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Convective redistribution of ozone and its precursors between the boundary layer (BL) and the free troposphere (FT) influences photochemistry, in particular that of the middle and upper troposphere (UT). We present a case study of convective transport during the GABRIEL campaign over the tropical rain forest in Suriname in October 2005. During a measurement flight on 12 October the inflow and outflow regions of a cumulonimbus cloud (Cb) have been characterized, providing evidence of convective transport. We identified a distinct layer between 9 and 11 km altitude with enhanced mixing ratios of CO, O3, HOx, acetone and acetonitrile. The elevated O3 contradicts the expectation that convective transport brings low ozone air from the boundary layer to the outflow region. The enhanced mixing ratio of ozone in the outflow was mainly of dynamical origin. Entrainment of ozone rich air at the outflow level into the convective outflow accounts for 62% (range: 33-91%) of the observed O3. Ozone is enhanced by only 5-6% by photochemical production in the outflow due to enhanced NO from lightning, based on steady state model calculations, using in-situ observations including the first reported HOx measurements over the tropical rainforest. The "excess" ozone in the outflow is most probably due to direct production by corona discharge associated with lightning. We deduce a production rate of 5.12 × 1028 molecules O3 flash-1 (range: 9.89 × 1026-9.82 × 1028 molecules O3 flash-1), which is at the upper limit of the range of the values reported previously. [ABSTRACT FROM AUTHOR]

New particle formation (NPF), which generates nucleation mode aerosol, was observed in the tropical Upper Troposphere (UT) and Tropical Tropopause Layer (TTL) by in situ airborne measurements over South America (January-March 2005), Australia (November-December 2005), West Africa (August 2006) and Central America (2004-2007). Particularly intense NPF was found at the bottom of the TTL. Measurements with a set of condensation particle counters (CPCs) with different dp50 (50% lower size detection efficiency diameter or "cut-off diameter") were conducted on board the M-55 Geophysica in the altitude range of 12.0-20.5 km and on board the DLR Falcon-20 at up to 11.5 km altitude. Onboard the NASA WB-57F size distributions were measured over Central America in the 4 to 1000 nm diameter range with a system of nucleation mode aerosol spectrometers. Nucleation mode particle concentrations were derived from these measurements which allow for identifying many NPF events with Nnm in the range of thousands of particles per cm³. Over Australia and West Africa, we identified NPF in the outflow of tropical convection, in particular of a Mesoscale Convective System (MCS). Newly formed particles with NNm > 1000 cm-3 were found to coexist with ice cloud particles (dp > 2 µm) as long as cloud particle concentrations remained below 2 cm-3. The occurrence of NPF within the upper troposphere and the TTL was generally confined within 340 K to 380 K potential temperature, but NPF was of particular strength between 350 K and 370 K (i.e. ~ 1-4 km below the cold point tropopause). Analyses of the aerosol volatility (at 250 °C) show that in the TTL on average 75-90 % of the particles were volatile, compared to typically only 50 % in the extra-tropical UT, indicative for the particles to mainly consist of H2SO4-H2O and possibly organic compounds. Along two flight segments over Central and South America (24 February 2005 and 7 August 2006, at 12.5 km altitude) in cloud free air, above thin cirrus, particularly high Nnm were observed. Recent lifting had influenced the probed air masses, and Nnm reached up to 16 000 particles cm-3 (ambient concentration). A sensitivity study using an aerosol model, which includes neutral and ion induced nucleation processes, simulates Nnm in reasonable agreement with the in situ observations of clear-air NPF. Based on new, stringent multi-CPC criteria, our measurements corroborate the hypothesis that the tropical UT and the TTL are regions supplying freshly nucleated particles. Our findings narrow the altitude of the main source region to the bottom TTL, i.e. to the level of main tropical convection outflow, and, by means of measurements of carbon monoxide, they indicate the importance of anthropogenic emissions in NPF. After growth and/or coalescence the nucleation mode particles may act as cloud condensation nuclei in the tropical UT, or, upon ascent into the stratosphere, contribute to maintain the stratospheric background aerosol. [ABSTRACT FROM AUTHOR]

