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Seasonal variation of ozone deposition to a tropical rain forest in southwest Amazonia

Within the project EUropean Studies on Trace gases and Atmospheric CHemistry as a contribution to Large-scale Biosphere-atmosphere experiment in Amazonia (LBA-EUSTACH), we performed tower-based eddy covariance measurements of O3 flux above an Amazonian primary rain forest at the end of the wet and dry season. Ozone deposition revealed distinct seasonal differences in the magnitude and diel variation. In the wet season, the rain forest was an effective O3 sink with a mean daytime (midday) maximum deposition velocity of 2.3 cm s−1, and a corresponding O3 flux of −11 nmol m−2 s−1. At the end of the dry season, the ozone mixing ratio was about four times higher (up to maximum values of 80 ppb) than in the wet season, as a consequence of strong regional biomass burning activity. However, the typical maximum daytime deposition flux was very similar to the wet season. This results from a strong limitation of daytime O3 deposition due to reduced plant stomatal aperture as a response to large values of the specific humidity deficit. As a result, the average midday deposition velocity in the dry burning season was only 0.5 cm s−1. The large diel ozone variation caused large canopy storage effects that masked the true diel variation of ozone deposition mechanisms in the measured eddy covariance flux, and for which corrections had to be made. In general, stomatal aperture was sufficient to explain the largest part of daytime ozone deposition. However, during nighttime, chemical reaction with nitrogen monoxide (NO) was found to contribute substantially to the O3 sink in the rain forest canopy. Further contributions were from non-stomatal plant uptake and other processes that could not be clearly identified. Measurements, made simultaneously on a 22 years old cattle pasture enabled the spatially and temporally direct comparison of O3 dry deposition values from this site with typical vegetation cover of deforested land in southwest Amazonia to the results from the primary rain forest. The mean ozone deposition to the pasture was found to be systematically lower than that to the forest by 30% in the wet and 18% in the dry season.
Diagnosis of processes controlling water vapour in the tropical tropopause layer by a Lagrangian cirrus model

We have developed a Lagrangian air-parcel cirrus model (LACM), to diagnose the processes controlling water in the tropical tropopause layer (TTL). LACM applies parameterised microphysics to air parcel trajectories. The parameterisation includes the homogeneous freezing of aerosol droplets, the growth/sublimation of ice particles, and sedimentation of ice particles, so capturing the main dehydration mechanism for air in the TTL. Rehydration is also considered by resetting the water vapour mixing ratio in an air parcel to the value at the point in the 4-D analysis/forecast data used to generate the trajectories, but only when certain conditions, indicative of convection, are satisfied. The conditions act to restrict rehydration of the Lagrangian air parcels to regions where convective transport of water vapour from below is significant, at least to the extent that the analysis/forecast captures this process. The inclusion of hydration and dehydration mechanisms in LACM results in total water fields near tropical convection that have more of the "stripy" character of satellite observations of high cloud, than do either the ECMWF analysis or trajectories without microphysics. The mixing ratios of total water in the TTL, measured by a high-altitude aircraft over Brazil (during the TROCCINOX campaign), have been reconstructed by LACM using trajectories generated from ECMWF analysis. Two other Lagrangian reconstructions are also tested: linear interpolation of ECMWF analysed specific humidity onto the aircraft flight track, and instantaneous dehydration to the saturation vapour pressure over ice along trajectories. The reconstructed total water mixing ratios along aircraft flight tracks are compared with observations from the FISH total water hygrometer. Process-oriented analysis shows that modelled cirrus cloud events are responsible for dehydrating the air parcels coming from lower levels, resulting in total water mixing ratios as low as 2 μmol/mol. Without adding water back to some of the trajectories, the LACM and instantaneous-dehydration reconstructions have a dry bias. The interpolated-ECMWF reconstruction does not suffer this dry bias, because convection in the ECMWF model moistens air parcels dramatically, by pumping moist air upwards. This indicates that the ECMWF model captures the gross features of the rehydration of air in the TTL by convection. Overall, the ECMWF models captures well the exponential decrease in total water mixing ratio with height above 250 hPa, so that all the reconstruction techniques capture more than 75% of the standard deviation in the measured total water mixing ratios over the depth of the TTL. By picking up the main contributing processes to dehydration and rehydration in the TTL, LACM reconstructs total water mixing ratios at the top of the TTL, close to the cold point, that are always in substantially better agreement with observations than instantaneous-dehydration reconstructions, and better than the ECMWF analysis for regions of high relative humidity and cloud.
ACE-FTS observation of a young biomass burning plume: first reported measurements of C2H4, C3H6O, H2CO and PAN by infrared occultation from space

