Search

The interactions between aerosols and ice clouds represent one of the largest uncertainties in global radiative forcing from pre-industrial time to the present. In particular, the impact of aerosols on ice crystal effective radius (Rei), which is a key parameter determining ice clouds' net radiative effect, is highly uncertain due to limited and conflicting observational evidence. Here we investigate the effects of aerosols on Rei under different meteorological conditions using 9-year satellite observations. We find that the responses of Rei to aerosol loadings are modulated by water vapor amount in conjunction with several other meteorological parameters. While there is a significant negative correlation between Rei and aerosol loading in moist conditions, consistent with the "Twomey effect" for liquid clouds, a strong positive correlation between the two occurs in dry conditions. Simulations based on a cloud parcel model suggest that water vapor modulates the relative importance of different ice nucleation modes, leading to the opposite aerosol impacts between moist and dry conditions. When ice clouds are decomposed into those generated from deep convection and formed in situ, the water vapor modulation remains in effect for both ice cloud types, although the sensitivities of Rei to aerosols differ noticeably between them due to distinct formation mechanisms. The water vapor modulation can largely explain the difference in the responses of Rei to aerosol loadings in various seasons. A proper representation of the water vapor modulation is essential for an accurate estimate of aerosol–cloud radiative forcing produced by ice clouds.

A set of parameterizations is developed for spectral single-scattering properties of clean and black carbon (BC)-contaminated snow based on geometric-optics surface wave (GOS) computations, which explicitly resolves BC–snow internal mixing and various snow grain shapes. GOS calculations show that, compared with nonspherical grains, volume-equivalent snow spheres show up to 20% larger asymmetry factors and hence stronger forward scattering, particularly at wavelengths 99%. Based on GOS calculations, BC–snow internal mixing enhances the snow single-scattering coalbedo at wavelengths 99%. Overall, in addition to snow grain size, both BC–snow internal mixing and snow grain shape play critical roles in quantifying BC effects on snow optical properties. The present parameterizations can be conveniently applied to snow, land surface, and climate models including snowpack radiative transfer processes.

Aerosol-cloud interactions (aerosol indirect effects) play an important role in regional meteorological variations, which could further induce feedback on regional air quality. While the impact of aerosol-cloud interactions on meteorology and climate has been extensively studied, their feedback on air quality remains unclear. Using a fully coupled meteorology-chemistry model, we find that increased aerosol loading due to anthropogenic activities in China substantially increases column cloud droplet number concentration and liquid water path (LWP), which further leads to a reduction in the downward shortwave radiation at surface, surface air temperature and planetary boundary layer (PBL) height. The shallower PBL and accelerated cloud chemistry due to larger LWP in turn enhance the concentrations of particulate matter with diameter less than 2.5 μm (PM2.5) by up to 33.2 μg m−3 (25.1%) and 11.0 μg m−3 (12.5%) in January and July, respectively. Such a positive feedback amplifies the changes in PM2.5 concentrations, indicating an additional air quality benefit under effective pollution control policies but a penalty for a region with a deterioration in PM2.5 pollution. Additionally, we show that the cloud processing of aerosols, including wet scavenging and cloud chemistry, could also have substantial effects on PM2.5 concentrations.

We investigate the snow albedo variation in spring over the southern Tibetan Plateau induced by the deposition of light-absorbing aerosols using remote sensing data from moderate resolution imaging spectroradiometer (MODIS) aboard Terra satellite during 2001–2012. We have selected pixels with 100 % snow cover for the entire period in March and April to avoid albedo contamination by other types of land surfaces. A model simulation using GEOS-Chem shows that aerosol optical depth (AOD) is a good indicator for black carbon and dust deposition on snow over the southern Tibetan Plateau. The monthly means of satellite-retrieved land surface temperature (LST) and AOD over 100 % snow-covered pixels during the 12 years are used in multiple linear regression analysis to derive the empirical relationship between snow albedo and these variables. Along with the LST effect, AOD is shown to be an important factor contributing to snow albedo reduction. We illustrate through statistical analysis that a 1-K increase in LST and a 0.1 increase in AOD indicate decreases in snow albedo by 0.75 and 2.1 % in the southern Tibetan Plateau, corresponding to local shortwave radiative forcing of 1.5 and 4.2 W m−2, respectively.

We quantify source contributions to springtime (April 2008) surface black carbon (BC) in the Arctic by interpreting surface observations of BC at five receptor sites (Denali, Barrow, Alert, Zeppelin, and Summit) using a global chemical transport model (GEOS-Chem) and its adjoint. Contributions to BC at Barrow, Alert, and Zeppelin are dominated by Asian anthropogenic sources (40–43 %) before April 18 and by Siberian open biomass burning emissions (29–41 %) afterward. In contrast, Summit, a mostly free tropospheric site, has predominantly an Asian anthropogenic source contribution (24–68 %, with an average of 45 %). We compute the adjoint sensitivity of BC concentrations at the five sites during a pollution episode (April 20–25) to global emissions from March 1 to April 25. The associated contributions are the combined results of these sensitivities and BC emissions. Local and regional anthropogenic sources in Alaska are the largest anthropogenic sources of BC at Denali (63 %), and natural gas flaring emissions in the Western Extreme North of Russia (WENR) are the largest anthropogenic sources of BC at Zeppelin (26 %) and Alert (13 %). We find that long-range transport of emissions from Beijing-Tianjin-Hebei (also known as Jing-Jin-Ji), the biggest urbanized region in Northern China, contribute significantly (~ 10 %) to surface BC across the Arctic. On average it takes ~ 12 days for Asian anthropogenic emissions and Siberian biomass burning emissions to reach Arctic lower troposphere, supporting earlier studies. Natural gas flaring emissions from the WENR reach Zeppelin in about a week. We find that episodic, direct transport events dominate BC at Denali (87 %), a site outside the Arctic front, a strong transport barrier. The relative contribution of direct transport to surface BC within the Arctic front is much smaller (~ 50 % at Barrow and Zeppelin and ~ 10 % at Alert). The large contributions from Asian anthropogenic sources are predominately in the form of ‘chronic’ pollution (~ 40 % at Barrow and 65 % at Alert and 57 % at Zeppelin) on 1–2 month timescales. As such, it is likely that previous studies using 5- or 10-day trajectory analyses strongly underestimated the contribution from Asia to surface BC in the Arctic. Both finer temporal resolution of biomass burning emissions and accounting for the Wegener-Bergeron-Findeisen (WBF) process in wet scavenging improve the source attribution estimates.

We estimate the snow albedo forcing and direct radiative forcing (DRF) of black carbon (BC) in the Tibetan Plateau using a global chemical transport model in conjunction with a stochastic snow model and a radiative transfer model. The annual mean BC snow albedo forcing is 2.9 W m−2 averaged over snow-covered plateau regions, which is a factor of 3 larger than the value over global land snowpack. BC-snow internal mixing increases the albedo forcing by 40–60% compared with external mixing, and coated BC increases the forcing by 30–50% compared with uncoated BC aggregates, whereas Koch snowflakes reduce the forcing by 20–40% relative to spherical snow grains. The annual BC DRF at the top of the atmosphere is 2.3 W m−2 with uncertainties of −70–85% in the plateau after scaling the modeled BC absorption optical depth to Aerosol Robotic Network observations. The BC forcings are attributed to emissions from different regions.