In this study we report measurements of hydrogen peroxide (H2O2), methyl hydroperoxide* (MHP* as a proxy of MHP based on an unspecific measurement of total organic peroxides) and formaldehyde (HCHO) from the HOx OVer EuRope (HOOVER) project (HOx = OH+HO2). HOOVER included two airborne field campaigns, in October 2006 and July 2007. Measurement flights were conducted from the base of operation Hohn (Germany, 54° N, 9° E) towards the Mediterranean and to the subpolar regions over Norway. We find negative concentration gradients with increasing latitude throughout the troposphere for H2O2 and CH3OOH*. In contrast, observed HCHO is almost homogeneously distributed over central and northern Europe and is elevated over the Mediterranean. In general, the measured gradients tend to be steepest entering the Mediterranean region, where we also find the highest abundances of the 3 species. Mixing ratios of these tracers generally decrease with altitude. H2O2 and CH3OOH* show maxima above the boundary layer at 2-5 km, being more distinct over southern than over northern Europe. We also present a comparison of our data with simulations by two global 3-D-models, MATCH-MPIC and EMAC, and with the box model CAABA. The models realistically represent altitude and latitude gradients for both HCHO and hydroperoxides (ROOH). In contrast, the models have problems reproducing the absolute mixing ratios, in particular of H2O2. Large uncertainties about retention coefficients and cloud microphysical parameters suggest that cloud scavenging might be a large source of error for the simulation of H2O2. A sensitivity study with EMAC shows a strong influence of cloud and precipitation scavenging on the budget of H2O2 as simulations improve significantly with this effect switched off. [ABSTRACT FROM AUTHOR]

Direct measurements of OH and HO2over a tropical rainforest were made for the first time during the GABRIEL campaign in October 2005, deploying the custom-built HORUS instrument (HydrOxyl Radical measurement Unit based on fluorescence Spectroscopy), adapted to fly in a Learjet wingpod. Biogenic hydrocarbon emissions were expected to strongly reduce the OH and HO2mixing ratios as the air is transported from the ocean over the forest. However, surprisingly high mixing ratios of both OH and HO2were encountered in the boundary layer over the rainforest. The HORUS instrumentation and calibration methods are described in detail and the measurement results obtained are discussed. The extensive dataset collected during GABRIEL, including measurements of many other trace gases and photolysis frequencies, has been used to quantify the main sources and sinks of OH. Comparison of these measurementderived formation and loss rates of OH indicates strong previously overlooked recycling of OH in the boundary layer over the tropical rainforest, occurring in chorus with isoprene emission. [ABSTRACT FROM AUTHOR]

A suite of diagnostics is applied to in-situ aircraft measurements and one Chemistry-Climate Model (CCM) data to characterize the vertical structure of the Tropical Tropopause Layer (TTL). The diagnostics are based on vertical tracer profiles and relative vertical tracer gradients, using tropopause-referenced coordinates, and tracer-tracer relationships in the tropical Upper Troposphere/Lower Stratosphere (UT/LS). Observations were obtained during four tropical campaigns performed from 1999 to 2006 with the research aircraft Geophysica and have been compared to the output of the ECHAM5/MESSy CCM. The model vertical resolution in the TTL (~500 m) allows for appropriate comparison with high-resolution aircraft observations and the diagnostics used highlight common TTL features between the model and the observational data. The analysis of the vertical profiles of water vapour, ozone, and nitrous oxide, in both the observations and the model, shows that concentration mixing ratios exhibit a strong gradient change across the tropical tropopause, due to the role of this latter as a transport barrier and that transition between the tropospheric and stratospheric regimes occurs within a finite layer. The use of relative vertical ozone and carbon monoxide gradients, in addition to the vertical profiles, helps to highlight the region where this transition occurs and allows to give an estimate of its thickness. The analysis of the CO-O3 and H2O-O3 scatter plots and of the Probability Distribution Function (PDF) of the H2O-O3 pair completes this picture as it allows to better distinguish tropospheric and stratospheric regimes that can be identified by their different chemical composition. The joint analysis and comparison of observed and modelled data allows to state that the model can represent the background TTL structure and its seasonal variability rather accurately. The model estimate of the thickness of the interface region between tropospheric and stratospheric regimes agrees well with average values inferred from observations. On the other hand, the measurements can be influenced by regional scale variability, local transport processes as well as deep convection, that can not be captured by the model. [ABSTRACT FROM AUTHOR]

