ALBERT

Description: The chemical composition of carbonaceous aerosols collected during the LBA-SMOCC field experiment, conducted in Rondônia, Brazil, in 2002 during the transition from the dry to the wet season, was investigated by a suite of state-of-the-art analytical techniques. The period of most intense biomass burning was characterized by high concentrations of submicron particles rich in carbonaceous material and water-soluble organic compounds (WSOC). At the onset of the rainy period, submicron total carbon (TC) concentrations decreased by about 20 times. In contrast, the concentration of supermicron TC was fairly constant throughout the experiment, pointing to a constant emission of coarse particles from the natural background. About 6–8% of TC (9–11% of WSOC) was speciated at the molecular level by GC-MS and liquid chromatography. Polyhydroxylated compounds, aliphatic and aromatic acids were the main classes of compounds accounted for by individual compound analysis. Functional group analysis by proton NMR and chromatographic separation on ion-exchange columns allowed characterization of ca. 50–90% of WSOC into broad chemical classes (neutral species/light acids/humic-like substances). In spite of the significant change in the chemical composition of tracer compounds from the dry to the wet period, the functional groups and the general chemical classes of WSOC changed only to a small extent. Model compounds representing size-resolved WSOC chemical composition for the different periods of the campaign are then proposed in this paper, based on the chemical characterization by both individual compound analysis and functional group analysis deployed during the LBA-SMOCC experiment. Model compounds reproduce quantitatively the average chemical structure of WSOC and can be used as best-guess surrogates in microphysical models involving organic aerosol particles over tropical areas affected by biomass burning.

Description: During SPURT (Spurenstofftransport in der Tropopausenregion, trace gas transport in the tropopause region) we performed measurements of a wide range of trace gases with different lifetimes and sink/source characteristics in the northern hemispheric upper troposphere (UT) and lowermost stratosphere (LMS). A large number of in-situ instruments were deployed on board a Learjet 35A, flying at altitudes up to 13.7 km, at times reaching to nearly 380 K potential temperature. Eight measurement campaigns (consisting of a total of 36 flights), distributed over all seasons and typically covering latitudes between 35° N and 75° N in the European longitude sector (10° W–20° E), were performed. Here we present an overview of the project, describing the instrumentation, the encountered meteorological situations during the campaigns and the data set available from SPURT. Measurements were obtained for N2O, CH4, CO, CO2, CFC12, H2, SF6, NO, NOy, O3 and H2O. We illustrate the strength of this new data set by showing mean distributions of the mixing ratios of selected trace gases, using a potential temperature-equivalent latitude coordinate system. The observations reveal that the LMS is most stratospheric in character during spring, with the highest mixing ratios of O3 and NOy and the lowest mixing ratios of N2O and SF6. The lowest mixing ratios of NOy and O3 are observed during autumn, together with the highest mixing ratios of N2O and SF6 indicating a strong tropospheric influence. For H2O, however, the maximum concentrations in the LMS are found during summer, suggesting unique (temperature- and convection-controlled) conditions for this molecule during transport across the tropopause. The SPURT data set is presently the most accurate and complete data set for many trace species in the LMS, and its main value is the simultaneous measurement of a suite of trace gases having different lifetimes and physical-chemical histories. It is thus very well suited for studies of atmospheric transport, for model validation, and for investigations of seasonal changes in the UT/LMS, as demonstrated in accompanying and elsewhere published studies.

Description: 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.

Description: A four year record of MODIS spaceborne data provides a new measurement tool to assess the aerosol direct radiative effect at the top of the atmosphere. MODIS derives the aerosol optical thickness and microphysical properties from the scattered sunlight at 0.55–2.1 μm. The monthly MODIS data used here are accumulated measurements across a wide range of view and scattering angles and represent the aerosol's spectrally resolved angular properties. We use these data consistently to compute with estimated accuracy of ±0.6 Wm−2 the reflected sunlight by the aerosol over global oceans in cloud free conditions. The MODIS high spatial resolution (0.5 km) allows observation of the aerosol impact between clouds that can be missed by other sensors with larger footprints. We found that over the clear-sky global ocean the aerosol reflected 5.3±0.6 Wm−2 with an average radiative efficiency of −49±2 Wm−2 per unit optical thickness. The seasonal and regional distribution of the aerosol radiative effects are discussed. The analysis adds a new measurement perspective to a climate change problem dominated so far by models.

Description: Carbon analysis consists in the evaluation of the carbonaceous content of the aerosol (TC) but, more importantly, of its distribution between the two components EC (Elemental Carbon) and OC (Organic Carbon) that are characterized by different physical-chemical properties. In spite of the numerous studies focused on this topic, nowadays a universal methodology for the determination of the two components EC and OC is not available. In fact OC and EC (also known as black carbon or soot) are operationally defined by the method of analysis and, as a consequence, different methods can produce different results. In this paper we present results on the application of TGA/FT-IR (Thermo-gravimetric Analysis/Fourier Transformed Infrared Spectroscopy) to the characterization of carbonaceous aerosols. The analytical methodology was applied to PM10 (particulate matter with aerodynamic diameter smaller than 10 μm) four-hour time resolution samples collected in Milan urban area. The method is a two-steps thermal one and it is based on the different thermal behaviour of OC and EC. It has been set up analyzing suitable standards containing both organic and elemental carbon. Carbon quantification is achieved by on-line, continuous monitoring of CO2 infrared absorption at 2361 cm−1. A good separation between OC and EC on particulate matter (PM) samples has been obtained. Ranges and average values were 12–70 μg/m3 and 20 μg/m3 for OC and 0.2–6 μg/m3 and 2 μg/m3 for EC. On average OC and EC made up 29 (±13)% and 2.5 (±1.8)% of the PM10 fraction, respectively. The method reliability has been verified by a preliminary comparison with TOT (Thermal Optical Transmission) technique. OC and EC values determined for ambient samples of PM10 were correlated with meteorological parameters as well as with Radon concentrations.