In situ measurements of carbon monoxide (CO) and ozone (O3) at the Pico Mountain Observatory (PMO) located in the Azores, Portugal, are analyzed together with results from an atmospheric chemical transport model (GEOS-Chem) and satellite remote sensing data (AIRS (Atmospheric Infrared Sounder) for CO, and TES (Tropospheric Emission Spectrometer) for O3) to examine the evolution of free-troposphere CO and O3 over the North Atlantic for 2001–2011. GEOS-Chem captured the seasonal cycles for CO and O3 well but significantly underestimated the mixing ratios of CO, particularly in spring. Statistically significant (using a significance level of 0.05) decreasing trends were found for both CO and O3 based on harmonic regression analysis of the measurement data. The best estimates of the possible trends for CO and O3 measurements are −0.31 ± 0.30 (2-σ) ppbv yr−1 and −0.21 ± 0.11 (2-σ) ppbv yr−1, respectively. Similar decreasing trends for both species were obtained with GEOS-Chem simulation results. The most important factor contributing to the decreases in CO and O3 at PMO over the past decade is the decline in anthropogenic emissions from North America, which more than compensate for the impacts from increasing Asian emissions. It is likely that climate change in the past decade has also affected the intercontinental transport of O3.

Geoengineering applications by injection of sulfate aerosols into the stratosphere are under consideration as a measure of last resort to counter global warming. Here a potential regional-scale application to offset the impacts of heat waves is critically examined. Using the Weather Research and Forecasting model with fully coupled chemistry (WRF-Chem), the effect of regional-scale sulfate aerosol emission over California in each of two days of the July 2006 heat wave is used to quantify potential reductions in surface temperature as a function of emission rates in a layer at 12 km altitude. Local meteorological factors yield geographical differences in surface air temperature sensitivity. For emission rates of approximately 30 μg m−2 s−1 of sulfate aerosols (with standard WRF-Chem size distribution) over the region, temperature decreases of around 7 °C result during the middle part of the day over the Central Valley, one of the areas hardest hit by the heat wave. Regions more ventilated with oceanic air such as Los Angeles have slightly smaller reductions. The length of the hottest part of the day is also reduced. Advection effects on the aerosol cloud must be more carefully forecast for smaller injection regions. Verification of the impacts could be done via measurements of differences in reflected and surface downward shortwave. Such regional geoengineering applications with specific near-term target effects but smaller cost and side effects could potentially provide a means of testing larger scale applications. However, design considerations for regional applications, such as a preference for injection at a level of relatively low wind speed, differ from those for global applications. The size of the required injections and the necessity of injection close to the target region raise substantial concerns. The evaluation of this regional-scale application is thus consistent with global model evaluations, emphasizing that mitigation via reduction of fossil fuels remains preferable to considering geoengineering with sulfate aerosols.

Atmospheric mineral dust particles exert significant direct radiative forcings and are important drivers of climate and climate change. We used the GEOS-Chem global three-dimensional chemical transport model (CTM) coupled with the Fu-Liou-Gu (FLG) radiative transfer model (RTM) to investigate the dust radiative forcing and heating rate based on different vertical profiles for April 2006. We attempt to actually quantify the sensitivities of radiative forcing to dust vertical profiles, especially the discrepancies between using realistic and climatological vertical profiles. In these calculations, dust emissions were constrained by observations of aerosol optical depth (AOD). The coupled calculations utilizing a more realistic dust vertical profile simulated by GEOS-Chem minimize the physical inconsistencies between 3-D CTM aerosol fields and the RTM. The use of GEOS-Chem simulated vertical profile of dust extinction, as opposed to the FLG prescribed vertical profile, leads to greater and more spatially heterogeneous changes in the estimated radiative forcing and heating rate produced by dust. Both changes can be attributed to a different vertical structure between dust and non-dust source regions. Values of the dust vertically resolved AOD per grid level (VRAOD) are much larger in the middle troposphere, though smaller at the surface when the GEOS-Chem simulated vertical profile is used, which leads to a much stronger heating rate in the middle troposphere. Compared to the FLG vertical profile, the use of GEOS-Chem vertical profile reduces the solar radiative forcing at the top of atmosphere (TOA) by approximately 0.2–0.25 W m−2 over the African and Asian dust source regions. While the Infrared (IR) radiative forcing decreases 0.2 W m−2 over African dust belt, it increases 0.06 W m−2 over the Asian dust belt when the GEOS-Chem vertical profile is used. Differences in the solar radiative forcing at the surface between the use of the GEOS-Chem and FLG vertical profiles are most significant over the Gobi desert with a value of about 1.1 W m−2. The radiative forcing effect of dust particles is more pronounced at the surface over the Sahara and Gobi deserts by using FLG vertical profile, while it is less significant over the downwind area of Eastern Asia.

[1] To improve estimates of remote contributions of dust to fine particulate matter (PM2.5) in the western United States, new dust particle size distributions (PSDs) based upon scale-invariant fragmentation theory (Kok_PSD) with constraints from in situ measurements (IMP_PSD) are implemented in a chemical transport model (GEOS-Chem). Compared to initial simulations, this leads to reductions in the mass of emitted dust particles with radii

A three-dimensional variational data assimilation (3-DVAR) algorithm for aerosols in a WRF/Chem model is presented. The WRF/Chem model uses the MOSAIC (Model for Simulating Aerosol Interactions and Chemistry) scheme, which explicitly treats eight major species (elemental/black carbon, organic carbon, nitrate, sulfate, chloride, ammonium, sodium and the sum of other inorganic, inert mineral and metal species) and represents size distributions using a sectional method with four size bins. The 3-DVAR scheme is formulated to take advantage of the MOSAIC scheme in providing comprehensive analyses of species concentrations and size distributions. To treat the large number of state variables associated with the MOSAIC scheme, this 3-DVAR algorithm first determines the analysis increments of the total mass concentrations of the eight species, defined as the sum of the mass concentrations across all size bins, and then distributes the analysis increments over four size bins according to the background error variances. The number concentrations for each size bin are adjusted based on the ratios between the mass and number concentrations of the background state. Additional flexibility is incorporated to further lump the eight mass concentrations, and five lumped species are used in the application presented. The system is evaluated using the analysis and prediction of PM2.5 in the Los Angeles basin during the CalNex 2010 field experiment, with assimilation of surface PM2.5 and speciated concentration observations. The results demonstrate that the data assimilation significantly reduces the errors in comparison with a simulation without data assimilation and improved forecasts of the concentrations of PM2.5 as well as individual species for up to 24 h. Some implementation difficulties and limitations of the system are discussed.

We examine the distribution of tropical tropospheric ozone (O3) from the Microwave Limb Sounder (MLS) and the Tropospheric Emission Spectrometer (TES) by using a global three-dimensional model of tropospheric chemistry (GEOS-Chem). MLS and TES observations of tropospheric O3 during 2005 to 2009 reveal a distinct, persistent O3 maximum, both in mixing ratio and tropospheric column, in May over the Equatorial Southern Indian Ocean (ESIO). The maximum is most pronounced in 2006 and 2008 and less evident in the other three years. This feature is also consistent with the total column O3 observations from the Ozone Mapping Instrument (OMI) and the Atmospheric Infrared Sounder (AIRS). Model results reproduce the observed May O3 maximum and the associated interannual variability. The origin of the maximum reflects a complex interplay of chemical and dynamic factors. The O3 maximum is dominated by the O3 production driven by lightning nitrogen oxides (NOx) emissions, which accounts for 62% of the tropospheric column O3 in May 2006. We find the contribution from biomass burning, soil, anthropogenic and biogenic sources to the O3 maximum are rather small. The O3 productions in the lightning outflow from Central Africa and South America both peak in May and are directly responsible for the O3 maximum over the western ESIO. The lightning outflow from Equatorial Asia dominates over the eastern ESIO. The interannual variability of the O3 maximum is driven largely by the anomalous anti-cyclones over the southern Indian Ocean in May 2006 and 2008. The lightning outflow from Central Africa and South America is effectively entrained by the anti-cyclones followed by northward transport to the ESIO.