In the course of our study of the upper tropospheric composition with the infrared Atmospheric Chemistry Experiment – Fourier Transform Spectrometer (ACE–FTS), we found an occultation sequence that on 8 October 2005, sampled a remarkable plume near the east coast of Tanzania. Model simulations of the CO distribution in the Southern hemisphere are performed for this period and they suggest that the emissions for this event likely originated from a nearby forest fire, after which the plume was transported from the source region to the upper troposphere. Taking advantage of the very high signal-to-noise ratio of the ACE–FTS spectra over a wide wavenumber range (750–4400 cm−1), we present in-depth analyses of the chemical composition of this plume in the middle and upper troposphere, focusing on the measurements of weakly absorbing pollutants. For this specific biomass burning event, we report simultaneous observations of an unprecedented number of organic species. Measurements of C2H4 (ethene), C3H4 (propyne), H2CO (formaldehyde), C3H6O (acetone) and CH3COO2NO2 (peroxyacetylnitrate, abbreviated as PAN) are the first reported detections using infrared occultation spectroscopy from satellites. Based on the lifetime of the emitted species, we discuss the photochemical age of the plume and also report, whenever possible, the enhancement ratios relative to CO.
The daytime mixing layer observed by radiosonde, profiler, and lidar during MILAGRO

During the MILAGRO campaign centered in the Mexico City area, Pacific Northwest National Laboratory (PNNL) and Argonne National Laboratory (ANL) operated atmospheric profiling systems at Veracruz and at two locations on the Central Mexican Plateau in the region around Mexico City. These systems included radiosondes, wind profilers, a sodar, and an aerosol backscatter lidar. An additional wind profiler was operated by the University of Alabama in Huntsville (UAH) at the Mexican Petroleum Institue (IMP) near the center of Mexico City. Because of the opportunity afforded by collocation of profilers, radiosondes, and a lidar, and because of the importance of boundary layer depth for aerosol properties, we have carried out a comparison of mixing layer depth as determined independently from these three types of measurement systems during the campaign. We have then used results of this comparison and additional measurements to develop a detailed description of the daily structure and evolution of the boundary layer on the Central Mexican Plateau during MILAGRO. Our analysis indicates that the profilers were more consistently successful in establishing the mixing layer depth during the daytime. The boundary layer growth was similar at the three locations, although the mixing layer tended to be slightly deeper in the afternoon in central Mexico City. The sodar showed that convection began about an hour after sunrise. Maximum daily mixing layer depths always reached 2000 m a.g.l. and frequently extended to 4000 m. The rate and variability of mixing layer growth was essentially the same as that observed during the IMADA-AVER campaign in the same season in 1997. This growth did not seem to be related to whether deep convection was reported on a given day. Wind speeds within the boundary layer exhibited a daily low-altitude maximum in the late afternoon with lighter winds aloft, consistent with previous reports of diurnal regional circulations. Norte events, which produced high winds at Veracruz, did not appreciably modulate the winds on the plateau. Finally, despite the typically dry conditions at the surface, radiosonde profiles showed that relative humidity often exceeded 50% in the early morning and in the upper part of the boundary layer. This suggests that aerosol particles would have experienced hygroscopic growth within the boundary layer on many days.
Contribution of primary carbonaceous aerosol to cloud condensation nuclei: processes and uncertainties evaluated with a global aerosol microphysics model

