ALBERT

Description: 〈b〉Syn- and post-orogenic exhumation of metamorphic rocks in North Aegean〈/b〉〈br〉 R. Lacassin, N. Arnaud, P. H. Leloup, R. Armijo, and B. Meyer〈br〉 eEarth, 2, 51-63, doi:10.5194/ee-2-51-2007, 2007〈br〉 The Olympos-Ossa-Pelion (OOP) ranges, in NW Aegean, encompass Greece highest summit and are located near the extremity of the North Anatolian Fault (NAF). Structural and thermochronological data gathered in the OOP ranges show that the main exhumation of metamorphic nappes occurred in the Eocene, at ca. 43–39 Ma. This early exhumation, associated with ductile, then brittle-ductile normal faulting with northeastward transport, is coeval with orogenic shortening in the close area. Cooling rates, and likely exhumation, have been low between ~40 Ma and ~20 Ma. 〈sup〉40〈/sup〉Ar/〈sup〉39〈/sup〉Ar crystallization ages (between 20 and 15 Ma) appears related to brittle-ductile normal faulting and likely associated with Neogene Aegean back-arc extension. The dating of a diabase dyke, and the geometry of associated brittle jointing, of onshore and offshore active normal faults suggest a shift in extension direction after 4Ma, possibly in relation with the propagation of the NAF in northern Aegean.

Description: 〈b〉Syn- and post-orogenic exhumation of metamorphic rocks in North Aegean〈/b〉〈br〉 R. Lacassin, N. Arnaud, P. H. Leloup, R. Armijo, and B. Meyer〈br〉 eEarth, 2, 51-63, doi:10.5194/ee-2-51-2007, 2007〈br〉 The Olympos-Ossa-Pelion (OOP) ranges, in NW Aegean, encompass Greece highest summit and are located near the extremity of the North Anatolian Fault (NAF). Structural and thermochronological data gathered in the OOP ranges show that the main exhumation of metamorphic nappes occurred in the Eocene, at ca. 43–39 Ma. This early exhumation, associated with ductile, then brittle-ductile normal faulting with northeastward transport, is coeval with orogenic shortening in the close area. Cooling rates, and likely exhumation, have been low between ~40 Ma and ~20 Ma. 〈sup〉40〈/sup〉Ar/〈sup〉39〈/sup〉Ar crystallization ages (between 20 and 15 Ma) appears related to brittle-ductile normal faulting and likely associated with Neogene Aegean back-arc extension. The dating of a diabase dyke, and the geometry of associated brittle jointing, of onshore and offshore active normal faults suggest a shift in extension direction after 4Ma, possibly in relation with the propagation of the NAF in northern Aegean.

Description: 〈b〉Impact vesiculation – a new trigger for volcanic bubble growth and degassing〈/b〉〈br〉 D. A. Rothery, J. M. Sumner, O. Spieler, and D. B. Dingwell〈br〉 eEarth Discuss., 2, 151-167, doi:10.5194/eed-2-151-2007, 2007〈br〉 〈b〉Revised manuscript has not been submitted〈/b〉 (discussion: closed, 3 comments)〈br〉 We highlight a potentially important trigger for bubble growth and degassing in volcanic bombs. We have successfully triggered bubble growth in previously unvesiculated samples of silicate melt during experiments to simulate volcanic bomb impact, by firing pellets at, and dropping weights onto, melt samples. We call this phenomenon "impact vesiculation". Further work is required on real volcanic bombs to establish the extent to which impact vesiculation occurs in nature. However, our experiments are sufficient to demonstrate that impact vesiculation is a viable processes and should be borne in mind in analysis of bubble populations and degassing histories of bombs and spatter-fed lava flows. Degassing caused by impact vesiculation can occur only at ground-level, so any attempt to calculate the amount of erupted gas available for transport high into the atmosphere by convection above the source of a fountain-fed lava flow that is based on subtracting the volatile content of fluid inclusions from the volatile content of the resulting lava flow would be an overestimate if significant impact vesiculation has occurred.

Description: 〈b〉Impact vesiculation – a new trigger for volcanic bubble growth and degassing〈/b〉〈br〉 D. A. Rothery, J. M. Sumner, O. Spieler, and D. B. Dingwell〈br〉 eEarth Discuss., 2, 151-167, doi:10.5194/eed-2-151-2007, 2007〈br〉 〈b〉Revised manuscript has not been submitted〈/b〉 (discussion: closed, 3 comments)〈br〉 We highlight a potentially important trigger for bubble growth and degassing in volcanic bombs. We have successfully triggered bubble growth in previously unvesiculated samples of silicate melt during experiments to simulate volcanic bomb impact, by firing pellets at, and dropping weights onto, melt samples. We call this phenomenon "impact vesiculation". Further work is required on real volcanic bombs to establish the extent to which impact vesiculation occurs in nature. However, our experiments are sufficient to demonstrate that impact vesiculation is a viable processes and should be borne in mind in analysis of bubble populations and degassing histories of bombs and spatter-fed lava flows. Degassing caused by impact vesiculation can occur only at ground-level, so any attempt to calculate the amount of erupted gas available for transport high into the atmosphere by convection above the source of a fountain-fed lava flow that is based on subtracting the volatile content of fluid inclusions from the volatile content of the resulting lava flow would be an overestimate if significant impact vesiculation has occurred.

Description: The early Carboniferous (Mississippian) sedimentary succession of the Montagne Noire is subdivided into three major lithostratigraphic units, in ascending order the Montagne Noire Griotte Group (Devonian to Early Tournaisian), the Tournaisian to Viséan Saint-Nazaire Group (with the Lydiennes, Faugères, Colonnes, and Puech Capel Formations, the latter new), and the Laurens Flysch Group (late Viséan). The ammonoid assemblages in these rock units are reviewed. A total of 29 Early Carboniferous ammonoid taxa at species level are determined. The new genus Nigrocyclus n. gen., and the new species Gattendorfia nazairensis n. sp., Globimitoceras albaillei n. sp., and Neogoniatites canovasi n. sp. are described. Die unterkarbonische Abfolge von Sedimentgesteinen in der Montagne Noire wird in drei lithostratigraphische Einheiten untergliedert, von unten nach oben die Montagne Noire Griotte Gruppe (Oberdevon bis Untertournai), die Saint-Nazaire Gruppe des Tournaisium und Viséum (mit den Lydiennes Faugères, Colonnes und Puech Capel Formationen, von denen die letzte neu ist), und der Laurens Flysch Gruppe (Oberviséum). Die Ammonoideen-Vergesellschaftungen in diesen Gesteinen werden revidiert. Insgesamt werden 29 unterkarbonische Ammonoideen-Taxa auf Artebene aufgeführt; neu beschrieben werden die Gattung Nigrocyclus n. gen. sowie die Arten Gattendorfia nazairensis n. sp., Globimitoceras albaillei n. sp. und Neogoniatites canovasi n. sp. doi:10.1002/mmng.200700002

Description: The occurrence of Triodus teberdaensis n. sp. teeth from the Pennsylvanian Tolstiy Bugor Formation (Moscovian) of Karachay-Cherkess Republic is the first evidence of xenacanthid remains from the Caucasus. The new species was found in carbonate sediments interpreted as resulting from short-term transgressions during the Pennsylvanian regressive phase – further evidence that xenacanthids, predominantly adapted to freshwater, have also lived in marine environments. Das Auftreten von Zähnen des Triodus teberdaensis n. sp. in der oberkarbonischen Tolstiy Bugor Formation (Moscovium) von Karatschai-Tscherkessien ist der erste Nachweis xenacanthider Überreste aus dem Kaukasus. Die neue Art wurde in karbonatischen Sedimenten, die als Transgressions-Intervalle innerhalb der globalen Oberkarbon-Regression interpretiert werden, abgelagert – ein Beleg dafür, dass die überwiegend aus Süßwasserablagerungen bekannten Xenacanthiden auch im marinen Milieu lebten. doi:10.1002/mmng.200700004

Description: Elemental carbon (EC), as one of the primary light-absorbing components in the atmosphere, has a significant impact on both regional and global climate. The environmental impacts of EC are strongly dependent on its particle size. Little is known about the size distribution characteristics of EC particles in the ambient environments of China. We here report size distributions of EC in the urban area of Shenzhen in South China. EC consistently exhibited two modes, a fine and a coarse mode. The majority of EC (~80%) in this coastal metropolitan city resided in particles smaller than 3.2 μm in diameter. The fine mode peaked at around either 0.42 μm or 0.75 μm. While the mode at 0.42 μm could be ascribed to fresh vehicular emissions in this region, the mode at 0.75 μm had to be a result of particle growth from smaller EC particles. We made a theoretical investigation of the particle growth processes that were responsible for EC particles to grow from 0.42 μm to 0.75 μm in the atmosphere. Our calculations indicate that the EC peak at 0.75 μm could not be produced through either coagulation or H2SO4 condensation; both were too slow to lead to significant EC growth. Hygroscopic growth was also calculated to be impossible. Instead, addition of sulfate through in-cloud processing was found to be able to significantly grow EC particles to explain the EC peak at 0.75 μm. We also estimated from the EC size distributions the mixing state of EC. In the droplet size, at least 45–60% of EC mass in the summer samples and 68% of EC mass in the winter samples was internally mixed with sulfate as a result of in-cloud processing. Such information on EC needs to be considered in modeling aerosol optical properties in this region. Our results also suggest that the in-cloud processing of primary EC particles could enhance light absorbing capacities through mixing EC and sulfate.

Description: An integrated sand and dust storm (SDS) forecasting system – CUACE/Dust (the Chinese Unified Atmospheric Chemistry Environment for Dust) has been developed, which consists of a comprehensive dust aerosol module with emission, dry/wet depositions and other atmospheric dynamic processes, and a data assimilation system (DAS) using observational data from the CMA (China Meteorological Administration) ground dust monitoring network and retrieved dust information from a Chinese geostationary satellite – FY-2C. This is the first time that a combination of surface network observations and satellite retrievals of the dust aerosol has been successfully used in the real time operational forecasts in East Asia through a DAS. During its application for the operational SDS forecasts in East Asia for spring 2006, this system captured the major 31 SDS episodes observed by both surface and satellite observations. Analysis shows that the seasonal mean threat score (TS) for 0–24 h forecast over the East Asia in spring 2006 increased from 0.22 to 0.31 by using the DAS, a 41% enhancement. The time series of the forecasted dust concentrations for a number of representative stations for the whole spring 2006 were also evaluated against the surface PM10 monitoring data, showing a very good agreement in terms of the SDS timing and magnitudes near source regions where dust aerosols dominate. This is a summary paper for a special issue of ACP featuring the development and results of the forecasting system.

Description: Chemical and physical processes, such as heterogeneous chemical reactions, light scattering, and metamorphism occur in the natural snowpack. To model these processes in the snowpack, the specific surface area (SSA) is a key parameter. In this study, two methods, computed tomography and methane adsorption, which have intrinsically different spatial resolutions –molecular and 30 μm, respectively – were used to determine the SSA of identical natural snow samples. The two methods give identical results, with an uncertainty of 3%. This implies that the surface of natural snow is smooth up to a scale of about 30 μm and that for optical methods a voxel size of 10 μm is sufficient to capture all structural features of natural snow. This smoothness can be physically explained by calculating sublimation and surface diffusion on the snow particles. The methane adsorption method is superior to computed tomography for very fresh snow, but thin layers typical for natural snowpacks can not be resolved. Computed tomography can measure SSA in layers of less than 1 mm thickness, and is therefore advantageous in layered snowpacks.

Description: Secondary organic aerosol (SOA) formation from the photooxidation of one monoterpene (α-pinene) and two sesquiterpenes (longifolene and aromadendrene) is investigated in the Caltech environmental chambers. The effect of NOx on SOA formation for these biogenic hydrocarbons is evaluated by performing photooxidation experiments under varying NOx conditions. The NOx dependence of α-pinene SOA formation follows the same trend as that observed previously for a number of SOA precursors, including isoprene, in which SOA yield (defined as the ratio of the mass of organic aerosol formed to the mass of parent hydrocarbon reacted) decreases as NOx level increases. The NOx dependence of SOA yield for the sesquiterpenes, longifolene and aromadendrene, however, differs from that determined for isoprene and α-pinene; the aerosol yield under high-NOx conditions substantially exceeds that under low-NOx conditions. The reversal of the NOx dependence of SOA formation for the sesquiterpenes is consistent with formation of relatively low-volatility organic nitrates, and/or the isomerization of large alkoxy radicals leading to less volatile products. Analysis of the aerosol chemical composition for longifolene confirms the presence of organic nitrates under high-NOx conditions. Consequently the formation of SOA from certain biogenic hydrocarbons such as sesquiterpenes (and possibly large anthropogenic hydrocarbons as well) may be more efficient in polluted air.

Description: The species and chemistry responsible for secondary organic aerosol (SOA) formation remain highly uncertain. Laboratory studies of the oxidation of individual, high-flux SOA precursors do not lead to particles with mass spectra (MS) matching those of ambient aged organic material. And, the complexity of real organic particles challenges efforts to identify their chemical origins. We have previously hypothesized that SOA can form from the atmospheric oxidation of a large suite of precursors with varying vapor pressures. Here, we support this hypothesis by using an aerosol mass spectrometer to track the chemical evolution of diesel exhaust as it is photochemically oxidized in an environmental chamber. With explicit knowledge of the condensed-phase MS of the primary emissions from our engine, we are able to decompose each recorded MS into contributing primary and secondary spectra throughout the experiment. We find that the SOA MS becomes increasingly oxidized as a function of time, eventually reaching a final MS that closely resembles that of ambient aged organic particulate matter. This observation is consistent with the idea that lower vapor pressure, semi-volatile organic emissions can form condensable products with fewer generations of oxidation, and therefore, they form relatively less oxidized SOA very quickly.

Description: The formation of formaldehyde via hydrogen atom transfer from the methoxy radical to molecular oxygen is a key step in the atmospheric photochemical oxidation of methane, and in the propagation of deuterium from methane to molecular hydrogen. We report the results of the first investigation of the branching ratio for HCHO and HCDO formation in the CH2DO+O2 reaction. Labeled methoxy radicals (CH2DO) were generated in a photochemical reactor by photolysis of CH2DONO. HCHO and HCDO concentrations were measured using FTIR spectroscopy. Significant deuterium enrichment was seen in the formaldehyde product, from which we derive a branching ratio of 88.2±1.1% for HCDO and 11.8±1.1% for HCHO. The implications of this fractionation on the propagation of deuterium in the atmosphere are discussed.

Description: The chemistry climate model ECHAM5/MESSy1 (E5/M1) in a setup extending from the surface to 80 km with a vertical resolution of about 600 m near the tropopause with nudged tropospheric meteorology allows a direct comparison with satellite data of chemical species at the same time and location. Here we present results out of a transient 10 years simulation for the period of the Antarctic vortex split in September 2002, where data of MIPAS on the ENVISAT-satellite are available. For the first time this satellite instrument opens the opportunity, to evaluate all stratospheric nitrogen containing species simultaneously with a good global coverage, including the source gas N2O which allows an estimate for NOx-production in the stratosphere. We show correlations between simulated and observed species in the altitude region between 10 and 50 hpa for different latitude belts, together with the Probability Density Functions (PDFs) of model results and observations. This is supplemented by global charts on pressure levels showing the satellite data and the simulated data sampled at the same time and location. We demonstrate that the model in most cases captures the partitioning in the nitrogen family, the diurnal cycles and the spatial distribution within experimental uncertainty. There appears to be, however, a problem to reproduce the observed nighttime partitioning between N2O5 and NO2 in the middle stratosphere.