This study used numerical experiments to investigate two important concerns in simulating the cold season snowpack: the impact of the alterations of snow albedo due to anthropogenic aerosol deposition on snowpack and the treatment of snow physics using a multi-layer snow model. The snow albedo component considered qualitatively future changes in anthropogenic emissions and the subsequent increase or decrease of black carbon deposition on the Sierra Nevada snowpack by altering the prescribed snow albedo values. The alterations in the snow albedo primarily affect the snowpack via surface energy budget with little impact on precipitation. It was found that a decrease in snow albedo (by as little as 5–10% of the reference values) due to an increase in local emissions enhances snowmelt and runoff (by as much as 30–50%) in the early part of a cold season, resulting in reduced snowmelt-driven runoff (by as much as 30–50%) in the later part of the cold season, with the greatest impacts at higher elevations. An increase in snow albedo associated with reduced anthropogenic emissions results in the opposite effects. Thus, the most notable impact of the decrease in snow albedo is to enhance early-season snowmelt and to reduce late-season snowmelt, resulting in an adverse impact on warm season water resources in California. The timing of the sensitivity of snow water equivalent (SWE), snowmelt, and runoff vary systematically according to terrain elevation; as terrain elevation increases, the peak response of these fields occurs later in the cold season. The response of SWE and surface energy budget to the alterations in snow albedo found in this study shows that the effects of snow albedo on snowpack are further enhanced via local snow-albedo feedback. Results from this experiment suggest that a reduction in local emissions, which would increase snow albedo, could alleviate the early snowmelt and reduced runoff in late winter and early spring caused by global climate change, at least partially. The most serious uncertainties associated with this part of the study are a quantification of the relationship between the amount of black carbon deposition and snow albedo—a subject of future study. The comparison of the spring snowpack simulated with a single- and multi-layer snow model during the spring of 1998 shows that a more realistic treatment of snow physics in a multi-layer snow model could improve snowpack simulations, especially during spring when snow ablation is significant, or in conjunction with climate change projections.

Forest fires are an important source to carbonaceous aerosols in the Western United States (WUS). We quantify the relative contribution of biomass burning to black carbon (BC) in the WUS mountain ranges by analyzing surface BC observations for 2006 from the Interagency Monitoring of PROtected Visual Environment (IMPROVE) network using the GEOS-Chem global chemical transport model. Observed surface BC concentrations show broad maxima during late June to early November. Enhanced potassium concentrations and potassium/sulfur ratios observed during the high-BC events indicate a dominant biomass burning influence during the peak fire season. Model surface BC reproduces the observed day-to day and synoptic variabilities in regions downwind of but near urban centers. Major discrepancies are found at elevated mountainous sites during the July-October fire season when simulated BC concentrations are biased low by a factor of two. We attribute these low biases largely to the underestimated (by more than a factor of two) and temporally misplaced biomass burning emissions of BC in the model. Additionally, we find that the biomass burning contribution to surface BC concentrations in the USA likely was underestimated in a previous study using GEOS-Chem (Park et al., 2003), because of the unusually low planetary boundary layer (PBL) heights in the GEOS-3 meteorological reanalysis data used to drive the model. PBL heights from GEOS-4 and GEOS-5 reanalysis data are comparable to those from the North American Regional Reanalysis (NARR). Model simulations show slightly improved agreements with the observations when driven by GEOS-5 reanalysis data, but model results are still biased low. The use of biomass burning emissions with diurnal cycle, synoptic variability, and plume injection has relatively small impact on the simulated surface BC concentrations in the WUS.

The column abundance of NO3 was measured over Table Mountain Facility, CA (34.4° N, 117.7° W) from May 2003 through September 2004, using lunar occultation near full moon with a grating spectrometer. The NO3 column retrieval was performed with the differential optical absorption spectroscopy (DOAS) technique using both the 623 and 662 nm NO3 absorption bands. Other spectral features such as Fraunhofer lines and absorption from water vapor and oxygen were removed using solar spectra obtained at different airmass factors. We observed a seasonal variation, with nocturnally averaged NO3 columns between 5−7 × 1013 molec cm−2 during October through March, and 5−22 × 1013 molec cm−2 during April through September. A subset of the data, with diurnal variability vastly different from the temporal profile obtained from one-dimensional stratospheric model calculations, clearly has boundary layer contributions; this was confirmed by simultaneous long-path DOAS measurements. However, even the NO3 columns that did follow the modeled time evolution were often much larger than modeled stratospheric partial columns constrained by realistic temperatures and ozone concentrations. This discrepancy is attributed to substantial tropospheric NO3 in the free troposphere, which may have the same time dependence as stratospheric NO3.

Concurrent tropospheric O3 and CO vertical profiles from the Tropospheric Emission Spectrometer (TES) during the MILAGRO/INTEX-B aircraft campaigns over the Mexico City Metropolitan Area (MCMA) and its surrounding regions were used to examine Mexico City pollution outflow on a regional scale. The pollution outflow from the MCMA occurred predominantly at 600–800 hPa as evident in O3, CO, and NOx enhancements in the in situ aircraft observations. TES O3 and CO are sensitive to the MCMA pollution outflow due to their relatively high sensitivities at 600–800 hPa. We examined O3, CO, and their correlation at 600–800 hPa from TES retrievals, aircraft measurements, and GEOS-Chem model results. TES captures much of the spatial and day-to-day variability of O3 seen in the in situ data. TES CO, however, shows much less spatial and day-to-day variability compared with the in situ observations. The DO3/DCO slope is significantly higher in the TES data (0.43) than the in situ data (0.28) due partly to the lack of variability in TES CO. Extraordinarily high DO3/DCO slope (0.81) from TES observations at 618 hPa over the Eastern U.S. was previously reported by Zhang et al. [Zhang, L., Jacob, D.J., Bowman, K.W., et al., 2006. Ozone–CO correlations determined by the TES satellite instrument in continental outflow regions. Geophys. Res. Lett. 33, L18804. 10.1029/2006GL026399.]. Thus the application of TES CO–O3 correlation to map continental pollution outflow needs further examination. Published by Elsevier Ltd.