This paper explores the impacts of primary carbonaceous aerosol on cloud condensation nuclei (CCN) concentrations in a global climate model with size-resolved aerosol microphysics. Organic matter (OM) and elemental carbon (EC) from two emissions inventories were incorporated into a preexisting model with sulfate and sea-salt aerosol. The addition of primary carbonaceous aerosol increased CCN(0.2%) concentrations by 65–90% in the globally averaged surface layer depending on the carbonaceous emissions inventory used. Sensitivity studies were performed to determine the relative importance of organic solubility/hygroscopicity in predicting CCN. In a sensitivity study where carbonaceous aerosol was assumed to be completely insoluble, concentrations of CCN(0.2%) still increased by 40–50% globally over the no carbonaceous simulation because primary carbonaceous emissions were able to become CCN via condensation of sulfuric acid. This shows that approximately half of the contribution of primary carbonaceous particles to CCN in our model comes from the addition of new particles (seeding effect) and half from the contribution of organic solute (solute effect). The solute effect tends to dominate more in areas where there is less inorganic aerosol than organic aerosol and the seeding effect tends to dominate in areas where there is more inorganic aerosol than organic aerosol. It was found that an accurate simulation of the number size distribution is necessary to predict the CCN concentration but assuming an average chemical composition will generally give a CCN concentration within a factor of 2. If a "typical" size distribution is assumed for each species when calculating CCN, such as is done in bulk aerosol models, the mean error relative to a simulation with size resolved microphysics is on the order of 35%. Predicted values of carbonaceous aerosol mass and aerosol number were compared to observations and the model showed average errors of a factor of 3 for carbonaceous mass and a factor of 4 for total aerosol number; however, errors in the accumulation mode concentrations were found to be lower in comparisons with European and marine observations.. The errors in CN and carbonaceous mass may be reduced by improving the emission size distributions of both primary sulfate and primary carbonaceous aerosol.
Analysis of Visible/SWIR surface reflectance ratios for aerosol retrievals from satellite in Mexico City urban area

The surface reflectance ratio between the visible (VIS) and shortwave infrared (SWIR) radiation is an important quantity for the retrieval of the aerosol optical depth (τa) from the MODIS sensor data. Based on empirically determined VIS/SWIR ratios, MODIS τa retrieval uses the surface reflectance in the SWIR band (2.1 µm), where the interaction between solar radiation and the aerosol layer is small, to predict the visible reflectances in the blue (0.47 µm) and red (0.66 µm) bands. Therefore, accurate knowledge of the VIS/SWIR ratio is essential for achieving accurate retrieval of aerosol optical depth from MODIS. We analyzed the surface reflectance over some distinct surface covers in and around the Mexico City metropolitan area (MCMA) using MODIS radiances at 0.66 µm and 2.1 µm. The analysis was performed at 1.5 km×1.5 km spatial resolution. Also, ground-based AERONET sun-photometer data acquired in Mexico City from 2002 to 2005 were analyzed for aerosol depth and other aerosol optical properties. In addition, a network of hand-held sun-photometers deployed in Mexico City, as part of the MCMA-2006 Study during the MILAGRO Campaign, provided an unprecedented measurement of τa in 5 different sites well distributed in the city. We found that the average RED/SWIR ratio representative of the urbanized sites analyzed is 0.73±0.06 for scattering angles <140° and goes up to 0.77±0.06 for higher ones. The average ratio for non-urban sites was significantly lower (approximately 0.55). In fact, this ratio strongly depends on differences in urbanization levels (i.e. relative urban to vegetation proportions and types of surface materials). The aerosol optical depth retrieved from MODIS radiances at a spatial resolution of 1.5 km×1.5 km and averaged within 10×10 km boxes were compared with collocated 1-h τa averaged from sun-photometer measurements. The use of the new RED/SWIR ratio of 0.73 in the MODIS retrieval over Mexico City led to a significant improvement in the agreement between the MODIS and sun-photometer AOD results; with the slope, offset, and the correlation coefficient of the linear regression changing from (τaMODIS=0.91τa sun-photometer+0.33, R2=0.66) to (τaMODIS=0.96 τa sun-photometer−0.006, R2=0.87). Indeed, an underestimation of this ratio in urban areas lead to a significant overestimation of the AOD retrieved from satellite. Therefore, we strongly encourage similar analyses in other urban areas to enhance the development of a parameterization of the surface ratios accounting for urban heterogeneities.
Characterizing mega-city pollution with TES O3 and CO measurements

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) allow us to characterize mega-city pollution. Outflow from the MCMA occurred predominantly at 600–800 hPa, evident in O3, CO, and NOx enhancements in the in situ observations. We examined O3, 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 O3 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 O3 and CO data are consistent with the aircraft observations on a daily mean basis (50–60 ppbv and 100–130 ppbv for O3 and CO respectively). The O3-CO correlation coefficients and enhancement ratios (ΔO3/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; ΔO3/ΔCO: 0.3–0.4), reflecting significant springtime photochemical production over MCMA and the surrounding region.
Technical Note: The air quality modeling system Polyphemus