Description: We investigate the extent to which commonly considered quantities, based on total column ozone observations and simulations, are applicable as measures of ozone loss in the polar vortices. Such quantities have been used frequently in ozone assessments by the World Meteorological Organization (WMO) and to assess the performance of chemistry-climate models. The most commonly considered quantity is monthly mean column ozone poleward of a latitude of 63° in spring. For the Arctic, these monthly means were found to be insensitive to the exact choice of the latitude threshold, unlike the Antarctic where greater sensitivity was found. Choosing a threshold based on the location of the transport barrier at the vortex boundary instead of geometric latitude led to a roughly similar year-to-year variability of the monthly means, but in particular years deviations of several tens of Dobson units occurred. Moreover, the minimum of daily total ozone minima poleward of a particular latitude, another popular measure, is debatable, insofar as it relies on one single measurement or model grid point. For Arctic conditions, this minimum value occurred often in air outside polar vortex, both in the observations and in a chemistry-climate model. As a result, we recommend that the minimum of daily minima no longer be used when comparing polar ozone loss in observations and models. As a possible alternative, we suggest considering the minimum of daily average total ozone poleward of a particular equivalent latitude (or in the vortex) in spring. This definition both obviates relying on one single data point and reduces the impact of year-to-year variability in the Arctic vortex breakup on ozone loss measures. However, compact relations of such simple measures with meteorological quantities that describe the potential for polar heterogeneous chlorine activation and thus ozone loss were not found. Therefore, we argue that where possible, more sophisticated measures of chemical polar ozone loss that include additional information to disentangle the impact of transport and chemistry on ozone, should be employed.

Description: Ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements were performed at Tsukuba, Japan (36.1° N, 140.1° E), in November–December 2006. The measured spectra of scattered sunlight are analyzed by DOAS and optimal estimation methods to retrieve the aerosol optical depth (τ) and the vertical profile of the aerosol extinction coefficient (σ) at 476 nm in the lower troposphere. We characterize these retrieved quantities through comparisons with coincident lidar and sky radiometer measurements. The retrieved σ values for layers of 0–1 and 1–2 km agree with lidar data to within 30% and 60%, respectively, for most cases, including partly cloudy conditions. Results similar to σ at 0–1 km are obtained for the retrieved τ values, demonstrating that MAX-DOAS provides the new, unique aerosol dataset in the lower troposphere.

Description: Ozone (O3) profiles recorded over Beijing from 1995 to 2005 by the Measurement of Ozone and Water Vapor by Airbus In-Service Aircraft (MOZAIC) program were analyzed to provide a first climatology of tropospheric O3 over Beijing and the North China Plains (NCPs), one of the most populated and polluted regions in China. A pooled method was adopted in the data analysis to reduce the influence of irregular sampling frequency. The tropospheric O3 over Beijing shows a seasonal and vertical distribution typical of mid-latitude locations in the Northern Hemisphere, but has higher daytime concentrations in the lower troposphere, when compared to New York City, Tokyo, and Paris at similar latitude. The tropospheric O3 over Beijing exhibits a common summer maximum and a winter minimum, with a broad summer maximum in the middle troposphere and a narrower early summer (June) peak in the lower troposphere. Examination of meteorological and satellite data suggests that the lower tropospheric O3 maximum in June is a result of strong photochemical production, transport of regional pollution, and possibly also more intense burnings of biomass in Central-Eastern China. Trajectory analysis indicates that in summer the regional pollution sources from the NCPs, maybe mixed with urban plumes from Beijing, played important roles on the high O3 concentrations in the boundary layer, but had limited impact on the O3 concentrations in the middle troposphere. A comparison of the data recorded before and after 2000 reveals that O3 in the lower troposphere over Beijing had a strong positive trend (approximately 2% per year from 1995 to 2005) in contrast to a flat or a decreasing trend over Tokyo, New York City, and Paris, indicating worsening photochemical pollution in Beijing and the NCPs.

Description: Organic carbon (OC) comprises a large fraction of fine particulate matter (PM2.5) in Mexico City. Daily and select 12-h PM2.5 samples were collected in urban and peripheral sites in Mexico City from 17–30 March 2006. Samples were analyzed for OC and elemental carbon (EC) using thermal-optical filter-based methods. Real-time water-soluble organic carbon (WSOC) was collected at the peripheral site. Organic compounds, particularly molecular markers, were quantified by soxhlet extraction with methanol and dichloromethane, derivitization, and gas chromatography with mass spectrometric detection (GCMS). A chemical mass balance model (CMB) based on molecular marker species was used to determine the relative contribution of major sources to ambient OC. Motor vehicles, including diesel and gasoline, consistently accounted for 47% of OC in the urban area and 31% on the periphery. The daily contribution of biomass burning to OC was highly variable, and ranged from 5–30% at the urban site and 11–50% at the peripheral site. The remaining OC unapportioned to primary sources showed a strong correlation with WSOC and was considered to be secondary in nature. Comparison of temporally resolved OC showed that contributions from primary aerosol sources during daylight hours were not significantly different from nighttime. This study provides quantitative understanding of the important sources of OC during the MILAGRO 2006 field campaign.

Description: Reliable reference profiles and estimates of variability are a necessity for a variety of processes relating to ENVISAT including the development of key aspects and inputs for the operational processor for the Michelson Interferometer for Passive Atmospheric Sounding. MIPAS reference atmospheres have therefore been produced in two forms, namely standard atmospheres for modelling and error analysis for typical atmospheric situations and the IG2 seasonal climatologies for initial guess profiles used as part of the operational processing. The reference states cover 36 species on a common altitude, pressure, and temperature grid from 0 to 120 km, and include both means and estimates of variability (maximum, minimum and one sigma values). This paper describes V3.1 of the standard atmospheres and V4.0 of the IG2 atmospheres which are the current versions of the reference atmospheres. Particular attention is paid to the MIPAS operational geophysical products (pressure/temperature, H2O, O3, CH4, N2O, HNO3 and NO2) and to CO2 whose mixing ratio is required for the retrieval of pressure and temperature. A dynamic representation of CO2 is presented which shows the presence of CO2 gradients in the troposphere and the lower stratosphere. Since these atmospheres have been produced independently of MIPAS data, it is also possible to compare the data to the MIPAS operational products and derive valuable information on both the reference atmospheres and on MIPAS data products themselves. This process has been performed for V4.61/V4.62 data from the year 2003 as part of the MIPAS validation activity. It is demonstrated that the agreement between the MIPAS mean data and the reference atmospheres is very good in mid-latitudes and the tropics, verifying these data to first order. There is also reasonable agreement in standard deviations between the IG2 atmospheres and the corresponding sigmas calculated from the MIPAS data. Knowledge of tropospheric concentrations of CH4 and N2O is used to examine the accuracy of the MIPAS data and their susceptibility to cloud effects. It is shown that for the highest accuracy, MIPAS data should be filtered with cloud index values of 2.5 for N2O and 3.5 for CH4. Once such filtering has been performed, the MIPAS data for these species appear to be accurate to within 10% in the upper troposphere. The use of cloud index data in combination with MIPAS data is recommended for studies of the polar winter stratosphere and the upper troposphere/lower stratosphere.

Description: A differential scanning calorimeter (DSC) was used to explore heterogeneous ice nucleation of emulsified aqueous suspensions of two Arizona test dust (ATD) samples with particle diameters of nominally 0–3 and 0–7 μm, respectively. Aqueous suspensions with ATD concentrations of 0.01–20 wt% have been investigated. The DSC thermograms exhibit a homogeneous and a heterogeneous freezing peak whose intensity ratios vary with the ATD concentration in the aqueous suspensions. Homogeneous freezing temperatures are in good agreement with recent measurements by other techniques. Depending on ATD concentration, heterogeneous ice nucleation occurred at temperatures as high as 256 K or down to the onset of homogeneous ice nucleation (237 K). For ATD-induced ice formation Classical Nucleation Theory (CNT) offers a suitable framework to parameterize nucleation rates as a function of temperature, experimentally determined ATD size, and emulsion droplet volume distributions. The latter two quantities serve to estimate the total heterogeneous surface area present in a droplet, whereas the suitability of an individual heterogeneous site to trigger nucleation is described by the compatibility function (or contact angle) in heterogeneous CNT. The intensity ratio of homogeneous to heterogeneous freezing peaks is in good agreement with the assumption that the ATD particles are randomly distributed amongst the emulsion droplets. The observed dependence of the heterogeneous freezing temperatures on ATD concentrations cannot be described by assuming a constant contact angle for all ATD particles, but requires the ice nucleation efficiency of ATD particles to be (log)normally distributed amongst the particles. Best quantitative agreement is reached when explicitly assuming that high-compatibility sites are rare and that therefore larger particles have on average more and better active sites than smaller ones. This analysis suggests that a particle has to have a diameter of at least 0.1 μm to exhibit on average one active site.

Description: The data assimilation of stratospheric constituents is reviewed. The data assimilation method is introduced, with particular consideration to its application to stratospheric constituent measurements. Differences from meteorological data assimilation are outlined. Historically, two approaches have been used to carry out constituent assimilation. One approach has carried constituent assimilation out as part of a numerical weather prediction system; the other has carried it out in a standalone chemical model, often with a more sophisticated representation of chemical processes. Whereas the aim of the numerical weather prediction approach has been to improve weather forecasts, the aims of the chemical model approach have included providing chemical forecasts and analyses of chemical constituents. A range of constituent assimilation systems developed in these two areas is presented and strengths and weaknesses discussed. The use of stratospheric constituent data assimilation to evaluate models, observations and analyses, and to provide analyses of constituents, monitor ozone, and make ozone forecasts is discussed. Finally, the current state of affairs is assessed, future directions are discussed, and potential key drivers identified.

Description: Elastic and polarization lidar was used to measure the vertical profiles of aerosol backscattering coefficients at wavelengths of 355, 532, 735, and 1064 nm, and the depolarization ratio at 532 nm in order to study the aerosol properties in the free troposphere over Tsukuba, Japan, in 2006. An elevated dust layer was observed at altitudes between 3 and 8.5 km on 1 April during the Asian dust period. The wavelength exponents of the aerosol backscattering coefficient (k) were –0.1 to 0.5, and the depolarization ratio (δp) was 25% for the dust layer, suggesting the predominance of supermicrometer-sized (coarse mode) nonspherical particles. An aerosol layer observed at altitudes between 1.5 and 5 km on 19 October during the less-dust period exhibited the values of k=1.0 to 1.6 and δp=1 to 13%, suggesting the predominance of submicrometer-sized (fine mode) particles. In those layers, the values of k and δp varied with height; they were also negatively correlated, suggesting that the proportion of the coarse nonspherical particles to total particles varied. The particle size distributions estimated from the observed values and the theoretical computation revealed number mode radii of 0.3 &mum; for the coarse mode and 0.1 &mum; for the fine mode, assuming bimodal distribution. These results were consistent with those obtained from the sky-radiometer measurements, although they revealed another mode in the larger radius. The column volume concentration derived from the lidar was 48% lower than that derived from the sky-radiometer on 1 April and 16% lower on 19 October. The optical thickness derived from the lidar was 12% lower than that obtained from the sky-radiometer on 1 April and 29% higher on 19 October. Further case study is necessary to validate the method for estimating aerosol properties based on the lidar measurement.

Description: Using three meteorological reanalyses and three outgoing long-wave radiation (OLR) datasets, we show that the Hadley circulation has a significant poleward expansion of about 2 to 4.5 degrees of latitude since 1979. The three reanalyses along with the MSU data all indicate that the poleward expansion of the Hadley circulation in each hemisphere occurs during its spring and fall seasons. Results from the OLR datasets do not have such seasonality. The expansion of the Hadley circulation implies a poleward expansion of the band of subtropical subsidence, leading to enhanced mid-latitude tropospheric warming and poleward shifts of the subtropical dry zone. This would contribute to an increased frequency of midlatitude droughts in both hemispheres.

Description: In spring 2006 a special meteorological situation occurred in the European Arctic region giving record high levels of air pollution. The synoptic situation resulted in extensive transport of pollution predominantly from agricultural fires in Eastern Europe into the Arctic region and record high air-pollution levels were measured at the Zeppelin observatory at Ny-Ålesund (78°54' N, 11°53' E) in the period from 25 April to 12 May. In the present study we investigate the optical properties of the aerosols from this extreme event and we estimate the radiative forcing of this episode. We examine the aerosol optical properties from the source region and into the European Arctic and explore the evolution of the episode and the changes in the optical properties. A number of sites in Eastern Europe, Northern Scandinavia and Svalbard are included in the study. In addition to AOD measurements, we explored lidar measurements from Minsk, ALOMAR (Arctic Lidar Observatory for Middle Atmosphere Research at Andenes) and Ny-Ålesund. For the AERONET sites included (Minsk, Toravere, Hornsund) we have further studied the evolution of the aerosol size. Importantly, at Svalbard it is consistency between the AERONET measurements and calculations of single scattering albedo based on aerosol chemical composition. We have found strong agreement between the satellite daily MODIS AOD and the ground-based AOD observations. This agreement is crucial for the radiative forcing calculations. We calculate a strong negative radiative forcing for the most polluted days employing the analysed ground based data, MODIS AOD and a multi-stream model for radiative transfer of solar radiation.

Description: A one-dimensional chemical transport model has been developed to investigate the vertical gradients of bromine and iodine compounds in the Antarctic coastal boundary layer. The model has been applied to interpret recent year-round observations of iodine and bromine monoxides (IO and BrO) at Halley Station, Antarctica. The model requires an equivalent I atom flux of ~109 molecule cm−2 s−1 from the snowpack in order to account for the measured IO levels, which are up to 20 ppt during spring. Using the current knowledge of gas-phase iodine chemistry, the model predicts significant gradients in the vertical distribution of iodine species. However, recent ground-based and satellite observations of IO imply that the radical is well-mixed in the boundary layer, indicating a longer than expected atmospheric lifetime for the radical. This can be modelled by including photolysis of the higher iodine oxides (I2O2, I2O3, I2O4 and I2O5), and rapid recycling of HOI and INO3 through sea-salt aerosol. The model also predicts significant concentrations (up to 25 ppt) of I2O5 in the lowest 10 m of the boundary layer, which could lead to the formation of ultrafine iodine oxide aerosols. Heterogeneous chemistry involving sea-salt aerosol is also necessary to account for the vertical profile of BrO. Iodine chemistry causes a large increase (typically more than 3-fold) in the rate of O3 depletion in the BL, compared with bromine chemistry alone. Rapid entrainment of O3 from the free troposphere is required to account for the observation that on occasion there is little O3 depletion at the surface in the presence of high concentrations of IO and BrO. The halogens also cause significant changes to the vertical profiles of HO and HO2 and the NO2/NO ratio. The average Hg0 lifetime against oxidation is also predicted to be about 10 h during springtime. Overall, our results show that halogens profoundly influence the oxidizing capacity of the Antarctic troposphere.

Description: Fast measurements of aerosol and gas-phase constituents coupled with the ISORROPIA-II thermodynamic equilibrium model are used to study the partitioning of semivolatile inorganic species and phase state of Mexico City aerosol sampled at the T1 site during the MILAGRO 2006 campaign. Overall, predicted semivolatile partitioning agrees well with measurements. PM2.5 is insensitive to changes in ammonia but is to acidic semivolatile species. Semi-volatile partitioning equilibrates on a timescale between 6 and 20 min. When the aerosol sulfate-to-nitrate molar ratio is less than 1, predictions improve substantially if the aerosol is assumed to follow the deliquescent phase diagram. Treating crustal species as "equivalent sodium" (rather than explicitly) in the thermodynamic equilibrium calculations introduces important biases in predicted aerosol water uptake, nitrate and ammonium; neglecting crustals further increases errors dramatically. This suggests that explicitly considering crustals in the thermodynamic calculations are required to accurately predict the partitioning and phase state of aerosols.