We develop and examine a microphysics-based black carbon (BC) aerosol aging scheme that accounts for condensation, coagulation, and heterogeneous chemical oxidation processes in a global 3-D chemical transport model (GEOS-Chem) by interpreting the BC measurements from the HIAPER Pole-to-Pole Observations (HIPPO, 2009–2011) using the model. We convert aerosol mass in the model to number concentration by assuming lognormal aerosol size distributions and compute the microphysical BC aging rate (excluding chemical oxidation aging) explicitly from the condensation of soluble materials onto hydrophobic BC and the coagulation between hydrophobic BC and preexisting soluble particles. The chemical oxidation aging is tested in the sensitivity simulation. The microphysical aging rate is ∼ 4 times higher in the lower troposphere over source regions than that from a fixed aging scheme with an e-folding time of 1.2 days. The higher aging rate reflects the large emissions of sulfate–nitrate and secondary organic aerosol precursors hence faster BC aging through condensation and coagulation. In contrast, the microphysical aging is more than 5-fold slower than the fixed aging in remote regions, where condensation and coagulation are weak. Globally, BC microphysical aging is dominated by condensation, while coagulation contribution is largest over eastern China, India, and central Africa. The fixed aging scheme results in an overestimate of HIPPO BC throughout the troposphere by a factor of 6 on average. The microphysical scheme reduces this discrepancy by a factor of ∼ 3, particularly in the middle and upper troposphere. It also leads to a 3-fold reduction in model bias in the latitudinal BC column burden averaged along the HIPPO flight tracks, with largest improvements in the tropics. The resulting global annual mean BC lifetime is 4.2 days and BC burden is 0.25 mg m−2, with 7.3 % of the burden at high altitudes (above 5 km). Wet scavenging accounts for 80.3 % of global BC deposition. We find that, in source regions, the microphysical aging rate is insensitive to aerosol size distribution, condensation threshold, and chemical oxidation aging, while it is the opposite in remote regions, where the aging rate is orders of magnitude smaller. As a result, global BC burden and lifetime show little sensitivity (< 5 % change) to these three factors.

We estimate black carbon (BC) emissions in the Western United States (WUS) for July–September 2006 by inverting surface BC concentrations from the Interagency Monitoring of PROtected Visual Environment (IMPROVE) network using a global chemical transport model (GEOS-Chem) and its adjoint. Our best estimate of the BC emissions is 49.9 Gg at 2° × 2.5° (a factor of 2.1 increase) and 47.3 Gg at 0.5° × 0.667° (1.9 times increase). Model results now capture the observed major fire episodes with substantial bias reductions (∼35% at 2° × 2.5° and ∼15% at 0.5° × 0.667°). The emissions are ∼20–50% larger than those from our earlier analytical inversions (Mao et al., 2014). The discrepancy is especially drastic in the partitioning of anthropogenic vs. biomass burning emissions. The August biomass burning BC emissions are 4.6–6.5 Gg and anthropogenic BC emissions 8.6–12.8 Gg, varying with the model resolution, error specifications, and subsets of observations used. On average both increase twofold relative to the respective a priori emissions, in distinct contrast to the halving of the anthropogenic and tripling of the biomass burning emissions in the analytical inversions. We attribute these discrepancies to the inability of the inversion system, with limited spatiotemporal coverage of the IMPROVE observations, to effectively distinguish collocated anthropogenic and biomass burning emissions on model grid scales. This calls for concurrent measurements of other tracers of biomass burning and fossil fuel combustion (e.g., carbon monoxide and carbon isotopes). We find that the inversion system as is has sufficient information content to constrain the total emissions of BC on the model grid scales.

The GEOS-CHEM global 3-D model of tropo- spheric chemistry predicts a summertime O3 maximum over the Middle East, with mean mixing ratios in the middle and upper troposphere in excess of 80 ppbv. This model feature is consistent with the few observations from commercial air- craft in the region. Its origin in the model reflects a complex interplay of dynamical and chemical factors, and of anthro- pogenic and natural influences. The anticyclonic circulation in the middle and upper troposphere over the Middle East funnels northern midlatitude pollution transported in the westerly subtropical jet as well as lightning outflow from the Indian monsoon and pollution from eastern Asia transported in an easterly tropical jet. Large-scale subsidence over the region takes place with continued net production of O3 and little mid-level outflow. Transport from the stratosphere does not contribute significantly to the Oa maximum. Sensi- tivity simulations with anthropogenic or lightning emissions shut off indicate decreases of 20-30% and 10-15% respec- tively in the tropospheric O3 column over the Middle East. More observations in this region are needed to confirm the presence of the O3 maximum.

We present a new formulation for the air mass factor (AMF) to convert slant column measurements of optically thin atmospheric species from space into total vertical columns. Because of atmospheric scattering, the AMF depends on the vertical distribution of the species. We formulate the AMF as the integral of the relative vertical distribution (shape factor) of the species over the depth of the atmosphere, weighted by altitude-dependent coefficients (scattering weights) computed independently from a radiative transfer model. The scattering weights are readily tabulated, and one can then obtain the AMF for any observation scene by using shape factors from a three dimensional (3-D) atmospheric chemistry model for the period of observation. This approach subsequently allows objective evaluation of the 3-D model with the observed vertical columns, since the shape factor and the vertical column in the model represent two independent pieces of information. We demonstrate the AMF method by using slant column measurements of formaldehyde at 346 nm from the Global Ozone Monitoring Experiment satellite instrument over North America during July 1996. Shape factors are cumputed with the Global Earth Observing System CHEMistry (GEOS-CHEM) global 3-D model and are checked for consistency with the few available aircraft measurements. Scattering weights increase by an order of magnitude from the surface to the upper troposphere. The AMFs are typically 20-40% less over continents than over the oceans and are approximately half the values calculated in the absence of scattering. Model-induced errors in the AMF are estimated to be approximately 10%. The GEOS-CHEM model captures 50% and 60% of the variances in the observed slant and vertical columns, respectively. Comparison of the simulated and observed vertical columns allows assessment of model bias.

Atmospheric mineral dust particles exert significant direct radiative forcings and are critical drivers of climate change. Here, we use the GEOS-Chem global three-dimensional chemical transport model (3-D CTM) coupled online with the Fu-Liou-Gu (FLG) radiative transfer model (RTM) to investigate the dust radiative forcing and heating rates based on different dust vertical profiles. The coupled calculations using a realistic dust vertical profile simulated by GEOS-Chem minimize the physical inconsistencies between 3-D CTM aerosol fields and the RTM. The use of GEOS-Chem simulated aerosol optical depth (AOD) vertical profiles as opposed to the FLG prescribed AOD vertical profiles leads to greater and more spatially heterogeneous changes in estimated radiative forcing and heating rate produced by dust. Both changes can be attributed to a different vertical structure between dust and non-dust source regions. Values of the dust AOD are much larger in the middle troposphere, though smaller at the surface when the GEOS-Chem simulated AOD vertical profile is used, which leads to a much stronger heating rate in the middle troposphere. Compared to FLG vertical profile, the use of GEOS-Chem vertical profile reduces the solar radiative forcing effect by about 0.2–0.25 W m−2 and the Infrared (IR) radiative forcing over the African and Asia dust source regions by about 0.1–0.2 W m−2. Differences in the solar radiative forcing at the surface between using the GEOS-Chem vertical profile and the FLG vertical profile are most significant over the Gobi desert with a value of about 1.1 W m−2. The radiative forcing effect of dust particles is more pronounced at the surface over the Sahara and Gobi deserts by using FLG vertical profile, while it is less significant over the downwind area of Eastern Asia.

Using in situ measurements, we find a semiannual oscillation (SAO) in the midtropospheric and surface CO_2. Chemistry transport models (2-D Caltech/JPL model, 3-D GEOS-Chem, and 3-D MOZART-2) are used to investigate possible sources for the SAO signal in the midtropospheric and surface CO_2. From model sensitivity studies, it is revealed that the SAO signal in the midtropospheric CO_2 originates mainly from surface CO_2 with a small contribution from transport fields. It is also found that the source for the SAO signal in surface CO_2 is mostly related to the CO_2 exchange between the biosphere and the atmosphere. By comparing model CO_2 with in situ CO_2 measurements at the surface, we find that models are able to capture both annual and semiannual cycles well at the surface. Model simulations of the annual and semiannual cycles of CO_2 in the tropical middle troposphere agree reasonably well with aircraft measurements.