Polyphemus is an air quality modeling platform which aims at covering the scope and the abilities of modern air quality systems. It deals with applications from local scale to continental scale, using two Gaussian models and two Eulerian models. It manages passive tracers, radioactive decay, photochemistry and aerosol dynamics. The structure of the system includes four independent levels with data management, physical parameterizations, numerical solvers and high-level methods such as data assimilation. This enables sensitivity and uncertainty analysis, primarily through multimodel approaches. On top of the models, drivers implement advanced methods such as model coupling or data assimilation.
Intercomparison of ground-based ozone and NO2 measurements during the MANTRA 2004 campaign

The MANTRA (Middle Atmosphere Nitrogen TRend Assessment) 2004 campaign took place in Vanscoy, Saskatchewan, Canada (52° N, 107° W) from 3 August to 15 September, 2004. In support of the main balloon launch, a suite of five zenith-sky and direct-Sun-viewing UV-visible ground-based spectrometers was deployed, primarily measuring ozone and NO2 total columns. Three Fourier transform spectrometers (FTSs) that were part of the balloon payload also performed ground-based measurements of several species, including ozone. Ground-based measurements of ozone and NO2 differential slant column densities from the zenith-viewing UV-visible instruments are presented herein. They are found to partially agree within NDACC (Network for the Detection of Atmospheric Composition Change) standards for instruments certified for process studies and satellite validation. Vertical column densities of ozone from the zenith-sky UV-visible instruments, the FTSs, a Brewer spectrophotometer, and ozonesondes are compared, and found to agree within the combined error estimates of the instruments (15%). NO2 vertical column densities from two of the UV-visible instruments are compared, and are also found to agree within combined error (15%).
Intercontinental transport of pollution and dust aerosols: implications for regional air quality

We use the global model GOCART to examine the impact of pollution and dust aerosols emitted from their major sources on surface fine particulate matter concentrations at regional and hemispheric scales. Focusing on the North America region in 2001, we use measurements from the IMPROVE network in the United States to evaluate the model-simulated surface concentrations of the "reconstructed fine mass" (RCFM) and its components of ammonium sulfate, black carbon (BC), organic matter (OM), and fine mode dust. We then quantify the RCFM budget in terms of the RCFM chemical composition, source type, and region of origin to find that in the eastern U.S., ammonium sulfate is the dominant RCFM component (~60%) whereas in the western U.S., dust and OM are just as important as sulfate but have considerable seasonal variations, especially in the NW. On an annual average, pollution aerosol (defined as aerosols from fuel combustion for industrial and transportation uses) from North America accounts for 65–70% of the surface RCFM in the eastern U.S. and for a lower proportion of 30–40% in the western U.S.; by contrast, pollution from outside of North America contributes to just 2–6% (~0.2 μg m−3) of the total RCFM over the U.S. In comparison, long-range transport of dust brings 3 to 4 times more fine particles than the transport of pollution to the U.S. (0.5–0.8 μg m−3 on an annual average) with a maximum influence in spring and over the NW. Of the major pollution regions, Europe has the largest potential to affect the surface aerosol concentrations in other continents due to its shorter distance from receptor continents and its larger fraction of sulfate-producing precursor gas in the outflow. With the IPCC emission scenario for the year 2000, we find that European emissions increase levels of ammonium sulfate by 1–5 μg m−3 over the surface of northern Africa and western Asia, and its contribution to eastern Asia (≥0.2 μg m−3) is twice as much as the Asian contribution to North America. Asia and North America pollution emissions exert strong impacts on their neighboring oceans, but their influences over other continents are relatively small (≤10%) due to long traveling distances across the oceans and efficient removal during transport. Among the major dust source regions, Asia displays a significant influence over large areas in the northern hemisphere except over the North Atlantic and the tropics, where African dust dominates. We also notice that the African dust and European pollution can travel eastward through a pathway spanning across Asia and North Pacific to western North America; such a pathway is difficult to detect because these aerosols usually merge and travel together with Asian dust and pollution labeled as "Asian outflow".