting. Black carbon generation results from varying combustion rates from a number of sources including industrial processes and biomass burning. Cases with primarily black carbon showed improved definition in the 870nm wavelength absorption weighting due to the increased absorption in the near-infrared wavelengths, while the 440nm wavelength provided better definition when black carbon mixed with dust. Utilization of this particle type scheme provides necessary information for remote sensing applications, which needs a priori knowledge of aerosol type to model the retrieved properties especially over semi-bright surfaces. In fact, this analysis reveals that the aerosol types occurred in mixtures with varying magnitudes of absorption and requires the use of more than one assumed aerosol mixture model. Furthermore, this technique will provide the aerosol transport model community a data set for validating aerosol type.

The Indo-Gangetic Plain (IGP) of the northern Indian subcontinent produces anthropogenic pollution from urban, industrial and rural combustion sources nearly continuously and is affected by convection-induced winds driving desert and alluvial dust into the atmosphere during the premonsoon period. Within the IGP, the NASA Aerosol Robotic Network (AERONET) project initiated the TIGERZ measurement campaign in May 2008 with an intensive operational period from May 1 to June 23, 2008. Mesoscale spatial variability of aerosol optical depth (AOD, tau) measurements at 500mn was assessed at sites around Kanpur, India, with averages ranging from 0.31 to 0.89 for spatial variability study (SVS) deployments. Sites located downwind from the city of Kanpur indicated slightly higher average aerosol optical depth (delta Tau(sub 500)=0.03-0.09). In addition, SVS AOD area-averages were compared to the long-tenn Kanpur AERONET site data: Four SVS area-averages were within +/- 1 cr of the climatological mean of the Kanpur site, while one SVS was within 2sigma below climatology. For a SVS case using AERONET inversions, the 440-870mn Angstrom exponent of approximately 0.38, the 440-870mn absorption Angstrom exponent (AAE) of 1.15-1.53, and the sphericity parameter near zero suggested the occurrence of large, strongly absorbing, non-spherical aerosols over Kanpur (e.g., mixed black carbon and dust) as well as stronger absorption downwind of Kanpur. Furthermore, the 3km and lOkm Terra and Aqua MODIS C005 aerosol retrieval algorithms at tau(sub 550) were compared to the TIGERZ data set. Although MODIS retrievals at higher quality levels were comparable to the MODIS retrieval uncertainty, the total number of MODIS matchups (N) were reduced with subsequent quality levels (N=25, QA>=0; N=9,QA>=l; N=6, QA>=2; N=1, QA=3) over Kanpur during the premonsoon primarily due to the semi-bright surface, complex aerosol mixture and cloud-contaminated pixels. The TIGERZ 2008 data set provided a unique opportunity to measure the spatial and temporal variations of aerosol loading in the IGP. The strong aerosol absorption derived from ground-based sun/sky radiometer measurements suggested the presence of a predominately black carbon and dust mixture during the pre-monsoon period. Consistent with the elevated heat-pump hypothesis, these absorbing aerosols found across Kanpur and the greater IGP region during the pre-monsoon period likely induced regional atmospheric warming, which lead to a more rapid advance of the southwest Asian monsoon and above normal precipitation over northern India in June 2008.

The photolysis frequencies of ozone and nitrogen dioxide were measured under a variety of conditions commonly found in the troposphere. Ozone photolysis frequencies show a strong dependence on solar zenith angle, overhead ozone column, and temperature, but only a weak dependence on altitude (when only downward radiation is detected). Nitrogen dioxide photolysis frequencies also show strong dependence on solar zenith angle, but show little dependence on temperature, pressure, or altitude. Both j values are strongly affected by cloud cover, but aerosol loading has much less effect. The disagreement of measured j(O3) and j(NO2) with many modeled values, especially disagreement over altitude dependence, shows that atmospheric UV radioactive processes are complicated and poorly understood, although experimental conditions may not always be applicable to conditions modeled.

Flow visualization techniques using ozone for tracing gas flows are proposed whereby ozone is detected through its strong absorption of ultraviolet light, which is easily made visible with fluorescent materials, or through its reaction with nitric oxide to form excited nitrogen dioxide, which in relaxing emits detectable light. It is shown that response speeds in the kHz range are possible with an ultraviolet detection system for initial ozone concentrations of about 1%.

Gas-phase kinetic calculations indicate that actinometric measurements of the rate of solar photolysis of NO2 in nitrogen can be in error by +5 to -15% or more, unless odd oxygen N2O5 chemistry, and trace oxygen content are considered. A field experiment confirms that the effect of the quartz tube on the measured photolysis rate is less than 1.7%.

The paper presents an experimental technique which measures j/O3-O(1-D)/, the rate of solar photolysis of ozone to singlet oxygen atoms. It is shown that a flow actinometer carries dilute O3 in N2O into direct sunlight where the O(1D) formed reacts with N2O to form NO which chemiluminescence detects, with a time resolution of about one minute. Measurements indicate a photolysis rate of 1.2 (+ or - .2) x 10 to the -5/s for a cloudless sky, 45 deg zenith angle, 0.345 cm ozone column and zero albedo. Finally, ground level results compare with theoretical calculations based on the UV actinic flux as a function of ozone column and solar zenith angle.

The paper describes a new flow-visualization technique based on the absorption of ultraviolet light by ozone. Ozone is an excellent tracer, because as a gas it has the same effective physical properties as air. Ozone strongly absorbs the principal line (253.7 nm) of a mercury lamp, so that when an ozone-traced flow passes between a mercury lamp and a fluorescent screen, a sharp, shadow-like image of the ozone tracer is cast on the screen. Quantitative photometry can be carried out by replacing the screen with ultraviolet detectors that yield the path-integrated column density of ozone in the flow. High-speed quantitative point monitoring (10 Hz at 10 ppb O3) is possible with capillary probes and chemiluminescent analysis.

The rate of odd nitrogen (NOx) production by electrical discharge through air was theoretically and experimentally estimated to be about 60,000 trillion NOx molecules per joule. The theoretical treatment employed a cylindrical shock-wave solution to calculate the rate of NOx production in high temperature reactions. The limits obtained were experimentally verified by subjecting a regulated air flow to electrical discharges followed by a measurement of NOx production using chemiluminescence. These measurements also indicated that water vapor content has no detectable effect on the NOx production rate. The results imply that lightning is a significant source of NOx, producing about 30-40 megatons NOx-N per year and possibly accounting for as much as 50% of the total atmospheric NOx source.