Description: A photochemical trajectory model has been used to simulate the chemical evolution of air masses arriving at the TORCH field campaign site in the southern UK during late July and August 2003, a period which included a widespread and prolonged photochemical pollution episode. The model incorporates speciated emissions of 124 non-methane anthropogenic VOC and three representative biogenic VOC, coupled with a comprehensive description of the chemistry of their degradation. A representation of the gas/aerosol absorptive partitioning of ca. 2000 oxygenated organic species generated in the Master Chemical Mechanism (MCM v3.1) has been implemented, allowing simulation of the contribution to organic aerosol (OA) made by semi- and non-volatile products of VOC oxidation; emissions of primary organic aerosol (POA) and elemental carbon (EC) are also represented. Simulations of total OA mass concentrations in nine case study events (optimised by comparison with observed hourly-mean mass loadings derived from aerosol mass spectrometry measurements) imply that the OA can be ascribed to three general sources: (i) POA emissions; (ii) a "ubiquitous" background concentration of 0.7 µg m-3; and (iii) gas-to-aerosol transfer of lower volatility products of VOC oxidation generated by the regional scale processing of emitted VOC, but with all partitioning coefficients increased by a species-independent factor of 500. The requirement to scale the partitioning coefficients, and the implied background concentration, are both indicative of the occurrence of chemical processes within the aerosol which allow the oxidised organic species to react by association and/or accretion reactions which generate even lower volatility products, leading to a persistent, non-volatile secondary organic aerosol (SOA). The contribution of secondary organic material to the simulated OA results in significant elevations in the simulated ratio of organic carbon (OC) to EC, compared with the ratio of 1.1 assigned to the emitted components. For the selected case study events, [OC]/[EC] is calculated to lie in the range 2.7-9.8, values which are comparable with the high end of the range reported in the literature.

Description: During several balloon flights inside the Arctic polar vortex in early 2003, unusual trace gas distributions were observed, which indicate a strong influence of mesospheric air in the stratosphere. The tuneable diode laser (TDL) instrument SPIRALE (Spectroscopie Infra-Rouge par Absorption de Lasers Embarqués) measured unusually high CO values (up to 600 ppb) on 27 January at about 30 km altitude. The cryosampler BONBON sampled air masses with very high molecular Hydrogen, extremely low SF6 and enhanced CO values on 6 March at about 25 km altitude. Finally, the MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) Fourier Transform Infra-Red (FTIR) spectrometer showed NOy values which are significantly higher than NOy* (the NOy derived from a correlation between N2O and NOy under undisturbed conditions), on 21 and 22 March in a layer centred at 22 km altitude. Thus, the mesospheric air seems to have been present in a layer descending from about 30 km in late January to 25 km altitude in early March and about 22 km altitude on 20 March. We present corroborating evidence from a model study using the KASIMA (KArlsruhe SImulation model of the Middle Atmosphere) model that also shows a layer of mesospheric air, which descended into the stratosphere in November and early December 2002, before the minor warming which occurred in late December 2002 lead to a descent of upper stratospheric air, cutting off a layer in which mesospheric air is present. This layer then descended inside the vortex over the course of the winter. The same feature is found in trajectory calculations, based on a large number of trajectories started in the vicinity of the observations on 6 March. Based on the difference between the mean age derived from SF6 (which has an irreversible mesospheric loss) and from CO2 (whose mesospheric loss is much smaller and reversible) we estimate that the fraction of mesospheric air in the layer observed on 6 March, must have been somewhere between 35% and 100%.

Description: This paper presents the new version 2.1 of the Kinetic PreProcessor (KPP). Taking a set of chemical reactions and their rate coefficients as input, KPP generates Fortran90, Fortran77, Matlab, or C code for the temporal integration of the kinetic system. Efficiency is obtained by carefully exploiting the sparsity structures of the Jacobian and of the Hessian. A comprehensive suite of stiff numerical integrators is also provided. Moreover, KPP can be used to generate the tangent linear model, as well as the continuous and discrete adjoint models of the chemical system.

Description: Surface-atmosphere exchange fluxes of CO2, estimated by an interannual atmospheric transport inversion from atmospheric mixing ratio measurements, are affected by several sources of errors, one of which is experimental errors. Quantitative information about such measurement errors can be obtained from regular co-located measurements done by different laboratories or using different experimental techniques. The present quantitative assessment is based on intercomparison information from the CMDL and CSIRO atmospheric measurement programs. We show that the effects of systematic measurement errors on inversion results are very small compared to other errors in the flux estimation (as well as compared to signal variability). As a practical consequence, this assessment justifies the merging of data sets from different laboratories or different experimental techniques (flask and in-situ), if systematic differences (and their changes) are comparable to those considered here. This work also highlights the importance of regular intercomparison programs.

Description: We discuss the quality of the two available SCIAMACHY limb ozone profile products. They were retrieved with the University of Bremen IFE's algorithm version 1.61 (hereafter IFE), and the official ESA offline algorithm (hereafter OL) versions 2.4 and 2.5. The ozone profiles were compared to a suite of correlative measurements from ground-based lidar and microwave, sondes, SAGE II and SAGE III (Stratospheric Aerosol and Gas Experiment). To correct for the expected Envisat pointing errors, which have not been corrected implicitly in either of the algorithms, we applied a constant altitude shift of -1.5 km to the SCIAMACHY ozone profiles. The IFE ozone profile data between 16 and 40 km are biased low by 3-6%. The average difference profiles have a typical standard deviation of 10% between 20 and 35 km. We show that more than 20% of the SCIAMACHY official ESA offline (OL) ozone profiles version 2.4 and 2.5 have unrealistic ozone values, most of these are north of 15° S. The remaining OL profiles compare well to correlative instruments above 24 km. Between 20 and 24 km, they underestimate ozone by 15±5%.

Description: Size- and time-resolved aerosol samples were collected using an eight-stage Davis rotating unit for monitoring (DRUM) sampler from 29 March to 29 May in 2002 at Gosan, Jeju Island, Korea, which is one of the representative background sites in East Asia. These samples were analyzed using synchrotron X-ray fluorescence for 3-h average concentrations of 19 elements consisting of S, Si, Al, Fe, Ca, Cl, Cu, Zn, Ti, K, Mn, Pb, Ni, V, Se, As, Rb, Cr, Br. The size-resolved data sets were then analyzed using the positive matrix factorization (PMF) technique in order to identify possible sources and estimate their contribution to particulate matter mass. PMF analysis uses the uncertainty of the measured data to provide an optimal weighting. Fifteen sources were resolved in eight size ranges (0.07~12 μm) and included continental soil, local soil, sea salt, biomass/biofuel burning, coal combustion, oil heating furnace, residual oil fired boiler, municipal incineration, nonferrous metal source, ferrous metal source, gasoline vehicle, diesel vehicle, copper smelter and volcanic emission. PMF analysis of size-resolved source contributions showed that natural sources represented by local soil, sea salt and continental soil contributed about 79% to the predicted primary particulate matter (PM) mass in the coarse size range (1.15~12 μm). On the other hand, anthropogenic sources such as coal combustion and biomass/biofuel burning contributed about 60% in the fine size range (0.56~2.5 μm). The diesel vehicle source contributed the most in the ultra-fine size range (0.07~0.56 μm) and was responsible for about 52% of the primary PM mass.