In-situ ice crystal size distribution measurements are presented within the tropical troposphere and lower stratosphere. The measurements were performed using a combination of a Forward Scattering Spectrometer Probe (FSSP-100) and a Cloud Imaging Probe (CIP), which were installed on the Russian high altitude research aircraft M55 "Geophysica" during the SCOUT-O3 campaign in Darwin, Australia. One of the objectives of the campaign was to characterise the Hector convective system, which appears on an almost daily basis during the pre-monsoon season over the Tiwi Islands, north of Darwin. In total 90 encounters with ice clouds, between 10 and 19 km altitude were selected from the dataset and were analysed. Six of these encounters were observed in the lower stratosphere, up to 1.4 km above the local tropopause. Concurrent lidar measurements on board "Geophysica" indicate that these ice clouds were a result of overshooting convection. Large ice crystals, with a maximum dimension up to 400 μm, were observed in the stratosphere. The stratospheric ice clouds included an ice water content ranging from 7.7×10-5 to 8.5×10-4 gm-3 and were observed at ambient relative humidities (with respect to ice) between 75 and 157%. Three modal lognormal size distributions were fitted to the average size distributions for different potential temperature intervals, showing that the shape of the size distribution of the stratospheric ice clouds are similar to those observed in the upper troposphere. In the tropical troposphere the effective radius of the ice cloud particles decreases from 100 μm at about 10 km altitude, to 3 μm at the tropopause, while the ice water content decreases from 0.04 to 10-5 gm-3. No clear trend in the number concentration was observed with altitude, due to the thin and inhomogeneous characteristics of the observed cirrus clouds. The ice water content calculated from the observed ice crystal size distribution is compared to the ice water content derived from two hygrometer instruments. This independent measurement of the ice water content agrees within the combined uncertainty of the instruments for ice water contents exceeding 3×10-4 gm-3. Stratospheric residence times, calculated based on gravitational settling, and evaporation rates show that the ice crystals observed in the stratosphere over the Hector storm system had a high potential of humidifying the stratosphere locally. Utilizing total aerosol number concentration measurements from a four channel condensation particle counter during two separate campaigns, it can be shown that the fraction of ice particles to the number of aerosol particles remaining ranges from 1:300 to 1:30 000 for tropical upper tropospheric ice clouds with ambient temperatures below -75°C. [ABSTRACT FROM AUTHOR]

We present the validation of a water vapour dataset obtained by the Airborne Microwave Stratospheric Observing System AMSOS, a passive microwave radiometer operating at 183 GHz. Vertical profiles are retrieved from spectra by an optimal estimation method. The useful vertical range lies in the upper troposphere up to the mesosphere with an altitude resolution of 8 to 16 km and a horizontal resolution of about 57 km. Flight campaigns were performed once a year from 1998 to 2006 measuring the latitudinal distribution of water vapour from the tropics to the polar regions. The obtained profiles show clearly the main features of stratospheric water vapour in all latitudinal regions. Data are validated against a set of instruments comprising satellite, ground-based, airborne remote sensing and in-situ instruments. It appears that AMSOS profiles have a dry bias of 0 to -20%, when compared to satellite experiments. Also a comparison between AMSOS and in-situ hygrosondes FISH and FLASH have been performed. A matching in the short overlap region in the upper troposphere of the lidar measurements from the DIAL instrument and the AMSOS dataset allowed water vapour profiling from the middle troposphere up to the mesosphere. [ABSTRACT FROM AUTHOR]