[1] Simple prototypes for forced advection-diffusion problems are known to produce passive tracer distributions that exhibit approximately exponential or stretched exponential tails. Having previously found an approximately exponential tail for the column integrated water vapor (CWV) distribution under high precipitation conditions, we conjectured that if such prototypes are relevant to more complex tropospheric tracer problems, we should find such tails for a wide set of tracers. Here it is shown that such tails are indeed ubiquitous in observed, model, and reanalysis data sets for a variety of tracers, either column integrated or averaged through a deep layer, including CO and CO2. The long tails in CWV are associated with vertical transport and can occur independent of a local precipitation sink. These non-Gaussian distributions can have consequences for source attribution studies of anthropogenic tracers, and for mechanisms of precipitation extremes; the properties of the tails may help constrain model tracer simulations.

Using internally consistent albedo, aerosol, cloud, and surface data from the Multiangle Imaging Spectroradiometer (MISR) instrument onboard the Terra satellite, top-of-atmosphere (TOA) spectral albedo change (dα) in the presence of aerosols over land is estimated and its dependence on aerosol and surface properties is analyzed. Linear regressions between spectral TOA albedo and aerosol optical depth (AOD) for different surface types are examined to derive the aerosol-free TOA albedo. MISR surface BiHemispherical Reflectance (BHR) values are used to differentiate surface types. We find relatively high correlations between spectral TOA albedo and AOD for BHR-stratified data in 2° × 2° grid cells. The global mean values of cloud-free dα over land for June–September 2007 are estimated to be 0.018 ± 0.003 (blue), 0.010 ± 0.003 (green), 0.007 ± 0.003 (red), and 0.008 ± 0.006 (near-infrared). Individual regions show large variations from these values. Global patterns of dα are determined mainly by AOD and aerosol radiative efficiency. Large positive values of dα are observed over regions with high aerosol loading and large single-scattering albedo, where the aerosol scattering effect is dominant. The presence of light-absorbing aerosols reduces aerosol radiative efficiency and dα. Surface reflectance influences both aerosol scattering and absorbing effects. Generally, the aerosol radiative efficiency decreases with increasing BHR. We also examined dα-AOD correlations over different vegetation types. We find the smallest dα values are over needleleaf forests and shrublands, whereas the largest values are over cropland and barren regions. The aerosol radiative efficiencies are lowest over needleleaf forests and barren regions and highest over grasslands and croplands.

The California Institute of Technology/Jet Propulsion Laboratory two-dimensional (2-D), three-dimensional (3-D) GEOS-Chem, and 3-D MOZART-2 chemistry and transport models (CTMs), driven respectively by NCEP2, GEOS-4, and NCEP1 reanalysis data, have been used to simulate upper tropospheric CO2 from 2000 to 2004. Model results of CO2 mixing ratios agree well with monthly mean aircraft observations at altitudes between 8 and 13 km (Matsueda et al., 2002) in the tropics. The upper tropospheric CO2 seasonal cycle phases are well captured by the CTMs. Model results have smaller seasonal cycle amplitudes in the Southern Hemisphere compared with those in the Northern Hemisphere, which are consistent with the aircraft data. Some discrepancies are evident between the model and aircraft data in the midlatitudes, where models tend to underestimate the amplitude of CO2 seasonal cycle. Comparison of the simulated vertical profiles of CO2 between the different models reveals that the convection in the 3-D models is likely too weak in boreal winter and spring. Model sensitivity studies suggest that convection mass flux is important for the correct simulation of upper tropospheric CO2.

Human activity has increased the concentration of the earth's atmospheric carbon dioxide, which plays a direct role in contributing to global warming. Mid-tropospheric CO_2 retrieved by the Atmospheric Infrared Sounder shows a substantial spatiotemporal variability that is supported by in situ aircraft measurements. The distribution of middle tropospheric CO_2 is strongly influenced by surface sources and large-scale circulations such as the mid-latitude jet streams and by synoptic weather systems, most notably in the summer hemisphere. In addition, the effects of stratosphere-troposphere exchange are observed during a final stratospheric warming event. The results provide the means to understand the sources and sinks and the lifting of CO_2 from surface layers into the free troposphere and its subsequent transport around the globe. These processes are not adequately represented in three chemistry-transport models that have been used to study carbon budgets.

[1] Measurements of NO, NO2, and NOy (total reactive nitrogen oxides) made at the Pico Mountain station, 38.47°N, 28.40°W, 2.2 km above sea level, from July 2002 to August 2005 are used to characterize the seasonal and diurnal variations of nitrogen oxides in the background lower free troposphere (FT) over the central North Atlantic Ocean. These observations reveal a well-defined seasonal cycle of nitrogen oxides (NOx = NO + NO2 and NOy), with higher mixing ratios during the summertime. Observed NOx and NOy levels are consistent with long-range transport of emissions, with significant removal en route to the measurement site. Larger summertime nitrogen oxides levels are attributed to boreal wildfire emissions and more efficient export and transport of NOy from eastern North America during that season. In addition, measurements of NOx and NOy obtained during in-cloud and cloud-free conditions are used to estimate PAN and HNO3 mixing ratios and examine the partitioning of the reactive nitrogen species. These estimates indicate that reactive nitrogen over the central North Atlantic lower FT largely exists in the form of PAN and HNO3 (∼80–90% of NOy) year-round. The composition of NOy shifts from dominance of PAN in winter-spring to dominance of HNO3 in summer-fall, as a result of changes in temperature and photochemistry over the region. A further comparison of the nitrogen oxides measurements with results from the global chemical transport model GEOS-Chem finds that simulated nitrogen oxides are significantly larger than the observations.

We investigate the modulation of aerosols by the Madden-Julian Oscillation (MJO) using multiple, global satellite aerosol products: aerosol index (AI) from the Total Ozone Mapping Spectrometer (TOMS) on Nimbus-7, and aerosol optical thickness (AOT) from the Moderate Resolution Imaging Spectroradiometer (MODIS) on Terra and Aqua and the Advanced Very High Resolution Radiometer (AVHRR) on NOAA satellites. A composite MJO analysis indicates that large variations in the TOMS AI and MODIS/AVHRR AOT are found over the equatorial Indian and western Pacific Oceans where MJO convection is active, as well as the tropical Africa and Atlantic Ocean where MJO convection is weak but the background aerosol level is high. A strong inverse linear relationship between the TOMS AI and rainfall anomalies, but a weaker, less coherent positive correlation between the MODIS/AVHRR AOT and rainfall anomalies, were found. The MODIS/AVHRR pattern is consistent with ground-based Aerosol Robotic Network data. These results indicate that the MJO and its associated cloudiness, rainfall, and circulation variability systematically influence the variability in remote sensing aerosol retrieval results. Several physical and retrieval algorithmic factors that may contribute to the observed aerosol-rainfall relationships are discussed. Preliminary analysis indicates that cloud contamination in the aerosol retrievals is likely to be a major contributor to the observed relationships, although we cannot exclude possible contributions from other physical mechanisms. Future research is needed to fully understand these complex aerosol-rainfall relationships.