Description: The retrieval of column densities and concentration profiles of atmospheric trace gas species from satellites is sensitive to light scattered by clouds. The SCanning Imaging Absorption SpectroMeter for Atmospheric CHartographY (SCIAMACHY) instrument on the Envisat satellite, principally designed to retrieve trace gases in the atmosphere, is also capable of detecting clouds. FRESCO (Fast Retrieval Scheme for Clouds from the Oxygen A-band) is a fast and robust algorithm providing cloud information from the O2 A-band for cloud correction of ozone. FRESCO provides a consistent set of cloud products by retrieving simultaneously effective cloud fraction and cloud top pressure. The FRESCO retrieved values are compared with the SCIAMACHY Level 2 operational cloud fraction of OCRA (Optical Cloud Recognition Algorithm) but, also, with cloud information from HICRU (Heidelberg Iterative Cloud Retrieval Utilities), SACURA (SemiAnalytical CloUd Retrieval Algorithm) and the MODIS (Moderate Resolution Imaging Spectroradiometer) instrument. The results correlate well, but FRESCO overestimates cloud fraction over deserts. Thus, to improve retrievals at these locations, the FRESCO surface albedo databases are decontaminated from the presence of desert dust aerosols. This is achieved by using the GOME Absorbing Aerosol Index. It is shown that this approach succeeds well in producing more accurate cloud information over the Sahara.

Description: SCIAMACHY, on board Envisat, has been in operation now for almost three years. This UV/visible/NIR spectrometer measures the solar irradiance, the earthshine radiance scattered at nadir and from the limb, and the attenuation of solar radiation by the atmosphere during sunrise and sunset, from 240 to 2380 nm and at moderate spectral resolution. Vertical columns and profiles of a variety of atmospheric constituents are inferred from the SCIAMACHY radiometric measurements by dedicated retrieval algorithms. With the support of ESA and several international partners, a methodical SCIAMACHY validation programme has been developed jointly by Germany, the Netherlands and Belgium (the three instrument providing countries) to face complex requirements in terms of measured species, altitude range, spatial and temporal scales, geophysical states and intended scientific applications. This summary paper describes the approach adopted to address those requirements. Since provisional releases of limited data sets in summer 2002, operational SCIAMACHY processors established at DLR on behalf of ESA were upgraded regularly and some data products – level-1b spectra, level-2 O3, NO2, BrO and clouds data – have improved significantly. Validation results summarised in this paper and also reported in this special issue conclude that for limited periods and geographical domains they can already be used for atmospheric research. Nevertheless, current processor versions still experience known limitations that hamper scientific usability in other periods and domains. Free from the constraints of operational processing, seven scientific institutes (BIRA-IASB, IFE/IUP-Bremen, IUP-Heidelberg, KNMI, MPI, SAO and SRON) have developed their own retrieval algorithms and generated SCIAMACHY data products, together addressing nearly all targeted constituents. Most of the UV-visible data products – O3, NO2, SO2, H2O total columns; BrO, OClO slant columns; O3, NO2, BrO profiles – already have acceptable, if not excellent, quality. Provisional near-infrared column products – CO, CH4, N2O and CO2 – have already demonstrated their potential for a variety of applications. Cloud and aerosol parameters are retrieved, suffering from calibration with the exception of cloud cover. In any case, scientific users are advised to read carefully validation reports before using the data. It is required and anticipated that SCIAMACHY validation will continue throughout instrument lifetime and beyond and will accompany regular processor upgrades.

Description: Numerical experiments were carried out using the Tel-Aviv University 2-D cloud model to investigate the effects of increased concentrations of Cloud Condensation Nuclei (CCN), giant CCN (GCCN) and Ice Nuclei (IN) on the development of precipitation and cloud structure in mixed-phase sub-tropical convective clouds. In order to differentiate between the contribution of the aerosols and the meteorology, all simulations were conducted with the same meteorological conditions. The results show that under the same meteorological conditions, polluted clouds (with high CCN concentrations) produce less precipitation than clean clouds (with low CCN concentrations), the initiation of precipitation is delayed and the lifetimes of the clouds are longer. GCCN enhance the total precipitation on the ground in polluted clouds but they have no noticeable effect on cleaner clouds. The increased rainfall due to GCCN is mainly a result of the increased graupel mass in the cloud, but it only partially offsets the decrease in rainfall due to pollution (increased CCN). The addition of more effective IN, such as mineral dust particles, reduces the total amount of precipitation on the ground. This reduction is more pronounced in clean clouds than in polluted ones. Polluted clouds reach higher altitudes and are wider than clean clouds and both produce wider clouds (anvils) when more IN are introduced. Since under the same vertical sounding the polluted clouds produce less rain, more water vapor is left aloft after the rain stops. In our simulations about 3.5 times more water evaporates after the rain stops from the polluted cloud as compared to the clean cloud. The implication is that much more water vapor is transported from lower levels to the mid troposphere under polluted conditions, something that should be considered in climate models.

Description: The potential impact of the uptake of HNO3 on ice on the distribution of NOy species, ozone and OH has been assessed using the global scale chemistry-transport model MATCH-MPIC. Assuming equilibrium uptake according to dissociative Langmuir theory results in significant reductions of gas phase HNO3. Comparison to a large set of observations provides support that significant uptake of HNO3 on ice is occurring, but the degree of the uptake cannot be inferred from this comparison alone. Sensitivity simulations show that the uncertainties in the total amount of ice formation in the atmosphere and the actual expression of the settling velocity of ice particles only result in small changes in our results. The largest uncertainty is likely to be linked to the actual theory describing the uptake process and the value of the initial uptake coefficient. The inclusion of non-methane hydrocarbon chemistry partially compensates for the absence of HNO3 uptake on ice when this is neglected in the model. The calculated overall effect on upper tropospheric ozone concentrations and the tropospheric methane lifetime are moderate to low. These results support a shift in the motivation for future experimental and theoretical studies of HNO3-ice interaction towards the role of HNO3 in hydrometeor surface physics.

Description: Airborne high resolution in situ measurements of a large set of trace gases including ozone (O3) and total water (H2O) in the upper troposphere and the lowermost stratosphere (UT/LMS) have been performed above Europe within the SPURT project. SPURT provides an extensive data coverage of the UT/LMS in each season within the time period between November 2001 and July 2003. In the LMS a distinct spring maximum and autumn minimum is observed in O3, whereas its annual cycle in the UT is shifted by 2–3 months later towards the end of the year. The more variable H2O measurements reveal a maximum during summer and a minimum during autumn/winter with no phase shift between the two atmospheric compartments. For a comprehensive insight into trace gas composition and variability in the UT/LMS several statistical methods are applied using chemical, thermal and dynamical vertical coordinates. In particular, 2-dimensional probability distribution functions serve as a tool to transform localised aircraft data to a more comprehensive view of the probed atmospheric region. It appears that both trace gases, O3 and H2O, reveal the most compact arrangement and are best correlated in the view of potential vorticity (PV) and distance to the local tropopause, indicating an advanced mixing state on these surfaces. Thus, strong gradients of PV seem to act as a transport barrier both in the vertical and the horizontal direction. The alignment of trace gas isopleths reflects the existence of a year-round extra-tropical tropopause transition layer. The SPURT measurements reveal that this layer is mainly affected by stratospheric air during winter/spring and by tropospheric air during autumn/summer. Normalised mixing entropy values for O3 and H2O in the LMS appear to be maximal during spring and summer, respectively, indicating highest variability of these trace gases during the respective seasons.