Measurements in nascent ice forming regions are very rare and help understand cirrus cloud formation and the interactions of trace gases with ice crystals. A tenuous cirrus cloud has been probed with in-situ and remote sensing instruments onboard the high altitude research aircraft Geophysica M55 in the tropical upper troposphere. Besides microphysical and optical particle properties, water (H2O) and reactive nitrogen species (NOy) have been measured. In slightly ice supersaturated air between 14.2 and 14.9 km altitude, an unusually low ice water content of 0.031 mgm-3 and small ice crystals with mean radii of 5 µm have been detected. A high nitric acid to water molar ratio (HNO3/H2O) of 5.4x10-5 has been observed in the ice crystals, about an order of magnitude higher compared to previous observations in cirrus at temperatures near 202 K. A model describing the trapping of HNO3 in growing ice particles shows that a high HNO3 content in ice crystals is expected during early growth stages, mainly originating from uptake in aerosol particles prior to freezing. Water vapor deposition on ice crystals and trapping of additional HNO3 reduces the molar ratio to values close to the ratio of HNO3/H2O in the gas phase while the cloud ages. [ABSTRACT FROM AUTHOR]

We present measurements of NO, NOy, O3, and N2O within the lowermost stratosphere (LMS) over Europe obtained during the SPURT project. The measurements cover all seasons between November 2001 and July 2003. They span a broad band of latitudes from 30° N to 75° N and a potential temperature range from 290 to 380 K. The measurements represent a comprehensive data set of these tracers and reveal atmospheric transport processes that influence tracer distributions in the LMS. Median mixing ratios of stratospheric tracers in equivalent latitude-potential temperature coordinates show a clear seasonal cycle related to the Brewer-Dobson circulation, with highest values in spring and lowest values in autumn. Vertical tracer profiles show strong gradients at the extratropical tropopause, suggesting that vertical (cross-isentropic) mixing is reduced above the tropopause. Pronounced meridional gradients in the tracer mixing ratios are found on potential temperature surfaces in the LMS. This suggests strongly reduced mixing along isentropes. Concurrent large gradients in static stability in the vertical direction, and of PV in the meridional direction, suggest the presence of a mixing barrier. Seasonal cycles were found in the correlation slopes ΔO3/ΔN2O and ΔNOy/ΔN2O well above the tropopause. Absolute slope values are smallest in spring indicating chemically aged stratospheric air originating from high altitudes and latitudes. Larger values were measured in summer and autumn suggesting that a substantial fraction of air takes a "short-cut" from the tropical tropopause region into the extratropical LMS. The seasonal change in the composition of the LMS has direct implications for the ozone chemistry in this region. Comparisons of measured NO with the critical NO value at which net ozone production changes from negative to positive, imply ozone production up to 20K above the local tropopause in spring, up to 30K in summer, and up to 40K in autumn. Above these heights, and in winter, net ozone production is negative. [ABSTRACT FROM AUTHOR]

Owing to the potential of cirrus clouds to vertically redistribute HNO3 in the upper troposphere, the uptake of HNO3 in ice particles is at the focus of recent research. Here, we investigate whether HNO3 residing in freezing aerosol particles could be a relevant source of HNO3 in ice clouds. To this end, model studies on the sensitivity of the uptake of HNO3 in aerosol particles to temperature, relative humidity with respect to ice (RHice), particle composition and amount of available HNO3 were performed. Combining the model results with the history of RHice during cirrus formation and comparison with field measurements indicates that at temperatures <200 K a considerable part of the HNO3 in ice may originate from freezing particles containing HNO3. [ABSTRACT FROM AUTHOR]

During a series of 8 measurement campaigns within the SPURT project (2001-2003), vertical profiles of CO and O3 have been obtained at subtropical, middle and high latitudes over western Europe, covering the troposphere and lowermost stratosphere up to ∼14 km altitude during all seasons. The seasonal and latitudinal variation of the measured trace gas profiles are compared to simulations with the chemical transport model MATCH. In the troposphere reasonable agreement between observations and model predictions is achieved for CO and O3, in particular at subtropical and mid-latitudes, while the model overestimates (underestimates) CO (O3) in the lowermost stratosphere particularly at high latitudes, indicating too strong simulated bi-directional exchange across the tropopause. By the use of tagged tracers in the model, long-range transport of Asian air masses is identified as the dominant source of CO pollution over Europe in the free troposphere. [ABSTRACT FROM AUTHOR]