Description: We present month-long observations of speciated acyl peroxy nitrates (APNs), including PAN, PPN, MPAN, APAN, and the sum of PiBN and PnBN, measured at the Mount Bachelor Observatory (MBO) as part of the INTEX-B collaborative field campaign during spring 2006. APN abundances, measured by thermal dissociation-chemical ionization mass spectrometry (TD-CIMS), are discussed in terms of differing contributions from the boundary layer and the free troposphere and in the context of previous APN measurements in the NE Pacific region. PAN mixing ratios range from 11 to 3955 pptv, with a mean value of 334 pptv for the full measurement period. PPN is linearly correlated with PAN (r2=0.96), with an average abundance of 6.5% relative to PAN; other APNs are generally

Description: We examined the response of surface ozone to future climate change over the eastern United States by performing simulations corresponding to present (1990s) and future (2050s) climates using an integrated model of global climate, tropospheric gas-phase chemistry, and aerosols. A future climate has been imposed using ocean boundary conditions corresponding to the IPCC SRES A2 scenario for the 2050 s decade, resulting in an increase in the global annual-average surface air temperature by 1.7°C, with a 1.4°C increase over the surface layer of the eastern United States. Present-day anthropogenic emissions and CO2/CH4 mixing ratios have been used in both simulations while climate-sensitive natural emissions were allowed to vary with the simulated climate. There is practically zero change in the spatiotemporally averaged ozone mixing ratios predicted over the eastern United States. However, the severity and frequency of ozone episodes over the eastern United States increased due to future climate change, primarily as a result of increased ozone chemical production due to increased natural isoprene emissions. The 95th percentile ozone mixing ratio increased by 5 ppbv and the largest frequency increase occured in the 80–90 ppbv range. The most substantial and statistically significant (p-value

Description: The global chemical transport model Oslo CTM2 has been extended to include the formation, transport and deposition of secondary organic aerosol (SOA). Precursor hydrocarbons which are oxidised to form condensible species include both biogenic species such as terpenes and isoprene, as well as species emitted predominantly by anthropogenic activities (toluene, m-xylene, methylbenzene and other aromatics). A model simulation for 2004 gives an annual global SOA production of approximately 55 Tg. Of this total, 2.5 Tg is found to consist of the oxidation products of anthropogenically emitted hydrocarbons, and about 15 Tg is formed by the oxidation products of isoprene. The global production of SOA is increased to about 76 Tg yr−1 by allowing semi-volatile species to condense on ammonium sulphate aerosol. This brings modelled organic aerosol values closer to those observed, however observations in Europe remain significantly underestimated, raising the possibility of an unaccounted for SOA source. Allowing SOA to form on ammonium sulphate aerosol increases the contribution of anthropogenic SOA from about 4.5% to almost 9% of the total production. The importance of NO3 as an oxidant of SOA precursors is found to vary regionally, causing up to 50%–60% of the total amount of SOA near the surface in polluted regions and less than 25% in more remote areas. This study underscores the need for SOA to be represented in a more realistic way in global aerosol models in order to better reproduce observations of organic aerosol burdens in industrialised and biomass burning regions.

Description: The CCN properties, surfactant characteristics, and droplet growth kinetics of secondary organic aerosol (SOA) formed from the ozonolysis of three parent alkene hydrocarbons (terpinolene, 1-methlycycloheptene and cycloheptene) are explored. Based on measurements of CCN activity, total carbon and inorganic ion concentrations, we estimate the average molar volume of the water-soluble organic component using Köhler Theory Analysis (KTA). The results suggest that the water-soluble organics in the SOA are composed of relatively low molecular weight species, with an effective molar mass less than 200 g mol−1. This finding is consistent with the speciated fraction for some of the SOA, and suggests that KTA can be applied to complex organic aerosol, such as that found in the atmosphere. From measurements of CCN activity and Köhler Theory, we apply a novel method to infer the surface tension at the point of activation; this is used to infer the presence of surface-active organics. It is found that the water-soluble carbon can be surface-active, depressing surface tension 10–15% from that of pure water at concentrations relevant for CCN activation. Although important, this level of surface tension depression is lower than expected for HULIS, which suggest that they are not likely in the SOA examined. In all cases, the CCN exhibit droplet growth kinetics similar to (NH4)2SO4.

Description: Solar irradiance spectral measurements were performed during a total solar eclipse. The spectral effect of the limb darkening to the global, direct irradiance and actinic flux measurements was investigated. This effect leads to wavelength dependent changes in the measured solar spectra showing a much more pronounced decrease in the radiation at the lower wavelengths. Radiative transfer model results were used for the computation of a correction for the total ozone measurements due to the limb darkening. This correction was found too small to explain the large decrease in total ozone column derived from the standard Brewer measurements, which is an artifact in the measured irradiance due to the increasing contribution of diffuse radiation against the decreasing direct irradiance caused by the eclipse. Calculations of the Extraterrestrial spectrum and the effective sun's temperatures, as measured from ground based direct irradiance measurements, showed an artificial change in the calculations of both quantities due to the fact that radiation coming from the visible part of the sun during the eclipse phases differs from the back body radiation described by the Planck's law.

Description: Correctly modeling stratospheric inorganic chlorine (Cly) is crucial for modeling the past and future evolution of stratospheric ozone. However, comparisons of the chemistry climate models used in the latest international assessment of stratospheric ozone depletion have shown large differences in the modeled Cly, with these differences explaining differences in the simulated evolution of ozone over the next century. Here in, we examine the role of transport in determining the simulated Cly using three simulations from the same off-line chemical transport model that have the same lower tropospheric boundary conditions and the same chemical solver, but differing resolution and/or meteorological fields. These simulations show that transport plays a key role in determining the Cly distribution, and that Cly depends on both the time scales and pathways of transport. The time air spends in the stratosphere (e.g., the mean age) is an important transport factor determining stratospheric Cly, but the relationship between mean age and Cly is not simple. Lower stratospheric Cly depends on the fraction of air that has been in the upper stratosphere, and transport differences between models having the same mean age can result in differences in the fraction of organic chlorine converted into Cly. Differences in transport pathways result in differences in vertical profiles of CFCs, and comparisons of observed and modeled CFC profiles provides a stringent test of transport pathways in models.

Description: We describe an estimation technique for biomass burning emissions in South America based on a combination of remote sensing fire products and field observations. For each fire pixel detected by remote sensing, the mass of the emitted tracer is calculated based on field observations of fire properties related to the type of vegetation burning. The burnt area is estimated from the instantaneous fire size retrieved by remote sensing, when available, or from statistical properties of the burn scars. The sources are then spatially and temporally distributed and assimilated daily by the Coupled Aerosol and Tracer Transport model to the Brazilian developments on the Regional Atmospheric Modeling System (CATT-BRAMS) in order to perform the prognostic of related tracer concentrations. Two other biomass burning inventories are simultaneously used to compare the emission strength in terms of the resultant tracer distribution. Several evaluations of the model with the three emission estimations were performed, comparing results with direct measurements of carbon monoxide both near-surface and airborne, as well as remote sensing derived products. Model results with the methodology of estimation introduced in this paper show a relatively good agreement with the direct measurements and MOPITT data product; pointing out the reliability of the model from local to regional scales.

Description: In radiative transfer simulations the simplification of cloud top structure by homogenous assumptions can breed to mistakes in comparison to realistic heterogeneous cloud top structures. This paper examines the influence of cloud top heterogeneity on the radiation at the top of the atmosphere. The use of cloud top measurements with a high temporal resolution allows to analyse small spatial cloud top heterogeneities by using the frozen turbulence assumption for the time – space conversion. Radiative observations are often based on satellite measurements, whereas small spatial structures are not considered in such treatments. A spectral analysis of the cloud top measurements showed slopes of power spectra between –1.8 and –2.0, this values are larger then the spectra of –5/3 which is often applied to generate cloud field variability. The comparison of 3-D radiative transfer results from cloud fields with homogenous and heterogeneous tops have been done for a single wavelength of 0.6 μm. The radiative transfer calculations result in lower albedos for heterogeneous cloud tops. The differences of albedos between heterogeneous and homogeneous cloud top decrease with increasing solar zenith angle. The influence of cloud top variability on radiances is shown. Explicitly in forward direction the reflectances for heterogeneous tops are larger, in backward direction lower. The largest difference of the mean reflectances (mean over cloud field) between homogeneous and heterogeneous cloud top is approximately 0.3, which is 30% of illumination.

Description: 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 demonstrate that the emissions for this event 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.

Description: Cirrus cloud formation is believed to be domi-nated by homogeneous freezing of supercooled liquid aerosols in many instances. Heterogeneous ice nuclei such as mineral dust, metallic, and soot particles, and some crystalline solids within partially soluble aerosols are suspected to modulate cirrus properties. Among those, the role of ubiqui-tous soot particles is perhaps the least understood. Because aviation is a major source of upper tropospheric soot particles, we put emphasis on ice formation in dispersing aircraft plumes. The effect of aircraft soot on cirrus formation in the absence of contrails is highly complex and depends on a wide array of emission and environmental parameters. We use a microphysical-chemical model predicting the formation of internally mixed, soot-containing particles up to two days after emission, and suggest two principal scenarios, both assuming soot particles to be moderate ice nuclei relative to cirrus formation by homogeneous freezing in the presence of few efficient dust ice nuclei: high concentrations of original soot emissions could slightly increase the number of ice crystals; low concentrations of particles originating from coagulation of emitted soot with background aerosols could lead to a significant reduction in ice crystal number. A critical discussion of laboratory experiments reveals that the ice nucleation efficiency of soot particles depends strongly on their source, and, by inference, on atmospheric aging processes. Mass and chemistry of soluble surface coatings appear to be crucial factors. Immersed soot particles tend to be poor ice nuclei, some bare ones nucleate ice at low supersaturations. However, a fundamental understanding of these studies is lacking, rendering extrapolations to atmospheric conditions speculative. In particular, we cannot yet decide which indirect aircraft effect scenario is more plausible, and options suggested to mitigate the problem remain uncertain.

Description: Transport and scavenging of chemical constituents in deep convection is important to understanding the composition of the troposphere and therefore chemistry-climate and air quality issues. High resolution cloud chemistry models have been shown to represent convective processing of trace gases quite well. To improve the representation of sub-grid convective transport and wet deposition in large-scale models, general characteristics, such as species mass flux, from the high resolution cloud chemistry models can be used. However, it is important to understand how these models behave when simulating the same storm. The intercomparison described here examines transport of six species. CO and O3, which are primarily transported, show good agreement among models and compare well with observations. Models that included lightning production of NOx reasonably predict NOx mixing ratios in the anvil compared with observations, but the NOx variability is much larger than that seen for CO and O3. Predicted anvil mixing ratios of the soluble species, HNO3, H2O2, and CH2O, exhibit significant differences among models, attributed to different schemes in these models of cloud processing including the role of the ice phase, the impact of cloud-modified photolysis rates on the chemistry, and the representation of the species chemical reactivity. The lack of measurements of these species in the convective outflow region does not allow us to evaluate the model results with observations.

Description: 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 seasons. 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.

Description: The role of polar stratospheric clouds in polar ozone loss has been well documented. The CALIPSO satellite mission offers a new opportunity to characterize PSCs on spatial and temporal scales previously impossible. A PSC detection algorithm based on a single wavelength threshold approach has been developed for CALIPSO. The method appears to accurately detect PSCs of all opacities, including tenuous clouds, with a very low rate of false positives and few missed clouds. We applied the algorithm to CALIOP data acquired during the 2006 Antarctic winter season from 13 June through 31 October. The spatial and temporal distribution of CALIPSO PSC observations is illustrated with weekly maps of PSC occurrence. The evolution of the 2006 PSC season is depicted by time series of daily PSC frequency as a function of altitude. Comparisons with "virtual" solar occultation data indicate that CALIPSO provides a different view of the PSC season than attained with previous solar occultation satellites. Measurement-based time series of PSC areal coverage and vertically-integrated PSC volume are computed from the CALIOP data. The observed area covered with PSCs is significantly smaller than would be inferred from the commonly used temperature-based proxy TNAT but is similar in magnitude to that inferred from TSTS . The potential of CALIOP measurements for investigating PSC composition is illustrated using combinations of lidar backscatter and volume depolarization for two CALIPSO PSC scenes.

Description: Mineral aerosol is of interest due to its physiochemical impacts on the Earth's atmosphere. However, adsorbed organics could influence the chemical and physical properties of atmospheric mineral particles and alter their impact on the biosphere and climate. In this work, the heterogeneous uptake of a series of small organic acids on the swelling clay, Na-montmorillonite, was studied at 212 K as a function of relative humidity (RH), organic acid pressure and clay mass. A high vacuum chamber equipped with a quadrupole mass spectrometer and a transmission Fourier transform infrared spectrometer was used to detect the gas and condensed phases, respectively. Sub-monolayer coverage of organic acid on montmorillonite was observed under dry conditions and relevant organic acid pressures. However, the organic acid content increased significantly with increasing humidity. Additionally, while the initial uptake efficiency was found to be independent of organic acid pressure, it increased linearly with increasing clay mass. Thus, the small masses studied allow access to the entire surface area of the clay sample with minimal effects due to surface saturation. Results from this study show that the initial uptake efficiency for n-butyric acid on the clay increases by an order of magnitude as the RH is raised from 0% to 45% RH at 212 K while the uptake of formic, acetic and propionic acids increase only slightly at higher humidities. Additionally, the presence of organic acids was found to slightly enhance the water content of the clay above 45% RH. Our results indicate that heterogeneous uptake of organic acids on swelling clay minerals provides an important heterogeneous sink for these species and may modify the cloud forming potential of the clay particles.

Description: We developed a new emission inventory for Asia (Regional Emission inventory in ASia (REAS) Version 1.1) for the period 1980–2020. REAS is the first inventory to integrate historical, present, and future emissions in Asia on the basis of a consistent methodology. We present here emissions in 2000, historical emissions for 1980–2003, and projected emissions for 2010 and 2020 of SO2, NOx, CO, NMVOC, black carbon (BC), and organic carbon (OC) from fuel combustion and industrial sources. Total energy consumption in Asia more than doubled between 1980 and 2003, causing a rapid growth in Asian emissions, by 28% for BC, 30% for OC, 64% for CO, 108% for NMVOC, 119% for SO2, and 176% for NOx. In particular, Chinese NOx emissions showed a marked increase of 280% over 1980 levels, and growth in emissions since 2000 has been extremely high. These increases in China were mainly caused by increases in coal combustion in the power plants and industrial sectors. NMVOC emissions also rapidly increased because of growth in the use of automobiles, solvents, and paints. By contrast, BC, OC, and CO emissions in China showed decreasing trends from 1996 to 2000 because of a reduction in the use of biofuels and coal in the domestic and industry sectors. However, since 2000, Chinese emissions of these species have begun to increase. Thus, the emissions of air pollutants in Asian countries (especially China) showed large temporal variations from 1980–2003. Future emissions in 2010 and 2020 in Asian countries were projected by emission scenarios and from emissions in 2000. For China, we developed three emission scenarios: PSC (policy success case), REF (reference case), and PFC (policy failure case). In the 2020 REF scenario, Asian total emissions of SO2, NOx, and NMVOC were projected to increase substantially by 22%, 44%, and 99%, respectively, over 2000 levels. The 2020 REF scenario showed a modest increase in CO (12%), a lesser increase in BC (1%), and a slight decrease in OC (–5%) compared with 2000 levels. However, it should be noted that Asian total emissions are strongly influenced by the emission scenarios for China.