Description: We present the results of an intercomparison exercise between six different radiative transfer (RT) models carried out in the framework of QUILT, an EU funded project based on the exploitation of the Network for the Detection of Stratospheric Change (NDSC). RT modelling is an important step in the interpretation of Differential Optical Absorption Spectroscopy (DOAS) observations. It allows the conversion of slant column densities (SCDs) into vertical column densities (VCDs) using calculated air mass factors (AMFs). The originality of our study resides in comparing SCD simulations in multi-axis (MAX) geometry (trace gases: NO2 and HCHO) and in taking into account photochemical enhancement for calculating SCDs of rapidly photolysing species (BrO, NO2, and OClO) in zenith-sky geometry. Concerning the zenith-sky simulations, the different models agree generally well, especially below 90° SZA. At higher SZA, larger discrepancies are obtained with relative differences ranging between 2% and 14% in some cases. In MAX geometry, good agreement is found between the models with the calculated NO2 and HCHO SCDs differing by no more than 5% in the elevation and solar zenith angle (SZA) ranges investigated (5°–20° and 35°–85°, respectively). The impacts of aerosol scattering, ground albedo, and relative azimuth on MAX simulations have also been tested. Significant discrepancies appear for the aerosol effect, suggesting differences between models in the treatment of aerosol scattering. A better agreement is found in case of the ground albedo and relative azimuth effects. The complete set of initialization data and results have been made publicly available through the QUILT project web site (http://nadir.nilu.no/quilt/), enabling the testing of other RT codes designed for the calculation of SCDs/AMFs.

Description: Eight super-pressure balloons floating at constant level between 50 and 80 hPa and three Infra-Red Montgolfier balloons of variable altitude (15 hPa daytime, 40–80 hPa night time) have been launched at 22° S from Brazil in February–May 2004 in the frame of the HIBISCUS project. The flights lasted for 7 to 79 days residing mainly in the tropics, but some of them passed the tropical barrier and went to southern midlatitudes. Compared to the balloon measurements just above the tropical tropopause the ECMWF operational temperatures show a systematic cold bias of 0.9 K and the easterly zonal winds are too strong by 0.7 m/s. This bias in the zonal wind adds to the ECMWF trajectory errors, but they still are relatively small with e.g. about an error of 700 km after 5 days. The NCEP/NCAR reanalysis trajectory errors are substantially larger (1300 km after 5 days). In the southern midlatitudes the cold bias is the same, but the zonal wind bias is almost zero. The trajectories are generally more accurate than in the tropics, but for one balloon a lot of the calculated trajectories end up on the wrong side of the tropical barrier and this leads to large trajectory errors.

Description: The Chisholm forest fire that burned in Alberta, Canada, in May 2001 resulted in injection of substantial amounts of smoke into the lower stratosphere. We used the cloud-resolving plume model ATHAM (Active Tracer High resolution Atmospheric Model) to investigate the importance of different contributing factors to the severe intensification of the convection induced by the Chisholm fire and the subsequent injection of biomass smoke into the lower stratosphere. The simulations show strong sensitivity of the pyro-convection to background meteorology. This explains the observed coincidence of the convective blow-up of the fire plume and the passage of a synoptic cold front. Furthermore, we performed model sensitivity studies to the rate of release of sensible heat and water vapor from the fire. The release of sensible heat by the fire plays a dominant role for the dynamic development of the pyro-cumulonimbus cloud (pyroCb) and the height to which smoke is transported. The convection is very sensitive to the heat flux from the fire. The emissions of water vapor play a less significant role for the injection height but enhance the amount of smoke transported beyond the tropopause level. The aerosol burden in the plume has a strong impact on the microphysical structure of the resulting convective cloud. The dynamic evolution of the pyroCb, however, is only weakly sensitive to the abundance of cloud condensation nuclei (CCN) from the fire. In contrast to previous findings by other studies of convective clouds, we found that fire CCN have a negative effect on the convection dynamics because they give rise to a delay in the freezing of cloud droplets. Even in a simulation without fire CCN, there is no precipitation formation within the updraft region of the pyroCb. Enhancement of convection by aerosols as reported from studies of other cases of convection is therefore not found in our study.

Description: Atmospheric aerosols play significant roles in climatic related phenomena. Size, density and shape of particles affect their fluid-dynamic parameters which in turn dictate their transport and lifecycle. Moreover, density and shape are also related to particles' optical properties, influencing their regional and global radiative effects. In the present study we have measured and compared the effective densities of humic like substances (HULIS) extracted from smoke and pollution aerosol particles to those of molecular weight-fractionated aquatic and terrestrial Humic Substances (HS). The effective density was measured by comparing the electro mobility and vacuum aerodynamic diameter of aerosol particles composed of these compounds. Characterization of chemical parameters such as molecular weight, aromaticity and elemental composition allow us to test how they affect the effective density of these important environmental macromolecules. It is suggested that atmospheric aging processes increase the effective density of HULIS due to oxidation, while packing due to the aromatic moieties plays important role in determining the density of the aquatic HS substances.

Description: Previous studies have presented clear evidence that the Northern Hemisphere total ozone field can be separated into distinct regimes (tropical, midlatitude, polar, and arctic) the boundaries of which are associated with the subtropical and polar upper troposphere fronts, and in the winter, the polar vortex. This paper presents a study of total ozone variability within these regimes, from 1979–2003, using data from the TOMS instruments. The change in ozone within each regime for the period January 1979–May 1991, a period of rapid total ozone change, was studied in detail. Previous studies had observed a zonal linear trend of −3.15% per decade for the latitude band 25°–60° N. When the ozone field is separated by regime, linear trends of −1.4%, 2.3%, and 3.0%, per decade for the tropical, midlatitude, and polar regimes, respectively, are observed. The changes in the relative areas of the regimes were also derived from the ozone data. The relative area of the polar regime decreased by about 20%; the tropical regime increased by about 10% over this period. No significant change was detected for the midlatitude regime. From the trends in the relative area and total ozone it is deduced that 35% of the trend between 25° and 60° N, from January 1979–May 1991 is due to movement of the upper troposphere fronts. The changes in the relative areas can be associated with a change in the mean latitude of the subtropical and polar fronts within the latitude interval 25° to 60° N. Over the period from January 1979 to May 1991, both fronts moved northward by 1.1±0.2 degrees per decade. Over the entire period of the study, 1979–2003, the subtropical front moved northward at a rate of 1.1±0.1 degrees per decade, while the polar front moved by 0.5±0.1 degrees per decade.