[1] The Tropospheric Emission Spectrometer (TES) is an infrared instrument that was launched on board NASA's Aura satellite in 2004. TES is the first instrument to provide vertical information on tropospheric ozone while simultaneously measuring CO on a global basis. Before they may be used for scientific study, TES profiles must first be validated to determine if there are any systematic biases present. In this study we present a validation of TES tropospheric ozone using airborne differential absorption lidar (DIAL) profiles obtained during the Intercontinental Chemical Transport Experiment-B (INTEX-B) campaign, which took place during March-May 2006. During INTEX-B the NASA DC-8 aircraft conducted several flights, which allowed the DIAL instrument to obtain ozone profile measurements that were spatially coincident with TES special observations in three different geographical regions. Here we present comparisons of TES and DIAL tropospheric ozone profiles that show that, on average, TES exhibits a small positive bias in the troposphere of 5-15%. We also examine the use of in situ profile observations for the validation of TES tropospheric ozone, and we find these to be of most use in clean regions where the background ozone field is homogeneous.

Global satellite observations of ozone and carbon monoxide from the Microwave Limb Sounder (MLS) on the EOS Aura spacecraft are discussed with emphasis on those observations in the 215-100 hPa region (the upper troposphere and lower stratosphere). The precision, resolution and accuracy of the data produced by the MLS "version 2.2'' processing algorithms are discussed and quantified. O-3 accuracy is estimated at similar to 40 ppbv + 5% (similar to 20 ppbv + 20% at 215 hPa) while the CO accuracy is estimated at similar to 30 ppbv + 30% for pressures of 147 hPa and less. Comparisons with expectations and other observations show good agreements for the O3 product, generally consistent with the systematic errors quoted above. In the case of CO, a persistent factor of similar to 2 high bias is seen at 215 hPa. However, the morphology is shown to be realistic, consistent with raw MLS radiance data, and useful for scientific study. The MLS CO data at higher altitudes are shown to be consistent with other observations.

Concurrent tropospheric O 3 and CO vertical profiles from the Tropospheric Emission Spectrometer (TES) during the MILAGRO/INTEX-B aircraft campaigns over the Mexico City Metropolitan Area (MCMA) allow us to characterize mega-city pollution. Outflow from the MCMA occurred predominantly at 600–800 hPa, evident in O 3 , CO, and NO x enhancements in the in situ observations. We examined O 3 , CO, and their correlation at 600–800 hPa from TES retrievals, aircraft measurements, and GEOS-Chem model results over the aircraft coverage (within a radius of ~700 km around MCMA). The enhancements in O 3 and CO seen in the in situ measurements are not apparent in TES data, due to the lack of TES coverage during several strong pollution events. However, TES O 3 and CO data are consistent with the aircraft observations on a daily mean basis (50–60 ppbv and 100–130 ppbv for O 3 and CO respectively). The O 3 -CO correlation coefficients and enhancement ratios (ΔO 3 /ΔCO) derived from TES data are in good agreements with those derived from the aircraft observations and GEOS-Chem model results ( r : 0.5–0.9; ΔO 3 /ΔCO: 0.3–0.4), reflecting significant springtime photochemical production over MCMA and the surrounding region.

We present results from the first assimilation of carbon monoxide (CO) observations from the Tropospheric Emission Spectrometer (TES) into a global three-dimensional (3-D) chemistry and transport model (CTM). A sequential sub-optimal Kalman filter assimilation scheme (Khattatov et al., 2000) was applied to assimilate TES CO profiles during November 2004 into the GEOS-Chem global 3-D CTM. The assimilation results were compared with MOPITT and MOZAIC observations. The assimilation significantly improves model simulation of CO in the middle to upper troposphere, where the MOPITT versus model bias was reduced by up to two-thirds. Assimilation results show higher levels of CO in the southern tropics, consistent with MOPITT observations. We find good agreement between the TES assimilated model estimates of CO and in situ measurements from the MOZAIC program, which shows a negative bias of up to 10 ppbv in middle and upper tropospheric TES CO. The results demonstrate how assimilation can be used for non-coincident validation of TES CO profile retrievals.

0.4– 1.0 mol mol � 1 and consistent with ICARTT data. The GEOS-Chem model reproduces the O3-CO enhancement ratios observed in continental outflow, but model correlations are stronger and more extensive. We show that the discrepancy can be explained by spectral measurement errors in the TES data. These errors will decrease in future data releases, which should enable TES to provide better information on O3-CO correlations. Citation: Zhang, L., et al. (2006), Ozone-CO correlations determined by the TES satellite instrument in continental outflow regions, Geophys. Res. Lett., 33, L18804, doi:10.1029/2006GL026399.

[1] Atmospheric carbon monoxide (CO) is measured by the EOS Microwave Limb Sounder (MLS) on NASA's recently-launched Aura satellite. Descent has been observed in the 2004–2005 Northern Hemisphere winter polar mesosphere and upper stratosphere. During August and September 2004 enhanced CO was observed in the upper troposphere over India and Tibet. The MLS CO measurements are described and the radiance signal due to the enhanced CO in the upper troposphere is demonstrated.

[1] Reducing surface ozone (O3) to concentrations in compliance with the national air quality standard has proven to be challenging, despite tighter controls on O3 precursor emissions over the past few decades. New evidence indicates that isoprene emissions changed considerably from the mid-1980s to the mid-1990s owing to land-use changes in the eastern United States (Purves et al., 2004). Over this period, U.S. anthropogenic VOC (AVOC) emissions decreased substantially. Here we apply two chemical transport models (GEOS-CHEM and MOZART-2) to test the hypothesis, put forth by Purves et al. (2004), that the absence of decreasing O3 trends over much of the eastern United States may reflect a balance between increases in isoprene emissions and decreases in AVOC emissions. We find little evidence for this hypothesis; over most of the domain, mean July afternoon (1300–1700 local time) surface O3 is more responsive (ranging from −9 to +7 ppbv) to the reported changes in anthropogenic NOx emissions than to the concurrent isoprene (−2 to +2 ppbv) or AVOC (−2 to 0 ppbv) emission changes. The estimated magnitude of the O3 response to anthropogenic NOx emission changes, however, depends on the base isoprene emission inventory used in the model. The combined effect of the reported changes in eastern U.S. anthropogenic plus biogenic emissions is insufficient to explain observed changes in mean July afternoon surface O3 concentrations, suggesting a possible role for decadal changes in meteorology, hemispheric background O3, or subgrid-scale chemistry. We demonstrate that two major uncertainties, the base isoprene emission inventory and the fate of isoprene nitrates (which influence surface O3 in the model by −15 to +4 and +4 to +12 ppbv, respectively), preclude a well-constrained quantification of the present-day contribution of biogenic or anthropogenic emissions to surface O3 concentrations, particularly in the high-isoprene-emitting southeastern United States. Better constraints on isoprene emissions and chemistry are needed to quantitatively address the role of isoprene in eastern U.S. air quality.

factor of 3 higher for young than from mature leaves. The atmospheric lifetime of methanol in the model is 7 days; gas-phase oxidation by OH accounts for 63% of the global sink, dry deposition to land 26%, wet deposition 6%, uptake by the ocean 5%, and aqueous-phase oxidation in clouds less than 1%. The resulting simulation of atmospheric concentrations is generally unbiased in the Northern Hemisphere and reproduces the observed correlations of methanol with acetone, HCN, and CO in Asian outflow. Accounting for decreasing emission from leaves as they age is necessary to reproduce the observed seasonal variation of methanol concentrations at northern midlatitudes. The main model discrepancy is over the South Pacific, where simulated concentrations are a factor of 2 too low. Atmospheric production from the CH3O2 self-reaction is the dominant model source in this region. A factor of 2 increase in this source (to 50–100 Tg yr � 1 ) would largely correct the discrepancy and appears consistent with independent constraints on CH3O2 concentrations. Our resulting best estimate of the global source of methanol is 240 Tg yr � 1 . More observations of methanol concentrations and fluxes are needed over tropical continents. Better knowledge is needed of CH3O2 concentrations in the remote troposphere and of the underlying organic chemistry.