Description: The paper presents a cloud filtering method for upper tropospheric humidity (UTH) measurements at 183.31±1.00 GHz. The method uses two criteria: The difference between the brightness temperatures at 183.31±7.00 and 183.31±1.00 GHz, and a threshold for the brightness temperature at 183.31±1.00 GHz. The robustness of this cloud filter is demonstrated by a mid-latitudes winter case-study. The paper then studies different biases on UTH climatologies. Clouds are associated with high humidity, therefore the dry bias introduced by cloud filtering is discussed and compared to the wet biases introduced by the clouds radiative effect if no filtering is done. This is done by means of a case study, and by means of a stochastic cloud database with representative statistics for midlatitude conditions. The consistent result is that both cloud wet bias (0.8% RH) and cloud filtering dry bias (–2.4% RH) are modest for microwave data, where the numbers given are for the stochastic cloud dataset. This indicates that for microwave data cloud-filtered UTH and unfiltered UTH can be taken as error bounds for errors due to clouds. This is not possible for the more traditional infrared data, since the radiative effect of clouds is much stronger there. The focus of the paper is on midlatitude data, since atmospheric data to test the filter for that case were readily available. The filter is expected to be applicable also to subtropical and tropical data, but should be further validated with case studies similar to the one presented here for those cases.

Description: The simulation of convection, lightning and subsequent NOx emissions with global atmospheric chemistry models is associated with large uncertainties since these processes are heavily parameterised. Each parameterisation by itself has deficiencies while the combination substantially increases the uncertainties from the individual parameterisations. In this study several combinations of state-of-the-art convection and lightning parameterisations are used in model simulations with the global atmospheric chemistry model ECHAM5/MESSy and are evaluated against lightning observations. A wide range in the spatial and temporal variability of the simulated flash densities is found, attributed to both types of parameterisations. Some combinations perform well, whereas others are hardly applicable. In addition to resolution dependent rescaling parameters, each combination of lightning and convection schemes requires individual scaling to reproduce the observed flash frequencies. The resulting NOx profiles are inter-compared, but definite conclusions about the most realistic profiles can currently not be provided.

Description: Data from a co-located imaging Doppler interferometer and SuperDARN radar recorded since 1996 have been analysed in a consistent manner to determine daily mean winds and tides in the upper mesosphere. By comparing only days when both techniques were recording good quality data it is shown that the SuperDARN radar winds and tides correlate best with the IDI height bin 90–95 km. On timescales of one hour the winds derived from each technique correlate poorly, whereas the daily mean winds are in much better agreement suggesting that the two radars are sensitive to different parts of the gravity wave spectrum. Regression analysis reveals that the observed SuperDARN daily mean meridional wind strength is approximately 65% that recorded by the IDI while the zonal winds are of similar magnitude, in good quantitative agreement with previous studies which have shown contamination to SuperDARN-derived winds due to the significant back lobe of the radar radiation pattern. Climatologically the two techniques observe similar monthly mean winds with the SuperDARN meridional winds suppressed compared to the IDI which tends to record winds more poleward and eastward than those derived by the SuperDARN radar during the summer months, and to be slightly more equatorward during the winter. The 12-h tidal amplitude and phase in both the zonal and meridional components derived from both techniques are in excellent agreement, whereas the 24-h tides are seen much more strongly in the SuperDARN radar, especially in wintertime, with poor phase agreement. Long term comparison of the two techniques reveals a tendency for the IDI meridional winds to be more poleward during solar maximum especially during summer time; an effect which is not reproduced in the meridional winds derived from the SuperDARN radar. These results are discussed in the context of previous studies to independently determine the veracity of each technique.

Description: Subvisible cirrus (SVC) clouds are often observed within the tropical tropopause layer (TTL) and have been shown to have a significant impact on the earth radiation budget. The Costa Rica Aura Validation Experiment (CR-AVE) sponsored by the National Aeronautics and Space Administration (NASA) took place near San Jose, Costa Rica from 14 January–15 February 2006. The NASA WB-57F sampled SVC in the TTL from −75°C to −90°C with an improved set of cloud particle probes. The first digital images of ice particles in the TTL are compared with replicator images of ice particles collected in 1973 by a WB-57F in the TTL. The newer measurements reveal larger particles, on the order of 100 μm compared with

Description: Continuous ambient measurements with aerosol time-of-flight mass spectrometry (ATOFMS) were carried out in an industrial/residential section in the northern part of Mexico City as part of the Mexico City Metropolitan Area – 2006 campaign (MCMA-2006) between 7–27 March, 2006. Biomass and organic carbon (OC) particle types were found to dominate the accumulation mode both day and night. The concentrations of both organic carbon and biomass particles were roughly equal early in the morning, but biomass became the largest contributor to the accumulation mode mass from the late morning until early evening. The diurnal pattern can be attributed to aging and/or a change in meteorology. Fresh elemental carbon (EC) particles were observed during rush hour. The majority of the EC particles were mixed with nitrate, sulfate, organic carbon and potassium. Submicron particles from industrial sources in the northeast were composed of an internal mixture of Pb, Zn, EC and Cl and peaked early in the morning. A unique nitrogen-containing organic (NOC) particle type was observed, and is hypothesized to be from industrial emissions based on the temporal profile and back trajectory analysis. This study provides unique insights into the real-time changes in single particle mixing state as a function of size and time for aerosols in Mexico City. These new findings indicate that biomass burning and industrial operations make significant contributions to particles in Mexico City. These sources have received relatively little attention in previous intensive field campaigns.

Description: In this paper we present an approach for the statistical analysis of multi-model ensemble results. The models considered here are operational long-range transport and dispersion models, also used for the real-time simulation of pollutant dispersion or the accidental release of radioactive nuclides. We first introduce the theoretical basis (with its roots sinking into the Bayes theorem) and then apply this approach to the analysis of model results obtained during the ETEX-1 exercise. We recover some interesting results, supporting the heuristic approach called "median model", originally introduced in Galmarini et al. (2004a, b). This approach also provides a way to systematically reduce (and quantify) model uncertainties, thus supporting the decision-making process and/or regulatory-purpose activities in a very effective manner.

Description: Snow on the ground is a complex multiphase photochemical reactor that dramatically modifies the chemical composition of the overlying atmosphere. A quantitative description of the emissions of reactive gases by snow requires the knowledge of snow physical properties. This overview details our current understanding of how those physical properties relevant to snow photochemistry vary during snow metamorphism. Properties discussed are density, specific surface area, optical properties, thermal conductivity, permeability and gas diffusivity. Inasmuch as possible, equations to parameterize these properties as a function of climatic variables are proposed, based on field measurements, laboratory experiments and theory. The potential of remote sensing methods to obtain information on some snow physical variables such as grain size, liquid water content and snow depth are discussed. The possibilities for and difficulties of building a snow photochemistry model by adapting current snow physics models are explored. Elaborate snow physics models already exist, and including variables of particular interest to snow photochemistry such as light fluxes and specific surface area appears possible. On the other hand, understanding the nature and location of reactive molecules in snow seems to be the greatest difficulty modelers will have to face for lack of experimental data, and progress on this aspect will require the detailed study of natural snow samples.

Description: The Michelson Interferometer for Passive Atmospheric Sounding (MIPAS), on-board the European ENVIronmental SATellite (ENVISAT) launched on 1 March 2002, is a middle infrared Fourier Transform spectrometer measuring the atmospheric emission spectrum in limb sounding geometry. The instrument is capable to retrieve the vertical distribution of temperature and trace gases, aiming at the study of climate and atmospheric chemistry and dynamics, and at applications to data assimilation and weather forecasting. MIPAS operated in its standard observation mode for approximately two years, from July 2002 to March 2004, with scans performed at nominal spectral resolution of 0.025 cm−1 and covering the altitude range from the mesosphere to the upper troposphere with relatively high vertical resolution (about 3 km in the stratosphere). Only reduced spectral resolution measurements have been performed subsequently. MIPAS data were re-processed by ESA using updated versions of the Instrument Processing Facility (IPF v4.61 and v4.62) and provided a complete set of level-2 operational products (geo-located vertical profiles of temperature and volume mixing ratio of H2O,O3, HNO3, CH4, N2O and NO2) with quasi continuous and global coverage in the period of MIPAS full spectral resolution mission. In this paper, we report a detailed description of the validation of MIPAS-ENVISAT operational ozone data, that was based on the comparison between MIPAS v4.61 (and, to a lesser extent, v4.62) O3 VMR profiles and a comprehensive set of correlative data, including observations from ozone sondes,ground-based lidar, FTIR and microwave radiometers, remote-sensing and in situ instruments on-board stratospheric aircraft and balloons, concurrent satellite sensors and ozone fields assimilated by the European Center for Medium-range Weather Forecasting. A coordinated effort was carried out, using common criteria for the selection of individual validation data sets, and similar methods for the comparisons. This enabled merging the individual results from a variety of independent reference measurements of proven quality (i.e., well characterised error budget) into an overall evaluation of MIPAS O3 data quality, having both statistical strength and the widest spatial and temporal coverage. Collocated measurements from ozone sondes and ground-based lidar and microwave radiometers of the Network for Detection Atmospheric Composition Change (NDACC) were selected to carry out comparisons with time series of MIPAS O3 partial columns and to identify groups of stations and time periods with a uniform pattern of ozone differences, that were subsequently used for a vertically resolved statistical analysis. The results of the comparison are classified according to synoptic and regional systems and to altitude intervals, showing a generally good agreement within the comparison error bars in the upper and middle stratosphere. Significant differences emerge in the lower stratosphere and are only partly explained by the larger contributions of horizontal and vertical smoothing differences and of collocation errors to the total uncertainty. Further results obtained from a purely statistical analysis of the same data set from NDACC ground-based lidar stations, as well as from additional ozone soundings at middle latitudes and from NDACC ground-based FTIR measurements, confirm the validity of MIPAS O3 profiles down to the lower stratosphere, with evidence of larger discrepancies at the lowest altitudes. The validation against O3 VMR profiles using collocated observations performed by other satellite sensors (SAGE II, POAM III, ODIN-SMR, ACE-FTS, HALOE, GOME) and ECMWF assimilated ozone fields leads to consistent results, that are to a great extent compatible with those obtained from the comparison with ground-based measurements. Excellent agreement in the full vertical range of the comparison is shown with respect to collocated ozone data from stratospheric aircraft and balloon instruments, that was mostly obtained in very good spatial and temporal coincidence with MIPAS scans. This might suggest that the larger differences observed in the upper troposphere and lowermost stratosphere with respect to collocated ground-based and satellite O3 data are only partly due to a degradation of MIPAS data quality. They should be rather largely ascribed to the natural variability of these altitude regions and to other components of the comparison errors. By combining the results of this large number of validation data sets we derived a general assessment of MIPAS v4.61 and v4.62 ozone data quality. A clear indication of the validity of MIPAS O3 vertical profiles is obtained for most of the stratosphere, where the mean relative difference with the individual correlative data sets is always lower than 10%. Furthermore, these differences always fall within the combined systematic error (from 1 hPa to 50 hPa) and the standard deviation is fully consistent with the random error of the comparison (from 1 hPa to ~30–40 hPa). A degradation in the quality of the agreement is generally observed in the lower stratosphere and upper troposphere, with biases up to 25% at 100 hPa and standard deviation of the global mean differences up to three times larger than the combined random error in the range 50–100 hPa. The larger differences observed at the bottom end of MIPAS retrieved profiles can be associated, as already noticed, to the effects of stronger atmospheric gradients in the UTLS that are perceived differently by the various measurement techniques. However, further components that may degrade the results of the comparison at lower altitudes can be identified as potentially including cloud contamination, which is likely not to have been fully filtered using the current settings of the MIPAS cloud detection algorithm, and in the linear approximation of the forward model that was used for the climatological estimate of systematic error components. The latter, when affecting systematic contributions with a random variability over the spatial and temporal scales of global averages, might result in an underestimation of the random error of the comparison and add up to other error sources, such as the possible underestimates of the p and T error propagation based on the assumption of a 1 K and 2% uncertainties, respectively, on MIPAS temperature and pressure retrievals. At pressure lower than 1 hPa, only a small fraction of the selected validation data set provides correlative ozone data of adequate quality and it is difficult to derive quantitative conclusions about the performance of MIPAS O3 retrieval for the topmost layers.

Description: Optimal estimation theory is used to retrieve the absolute Na density profiles in the mesosphere/lower thermosphere from limb-scanning measurements of the Na radiance at 589 nm in the dayglow. Two years of observations (2003 and 2004), recorded by the OSIRIS spectrometer on the Odin satellite, have been analysed to yield the seasonal and latitudinal variation of the Na layer column abundance, peak height, and peak width. The layer shows little seasonal variation at low latitudes, but the winter/summer ratio increases from a factor of ~3 at mid-latitudes to ~10 in the polar regions. Comparison of the measurements made at about 06:00 and 18:00 LT shows little diurnal variation in the layer, apart from the equatorial region where, during the equinoxes, there is a two-fold increase in Na density below 94 km between morning and evening. This is most likely caused by the strong downward wind produced by the diurnal tide between ~02:00 and 10:00 LT. The dramatic removal of Na below 85 km at latitudes above 50° during summer is explained by the uptake of sodium species on the ice surfaces of polar mesospheric clouds, which were simultaneously observed by the Odin satellite.

Description: The demand for intercontinental transportation is increasing and people are requesting short travel times, which supersonic air transportation would enable. However, besides noise and sonic boom issues, which we are not referring to in this investigation, emissions from supersonic aircraft are known to alter the atmospheric composition, in particular the ozone layer, and hence affect climate significantly more than subsonic aircraft. Here, we suggest a metric to quantitatively assess different options for supersonic transport with regard to the potential destruction of the ozone layer and climate impacts. Options for fleet size, engine technology (nitrogen oxide emission level), cruising speed, range, and cruising altitude, are analyzed, based on SCENIC emissions scenarios for 2050, which underlay the requirements to be as realistic as possible in terms of e.g. economic markets and profitable market penetration. This methodology is based on a number of atmosphere-chemistry and climate models to reduce model dependencies. The model results differ significantly in terms of the response to a replacement of subsonic aircraft by supersonic aircraft. However, model differences are smaller when comparing the different options for a supersonic fleet. The base scenario, where supersonic aircraft get in service in 2015, a first fleet fully operational in 2025 and a second in 2050, lead in our simulations to a near surface temperature increase in 2050 of around 7 mK and with constant emissions afterwards to around 21 mK in 2100. The related total radiative forcing amounts to 22 mWm²in 2050, with an uncertainty between 9 and 29 mWm². A reduced supersonic cruise altitude or speed (from March 2 to Mach 1.6) reduces both, climate impact and ozone destruction, by around 40%. An increase in the range of the supersonic aircraft leads to more emissions at lower latitudes since more routes to SE Asia are taken into account, which increases ozone depletion, but reduces climate impact compared to the base case.

Description: With the global aerosol-climate model ECHAM5-HAM we investigate the potential influence of organic aerosol originating from the ocean on aerosol mass and chemical composition and the droplet concentration and size of marine clouds. We present sensitivity simulations in which the uptake of organic matter in the marine aerosol is prescribed for each aerosol mode with varying organic mass and mixing state, and with a geographical distribution and seasonality similar to the oceanic emission of dimethyl sulfide. Measurements of aerosol mass and chemical composition serve to evaluate the representativity of the model initializations. Good agreement with the measurements is obtained when organic matter is added to the Aitken, accumulation and coarse modes simultaneously. Representing marine organics in the model leads to higher cloud drop number concentrations, smaller cloud drop effective radii, and a better agreement with remote sensing measurements. The mixing state of the organics and the other aerosol matter, i.e., internal or external depending on the formation process of aerosol organics, is an important factor for this. We estimate that globally about 75 Tg C yr−1 of organic matter from marine origin enters the aerosol phase. An approximate 35% of this occurs through formation of secondary organic aerosol and 65% through emission of primary particles.