Description: Ions, which are generated in the atmosphere by galactic cosmic rays and other ionization sources, may play an important role in the formation of atmospheric aerosols. In the paper, a new second-generation ion-mediated nucleation (IMN) model is presented. The new model explicitly treats the evaporation of neutral and charged clusters and it describes the evolution of the size spectra and composition of both charged and neutral clusters/particles ranging from small clusters of few molecules to large particles of several micrometers in diameter. Schemes used to calculate the evaporation coefficients for small neutral and charged clusters are consistent with the experimental data within the uncertainty range. The present IMN model, which is size-, composition-, and type-resolved, is a powerful tool for investigating the dominant mechanisms and key parameters controlling the formation and subsequent growth of nanoparticles in the atmosphere. This model can be used to analyze simultaneous measurements of the ion-mobility spectra and particle size distributions, which became available only recently. General features of the spectra for ions smaller than the critical size, size-dependent fractions of charged nanoparticles, and asymmetrical charging of freshly nucleated particles predicted by the new IMN model are consistent with recent measurements. Results obtained using the second generation IMN model, in which the most recent thermodynamic data for neutral and charged H2SO4-H2O clusters were used, suggest that ion-mediated nucleation of H2SO4-H2O can lead to a significant production of new particles in the lower atmosphere (including the boundary layer) under favorable conditions. It has been shown that freshly nucleated particles of few nanometers in size can grow by the condensation of low volatile organic compounds to the size of cloud condensation nuclei. In such cases, the chemical composition of nucleated particles larger than ~10 nm is dominated by organics.

Description: This paper presents key results achieved by an analysis of the relation between high-quality simultaneous Dobson, Brewer ground and TOMS-V8, GOME-WFDOAS satellite total ozone observations for Hradec Kralove, Czech Republic. Statistically significant seasonal differences with maxima up to 4% of monthly averages have been found between Dobson and Brewer measurements during the winter/spring months. These differences can influence estimations of ozone trends if combined data series are used after replacing a Dobson instrument by a Brewer spectrophotometer. The differences can be attributed mostly to the influence of temperature on ozone absorption coefficients and to total sulphur dioxide. Similar seasonal differences exist between Dobson, GOME and Brewer, TOMS data sets at Hradec Kralove while Dobson versus TOMS and Brewer versus GOME observations fit well with each other within the instrumental accuracy of spectrophotometers. The above findings are supposed to be relevant to other mid and high latitude stations and they have been confirmed by several independent analyses. The conclusions should be considered by data users because the differences between particular ground and satellite data sets can influence validation of satellite ozone observing systems and analyses of recovery of the ozone layer in mid and high latitudes, among others.

Description: Methane in air and seawater was measured in the Eastern Black Sea during the 10–18 December 1999 BIGBLACK project cruise. The measurements allowed for the calculation of supersaturation ratios and methane fluxes across the air-sea interface. CH4 mixing ratios in air were generally in the 1.8–2.0 ppmv range, while surface (4 m depth) seawater concentrations varied from 4 to 93 ppmv. Above active seep areas, the water was supersaturated to around 500% with respect to the overlying atmosphere. Accordingly, flux densities varied greatly and were up to 3300 umol m−2 day−1. In the Sevastopol harbour, supersaturations up to around 3000%, similar to those at the Danube Delta, were observed, while in the Istanbul harbour supersaturations could not be determined because the very high values of water concentrations led to detector saturation. Simple modelling shows that the observed fluxes do not have any substantial impact on the methane content of the Black Sea atmosphere, as they would only raise its concentrations by less than 50 ppt. On the other hand, calculations performed as part of the CRIMEA project show that mud volcano eruptions could episodically raise the methane concentrations well above their regional background for several tens of kilometres downwind. These calculations, which also apply to mud volcano eruptions elsewhere on the globe, indicate that the spatial extend and the magnitude of the atmospheric perturbation is such that its observation might lie within the capabilities of existing satellite instrumentation such as SCIAMACHY on ENVISAT.

Description: Aerosol samples were collected at a rural background site in southern Finland in May 2004 during pollution episode (PM1~16 µg m−3, backward air mass trajectories from south-east), intermediate period (PM1~5 µg m−3, backtrajectories from north-east) and clean period (PM1~2 µg m−3, backtrajectories from north-west/north). The elemental composition, morphology and mixing state of individual aerosol particles in three size fractions were studied using transmission electron microscopy (TEM) coupled with energy dispersive X-ray (EDX) microanalyses. The TEM/EDX results were complemented with the size-segregated bulk chemical measurements of selected ions and organic and elemental carbon. Many of the particles in PM0.2–1 and PM1–3.3 size fractions were strongly internally mixed with S, C and/or N. The major particle types in PM0.2–1 samples were 1) soot and 2) (ammonium)sulphates and their mixtures with variable amounts of C, K, soot and/or other inclusions. Number proportions of those two particle groups in PM0.2–1 samples were 0–12% and 83–97%, respectively. During the pollution episode, the proportion of Ca-rich particles was very high (26–48%) in the PM1–3.3 and PM3.3–11 samples, while the PM0.2–1 and PM1–3.3 samples contained elevated proportions of silicates (22–33%), metal oxides/hydroxides (1–9%) and tar balls (1–4%). These aerosols originated mainly from polluted areas of Eastern Europe, and some open biomass burning smoke was also brought by long-range transport. During the clean period, when air masses arrived from the Arctic Ocean, PM1–3.3 samples contained mainly sea salt particles (67–89%) with a variable rate of Cl substitution (mainly by NO3−). During the intermediate period, the PM1–3.3 sample contained porous (sponge-like) Na-rich particles (35%) with abundant S, K and O. They might originate from the burning of wood pulp wastes of paper industry. The proportion of biological particles and C-rich fragments (probably also biological origin) were highest in the PM3.3–11 samples (0–81% and 0–22%, respectively). The origin of different particle types and the effect of aging processes on particle composition and their hygroscopic and optical properties are discussed.