[1] We present a simple approach to estimating ground-level fine particulate matter (PM2.5, particles smaller than 2.5 mm in diameter) concentrations by applying local scaling factors from a global atmospheric chemistry model (GEOS-CHEM with GOCART dust and sea salt data) to aerosol optical thickness (AOT) retrieved by the Multiangle Imaging Spectroradiometer (MISR). The resulting MISR PM2.5 concentrations are compared with measurements from the U.S. Environmental Protection Agency’s (EPA) PM2.5 compliance network for the year 2001. Regression analyses show that the annual mean MISR PM2.5 concentration is strongly correlated with EPA PM2.5 concentration (correlation coefficient r = 0.81), with an estimated slope of 1.00 and an insignificant intercept, when three potential outliers from Southern California are excluded. The MISR PM2.5 concentrations have a root mean square error (RMSE) of 2.20 mg/m 3 , which corresponds to a relative error (RMSE over mean EPA PM2.5 concentration) of approximately 20%. Using simulated aerosol vertical profiles generated by the global models helps to reduce the uncertainty in estimated PM2.5 concentrations due to the changing correlation between lower and upper tropospheric aerosols and therefore to improve the capability of MISR AOT in estimating surface-level PM2.5 concentrations. The estimated seasonal mean PM2.5 concentrations exhibited substantial uncertainty, particularly in the west. With improved MISR cloud screening algorithms and the dust simulation of global models, as well as a higher model spatial resolution, we expect that this approach will be able to make reliable estimation of seasonal average surface-level PM2.5 concentration at higher temporal and spatial resolution. INDEX TERMS: 0305 Atmospheric Composition and Structure: Aerosols and particles (0345, 4801); 0345 Atmospheric Composition and Structure: Pollution—urban and regional (0305); 0394 Atmospheric Composition and Structure: Instruments and techniques; KEYWORDS: MISR AOT, GEOS-CHEM, PM2.5

[1] We construct global atmospheric budgets of HCN and CH3CN through a three-dimensional (3-D) model simulation of the HCN-CH3CN-CO system constrained and evaluated with aircraft observations from the Transport and Chemical Evolution Over the Pacific (TRACE-P) mission over the NW Pacific in February–April 2001. Observed background vertical gradients of HCN and CH3CN imply a dominant ocean sink for both gases, with deposition velocity of 0.13 cm s−1 for both and saturation ratios of 0.79 for HCN and 0.88 for CH3CN. Observations for both gases in the free troposphere imply a dominant source from biomass burning. Enhancement of HCN observed in Chinese urban plumes is attributed tentatively to residential coal burning. Biomass burning and residential coal burning emission ratios relative to CO of 0.27% and 1.6%, respectively, for HCN, and of 0.20% and 0.25%, respectively, for CH3CN, are consistent with observations in biomass burning and Chinese urban plumes. They provide the best model simulation of the ensemble of TRACE-P observations including vertical profiles and HCN-CH3CN-CO correlations. They also allow successful simulation of the long-term observations of HCN columns at sites in the Northern Hemisphere, and of the CH3CN vertical distribution observed over the northern Indian Ocean. Global biomass burning and Asian residential coal burning sources in the model are 0.63 and 0.2 Tg N yr−1, respectively, for HCN and 0.47 and 0.03 Tg N yr−1, respectively, for CH3CN. Ocean uptake is the dominant sink for both gases, with oxidation by OH representing an additional minor sink. The resulting tropospheric lifetimes are 5.3 months for HCN and 5.8 months for CH3CN. The model predicts very low HCN and CH3CN concentrations at high southern latitudes, reflecting the assumption of a uniform saturation ratio for ocean uptake; observations in that region are needed. In the free troposphere, the dominance of biomass burning sources (70–85% for HCN and 90–95% for CH3CN) implies that both gases can be used as biomass burning tracers. In the boundary layer, CH3CN appears to be a better biomass burning tracer. More work is needed to identify the origin of the Chinese urban source of HCN.

[1] We report the first in situ measurements of hydrogen cyanide (HCN) and methyl cyanide (CH3CN, acetonitrile) from the Pacific troposphere (0–12 km) obtained during the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) airborne mission (February–April 2001). Mean HCN and CH3CN mixing ratios of 243 ± 118 (median 218) ppt and 149 ± 56 (median 138) ppt, respectively, were measured. These in situ observations correspond to a mean tropospheric HCN column of 4.2 × 1015 molecules cm−2 and a CH3CN column of 2.5 × 1015 molecules cm−2. This is in good agreement with the 0–12 km HCN column of 4.4 (±0.6) × 1015 molecules cm−2 derived from infrared solar spectroscopic observations over Japan. Mixing ratios of HCN and CH3CN were greatly enhanced in pollution outflow from Asia and were well correlated with each other as well as with known tracers of biomass combustion (e.g., CH3Cl, CO). Volumetric enhancement (or emission) ratios (ERs) relative to CO in free tropospheric plumes, likely originating from fires, were 0.34% for HCN and 0.17% for CH3CN. ERs with respect to CH3Cl and CO in selected biomass burning (BB) plumes in the free troposphere and in boundary layer pollution episodes are used to estimate a global BB source of 0.8 ± 0.4 Tg (N) yr−1 for HCN and 0.4 ± 0.1 Tg (N) yr−1 for CH3CN. In comparison, emissions from industry and fossil fuel combustion are quite small (

We present a retrieval of tropospheric nitrogen dioxide (NO2) columns from the Global Ozone Monitoring Experiment (GOME) satellite instrument that improves in several ways over previous retrievals, especially in the accounting of Rayleigh and cloud scattering. Slant columns, which are directly fitted without low-pass filtering or spectral smoothing, are corrected for an artificial offset likely induced by spectral structure on the diffuser plate of the GOME instrument. The stratospheric column is determined from NO2 columns over the remote Pacific Ocean to minimize contamination from tropospheric NO2. The air mass factor (AMF) used to convert slant columns to vertical columns is calculated from the integral of the relative vertical NO2 distribution from a global 3-D model of tropospheric chemistry driven by assimilated meteorological data (Global Earth Observing System (GEOS)-CHEM), weighted by altitude-dependent scattering weights computed with a radiative transfer model (Linearized Discrete Ordinate Radiative Transfer), using local surface albedos determined from GOME observations at NO2 wavelengths. The AMF calculation accounts for cloud scattering using cloud fraction, cloud top pressure, and cloud optical thickness from a cloud retrieval algorithm (GOME Cloud Retrieval Algorithm). Over continental regions with high surface emissions, clouds decrease the AMF by 20–30% relative to clear sky. GOME is almost twice as sensitive to tropospheric NO2 columns over ocean than over land. Comparison of the retrieved tropospheric NO2 columns for July 1996 with GEOS-CHEM values tests both the retrieval and the nitrogen oxide radical (NOx) emissions inventories used in GEOS-CHEM. Retrieved tropospheric NO2 columns over the United States, where NOx emissions are particularly well known, are within 18% of GEOS-CHEM columns and are strongly spatially correlated (r = 0.78, n = 288, p < 0.005). Retrieved columns show more NO2 than GEOS-CHEM columns over the Transvaal region of South Africa and industrial regions of the northeast United States and Europe. They are lower over Houston, India, eastern Asia, and the biomass burning region of central Africa, possibly because of biases from absorbing aerosols.