Description: Nitric acid (HNO3) is one of the key products that are operationally retrieved by the European Space Agency (ESA) from the emission spectra measured by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) onboard ENVISAT. The product version 4.61/4.62 for the observation period between July 2002 and March 2004 is validated by comparisons with a number of independent observations from ground-based stations, aircraft/balloon campaigns, and satellites. Individual HNO3 profiles of the ESA MIPAS level-2 product show good agreement with those of MIPAS-B and MIPAS-STR (the balloon and aircraft version of MIPAS, respectively), and the balloon-borne infrared spectrometers MkIV and SPIRALE, mostly matching the reference data within the combined instrument error bars. In most cases differences between the correlative measurement pairs are less than 1 ppbv (5–10%) throughout the entire altitude range up to about 38 km (~6 hPa), and below 0.5 ppbv (15–20% or more) above 30 km (~17 hPa). However, differences up to 4 ppbv compared to MkIV have been found at high latitudes in December 2002 in the presence of polar stratospheric clouds. The degree of consistency is further largely affected by the temporal and spatial coincidence, and differences of 2 ppbv may be observed between 22 and 26 km (~50 and 30 hPa) at high latitudes near the vortex boundary, due to large horizontal inhomogeneity of HNO3. Similar features are also observed in the mean differences of the MIPAS ESA HNO3 VMRs with respect to the ground-based FTIR measurements at five stations, aircraft-based SAFIRE-A and ASUR, and the balloon campaign IBEX. The mean relative differences between the MIPAS and FTIR HNO3 partial columns are within ±2%, comparable to the MIPAS systematic error of ~2%. %This should be the systematic error without spectroscopy since the ground-based data were retrieved using the same version of the HITRAN database. For the vertical profiles, the biases between the MIPAS and FTIR data are generally below 10% in the altitudes of 10 to 30 km. The MIPAS and SAFIRE chem{HNO_3} data generally match within their total error bars for the mid and high latitude flights, despite the larger atmospheric inhomogeneities that characterize the measurement scenario at higher latitudes. The MIPAS and ASUR comparison reveals generally good agreements better than 10–13% at 20–34 km. The MIPAS and IBEX measurements agree reasonably well (mean relative differences within ±15%) between 17 and 32 km. Statistical comparisons of the MIPAS profiles correlated with those of Odin/SMR, ILAS-II, and ACE-FTS generally show good consistency. The mean differences averaged over individual latitude bands or all bands are within the combined instrument errors, and generally within 1, 0.5, and 0.3 ppbv between 10 and 40 km (~260 and 4.5 hPa) for Odin/SMR, ILAS-II, and ACE-FTS, respectively. The standard deviations of the differences are between 1 to 2 ppbv. The standard deviations for the satellite comparisons and for almost all other comparisons are generally larger than the estimated measurement uncertainty. This is associated with the temporal and spatial coincidence error and the horizontal smoothing error which are not taken into account in our error budget. Both errors become large when the spatial variability of the target molecule is high.

Description: Stratospheric O3 profiles obtained by the satellite limb sounders Aura/MLS, ENVISAT/MIPAS, ENVISAT/GOMOS, SAGE-II, SAGE-III, UARS/HALOE are compared to coincident O3 profiles of the ground-based microwave radiometer SOMORA in Switzerland. Data from the various measurement techniques are within 10% at altitudes below 45 km. At altitudes 45–60 km, the relative O3 differences are within a range of 50% Larger deviations at upper altitudes are attributed to larger relative measurement errors caused by lower O3 concentrations. The spatiotemporal characteristics of the O3 differences (satellite – ground station) are investigated by analyzing about 5000 coincident profile pairs of Aura/MLS (retrieval version 1.5) and SOMORA. The probability density function of the O3 differences is represented by a Gaussian normal distribution (except for profile pairs around the stratopause at noon). The dependence of the O3 differences on the horizontal distance between the sounding volumes of Aura/MLS and SOMORA is derived. While the mean bias (Aura/MLS – SOMORA) is constant with increasing horizontal distance (up to 800 km), the standard deviation of the O3 differences increases from around 8 to 12% in the mid-stratosphere. Geographical maps yield azimuthal dependences and horizontal gradients of the O3 difference field around the SOMORA ground station. Coherent oscillations of O3 are present in the time series of Aura/MLS and SOMORA (e.g., due to traveling planetary waves). Ground- and space-based measurements often complement one another. We introduce the double differencing technique which allows both the cross-validation of two satellites by means of a ground station and the cross-validation of distant ground stations by means of one satellite. Temporal atmospheric noise in the geographical ozone map over Payerne is significantly reduced by combination of the data from SOMORA and Aura/MLS. These analyses illustrate the synergy between ground-based and space-based measurements.

Description: The analysis of the atmospheric isotopologic water vapour composition provides valuable information on many climate, chemical and atmospheric circulation processes. The remote-sensing of the water isotopologues remains a challenge, which is enhanced by the large and fast variations of their spatial distributions. This paper presents for the first time the simultaneous retrieval of global distributions of the main water isotopologues (i.e.~H216O, H218O, HOD) and their ratios. The results are obtained by exploiting the high resolution infrared spectra recorded by the Interferometric Monitor for Greenhouse gases (IMG) instrument, which operated in the nadir geometry onboard the ADEOS satellite between 1996 and 1997. The retrievals are performed on a series of cloud-free radiance measurements in two atmospheric windows (1205–1228 cm–1; 2004–2032 cm–1) using a line-by-line radiative transfer model and an inversion procedure based on the Optimal Estimation Method (OEM). Characterizations in terms of vertical sensitivity and error budget are provided. A relatively high vertical resolution is achieved for H216O (~4–5 km), and we show that the retrieved profiles are in good agreement with local sonde measurements, representative of different latitudes. The retrieved global distributions of H216O, H218O, HOD and their ratios are also found to be consistent with previous experimental studies and models. The ocean-earth difference, the latitudinal and vertical dependence of the water vapour amount and the isotopologic depletion are notably well reproduced. Others trends, possibly related to smaller scales variations in the vertical profiles are also discussed. Despite the difficulties encountered for computing accurately the isotopologic ratios, our results demonstrate the ability of the infrared nadir sounding for monitoring atmospheric isotopologic water vapour distributions on a global scale.

Description: The sensitivity of an operational CO2-responsive land surface model (the ISBA-A-gs model of Météo-France) to the atmospheric CO2 concentration, [CO2], is investigated for 3 vegetation types (winter wheat, irrigated corn, coniferous forest). Past (1960) and future (2050) scenarios of [CO2] corresponding to 320 ppm and 550 ppm, respectively, are explored. The sensitivity study is performed for 4 annual cycles presenting contrasting conditions of precipitation regime and air temperature, based on continuous measurements performed on the SMOSREX site near Toulouse, in southwestern France. A significant CO2-driven reduction of canopy conductance is simulated for the irrigated corn and the coniferous forest. The reduction is particularly large for corn, from 2000 to 2050 (–18%), and triggers a drop in optimum irrigation (–30 mm y−1). In the case of wheat, the response is more complex, with an equal occurrence of enhanced or reduced canopy conductance.

Description: Three independent single particle mass spectrometers measured Pb in individual aerosol particles. These data provide unprecedented sensitivity and statistical significance for the measurement of Pb in single particles. This paper explores the reasons for the frequency of Pb in fine particles now that most gasoline is unleaded. Trace amounts of Pb were found in 5 to 25% of 250 to 3000 nm diameter particles sampled by both aircraft and surface instruments in the eastern and western United States. Over 5% of particles at a mountain site in Switzerland contained Pb. Particles smaller than 100 nm with high Pb content were also observed by an instrument that was only operated in urban areas. Lead was found on all types of particles, including Pb present on biomass burning particles from remote fires. Less common particles with high Pb contents contributed a majority of the total amount of Pb. Single particles with high Pb content often also contained alkali metals, Zn, Cu, Sn, As, and Sb. The association of Pb with Zn and other metals is also found in IMPROVE network filter data from surface sites. Sources of airborne Pb in the United States are reviewed for consistency with these data. The frequent appearance of trace Pb is consistent with widespread emissions of fine Pb particles from combustion sources followed by coagulation with larger particles during long-range transport. Industrial sources that directly emit Pb-rich particles also contribute to the observations. Clean regions of the western United States show some transport of Pb from Asia but most Pb over the United States comes from North American sources. Resuspension of Pb from soil contaminated by the years of leaded gasoline was not directly apparent.

Description: In this study, we characterize the CCN activity of the water-soluble organics in biomass burning aerosol. The aerosol after collection upon filters is dissolved in water using sonication. Hydrophobic and hydrophilic components are fractionated from a portion of the original sample using solid phase extraction, and subsequently desalted. The surface tension and CCN activity of these different samples are measured with a KSV CAM 200 goniometer and a DMT Streamwise Thermal Gradient CCN Counter, respectively. The measurements show that the strongest surfactants are isolated in the hydrophobic fraction, while the hydrophilics exhibit negligible surface tension depression. The presence of salts (primarily (NH4)2SO4) in the hydrophobic fraction substantially enhances surface tension depression; their synergistic effects considerably enhance CCN activity, exceeding that of pure (NH4)2SO4. For our analysis, average thermodynamic properties (i.e., molar volume) are determined for samples using our newly developed Köhler Theory Analysis (KTA) method. We have found that, the molar mass of the hydrophilic and hydrophobic aerosol components is estimated to be 87±26 g mol−1 and 780±231 g mol−1, respectively. KTA also suggests that the relative proportion (in moles) of hydrophobic to hydrophilic compounds in the original sample to be 1:3. For the first time, KTA is applied to an aerosol with this level of complexity and displays its potential for providing physically-based constraints for GCM parameterizations of the aerosol indirect effect.

Description: The Convective Storm Initiation Project (CSIP) took place during the summers of 2004 and 2005, centred on the research radar at Chilbolton, UK. Precursors to convective precipitation were studied, using a comprehensive and broad-based range of fieldwork and modelling. The principal aim of CSIP was the detection of the primary and secondary initiation of convective cells. The Universities Facility for Atmospheric Measurements (UFAM) Cessna 182 was used to map temperature and humidity fields over a broad area within and beyond the Chilbolton radar beam. Additionally, air motion was measured using a new turbulence probe, the AIMMS20AQ. The performance of the probe is critically appraised, based on calibrations, test flights and data flights flown during CSIP intensive operating periods. In general, the probe performed well, although some aspects require more careful data interpretation which we describe in detail.

Description: GEM/POPs was developed to simulate the transport, deposition and partitioning of semi-volatile persistent organic pollutants (POPs) in the atmosphere within the framework of Canadian weather forecasting model GEM. In addition to the general processes such as anthropogenic emissions, atmosphere/water and atmosphere/soil exchanges, GEM/POPs incorporates a dynamic aerosol module to provide the aerosol surface areas for the semi-volatile POPs to partition between gaseous and particle phases and a mechanism for particle-bound POPs to be removed. Simulation results of three PCBs (28, 153 and 180) for year 2000 indicate that the model captured the main features of global atmospheric PCBs when compared with observations from EMEP, IADN and Alert stations. The annual averaged concentrations and the fractionation of the three PCBs as a function of latitudes are agreed reasonably well with observations. The impacts of atmospheric aerosols on the transports and partitioning of the three PCBs are reasonably simulated. The ratio of particulate to gaseous PCBs ranges from less than 0.1 for PCB28 to as high as 100 for PCB180, increasing from the warm lower latitudes to the cold high latitudes. Application of GEM/POPs in a study of the global transports and budgets of various PCBs accompanies this paper.

Description: We present the MESSy submodel MECCA-AERO, which simulates both aerosol and gas phase chemistry with the same mechanism. Including the aerosol phase into the chemistry mechanism increases the stiffness of the resulting set of differential equations. The numerical aspects of the approach followed in MECCA-AERO are presented. MECCA-AERO requires input of an aerosol dynamical/microphysical model to provide the aerosol size and particle number information of the modes/bins for which the chemistry is explicitly calculated. Additional precautions are required to avoid the double counting of processes, especially for sulphate in the aerosol dynamical and the chemistry model. This coupling is explained in detail. To illustrate the capabilities of the new aerosol submodel, examples for species usually treated in aerosol dynamical models are shown. The aerosol chemistry as provided by MECCA-AERO is very sumptuous and not readily applicable for long-term simulations, though it provides a reference to evaluate simplified approaches.

Description: The ground-based measurements of the Global Positioning System (GPS) allow estimation of the tropospheric delay along the slanted signal paths through the atmosphere. The meteorological exploitation of such slant delay (SD) observations relies on the hypothesis of azimuthal asymmetry of the information content. This article addresses the validity of the hypothesis. The asymmetric properties of the SD observations and their model counterparts are investigated. In this study, the model counterparts are based on 3-h forecasts of a numerical weather prediction (NWP) model, run with four different horizontal resolutions. The SD observations are compared with their model counterparts with emphasis on cases of high asymmetry in order to see whether the observed asymmetry is a real atmospheric signature. The asymmetric delay component is found to be of the order of a few parts per thousand of the absolute SD value, thus barely exceeding the assumed standard deviation of the SD observation error. However, the observed asymmetric delay components show a statistically significant meteorological signal. Benefit of the asymmetric SD observations is therefore expected to be taken in future, when NWP systems will explicitly represent the small-scale atmospheric features revealed by the SD observations.

Description: There have been numerous recent publications showing that mineral dust might be a good absorber for solar radiation in addition to its capability as cloud condensation nuclei (CCN) and ice forming nuclei (IFN), and could lead to reduced cloud cover and precipitation in the region it presents. This effect is investigated using a cloud model with detailed microphysics of both warm and ice phase processes. The model is initialized using measured distributions and concentration of mineral dust particles. Our results show that when the dust layer with peak concentration appears at the cloud-base height and below 3 km, where the temperature is warmer than –5°C, inhibits the development of cloud particles and precipitation, and together with early activation of larger cloud droplets on giant cloud condensation nuclei, which accelerates drizzle formation through collision coalescence process, reduces the cloud optical depth and albedo. It is also found that only when the dust layer locates at altitudes with temperature colder than –5°C, mineral aerosols can act as effective ice nuclei and intensify the ice-forming processes. Under this condition, the existence of dust layer can either increase or decrease cloud optical depth and albedo, depending on the concentration and chemical composition of the absorbing components, or the time the mineral aerosols suspended in the atmosphere.

Description: Sulfate aerosol produced after injection of sulfur dioxide (SO2) into the stratosphere by volcanic eruptions can trigger climate change. We present new satellite data from the Ozone Monitoring Instrument (OMI) and Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) missions that reveal the composition, structure and longevity of a stratospheric SO2 cloud and derived sulfate layer following a modest eruption (0.2 Tg total SO2) of Soufriere Hills volcano, Montserrat on 20 May 2006. The SO2 cloud alone was tracked for over 3 weeks and a distance of over 20 000 km; unprecedented for an eruption of this size. Derived sulfate aerosol at an altitude of ~20 km had circled the globe by 22 June and remained visible in CALIPSO data until at least 6 July. These synergistic NASA A-Train observations permit a new appreciation of the potential effects of frequent, small-to-moderate volcanic eruptions on stratospheric composition and climate.