Description: A thermodynamical model for treatment of gas/aerosol partitioning of semi volatile inorganic aerosols has been implemented in a global chemistry and aerosol transport model (Oslo CTM2). The sulphur cycle and sea salt particles have been implemented earlier in the Oslo CTM2 and the focus of this study is on nitrate partitioning to the aerosol phase and if particulate nitrate is expected to form in fine or coarse mode aerosols. Modelling of the formation of fine mode nitrate particles is complicated since it depends on other aerosol components and aerosol precursors as well as meteorological condition. The surface concentrations from the model are compared to observed surface concentrations at around 20 sites around Europe for nitrate and ammonium. The agreement for nitrate is good but the modelled values are somewhat underestimated compared to observations at high concentrations, whereas for ammonium the agreement is very good. However, we underscore that such a comparison is not of large importance for the aerosol optical depth of particulate nitrate since the vertical profile of aerosol components and their precursors are so important. Fine mode nitrate formation depends on vertical profiles of both ammonia/ammonium and sulphate. The model results show that fine mode particulate nitrate play a non-negligible role in the total aerosol composition in certain industrialized regions and therefore have a significant local radiative forcing. On a global scale the aerosol optical depth of fine mode nitrate is relatively small due to limited availability of ammonia and loss to larger sea salt particles. Inclusion of sea salt in the calculations reduces the aerosol optical depth and burden of fine mode nitrate by 25% on a global scale but with large regional variations.

Description: Ultrafine vehicular particle (

Description: We present regional model simulations of the dust emission events during the Bodélé Dust Experiment (BoDEx) that was carried out in February and March 2005 in Chad. A box model version of the dust emission model is used to test different input parameters for the emission model, and to compare the dust emissions computed with observed wind speeds to those calculated with wind speeds from the regional model simulation. While field observations indicate that dust production occurs via self-abrasion of saltating diatomite flakes in the Bodélé, the emission model based on the assumption of dust production by saltation and using observed surface wind speeds as input parameters reproduces observed dust optical thicknesses well. Although the peak wind speeds in the regional model underestimate the highest wind speeds occurring on 10–12 March 2005, the spatio-temporal evolution of the dust cloud can be reasonably well reproduced by this model. Dust aerosol interacts with solar and thermal radiation in the regional model; it is responsible for a decrease in maximum daytime temperatures by about 5 K at the beginning the dust storm on 10 March 2005. This direct radiative effect of dust aerosol accounts for about half of the measured temperature decrease compared to conditions on 8 March. Results from a global dust model suggest that the dust from the Bodélé is an important contributor to dust crossing the African Savannah region towards the Gulf of Guinea and the equatorial Atlantic, where it can contribute up to 40% to the dust optical thickness.

Description: This paper summarizes and classifies the various approaches to validation of remote measurements of atmospheric state variables, and tries to recommend a clear and unambiguous terminology. The following approaches have been identified: Intercomparison of individual profiles for accuracy validation; statistical comparison of matched pairs of measurements with respect to bias determination and precision validation; statistical intercomparison of randomly sampled measurements by two instruments, and comparison of a single measurement to an ensemble of measurements. Applicable statistics are shortly reviewed, and recipes for evaluation of the co-incidence error due to less than perfect co-incidences are presented. An approach is suggested to quantitatively validate profile measurements when full covariance matrices are unavailable.

Description: After briefly discussing several reasons for the energy balance closure problem in the surface layer, the paper focuses on the influence of the low frequency part of the turbulence spectrum on the residual. Changes in the turbulent fluxes in this part of the turbulence spectrum were found to have a significant influence on the changes of the residual. Using the ogive method, it was found that the eddy-covariance method underestimates turbulent fluxes in the case of ogives converging for measuring times longer than the typical averaging interval of 30 min. Additionally, the eddy-covariance method underestimates turbulent fluxes for maximal ogive functions within the averaging interval, both mainly due to advection and non-steady state conditions. This has a considerable influence on the use of the eddy-covariance method.

Description: A high-order modelling approach to interpret "continental-type" particle formation bursts in the anthropogenically influenced convective boundary layer (CBL) is proposed. The model considers third-order closure for planetary boundary layer turbulence, sulphur and ammonia chemistry as well as aerosol dynamics. In Paper I of four papers, previous observations of ultrafine particle evolution are reviewed, model equations are derived, the model setup for a conceptual study on binary and ternary homogeneous nucleation is defined and shortcomings of process parameterisation are discussed. In the subsequent Papers II, III and IV simulation results, obtained within the framework of a conceptual study on the CBL evolution and new particle formation (NPF), will be presented and compared with observational findings.

Description: The ozone variability observed by tropospheric ozone lidars during the ESCOMPTE campaign is analyzed by means of a hybrid-Lagrangian modeling study. Transport processes responsible for the formation of ozone-rich layers are identified using a semi-Lagrangian analysis of mesoscale simulations to identify the planetary boundary layer (PBL) footprint in the free troposphere. High ozone concentrations are related to polluted air masses exported from the Iberian PBL. The chemical composition of air masses coming from the PBL and transported in the free troposphere is evaluated using a Lagrangian chemistry model. The initial concentrations are provided by a model of chemistry and transport. Different scenarios are tested for the initial conditions and for the impact of mixing with background air in order to perform a quantitative comparison with the lidar observations. For this meteorological situation, the characteristic mixing time is of the order of 2 to 6 days depending on the initial conditions. Ozone is produced in the free troposphere within most air masses exported from the Iberian PBL at an average rate of 0.2 ppbv h−1, with a maximum ozone production of 0.4 ppbv h−1. Transport processes from the PBL are responsible for an increase of 13.3 ppbv of ozone concentrations in the free troposphere compared to background levels; about 45% of this increase is attributed to in situ production during the transport rather than direct export of ozone.

Description: We have developed a merged ozone data set (MOD) for the period October 1978 through June 2006 combining total ozone measurements (Version 8 retrieval) from the TOMS (Nimbus 7, Earth Probe) and SBUV/SBUV2 (Nimbus 7, NOAA 9/11/16) series of satellite instruments. We use the MOD data set to search for evidence of ozone recovery in response to the observed leveling off of chlorine and bromine compounds in the stratosphere. A crucial step in any time series analysis is the evaluation of uncertainties. In addition to the standard statistical time series uncertainties, we evaluate the possible instrument drift uncertainty for the MOD data set. We combine these two sources of uncertainty and apply them to a cumulative sum of residuals (CUSUM) analysis for trend slow-down. For the extra-polar mean between 60° S and 60° N, the apparent slow-down in trend is found to be clearly significant if instrument uncertainties are ignored. When instrument uncertainties are added, the slow-down becomes marginally significant at the 2σ level. For the mid-latitudes of the northern hemisphere (30° to 60° N) the trend slow-down is highly significant at the 2σ level, while in the southern hemisphere the trend slow-down has yet to meet the 2σ significance criterion. The rate of change of chlorine/bromine compounds is similar in both hemispheres, and we expect the ozone response to be similar in both hemispheres as well. The asymmetry in the trend slow-down between hemispheres likely reflects the influence of dynamical variability, and thus a clearly statistically significant response of total ozone to the leveling off of chlorine and bromine in the stratosphere is not yet indicated.

