-
We have studied the effects of the 2006 El Niño on tropospheric O<sub>3</sub> and CO at tropical and sub-tropical latitudes measured from the OMI and MLS instruments on the Aura satellite. The 2006 El Niño-induced drought caused forest fires (largely set to clear land) to burn out of control during October and November in the Indonesian region. The effects of these fires are clearly seen in the enhancement of CO concentration measured from the MLS instrument. We have used a global model of atmospheric chemistry and transport (GMI CTM) to quantify the relative importance of biomass burning and large scale transport in producing observed changes in tropospheric O<sub>3</sub> and CO. The model results show that during October and November biomass burning and meteorological changes contributed almost equally to the observed increase in tropospheric O<sub>3</sub> in the Indonesian region. The biomass component was 4–6 DU but it was limited to the Indonesian region where the fires were most intense. The dynamical component was 4–8 DU but it covered a much larger area in the Indian Ocean extending from South East Asia in the north to western Australia in the south. By December 2006, the effect of biomass burning was reduced to zero and the observed changes in tropospheric O<sub>3</sub> were mostly due to dynamical effects. The model results show an increase of 2–3% in the global burden of tropospheric ozone. In comparison, the global burden of CO increased by 8–12%.
-
In the present study, we show evidence of significant stratospheric warming over Southern Hemisphere high latitudes and large portions of the Antarctic polar region in winter and spring seasons, with a maximum warming of 7–8°C in September and October, using satellite Microwave Sounding Unit observations for 1979–2006. It is found that this warming is associated with increasing wave activity from the troposphere into the stratosphere, suggesting that the warming is caused by enhanced wave-driven adiabatic heating. We show that the stratospheric warming in Southern Hemisphere high latitudes has close correlations with sea surface temperature (SST) increases, and that general circulation model simulations forced with observed time-varying SSTs reproduce similar warming trend patterns in the Antarctic stratosphere. The simulated stratospheric warming is closely related to increasing wave activity in the Southern Hemisphere. These findings suggest that the stratospheric warming is likely induced by SST warming. As SST warming continues as a consequence of greenhouse gas increases due to anthropogenic activity, the stratospheric warming would also continue, which has important implications to the recovery of the Antarctic ozone hole.
-
Global-scale chemical transport model simulations indicate lightning NO<sub>x</sub> dominates upper tropospheric O<sub>3</sub> production above Eastern North America during summertime but vary in their estimates. To improve our understanding, a regional-scale model (REAM) with higher resolution is applied. To examine the uncertainties in modeling the impact of convective transport and lightning NO<sub>x</sub> production on upper tropospheric chemical tracer distributions, REAM simulations of chemical tracers are driven by two meteorological models, WRF and MM5, with different cumulus convective parameterizations. The model simulations are evaluated using INTEX-A aircraft measurements and satellite measurements of NO<sub>2</sub> columns and cloud top pressure, and we find that mid and upper tropospheric trace gas concentrations are affected strongly by convection and lightning NO<sub>x</sub> production. WRF with the KF-eta convection scheme simulates larger convective updraft mass fluxes below 150 hPa than MM5 with the Grell scheme. The inclusion of the entrainment and detrainment processes leads to more outflow in the mid troposphere in WRF than MM5. The ratio of C<sub>2</sub>H<sub>6</sub>/C<sub>3</sub>H<sub>8</sub> is found to be a sensitive parameter to convective outflow; the simulation by WRF-REAM is in closer agreement with INTEX-A measurements than MM5-REAM, implying that convective mass fluxes by WRF are more realistic. WRF also simulates lower cloud top heights (10–12 km) than MM5 (up to 16 km), and hence smaller amounts of estimated (intra-cloud) lightning NO<sub>x</sub> and lower emission altitudes. WRF simulated cloud top heights are in better agreement with GOES satellite measurements than MM5. Simulated lightning NO<sub>x</sub> production difference (due primarily to cloud top height difference) is mostly above 12 km. At 8–12 km, the models simulate a contribution of 60–75% of NO<sub>x</sub> and up to 20 ppbv of O<sub>3</sub> from lightning, although the decrease of lightning NO<sub>x</sub> effect from the Southeast to Northeast and eastern Canada is overestimated. The model differences and biases found in this study reflect some major uncertainties of upper tropospheric NO<sub>x</sub> and O<sub>3</sub> simulations driven by those in meteorological simulations and lightning parameterizations.