Description: At ultraviolet wavelengths the albedo of most natural surfaces is small with the striking exception of snow and ice. Therefore, snow cover is a major challenge for various applications based on radiative transfer modelling. The aim of this work was to determine the characteristic effective UV range surface albedo of various land cover types when covered by snow. First we selected 1 by 1 degree sample regions that met three criteria: the sample region contained dominantly subpixels of only one land cover type according to the 8 km global land cover classification product from the University of Maryland; the average slope of the sample region was less than 2 degrees according to the USGS's HYDRO1K slope data; the sample region had snow cover in March according to the NSIDC Northern Hemisphere weekly snow cover data. Next we generated 1 by 1 degree gridded 360 nm surface albedo data from the Nimbus-7 TOMS Lambertian equivalent reflectivity data, and used them to construct characteristic effective surface albedo distributions for each land cover type. The resulting distributions showed that each land cover type experiences a characteristic range of surface albedo values when covered by snow. The result is explained by the vegetation that extends upward beyond the snow cover and masks the bright snow covered surface.

Description: In the present study, ambient aerosol (PM10) concentrations of elemental carbon (EC), organic carbon (OC), and total carbon (TC) are reported for 12 European rural background sites and two urban background sites following a one-year (1 July 2002–1 July 2003) sampling campaign within the European Monitoring and Evaluation Programme, EMEP (http://www.emep.int/). The purpose of the campaign was to assess the feasibility of performing EC and OC monitoring on a regular basis and to obtain an overview of the spatial and seasonal variability on a regional scale in Europe. Analyses were performed using the thermal-optical transmission (TOT) instrument from Sunset Lab Inc., operating according to a NIOSH derived temperature program. The annual mean mass concentration of EC ranged from 0.17±0.19 μg m−3 (mean ± SD) at Birkenes (Norway) to 1.83±1.32 μg m−3 at Ispra (Italy). The corresponding range for OC was 1.20±1.29 μg m−3 at Mace Head (Ireland) to 7.79±6.80 μg m−3 at Ispra. On average, annual concentrations of EC, OC, and TC were three times higher for rural background sites in Central, Eastern and Southern Europe compared to those situated in the Northern and Western parts of Europe. Wintertime concentrations of EC and OC were higher than those recorded during summer for the majority of the sites. Moderate to high Pearson correlation coefficients (rp) (0.50–0.94) were observed for EC versus OC for the sites investigated. The lowest correlation coefficients were noted for the three Scandinavian sites: Aspvreten (SE), Birkenes (NO), and Virolahti (FI), and the Slovakian site Stara Lesna, and are suggested to reflect biogenic sources, wild and prescribed fires. This suggestion is supported by the fact that higher concentrations of OC are observed for summer compared to winter for these sites. For the rural background sites, total carbonaceous material accounted for 30±9% of PM10, of which 27±9% could be attributed to organic matter (OM) and 3.4±1.0% to elemental matter (EM). OM was found to be more abundant than SO42− for sites reporting both parameters.

Description: During the TROCCINOX field experiments in February–March 2004 and February 2005, airborne in situ measurements of NO, NOy, CO, and O3 mixing ratios and the J(NO2) photolysis rate were carried out in the anvil outflow of thunderstorms over southern Brazil. Both tropical and subtropical thunderstorms were investigated, depending on the location of the South Atlantic convergence zone. Tropical air masses were discriminated from subtropical ones according to the higher equivalent potential temperature (Θe) in the lower and mid troposphere, the higher CO mixing ratio in the mid troposphere, and the lower wind velocity and proper wind direction in the upper troposphere. During thunderstorm anvil penetrations, typically at 20–40 km horizontal scales, NOx mixing ratios were on average enhanced by 0.2–1.6 nmol mol−1. This enhancement was mainly attributed to NOx production by lightning and partly due to upward transport from the NOx-richer boundary layer. In addition, CO mixing ratios were occasionally enhanced, indicating upward transport from the boundary layer. For the first time, the composition of the anvil outflow from a large, long-lived mesoscale convective system (MCS) advected from northern Argentina and Uruguay was investigated in more detail. Over a horizontal scale of about 400 km, NOx, CO and O3 mixing ratios were significantly enhanced in these air masses in the range of 0.6–1.1, 110–140 and 60–70 nmol mol−1, respectively. Analyses from trace gas correlations and a Lagrangian particle dispersion model indicate that polluted air masses, probably from the Buenos Aires urban area and from biomass burning regions, were uplifted by the MCS. Ozone was distinctly enhanced in the aged MCS outflow, due to photochemical production and entrainment of O3-rich air masses from the upper troposphere – lower stratosphere region. The aged MCS outflow was transported to the north, ascended and circulated, driven by the Bolivian High over the Amazon basin. In the observed case, the O3-rich MCS outflow remained over the continent and did not contribute to the South Atlantic ozone maximum.

Description: Impacts of NOx, H2O and aerosol emissions from a projected 2050 aircraft fleet, provided in the EU project SCENIC, are investigated using the Oslo CTM2, a 3-D chemical transport model including comprehensive chemistry for the stratosphere and the troposphere. The aircraft emission scenarios comprise emissions from subsonic and supersonic aircraft. The increases in NOy due to emissions from the mixed fleet are comparable for subsonic (at 11–12 km) and supersonic (at 18–20 km) aircraft, with annual zonal means of 1.35 ppbv and 0.83 ppbv, respectively. H2O increases are also comparable at these altitudes: 630 and 599 ppbv, respectively. The aircraft emissions increase tropospheric ozone by about 10 ppbv in the Northern Hemisphere due to increased ozone production, mainly because of subsonic aircraft. Supersonic aircraft contribute to a reduction of stratospheric ozone due to increased ozone loss at higher altitudes. In the Northern Hemisphere the reduction is about 39 ppbv, but also in the Southern Hemisphere a 22 ppbv stratospheric decrease is modeled due to transport of supersonic aircraft emissions and ozone depleted air. The total ozone column is increased in lower and Northern mid-latitudes, otherwise the increase of ozone loss contributes to a decrease of the total ozone column. Two exceptions are the Northern Hemispheric spring, where the ozone loss increase is small due to transport processes, and tropical latitudes during summer where the effect of subsonic aircraft is low due to a high tropopause. Aerosol particles emitted by aircraft reduce both aircraft and background NOx, more than counterweighting the effect of NOx and H2O aircraft emissions in the stratosphere. Above about 20 km altitude, the NOx (and thus ozone loss) reduction is large enough to give an increase in ozone due to aircraft emissions. This effect is comparable in the Northern and Southern Hemisphere. At 11–20 km altitude, however, ozone production is reduced due to less NOx. Also ClONO2 is increased at this altitude due to enhanced heterogeneous reactions (lowered HCl), and ClO is increased due to less NOx, further enhancing ozone loss in this region. This results in a 14 ppbv further reduction of ozone. Mainly, this results in an increase of the total ozone column due to a decrease in ozone loss caused by the NOx cycle (at the highest altitudes). At the lowermost latitudes, the reduced loss due to the NOx cycle is small. However, ozone production at lower altitudes is reduced and the loss due to ClO is increased, giving a decrease in the total ozone column. Also, at high latitudes during spring the heterogeneous chemistry is more efficient on PSCs, increasing the ozone loss.

Description: We describe the large-scale meteorological conditions that affected atmospheric chemistry over Mexico during March 2006 when several field campaigns were conducted in the region. In-situ and remote-sensing instrumentation was deployed to obtain measurements of wind, temperature, and humidity profiles in the boundary layer and free atmosphere at four primary sampling sites in central Mexico. Several models were run operationally during the field campaign to provide forecasts of the local, regional, and synoptic meteorology as well as the predicted location of the Mexico City pollutant plume for aircraft flight planning purposes. Field campaign measurements and large-scale analyses are used to define three regimes that characterize the overall meteorological conditions: the first regime prior to 14 March, the second regime between 14 and 23 March, and the third regime after 23 March. Mostly sunny and dry conditions with periods of cirrus and marine stratus along the coast occurred during the first regime. The beginning of the second regime was characterized by a sharp increase in humidity over the central plateau and the development of late afternoon convection associated with the passage of a weak cold surge on 14 March. Over the next several days, the atmosphere over the central plateau became drier so that deep convection gradually diminished. The third regime began with the passage of a strong cold surge that lead to humidity, afternoon convection, and precipitation over the central plateau that was higher than during the second regime. The frequency and intensity of fires, as determined by satellite measurements, also diminished significantly after the third cold surge. The synoptic-scale flow patterns that govern the transport of pollutants in the region are described and compared to previous March periods to put the transport into a climatological context. The complex terrain surrounding Mexico City produces local and regional circulations that govern short-range transport; however, the mean synoptic conditions modulate the thermally-driven circulations and on several days the near-surface flow is coupled to the ambient winds aloft.

Description: We present Multi AXis-Differential Optical Absorption Spectroscopy (MAX-DOAS) observations of tropospheric BrO carried out on board the German research vessel Polarstern during the Antarctic winter 2006. Polarstern entered the area of first year sea ice around Antarctica on 24 June 2006 and stayed within this area until 15 August 2006. For the period when the ship cruised inside the first year sea ice belt, enhanced BrO concentrations were almost continuously observed. One interesting exception appeared on 7 July 2006, when the sun elevation angle was 〈 about –2.8° indicating that for low insulation the photolysis of Br2 and/or HOBr is too slow to provide sufficient amounts of Br radicals. Before and after the period inside the first year sea ice belt, typically low BrO concentrations were observed. Our observations indicate that enhanced BrO concentrations around Antarctica exist about one month earlier than observed by satellite instruments. The small BrO concentrations over the open oceans indicate a short atmospheric lifetime of activated bromine without contact to areas of first year sea ice. From detailed radiative transfer simulations we find that MAX-DOAS observations are about one order of magnitude more sensitive to near-surface BrO than satellite observations. In contrast to satellite observations the MAX-DOAS sensitivity hardly decreases for large solar zenith angles and is almost independent from the ground albedo. Thus this technique is very well suited for observations in polar regions close to the solar terminator. Furthermore, combination of both techniques could yield additional information on the vertical distribution of BrO in the lower troposphere.

Description: 222Rn is commonly used as a natural tracer for validating climate models. To improve such models a better source term for 222Rn than currently used is necessary. The aim of this work is to establish a method for mapping this source term by using a commonly measured proxy, the gamma dose rate (GDR). Automatic monitoring of GDR has been networked in 25 European countries by the Institute for Environment and Sustainability at the Joint Research Centre (JRC IES) in Ispra, Italy, using a common data format. We carried out simultaneous measurements of 222Rn flux and GDR at 63 locations in Switzerland, Germany, Finland and Hungary in order to cover a wide range of GDR. Spatial variations in GDR resulted from different radionuclide concentrations in soil forming minerals. A relatively stable fraction (20%) of the total terrestrial GDR originates from the 238U decay series, of which 222Rn is a member. Accordingly, spatial variation in terrestrial GDR was found to describe almost 60% of the spatial variation in 222Rn flux. Furthermore, temporal variation in GDR and 222Rn was found to be correlated. Increasing soil moisture reduces gas diffusivity and the rate of 222Rn flux but it also decreases GDR through increased shielding of photons. Prediction of 222Rn flux through GDR for individual measurement points is imprecise but un-biased. Verification of larger scale prediction showed that estimates of mean 222Rn fluxes were not significantly different from the measured mean values.

Description: The black carbon mass (BCM) of individual, internally mixed aerosol particles was measured with the Single Particle Soot Photometer (SP2) in April of 2003 and 2005. The average BCM, single particle BC mass fraction and BCM equivalent diameter were evaluated with respect to concentrations of carbon monoxide (CO), particle bound polycyclic aromatic hydrocarbons (PPAH) and condensation nuclei (CN). The BCM and CO have matching diurnal trends that are linked to traffic patterns and boundary layer growth. The PPAH reaches a maximum at the same hour as CO and BCM but returns rapidly back to nighttime values within three hours of the peak. The number of particles containing BCM ranges between 10% to 40% of all particles between 200 nm and 700 nm and the BCM is between 4% and 12% of the total mass in this size range. The average BC equivalent mass diameter varies between 300 and 400 nm and reaches its daily minimum value when BCM is a maximum. The BC particles have the thinnest coating of non-light absorbing material during periods of maximum BCM. The scattering and absorption coefficients, Bscat and Babs , derived from the SP2 measurements were compared with direct measurements from a nephelometer and soot photometer. The measured and derived Babs are in close agreement whereas the Bscat comparisons show larger discrepancies in absolute value and daily trends. Even though approximately 40% of the BCM is in particles with diameters smaller than 200 nm, the extinction coefficient is dominated by the BCM in particles larger than this size. The BCM contributes up to 20% of the total extinction in this size range. BCM is emitted at a rate of 1200 metric tons per year in Mexico City, based upon the SP2 measurements and correlations between BCM and CO.

Description: Sun photometer measurements at the AERONET station at the North Sea coast in The Hague (The Netherlands) provide a climatology of optical and physical aerosol properties for the area. Results are presented from the period January 2002 to July 2003. For the analysis and interpretation these data are coupled to chemical aerosol data from a nearby station of the Dutch National Air Quality Network. This network provides PM10 and black carbon concentrations. Meteorological conditions and air mass trajectories are also used. Due to the location close to the coast, the results are strongly dependent on wind direction, i.e.~air mass trajectory. In general the aerosol optical properties are governed by industrial aerosol emitted form various industrial, agricultural and urban areas surrounding the site in almost all directions over land. For maritime air masses industrial aerosols are transported from over the North Sea, whereas very clean air is transported from the NW in clean polar air masses from the North Atlantic. In the winter the effect of the production of sea salt aerosol at high wind speeds is visible in the optical and physical aerosol data. In these cases fine and coarse mode radii are similar to those reported in the literature for marine aerosol. Relations are derived between the Ångström coefficients with both the fine/coarse mode fraction and the ratio of black carbon and PM10.

Description: An optical particle counter (OPC) is used in conjunction with lidar measurements to examine the characteristics of the particle size distribution in cirrus cloud at the tropical tropopause (TT) over Thailand. Of 11 OPC launches, cirrus cloud was detected at 10–15 km high on 7 occasions, cirrus was detected at the TT in 6 cases, and simultaneous OPC and lidar measurements were made on two occasions. Comparison of lidar and OPC measurements reveal that the cloud height of cirrus in the TT varies by several hundred meters over distances of tens kilometers; hence the height is not horizontally uniform. The mode radii of particles constituting the clouds are estimated by lidar and OPC measurements to be less than approximately 10 μm. The regression lines of the particle size distribution with and without cirrus cloud exhibit similar features at equivalent radii of

Description: This study aims to assess the potential and limits of an advanced inversion method to estimate pollutant precursor sources mainly from observations. Ozone, sulphur dioxide, and partly nitrogen oxides observations are taken to infer source strength estimates. As methodology, the four–dimensional variational data assimilation technique has been generalised and employed to include emission rate optimisation, in addition to chemical state estimates as usual objective of data assimilation. To this end, the optimisation space of the variational assimilation system has been complemented by emission rate correction factors of 19 emitted species at each emitting grid point, involving the University of Cologne mesoscale EURAD model. For validation, predictive skills were assessed for an August 1997 ozone episode, comparing forecast performances of pure initial value optimisation, pure emission rate optimisation, and joint emission rate/initial value optimisation. Validation procedures rest on both measurements withheld from data assimilation and prediction skill evaluation of forecasts after the inversion procedures. Results show that excellent improvements can be claimed for sulphur dioxide forecasts, after emission rate optimisation. Significant improvements can be claimed for ozone forecasts after initial value and joint emission rate/initial value optimisation of precursor constituents. The additional benefits applying joint emission rate/initial value optimisation are moderate, and very useful in typical cases, where upwind emission rate optimisation is essential. In consequence of the coarse horizontal model grid resolution of 54 km, applied in this study, comparisons indicate that the inversion improvements can rest on assimilating ozone observations only, as the inclusion of NOx observations does not provide additional forecast skill. Emission estimates were found to be largely independent from initial guesses from emission inventories, demonstrating the potential of the 4D-var method to infer emission rate improvements. The study also points to the need for improved horizontal model resolution to more efficient use of NOx observations.