Description: Nitrogen exchange between the atmosphere and biosphere directly influences atmospheric composition. While much is known about mechanisms of NO and N2O emissions, instrumentation for the study of mechanisms contributing to exchange of other major nitrogen species is quite limited. Here we describe the application of a new technique, thermal dissociation-laser induced fluorescence (TD-LIF), to eddy covariance measurements of the fluxes of NO2, total peroxy acyl and peroxy nitrates, total alkyl and multifunctional alkyl nitrates, and nitric acid. The technique offers the potential for investigating mechanisms of exchange of these species at the canopy scale over timescales from days to years. Examples of flux measurements at a ponderosa pine plantation in the mid-elevation Sierra Nevada Mountains in California are reported and used to evaluate instrument performance.

Description: A new mathematical model describing air ion balance was developed and tested. It has improved approximations and includes dry deposition of ions onto the forest canopy. The model leads to an explicit algebraic solution of the balance equations. This allows simple calculation of both the ionization rate and the average charge of aerosol particles from measurements of air ions and aerosol particles, with some parameters of the forest. Charged aerosol particles are distinguished from cluster ions by their size, which exceeds 1.6 nm diameter. The relative uncertainty of the ionization rate is about the same or less than the relative uncertainties of the measurements. The model was tested with specific air ion measurements carried out simultaneously at two heights at the Hyytiälä forest station, Finland. Earlier studies have shown a difference in the predictions of the ionization rate in the Hyytiälä forest when calculated in two different ways: based on the measurements of the environmental radioactivity and based on the air ion and aerosol measurements. The new model explains the difference as a consequence of neglecting dry deposition of ions in the earlier models. The ionization rate during the 16 h campaign was 5.6±0.8 cm−3 s−1 at the height of 2 m and 3.9±0.2 cm−3 s−1 at the height of 14 m, between the tops of the trees. The difference points out the necessity to consider the height variation when the ionization rate is used as a parameter in studies of ion-induced nucleation. Additional results are some estimates of the parameters of air ion balance. The recombination sink of cluster ions on the ions of opposite polarity made up 9–13%, the sink on aerosol particles 65–69%, and the sink on forest canopy 18–26% of the total sink of cluster ions. The average lifetime of cluster ions was about 130 s for positive and about 110 s for negative ions. At the height of 2 m, about 70% of the space charge of air was carried by aerosol particles, and at the height of 14 m, about 84%.

Description: Two-dimensional radiance maps from Channel 9 (~60–90 hPa) of the Advanced Microwave Sounding Unit (AMSU-A), acquired over southern Scandinavia on 14 January 2003, show plane-wave-like oscillations with a wavelength λh of ~400–500 km and peak brightness temperature amplitudes of up to 0.9 K. The wave-like pattern is observed in AMSU-A radiances from 8 overpasses of this region by 4 different satellites, revealing a growth in the disturbance amplitude from 00:00 UTC to 12:00 UTC and a change in its horizontal structure between 12:00 UTC and 20:00 UTC. Forecast and hindcast runs for 14 January 2003 using high-resolution global and regional numerical weather prediction (NWP) models generate a lower stratospheric mountain wave over southern Scandinavia with peak 90 hPa temperature amplitudes of ~5–7 K at 12:00 UTC and a similar horizontal wavelength, packet width, phase structure and time evolution to the disturbance observed in AMSU-A radiances. The wave's vertical wavelength is ~12 km. These NWP fields are validated against radiosonde wind and temperature profiles and airborne lidar profiles of temperature and aerosol backscatter ratios acquired from the NASA DC-8 during the second SAGE III Ozone Loss and Validation Experiment (SOLVE II). Both the amplitude and phase of the stratospheric mountain wave in the various NWP fields agree well with localized perturbation features in these suborbital measurements. In particular, we show that this wave formed the type II polar stratospheric clouds measured by the DC-8 lidar. To compare directly with the AMSU-A data, we convert these validated NWP temperature fields into swath-scanned brightness temperatures using three-dimensional Channel 9 weighting functions and the actual AMSU-A scan patterns from each of the 8 overpasses of this region. These NWP-based brightness temperatures contain two-dimensional oscillations due to this resolved stratospheric mountain wave that have an amplitude, wavelength, horizontal structure and time evolution that closely match those observed in the AMSU-A data. These comparisons not only verify gravity wave detection and horizontal imaging capabilities for AMSU-A Channel 9, but provide an absolute validation of the anticipated radiance signals for a given three-dimensional gravity wave, based on the modeling of Eckermann and Wu (2006).

Description: Using a simplified model of in-orbit radiance acquisition by the Advanced Microwave Sounding Unit (AMSU-A), we derive three-dimensional temperature weighting functions for Channel 9 measurements (peaking at ~60–90 hPa) at all 30 cross-track beam positions and use them to investigate the sensitivity of these radiances to gravity waves. The vertical widths of the weighting functions limit detection to waves with vertical wavelengths of ≳10 km, with slightly better vertical wavelength sensitivity at the outermost scan angles due to the limb effect. Fourier Transforms of two-dimensional cross-track weighting functions reveal optimal sensitivity to cross-track wavelengths at the near-nadir scan angles, where horizontal measurement footprints are smallest. This sensitivity is greater for the AMSU-A on the Aqua satellite than for the identical instruments on the NOAA meteorological satellites, due to a lower orbit altitude and thus smaller horizontal footprints from antenna spreading. Small cross-track asymmetries in the radiance response to gravity waves are found that peak at the mid-range scan angles, with more symmetric responses at near-nadir and far off-nadir scan angles. Three-dimensional simulations show gravity wave oscillations imaged in horizontal AMSU-A radiance maps swept out by the scan pattern and satellite motion. A distorting curvature is added to imaged wave phase lines due to vertical variations in weighting function peaks with cross-track scan angle. This wave distortion is analogous to the well-known "limb darkening" and "limb brightening" of microwave radiances acquired from purely vertical background temperature profiles by cross-track scanners. Waves propagating along track are more visible in these images at the outermost scan angles than those propagating cross track, due to oversampling and narrower widths of the horizontal measurement footprints in the along track direction. Based on nominal noise floors and representative lower stratospheric wave temperature amplitudes, our modeling indicates that Channel 9 AMSU-A radiances can resolve and horizontally image gravity waves with horizontal wavelengths of ≳150 km and vertical wavelengths of ≳10 km.