[1] We interpret the distribution of tropical tropospheric ozone columns (TTOCs) from the Total Ozone Mapping Spectrometer (TOMS) by using a global three-dimensional model of tropospheric chemistry (GEOS-CHEM) and additional information from in situ observations. The GEOS-CHEM TTOCs capture 44% of the variance of monthly mean TOMS TTOCs from the convective cloud differential method (CCD) with no global bias. Major discrepancies are found over northern Africa and south Asia where the TOMS TTOCs do not capture the seasonal enhancements from biomass burning found in the model and in aircraft observations. A characteristic feature of these northern tropical enhancements, in contrast to southern tropical enhancements, is that they are driven by the lower troposphere where the sensitivity of TOMS is poor due to Rayleigh scattering. We develop an efficiency correction to the TOMS retrieval algorithm that accounts for the variability of ozone in the lower troposphere. This efficiency correction increases TTOCs over biomass burning regions by 3–5 Dobson units (DU) and decreases them by 2–5 DU over oceanic regions, improving the agreement between CCD TTOCs and in situ observations. Applying the correction to CCD TTOCs reduces by � 5 DU the magnitude of the ‘‘tropical Atlantic paradox’’ [Thompson et al., 2000], i.e. the presence of a TTOC enhancement over the southern tropical Atlantic during the northern African biomass burning season in December–February. We reproduce the remainder of the paradox in the model and explain it by the combination of upper tropospheric ozone production from lightning NOx, persistent subsidence over the southern tropical Atlantic as part of the Walker circulation, and cross-equatorial transport of upper tropospheric ozone from northern midlatitudes in the African ‘‘westerly duct.’’ These processes in the model can also account for the observed 13–17 DU persistent wave-1 pattern in TTOCs with a maximum over the tropical Atlantic and a minimum over the tropical Pacific during all seasons. The photochemical effects of mineral dust have only a minor role on the modeled distribution of TTOCs, including over northern Africa, due to multiple competing effects. The photochemical effects of mineral dust globally decrease annual mean OH concentrations by 9%. A global lightning NOx source of 6 Tg N yr � 1 in the model produces a simulation that is most consistent with TOMS and in situ observations. INDEX TERMS: 0343 Atmospheric Composition and Structure: Planetary atmospheres (5405, 5407, 5409, 5704, 5705, 5707); 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry

The Global Ozone Monitoring Experiment (GOME) was launched on the European Space Agency's ERS-2 satellite on April 20, 1995. GOME measures the Earth's atmosphere in the nadir geometry, using a set of spectrometers that cover the UV and visible (240-790 nm) at moderate resolution (0.2 nm in the UV, 0.4 nm in the visible), employing silicon diode array detectors. GOME takes some 30,000 spectra per day, obtaining full global coverage in three days. We directly fit GOME radiance spectra using nonlinear least-squares analysis to obtain column amounts of several trace species with significant tropospheric concentrations, including ozone (O3), nitrogen dioxide (NO2), sulfur dioxide (SO2), and formaldehyde (HCHO). Measurements of HCHO due to biogenic activity in the troposphere are presented here.

We present a first description and evaluation of GEOS-CHEM, a global three-dimensional (3-D) model of tropospheric chemistry driven by assimilated meteorological observations from the Goddard Earth Observing System (GEOS) of the NASA Data Assimilation Office (DAO). The model is applied to a 1-year simulation of tropospheric ozone-NOx-hydrocarbon chemistry for 1994, and is evaluated with observations both for 1994 and for other years. It reproduces usually to within 10 ppb the concentrations of ozone observed from the worldwide ozonesonde data network. It simulates correctly the seasonal phases and amplitudes of ozone concentrations for different regions and altitudes, but tends to underestimate the seasonal amplitude at northern midlatitudes. Observed concentrations of NO and peroxyacetylnitrate (PAN) observed in aircraft campaigns are generally reproduced to within a factor of 2 and often much better. Concentrations of HNO3 in the remote troposphere are overestimated typically by a factor of 2-3, a common problem in global models that may reflect a combination of insufficient precipitation scavenging and gas-aerosol partitioning not resolved by the model. The model yields an atmospheric lifetime of methylchloroform (proxy for global OH) of 5.1 years, as compared to a best estimate from observations of 5.5 plus or minus 0.8 years, and simulates H2O2 concentrations observed from aircraft with significant regional disagreements but no global bias. The OH concentrations are approximately 20% higher than in our previous global 3-D model which included an UV-absorbing aerosol. Concentrations of CO tend to be underestimated by the model, often by 10-30 ppb, which could reflect a combination of excessive OH (a 20% decrease in model OH could be accommodated by the methylchloroform constraint) and an underestimate of CO sources (particularly biogenic). The model underestimates observed acetone concentrations over the South Pacific in fall by a factor of 3; a missing source from the ocean may be implicated.

[1] The atmospheric budget and distribution of acetone are investigated by using a priori estimates of sources and sinks to constrain a global three-dimensional atmospheric model simulation and then using atmospheric observations from 14 surface sites and 5 aircraft missions to improve these estimates through an inversion analysis. Observations over the South Pacific imply a large photochemical marine source of acetone, either from the ocean or from marine organic aerosol. Low concentrations of acetone measured at European sites in winter-spring and in the Arctic in summer suggest a large microbial ocean sink. The summer-to-fall decrease of concentrations observed in Europe argues against a large source from plant decay. Continental observations in the tropics and at northern midlatitudes in summer imply a large source from terrestrial vegetation. Observations in the Northern Hemisphere outside summer imply a large source from atmospheric oxidation of anthropogenic isoalkanes (propane, isobutane, isopentane). Model simulation of isoalkanes and comparison to observations yields best global emission estimates of 12 Tg C yr−1 for propane (including only 0.6 Tg C yr−1 from biomass burning), 3.6 Tg C yr−1 for isobutane, and 5.0 Tg C yr−1 for isopentane. Our best estimate of the global acetone source is 95 Tg yr−1. The mean tropospheric lifetime of acetone is estimated to be 15 days. Terrestrial vegetation and oceans are the principal sources of acetone in the tropopause region (0.1–0.7 ppbv) except in the extratropical Northern Hemisphere, where oxidation of isoalkanes is more important.

The observed seasonal amplitude of atmospheric HCN concentrations implies an atmospheric lifetime of only a few months for HCN, much shorter than is commonly assumed from oxidation by OH (a few years). We propose that ocean uptake provides the missing sink, and show with a global 3-D model simulation that the observations of atmospheric HCN can be roughly reproduced in a scenario where biomass burning provides the main source (1.4–2.9 Tg N yr−1) and ocean uptake provides the main sink (HCN atmospheric lifetime of 2–4 months). Such a budget implies that HCN is a sensitive tracer of biomass burning on large scales, of particular value because it is readily observed from space. The ocean sink hypothesis can be tested with measurements of HCN concentrations in marine air and seawater.