Description: In this study, ambient atmospheric particulate matter (PM) samples were collected using a size-resolved impactor sampler from three urban sites. The purpose of this study is to gain a better understanding of transformations of aerosol-bound iron as it is processed in the atmosphere. Thus, the aerosol samples were artificially aged to represent long-term transport (10 to 40 days) or short-term transport (1 to 10 days) and were measured for iron at several time points. At each time point, iron was measured in each size fraction using three different techniques; 1) inductively coupled plasma-mass spectrometry (ICPMS) for total iron, 2) x-ray absorbance near edge structure (XANES) spectroscopy for the measurement of total Fe(II) and Fe(III), and 3) a wet-chemical method to measure soluble Fe(II) and Fe(III). Prior to aging, the XANES spectroscopy results show that a majority (〉60% for each size fraction) of the total iron in the PM is in the form of Fe(III). Fe(III) was shown to be a significant fraction of the soluble iron (sometimes 〉 50%), but the relative significance of Fe(III) was found to vary depending on the site. Overall, the total soluble iron depended on the sampling site, but values ranged from less than 1% up to about 18% of the total iron. Over the course of the 40 day aging period, we found moderate changes in the relative Fe(II)/Fe(III) content. A slight increase was noted in the coarse (〉2.5 μm) fraction and a slight decrease in the 0.25 to 0.5 μm fraction. The soluble fraction generally showed (excepting one day) a decrease of soluble Fe(II) prior to 10 days of aging, followed by a relatively constant concentration. In the short-term transport condition, we found that the sub-micron fraction of soluble Fe(II) spikes at 1 to 3 days of aging, then decreases to near the initial value at around 6 to 10 days. Very little change in soluble Fe(II) was observed in the super-micron fraction. These results show that changes in the soluble iron fraction occur within the lifetime of urban aerosols (1–3 days) and, therefore, atmospheric processing can have a large effect on human exposure to soluble iron.

Description: Meteoric smoke particles have been proposed as a key player in the formation and evolution of mesospheric phenomena. Despite their apparent importance still very little are known about these particles. Sounding rockets are used to measure smoke in situ, but aerodynamics has remained a major challenge. Basically, smoke particles are so small that they tend to follow the gas flow around the payload rather than reaching the detector if aerodynamics is not considered carefully in the detector design. So far only indirect evidence for the existence of these smoke particles has been available in the form of measurements of heavy charge carriers. Important questions concern the smoke number density and size distribution as a function of altitude as well as the fraction of charged particles. Therefore, quantitative ways are needed that relate the measured particle population to the atmospheric particle population. In particular, we need to determine the size-dependent, altitude-dependent and charge-dependent detection efficiency for a given instrument design. In this paper, we investigate the aerodynamics for a typical electrostatic detector design. We first quantify the flow field of the background gas, then introduce particles in the flow field and determine their trajectories around the payload structure. We use two different models to trace particles in the flow field, a Continuous motion model and a Brownian motion model. Brownian motion is shown to be of basic importance for the smallest particles. By defining an effective relative cross section we compare different model runs and quantitatively investigate the difference between the two particle motion models. Detection efficiencies are determined for three detector designs, two with ventilation holes to allow airflow through the detector, and one without such ventilation holes. Results from this investigation show that rocket-borne smoke detection with conventional detectors is largely limited to altitudes above 75 km. The flow through a ventilated detector has to be relatively large for there to be an increase in the detection efficiency.

Description: We present a case study of interleaving in the free troposphere of 4 layers of non-tropospheric origin, with emphasis on their residence time in the troposphere. Two layers are stratospheric intrusions at 4.7 and 2.2 km altitude with residence times of about 2 and 6.5 days, respectively. The two other layers at 7 and 3 km altitude were extracted from the maritime planetary boundary layer by warm conveyor belts associated with two extratropical lows and have residence times of about 2 and 5.75 days, respectively. The event took place over Frankfurt (Germany) in February 2002 and was observed by a commercial airliner from the MOZAIC programme with measurements of ozone, carbon monoxide and water vapour. Origins and residence times in the troposphere of these layers are documented with a trajectory and particle dispersion model. The combination of forward and backward simulations of the Lagrangian model allows the period of time during which the residence time can be assessed to be longer, as shown by the capture of the stratospheric-origin signature of the lowest tropopause fold just about to be completely mixed above the planetary boundary layer. This case study is of interest for atmospheric chemistry because it emphasizes the importance of coherent airstreams that produce laminae in the free troposphere and that contribute to the average tropospheric ozone. The interleaving of these 4 layers also provides the conditions for a valuable case study for the validation of global chemistry transport models used to perform tropospheric ozone budgets.

Description: Particulate pollutant exchanges between the streets and the Planetary Boundary Layer (PBL), and their daily evolution linked to human activity were studied in the framework of the LIdar pour la Surveillance de l'AIR (LISAIR) experiment. This program lasted from 10 to 30 May 2005. A synergetic approach combining dedicated active (lidar) and passive (sunphotometer) remote sensors as well as ground based in situ instrumentation (nephelometer, aethalometer and particle sizers) was used to investigate urban aerosol optical properties within Paris. Aerosol complex refractive indices were assessed to be 1.56–0.034i at 355 nm and 1.59–0.040i at 532 nm, thus leading to single-scattering albedo values between 0.80 and 0.88. These retrievals are consistent with soot components in the aerosol arising from traffic exhausts indicating that these pollutants have a radiative impact on climate. We also discussed the influence of relative humidity on aerosol properties. A good agreement was found between vertical extinction profile derived from lidar backscattering signal and retrieved from the coupling between radiosounding and ground in situ measurements.

Description: This paper discusses the variation and validation of the precision, or estimated random error, associated with the ESA Level 2 products from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS). This quantity represents the propagation of the radiometric noise from the spectra through the retrieval process into the Level 2 profile values. The noise itself varies with time, steadily rising between decontamination events, but the Level 2 precision has a greater variation due to the atmospheric temperature which controls the total radiance received. Hence, for all species, the precision varies latitudinally/seasonally with temperature, with a small superimposed temporal structure determined by the degree of ice contamination on the detectors. The precision validation involves comparing two MIPAS retrievals at the intersections of ascending/descending orbits. For 5 days per month of full resolution MIPAS operation, the standard deviation of the matching profile pairs is computed and compared with the precision given in the MIPAS Level 2 data. Even taking into account the propagation of the pressure-temperature retrieval errors into the VMR retrieval, the standard deviation of the matching pairs is usually a factor 1–2 larger than the precision. This is thought to be due to effects such as horizontal inhomogeneity of the atmosphere and instability of the retrieval.

Description: We use limb emission spectra of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) onboard the ENVIronmental SATellite (ENVISAT) to derive the first global distribution of peroxyacetyl nitrate (PAN) in the upper troposphere. PAN is generated in tropospheric air masses polluted by fuel combustion or biomass burning and acts as a reservoir and carrier of NOx in the cold free troposphere. Since PAN exhibits continuum-like broadband structures in the mid-infrared region, we have applied a contiguous analysis window covering the wavenumber region 775–800 cm−1 for retrieval. The interfering species CCl4, HCFC-22, H2O, ClONO2, CH3CCl3 and C2H2 were fitted along with PAN, whereas pre-fitted profiles were used to model the contribution of other contaminants like ozone. Sensitivity tests consisting in retrieval without consideration of PAN have demonstrated the existence of PAN signatures in MIPAS spectra obtained from polluted air masses. The analysed dataset consists of 10 days between 4 October and 1 December 2003. This period covers the end of the biomass burning season in South America and South and East Africa, in which generally large amounts of pollutants are produced and distributed over wide areas in the southern hemispheric free troposphere. Elevated PAN amounts of 200–700 pptv were measured in a large plume extending from Brasil over the Southern Atlantic, Central and South Africa, the South Indian Ocean as far as Australia at altitudes between 8 and 16 km. Enhanced PAN values were also found in a much more restricted area between northern subtropical Africa and India. The most significant northern midlatitude PAN signal in MIPAS data is an area extending at 8 km altitude from China into the Chinese Sea. The average mid and high latitude PAN amounts found at 8 km were around 125 pptv in the northern, but only between 75 and 50 pptv in the southern hemisphere. The PAN distribution found in the southern hemispheric tropics and subtropics is highly correlated with the jointly fitted acetylene (C2H2), which is another pollutant produced by biomass burning, and agrees reasonably well with the CO plume detected during end of September 2003 at the 275 hPa level (~10 km) by the Measurement of Pollution in the Troposphere (MOPITT) instrument on the Terra satellite. Similar southern hemispheric PAN amounts were also observed by previous airborne measurements performed in September/October 1992 and 1996 above the South Atlantic and the South Pacific, respectively.

Description: A physicochemical characterization of the urban fine aerosol (aerosol number size distribution, chemical composition and mass concentrations) in Milan, Barcelona and London is presented in this article. The objective is to obtain a comprehensive picture on the involvement of the microphysical processes of the aerosol dynamic in the: 1) regular evolution of the urban aerosol (daily, weekly and seasonal basis) and in the day-to-day variations (from clean-air to pollution-events), and 2) link between "aerosol chemistry and mass concentrations" with the "number size distribution". The mass concentrations of the fine PM2.5 aerosol exhibit a high correlation with the number concentration of particles 〉100 nm (which only accounts for 100(nm) (attributed to gas-to-particle transformation mechanisms and some primary emissions). Time series of the aerosol DpN diameter (dN/dlogD mode), mass PM2.5 concentrations and number N〉100(nm) concentrations, exhibit correlated day-to-day variations which point to a significant involvement of condensation of semi-volatile compounds during urban pollution events. This agrees with the fact that ammonium-nitrate is the component exhibiting the highest increases from mid-to-high pollution episodes, when the highest DpN increases are observed. The results indicates that "fine PM2.5 particles urban pollution events" tend to occur when condensation processes have made particles grow enough to produce significant concentrations of N〉100(nm). In contrast, because the low contribution of ultrafine particles to the fine aerosol mass concentrations, high "ultrafine particles N100 nm and PM2.5").

Description: We estimated the isoprene and monoterpene source strengths of a pristine tropical forest north of Manaus in the central Amazon Basin using three different micrometeorological flux measurement approaches. During the early dry season campaign of the Cooperative LBA Airborne Regional Experiment (LBA-CLAIRE-2001), a tower-based surface layer gradient (SLG) technique was applied simultaneously with a relaxed eddy accumulation (REA) system. Airborne measurements of vertical profiles within and above the convective boundary layer (CBL) were used to estimate fluxes on a regional scale by application of the mixed layer gradient (MLG) technique. The mean daytime fluxes of organic carbon measured by REA were 2.1 mg C m−2 h−1 for isoprene, 0.20 mg C m−2 h−1 for α-pinene, and 0.39 mg C m−2 h−1 for the sum of monoterpenes. These values are in reasonable agreement with fluxes determined with the SLG approach, which exhibited a higher scatter, as expected for the complex terrain investigated. The observed VOC fluxes are in good agreement with simulations using a single-column chemistry and climate model (SCM). In contrast, the model-derived mixing ratios of VOCs were by far higher than observed, indicating that chemical processes may not be adequately represented in the model. The observed vertical gradients of isoprene and its primary degradation products methyl vinyl ketone (MVK) and methacrolein (MACR) suggest that the oxidation capacity in the tropical CBL is much higher than previously assumed. A simple chemical kinetics model was used to infer OH radical concentrations from the vertical gradients of (MVK+MACR)/isoprene. The estimated range of OH concentrations during the daytime was 3–8×106 molecules cm−3, i.e., an order of magnitude higher than is estimated for the tropical CBL by current state-of-the-art atmospheric chemistry and transport models. The remarkably high OH concentrations were also supported by results of a simple budget analysis, based on the flux-to-lifetime relationship of isoprene within the CBL. Furthermore, VOC fluxes determined with the airborne MLG approach were only in reasonable agreement with those of the tower-based REA and SLG approaches after correction for chemical decay by OH radicals, applying a best estimate OH concentration of 5.5×106 molecules cm−3. The SCM model calculations support relatively high OH concentration estimates after specifically being constrained by the mixing ratios of chemical constituents observed during the campaign. The relevance of the VOC fluxes for the local carbon budget of the tropical rainforest site during the measurements campaign was assessed by comparison with the concurrent CO2 fluxes, estimated by three different methods (eddy correlation, Lagrangian dispersion, and mass budget approach). Depending on the CO2 flux estimate, 1–6% or more of the carbon gained by net ecosystem productivity appeared to be re-emitted through VOC emissions.

Description: Spectral measurements of the aerosol optical depth (AOD) and the Angstrom coefficient were conducted at Thessaloniki, Greece (40.5° N, 22.9° E) between January 1997 and December 2005 with a Brewer MKIII double-monochromator spectroradiometer. The dataset was compared with collocated measurements of a second spectroradiometer (Brewer MKII) and a CIMEL sun-photometer, showing correlations of 0.93 and 0.98 respectively. A seasonal variation of the AOD was observed at Thessaloniki, with AOD values at 340 nm of 0.52 and 0.28 for August and December respectively. Back trajectories of air masses for up to 4 days were used to assess the influence of long-range transport from various regions to the aerosol load over Thessaloniki. It is shown that part of the observed seasonality can be attributed to air masses with high AOD originating from North-Eastern and Eastern directions during summertime. The analysis of the long-term record (9 years) of AOD showed a downward tendency. A similar decreasing tendency was found in the record of the PM-10 aerosol measurements, which are conducted near the surface at 4 air-quality monitoring stations in the area of the city of Thessaloniki.

Description: Water vapour is an important component in the radiative balance of the polar atmosphere. We present a study covering fourteen-years of data of tropopsheric humidity profiles measured with standard radiosondes at Ny-Ålesund (78°55' N 11°52' E) during the period from 1991 to 2005. It is well known that relative humidity measurements are less reliable at cold temperatures when measured with standard radiosondes. The data were corrected for errors and used to determine key characteristic features of the vertical and temporal RH evolution in the Arctic troposphere over Ny-Ålesund. We present frequency occurrence of ice-supersaturation layers in the troposphere, their vertical span, temperature and statistical distribution. Supersaturation with respect to ice shows a clear seasonal behaviour. In winter (October–February) it occurred in 22% of all cases and less frequently in spring (March–May 13%), and summer (June–September, 10%). The results are finally compared with findings from the SAGE II satellite instrument on subvisible clouds.

Description: Diurnal variations of upper tropospheric humidity (UTH) as well as middle tropospheric humidity (MTH) were examined in conjunction with the diurnal cycle of convection over tropical Africa and the adjacent tropical Atlantic Ocean using Meteosat-8 measurements. Cloud and humidity features were also tracked to document the diurnal variations of humidity and clouds in the Lagrangian framework. A distinct diurnal variation of UTH (and MTH) is noted over regions where tropical deep convective cloud systems are commonly observed. The amplitude of the UTH diurnal variation is larger over land, while its variations over convectively inactive subtropical regions are much smaller. The diurnal variation of UTH tends to peak during nighttime over land, lagging deep convection and high cloud whose maxima occurred in the late afternoon and the evening, respectively. The time lag between the maximum UTH and deep convection/high cloud maxima over the ocean appears to be longer in comparison to that found over land. It was also indicated that both the UTH (and MTH) and the cirrus anvil cloud show a variation which is in phase, implying that moistening of the upper troposphere is closely linked to process of development and dissipation of deep convective clouds.