-
As part of the MILAGRO field campaign, the DOE G-1 aircraft was used to make measurements over and downwind of Mexico City with the objective of determining growth characteristics of aerosols from a megacity urban source. This study focuses on number concentration and size distributions. It is found that a 5-fold increase in aerosol volume is accompanied by about a 5-fold increase in accumulation mode number concentration. There is growth in aerosol volume because there are more accumulation mode particles, not because of an increase in the average size of accumulation particles. Condensation and volume growth laws were examined to see whether either is consistent with observations. Condensation calculations show that the growth of Aitken mode particles into the accumulation mode size range gives the required increase in number concentration. There are minimal changes in the accumulation mode size distribution with age, consistent with observations. Volume-growth in contrast yields a population of large particles, distinctly different from what is observed. Detailed model calculations are required to translate our observations into specific information on the volatility and properties of secondary organic aerosol.
-
Contact freezing of single supercooled water droplets colliding with kaolinite dust particles has been investigated. The experiments were performed with droplets levitated in an electrodynamic balance at temperatures from 240 to 268 K. Under relatively dry conditions (when no water vapor was added) freezing was observed to occur below 249 K, while a freezing threshold of 267 K was observed when water vapor was added to the air in the chamber. <br><br> The effect of relative humidity is attributed to an influence on the contact freezing process for the kaolinite-water droplet system, and it is not related to the lifetime of the droplets in the electrodynamic balance. Freezing probabilities per collision were derived assuming that collisions at the lowest temperature employed had a probability of unity. Mechanisms for contact freezing are briefly discussed.
-
We investigate the spatial and temporal distribution of hydrogen cyanide (HCN) in the upper troposphere through numerical simulations and comparison with observations from a space-based instrument. To perform the simulations, we used the Global Environmental Multiscale Air Quality model (GEM-AQ), which is based on the three-dimensional global multiscale model developed by the Meteorological Service of Canada for operational weather forecasting. The model was run for the period 2004–2006 on a 1.5°×1.5° global grid with 28 hybrid vertical levels from the surface up to 10 hPa. Objective analysis data from the Canadian Meteorological Centre were used to update the meteorological fields every 24 h. Fire emission fluxes of gas species were generated by using year-specific inventories of carbon emissions with 8-day temporal resolution from the Global Fire Emission Database (GFED) version 2. The model output is compared with HCN profiles measured by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) instrument onboard the Canadian SCISAT-1 satellite. High values of up to a few ppbv are observed in the tropics in the Southern Hemisphere; the enhancement in HCN volume mixing ratios in the upper troposphere is most prominent in October. Low upper-tropospheric mixing ratios of less than 100 pptv are mostly recorded at middle and high latitudes in the Southern Hemisphere in May–July. Mixing ratios in Northern Hemisphere peak in the boreal summer. The amplitude of the seasonal variation is less pronounced than in the Southern Hemisphere. The comparison with the satellite data shows that in the upper troposphere GEM-AQ performs well globally for all seasons, except at northern high and middle latitudes in summer, where the model has a large negative bias, and in the tropics in winter and spring, where it exhibits large positive bias. This may reflect inaccurate emissions or possible inaccuracies in the emission profile. The model is able to explain most of the observed variability in the upper troposphere HCN field, including the interannual variations in the observed mixing ratio. A complementary comparison with daily total columns of HCN from two middle latitude ground-based stations in Northern Japan for the same simulation period shows that the model captures the observed seasonal variation and also points to an underestimation of model emissions in the Northern Hemisphere in the summer. The estimated average global emission equals 1.3 Tg N yr<sup>−1</sup>. The average atmospheric burden is 0.53 Tg N, and the corresponding lifetime is 4.9 months.
-
A detailed <i>α</i>-pinene oxidation mechanism was reduced systematically through the successive application of five mechanism reduction techniques. The resulting reduced mechanism preserves the ozone- and organic aerosol-forming properties of the original mechanism, while using less species. The methodologies employed included a directed relation graph method with error propagation (DRGEP, which removed a large number of redundant species and reactions), principal component analysis of the rate sensitivity matrix (PCA, used to remove unnecessary reactions), the quasi-steady-state approximation (QSSA, used to remove some QSS species), an iterative screening method (ISSA, which removes redundant species and reactions simultaneously), and a new lumping approach dependent on the hydrocarbon to NO<sub>x</sub> ratio (which reduced the number of species in mechanism subsets for specific hydrocarbon to NO<sub>x</sub> ranges). <br><br> This multistage methodology results in a reduction ratio of 2.5 for the number of both species and reactions compared with the full mechanism. The simplified mechanism reproduces the important gas and aerosol phase species (the latter are examined in detail by individual condensing species as well as in classes according to four functional groups: PANs, nitrates, organic peroxides, and organic acids). The total SOA mass is also well represented in the condensed mechanism, to within 16% of the detailed mechanism under a wide range of conditions. The methodology described here is general, and may be used in general mechanism reduction problems.
-
Aerosol composition was measured by the NOAA single-particle mass spectrometer (PALMS) aboard the NASA WB-57 high altitude aircraft platform during two Aura Validation Experiment (AVE) campaigns based in Costa Rica in 2004 and 2006. These studies yielded the most complete set of aerosol composition measurements to date throughout the tropical tropopause layer (TTL) and tropical lower stratosphere. We describe the aerosol properties of the tropical atmosphere and use composition tracers to examine particle sources, the role of recent convection, and cirrus-forming potential in the TTL. Tropical dynamics and regional air sources played principal roles in dictating tropospheric aerosol properties. There was a sharp change in aerosol chemical composition at about 12 km altitude coincident with a change in convective influence. Below this level, maritime convection lofted condensable material that generated acidic, sulfate-rich aerosol. These particles contained significant amounts of methanesulfonic acid (MSA) and showed evidence of cloud processes. In contrast, continental convection injected particles and precursors directly into the TTL, yielding a population of neutralized, organic-rich aerosol. The organics were often highly oxidized and particles with oxidized organics also contained nitrate. Above the tropopause, chemical composition gradually changed toward sulfuric acid particles but neutralized particles were still abundant 2 km above the tropopause. Deep continental convection, though sporadic and geographically localized, may strongly influence TTL aerosol properties on a global scale. The abundance of organic-rich aerosol may inhibit ice nucleation and formation of tropopause level cirrus.
-
The Hygrosonde-2 campaign took place on 16 December 2001 at Esrange/Sweden (68° N, 21° E) with the aim to investigate the small scale distribution of water vapour in the middle atmosphere in the vicinity of the Arctic polar vortex. In situ balloon and rocket-borne measurements of water vapour were performed by means of OH fluorescence hygrometry. The combined measurements yielded a high resolution water vapour profile up to an altitude of 75 km. Using the characteristic of water vapour being a dynamical tracer it was possible to directly relate the water vapour data to the location of the polar vortex edge, which separates air masses of different character inside and outside the polar vortex. The measurements probed extra-vortex air in the altitude range between 45 km and 60 km and vortex air elsewhere. Transitions between vortex and extra-vortex usually coincided with wind shears caused by gravity waves which advect air masses with different water vapour volume mixing ratios. <br><br> From the combination of the results from the Hygrosonde-2 campaign and the first flight of the optical hygrometer in 1994 (Hygrosonde-1) a clear picture of the characteristic water vapour distribution inside and outside the polar vortex can be drawn. Systematic differences in the water vapour concentration between the inside and outside of the polar vortex can be observed all the way up into the mesosphere. It is also evident that in situ measurements with high spatial resolution are needed to fully account for the small-scale exchange processes in the polar winter middle atmosphere.
-
Accurate numerical simulations of the complex wind flows in the Mexico City Metropolitan Area (MCMA) can be an invaluable tool for interpreting the MILAGRO field campaign results. This paper uses three methods to evaluate numerical simulations of basin meteorology using the MM5 and WRF models: statistical comparisons with observations, "Concentration Field Analysis" (CFA) using measured air pollutant concentrations, and comparison of flow features using cluster analysis. CFA is shown to be a better indication of simulation quality than statistical metrics, and WRF simulations are shown to be an improvement on the MM5 ones. Comparisons with clusters identifies an under-representation of the drainage flows into the basin and an over-representation of wind shear in the boundary layer. Particle trajectories simulated with WRF-FLEXPART are then used to analyse the transport of the urban plume and show rapid venting and limited recirculation during MILAGRO. Lagrangian impacts were identified at the campaign supersites, and age spectra of the pollutants evaluated at those same sites. The evaluation presented in the paper show that mesoscale meteorological simulations are of sufficient accuracy to be useful for MILAGRO data analysis.