Description: Although aliphatic amines have been detected in both urban and rural atmospheric aerosols, little is known about the chemistry leading to particle formation or the potential aerosol yields from reactions of gas-phase amines. We present here the first systematic study of aerosol formation from the atmospheric reactions of amines. Based on laboratory chamber experiments and theoretical calculations, we evaluate aerosol formation from reaction of OH, ozone, and nitric acid with trimethylamine, methylamine, triethylamine, diethylamine, ethylamine, and ethanolamine. Entropies of formation for alkylammonium nitrate salts are estimated by molecular dynamics calculations enabling us to estimate equilibrium constants for the reactions of amines with nitric acid. Though subject to significant uncertainty, the calculated dissociation equilibrium constant for diethylammonium nitrate is found to be sufficiently small to allow for its atmospheric formation, even in the presence of ammonia which competes for available nitric acid. Experimental chamber studies indicate that the dissociation equilibrium constant for triethylammonium nitrate is of the same order of magnitude as that for ammonium nitrate. All amines studied form aerosol when photooxidized in the presence of NOx with the majority of the aerosol mass present at the peak of aerosol growth consisting of aminium (R3NH+) nitrate salts, which repartition back to the gas phase as the parent amine is consumed. Only the two tertiary amines studied, trimethylamine and triethylamine, are found to form significant non-salt organic aerosol when oxidized by OH or ozone; calculated organic mass yields for the experiments conducted are similar for ozonolysis (15% and 5% respectively) and photooxidation (23% and 8% respectively). The non-salt organic aerosol formed appears to be more stable than the nitrate salts and does not quickly repartition back to the gas phase.

Description: The PAES (French acronym for synoptic scale atmospheric pollution) network focuses on the chemical composition (ozone, CO, NOx/y and aerosols) of the lower troposphere (0–3000 m). Its high-altitude surface stations located in different mountainous areas in France complete the low-altitude rural MERA stations (the French contribution to the european program EMEP, European Monitoring and Evaluation Program). They are representative of pollution at the scale of the French territory because they are away from any major source of pollution. This study deals with ozone observations between 2001 and 2004 at 11 stations from PAES and MERA, in addition to 16 elevated stations located in mountainous areas of Switzerland, Germany, Austria, Italy and Spain. The set of stations covers a range of altitudes between 115 and 3550 m. The comparison between recent ozone mixing ratios with those of the last decade found in the literature for two high-elevation sites (Pic du Midi, 2877 m and Jungfraujoch, 3580 m) leads to a trend that has slowed down compared to old trends but remains positive. This could be attribuable to the reduction of ozone precursors at European scale, that however do not compensate an ozone increase at the global scale. Averaged levels of ozone increase with elevation in good agreement with data provided by the airborne observation system MOZAIC (Measurement of OZone and water vapour by Airbus In-service airCraft), showing a highly stratified ozone field in the lower troposphere, with a transition at about 1000 m asl between a sharp gradient (30 ppb/km) below but a gentler gradient (3 ppb/km) above. Ozone variability also reveals a clear transition between boundary-layer and free-tropospheric regimes at the same altitude. Below, diurnal photochemistry accounts for about the third of the variability in summer, but less than 20% above – and at all levels in winter – where ozone variability is mostly due to day-to-day changes (linked to weather conditions or synoptic transport). Monthly-mean ozone mixing-ratios show at all levels a minimum in winter and the classical summer broad maximum in spring and summer – which is actually the superposition of the tropospheric spring maximum (April–May) and regional pollution episodes linked to persistent anticyclonic conditions that may occur from June to September. To complement this classical result it is shown that summer maxima are associated with considerably more variability than the spring maximum. This ensemble of findings support the relevance of mountain station networks such as PAES for the long-term observation of free-tropospheric ozone over Europe.

Description: A global estimate of the seasonal direct radiative effect (DRE) of natural plus anthropogenic aerosols on solar radiation under all-sky conditions is obtained by combining satellite measurements and reanalysis data with a spectral radiative transfer model. The estimates are obtained with detailed spectral model computations separating the ultraviolet (UV), visible and near-infrared wavelengths. The global distribution of spectral aerosol optical properties was taken from the Global Aerosol Data Set (GADS) whereas data for clouds, water vapour, ozone, carbon dioxide, methane and surface albedo were taken from various satellite and reanalysis datasets. Using these aerosol properties and other related variables, we generate climatological (for the 12-year period 1984–1995) monthly mean aerosol DREs. The global annual mean DRE on the outgoing SW radiation at the top of atmosphere (TOA, ΔFTOA) is 1.62 Wm−2 (with a range of –10 to 15 Wm−2, positive values corresponding to planetary cooling), the effect on the atmospheric absorption of SW radiation (ΔFatmab) is 1.6 Wm−2 (values up to 35 Wm−2, corresponding to atmospheric warming), and the effect on the surface downward and absorbed SW radiation (Δ Fsurf, and ΔFsurfnet, respectively) is –3.93 and –3.22 Wm−2 (values up to –45 and –35 Wm−2, respectively, corresponding to surface cooling.) According to our results, aerosols decrease/increase the planetary albedo by –3 to 13% at the local scale, whereas on planetary scale the result is an increase of 1.5%. Aerosols can warm locally the atmosphere by up to 0.98 K day−1, whereas they can cool the Earth's surface by up to –2.9 K day−1. Both these effects, which can significantly modify atmospheric dynamics and the hydrological cycle, can produce significant planetary cooling on a regional scale, although planetary warming can arise over highly reflecting surfaces. The aerosol DRE at the Earth's surface compared to TOA can be up to 15 times larger at the local scale. The largest aerosol DRE takes place in the northern hemisphere both at the surface and the atmosphere, arising mainly at ultraviolet and visible wavelengths.

Description: The atmospheric-chemistry general circulation model ECHAM5/MESSy1 is evaluated with observations of different organic ozone precursors. This study continues a prior analysis which focused primarily on the representation of atmospheric dynamics and ozone. We use the results of the same reference simulation and apply a statistical analysis using data from numerous field campaigns. The results serve as a basis for future improvements of the model system. ECHAM5/MESSy1 generally reproduces the spatial distribution and the seasonal cycle of carbon monoxide (CO) very well. However, for the background in the northern hemisphere we obtain a negative bias (mainly due to an underestimation of emissions from fossil fuel combustion), and in the high latitude southern hemisphere a yet unexplained positive bias. The model results agree well with observations of alkanes, whereas severe problems in the simulation of alkenes are present. For oxygenated compounds the results are ambiguous: The model results are in good agreement with observations of formaldehyde, but systematic biases are present for methanol and acetone. The discrepancies between the model results and the observations are explained (partly) by means of sensitivity studies.

Description: Air quality models that generate the concentrations of semi-volatile and other condensable organic compounds using an explicit reaction mechanism require estimates of the physical and thermodynamic properties of the compounds that affect gas/aerosol partitioning: vapour pressure (as a subcooled liquid), and activity coefficients in the aerosol phase. The model of Griffin, Kleeman and co-workers (e.g., Griffin et al., 1999; Kleeman et al., 1999) assumes that aerosol particles consist of an aqueous phase, containing inorganic electrolytes and soluble organic compounds, and a hydrophobic phase containing mainly primary hydrocarbon material. Thirty eight semi-volatile reaction products are grouped into ten surrogate species which partition between the gas phase and both phases in the aerosol. Activity coefficients of the organic compounds are calculated using UNIFAC. In a companion paper (Clegg et al., 2007) we examine the likely uncertainties in the vapour pressures of the semi-volatile compounds and their effects on partitioning over a range of atmospheric relative humidities. In this work a simulation for the South Coast Air Basin surrounding Los Angeles, using lower vapour pressures of the semi-volatile surrogate compounds consistent with estimated uncertainties in the boiling points on which they are based, yields a doubling of the predicted 24-h average secondary organic aerosol concentrations. The dependency of organic compound partitioning on the treatment of inorganic electrolytes in the air quality model, and the performance of this component of the model, are determined by analysing the results of a trajectory calculation using an extended version of the Aerosol Inorganics Model of Wexler and Clegg (2002). Simplifications are identified where substantial efficiency gains can be made, principally: the omission of dissociation of the organic acid surrogates; restriction of aerosol organic compounds to one of the two phases (aqueous or hydrophobic) where equilibrium calculations suggest partitioning strongly in either direction; a single calculation of activity coefficients of the organic compounds for simulations where they are determined by the presence of one component at high concentration in either phase (i.e., water in the aqueous phase, or a hydrocarbon surrogate compound P8 in the hydrophobic phase) and are therefore almost invariant. The implications of the results for the development of aerosol models are discussed.

Description: Volatile organic compound concentration ratios can be used as indicators of halogen chemistry that occurs during ozone depletion events in the Arctic during spring. Here we use a combination of modeling and measurements of [acetone]/[propanal] as an indicator of bromine chemistry, and [isobutane]/[n-butane] and [methyl ethyl ketone]/[n-butane] are used to study the extent of chlorine chemistry during four ozone depletion events during the Polar Sunrise Experiment of 1995. Using a 0-D photochemistry model in which the input of halogen atoms is controlled and varied, the approximate ratio of [Br]/[Cl] can be estimated for each ozone depletion event. It is concluded that there must be an additional source of propanal (likely from the snowpack) to correctly simulate the VOC chemistry of the Arctic, and that the ratio of Br atoms to Cl atoms can vary greatly during ozone depletion events.

Description: The design of a Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC) is described and initial results obtained from HIRAC are presented. The ability of HIRAC to perform in-situ laser-induced fluorescence detection of OH and HO2 radicals with the Fluorescence Assay by Gas Expansion (FAGE) technique establishes it as internationally unique for a chamber of its size and pressure/temperature variable capabilities. In addition to the FAGE technique, HIRAC features a suite of analytical instrumentation, including: a multipass FTIR system; a conventional gas chromatography (GC) instrument and a GC instrument for formaldehyde detection; and NO/NO2, CO, O3, and H2O vapour analysers. Ray tracing simulations and measurements of the blacklamp flux have been utilized to develop a detailed model of the radiation field within HIRAC. Comparisons between the analysers and the FTIR coupled to HIRAC have been performed, and HIRAC has also been used to investigate pressure dependent kinetics of the chlorine atom reaction with ethene and the reaction of O3 and t-2-butene. The results obtained are in good agreement with literature recommendations and Master Chemical Mechanism predictions. HIRAC thereby offers a highly instrumented platform with the potential for: (1) high precision kinetics investigations over a range of atmospheric conditions; (2) detailed mechanism development, significantly enhanced according to its capability for measuring radicals; and (3) field instrument intercomparison, calibration, development, and investigations of instrument response under a range of atmospheric conditions.

Description: We present the chemistry-climate model UM_CAM in which a relatively detailed tropospheric chemical module has been incorporated into the UK Met Office's Unified Model version 4.5. We obtain good agreements between the modelled ozone/nitrogen species and a range of observations including surface ozone measurements, ozone sonde data, and some aircraft campaigns. Four 2100 calculations assess model responses to projected changes of anthropogenic emissions (SRES A2), climate change (due to doubling CO2), and idealised climate change associated changes in biogenic emissions (i.e. 50% increase of isoprene emission and doubling emissions of soil-NOx). The global tropospheric ozone burden increases significantly for all the 2100 A2 simulations, with the largest response caused by the increase of anthropogenic emissions. Climate change has diverse impacts on O3 and its budgets through changes in circulation and meteorological variables. Increased water vapour causes a substantial ozone reduction especially in the tropical lower troposphere (〉10 ppbv reduction over the tropical ocean). On the other hand, an enhanced stratosphere-troposphere exchange of ozone, which increases by 80% due to doubling CO2, contributes to ozone increases in the extratropical free troposphere which subsequently propagate to the surface. Projected higher temperatures favour ozone chemical production and PAN decomposition which lead to high surface ozone levels in certain regions. Enhanced convection transports ozone precursors more rapidly out of the boundary layer resulting in an increase of ozone production in the free troposphere. Lightning-produced NOx increases by about 22% in the doubled CO2 climate and contributes to ozone production. The response to the increase of isoprene emissions shows that the change of ozone is largely determined by background NOx levels: high NOx environment increases ozone production; isoprene emitting regions with low NOx levels see local ozone decreases, and increase of ozone levels in the remote region due to the influence of PAN chemistry. The calculated ozone changes in response to a 50% increase of isoprene emissions are in the range of between –8 ppbv to 6 ppbv. Doubling soil-NOx emissions will increase tropospheric ozone considerably, with up to 5 ppbv in source regions.

Description: We investigate the ability of a mesoscale model to reconstruct CO2 fluxes at regional scale. Formally, we estimate the reduction of error for a CO2 flux inversion at 8 km resolution in the South West of France, during four days of the CarboEurope Regional Experiment (CERES) in spring 2005. Measurements from two towers and two airplanes are available for this campaign. The lagrangian particle dispersion model LPDM was coupled to the non-hydrostatic model Meso-NH and integrated in a matrix inversion framework. Impacts of aircraft and tower measurements are quantified separately and together. We find that the configuration with both towers and aircraft is able to significantly reduce uncertainties on the 4-day averaged CO2 fluxes over about half of the 300×300 km domain. Most of this reduction comes from the tower measurements, even though the impact of aircraft measurements remains noticeable. The noise contributed by imperfect knowledge of boundary inflows does not significantly impair the resolution. We test alternative strategies to improve the impact of aircraft measurements and find that most information comes from measurements inside the boundary layer.

Description: The first three Canadian Arctic Atmospheric Chemistry Experiment (ACE) Validation Campaigns at Eureka (80° N, 86° W) were during two extremes of Arctic winter variability: Stratospheric sudden warmings (SSWs) in 2004 and 2006 were among the strongest, most prolonged on record; 2005 was a record cold winter. New satellite measurements from ACE-Fourier Transform Spectrometer (ACE-FTS), Sounding of the Atmosphere using Broadband Emission Radiometry, and Aura Microwave Limb Sounder (MLS), with meteorological analyses and Eureka lidar and radiosonde temperatures, are used to detail the meteorology in these winters, to demonstrate its influence on transport and chemistry, and to provide a context for interpretation of campaign observations. During the 2004 and 2006 SSWs, the vortex broke down throughout the stratosphere, reformed quickly in the upper stratosphere, and remained weak in the middle and lower stratosphere. The stratopause reformed at very high altitude, above where it could be accurately represented in the meteorological analyses. The 2004 and 2006 Eureka campaigns were during the recovery from the SSWs, with the redeveloping vortex over Eureka. 2005 was the coldest winter on record in the lower stratosphere, but with an early final warming in mid-March. The vortex was over Eureka at the start of the 2005 campaign, but moved away as it broke up. Disparate temperature profile structure and vortex evolution resulted in much lower (higher) temperatures in the upper (lower) stratosphere in 2004 and 2006 than in 2005. Satellite temperatures agree well with Eureka radiosondes, and with lidar data up to 50–60 km. Consistent with a strong, cold upper stratospheric vortex and enhanced radiative cooling after the SSWs, MLS and ACE-FTS trace gas measurements show strongly enhanced descent in the upper stratospheric vortex during the 2004 and 2006 Eureka campaigns compared to that in 2005.