Description: The Royal Society expedition to Antarctica established a base at Halley Bay, in support of the International Geophysical Year of 1957–1958. Surface ozone was measured during 1958 only, using a prototype Brewer-Mast sonde. The envelope of maximum ozone was an annual cycle from 10 ppbv in January to 22 ppbv in August. These values are 35% less at the start of the year and 15% less at the end than modern values from Neumayer, also a coastal site. This may reflect a general increase in surface ozone since 1958 and differences in summer at the less windy site of Halley, or it may reflect ozone loss on the inlet together with long-term conditioning. There were short periods in September when ozone values decreased rapidly to near-zero, and some in August when ozone values were rapidly halved. Such ozone-loss episodes, catalysed by bromine compounds, became well-known in the Artic in the 1980s, and were observed more recently in the Antarctic. In 1958, very small ozone values were recorded for a week in midwinter during clear weather with light winds. The absence of similar midwinter reductions at Neumayer, or at Halley in the few measurements during 1987, means we must remain suspicious of these small values, but we can find no obvious reason to discount them. The dark reaction of ozone and seawater ice observed in the laboratory may be fast enough to explain them if the salinity and surface area of the ice is sufficiently amplified by frost flowers.

Description: Aerosol chemical and optical properties are extensively investigated for the first time over the Paris Basin in July 2000 within the ESQUIF project. The measurement campaign offers an exceptional framework to evaluate the performances of the chemistry-transport model CHIMERE in simulating concentrations of gaseous and aerosol pollutants, as well as the aerosol-size distribution and composition in polluted urban environments against ground-based and airborne measurements. A detailed comparison of measured and simulated variables during the second half of July with particular focus on 19 and 31 pollution episodes reveals an overall good agreement for gas-species and aerosol components both at the ground level and along flight trajectories, and the absence of systematic biases in simulated meteorological variables such as wind speed, relative humidity and boundary layer height as computed by the MM5 model. A good consistency in ozone and NO concentrations demonstrates the ability of the model to reproduce the plume structure and location fairly well both on 19 and 31 July, despite an underestimation of the amplitude of ozone concentrations on 31 July. The spatial and vertical aerosol distributions are also examined by comparing simulated and observed lidar vertical profiles along flight trajectories on 31 July and confirm the model capacity to simulate the plume characteristics. The comparison of observed and modeled aerosol components in the southwest suburb of Paris during the second half of July indicates that the aerosol composition is rather correctly reproduced, although the total aerosol mass is underestimated by about 20%. The simulated Parisian aerosol is dominated by primary particulate matter that accounts for anthropogenic and biogenic primary particles (40%), and inorganic aerosol fraction (40%) including nitrate (8%), sulfate (22%) and ammonium (10%). The secondary organic aerosols (SOA) represent 12% of the total aerosol mass, while the mineral dust accounts for 8%. The comparison demonstrates the absence of systematic errors in the simulated sulfate, ammonium and nitrates total concentrations. However, for nitrates the observed partition between fine and coarse mode is not reproduced. In CHIMERE there is a clear lack of coarse-mode nitrates. This calls for additional parameterizations in order to account for the heterogeneous formation of nitrate onto dust particles. Larger discrepancies are obtained for the secondary organic aerosols due to both inconsistencies in the SOA formation processes in the model leading to an underestimation of their mass and large uncertainties in the determination of the measured aerosol organic fraction. The observed mass distribution of aerosols is not well reproduced, although no clear explanation can be given.

Description: Vehicular emission is an important source of air pollutants in urban cities in the Pearl River Delta (PRD) region of South China. In order to study the impact of evaporative loss of vehicular fuel on air quality, several commonly used fuel samples were collected in four main cities in the PRD region – Hong Kong, Guangzhou, Macau and Zhuhai, and analyzed for their volatile organic compounds (VOCs) composition. Source profiles of vapors of the vehicular fuels used in these cities were constructed and are believed to be the first reported for the PRD region. The C8-C10 hydrocarbons were the main constituents of diesel. Different from diesel, gasoline used in the PRD region was mainly comprised of lighter C4-C7 hydrocarbons, with toluene and i-pentane being the two most abundant species. The toluene content in the Hong Kong and Macau gasoline samples were higher than that in Guangzhou and Zhuhai, while the reverse was true for the benzene content. The benzene levels in Guangzhou and Zhuhai exceeded the maximum allowable benzene levels for Mainland China unleaded gasoline. Liquefied Petroleum Gas (LPG) samples were collected only in Hong Kong and were comprised mainly of n-butane, propane and i-butane. Traffic samples indicated that evaporative loss and vehicular combustion were the primary contributors to elevated VOC levels in roadside atmospheres. Significant i-pentane and toluene concentrations were observed in roadside atmospheres in all four cities. Ratio of i-pentane in gasoline vapors to that in roadside samples were calculated and this showed that the degree of evaporative loss were higher in Guangzhou and Zhuhai than that in Hong Kong and Macau. We suggest the difference is due to the better maintenance and more new cars in Hong Kong and Macau. From tunnel samples collected in Hong Kong in two different years, we found that the relative amount of propane, i-butane, and n-butane increased between 2001 to 2003, consistent with the 40% increase in LPG fueled vehicles. Propane to butanes ratios were calculated for LPG samples and tunnels samples, and the comparable ratios illustrated the LPG leakages from LPG fueled vehicles crossing the tunnel.

Description: This technical note describes a method for the rediscretisation of "gridded" geo-scientific data. A recursive algorithm (NREGRID) is derived to solve the rediscretisation problem for orthogonal grids (including curvilinear) of arbitrary dimension. The algorithm is used within the program NCREGRID to handle geo-scientific data. These data are typically 2-dimensional (latitude-longitude grid), or 3-dimensional (latitude-longitude grid with a vertical pressure, or hybrid pressure coordinate, as used in atmospheric modelling). NCREGRID can be used as stand-alone program for the transformation ("regridding") of data from and to data files in netCDF format. Moreover, NCREGRID constitutes the core of the Modular Earth Submodel System (MESSy) data import interface, providing a powerful tool for accessing data independently of the applied grid resolution ("automatic regridding").

Description: Aerosol chemical composition was measured over the Atlantic Ocean in November–December 1999 and at the Finnish Antarctic research station Aboa in January 2000. The concentrations of all anthropogenic aerosol compounds decreased clearly from north to south. An anthropogenic influence was still evident in the middle of the tropical South Atlantic, background values were reached south of Cape Town. Chemical mass apportionment was calculated for high volume filter samples (Dp80% in the Southern Ocean, and 10% in most samples, also at Aboa. The correlation of biomass-burning-related aerosol components with 210Pb was very high compared with that between nss calcium and 210Pb which suggests that 210Pb is a better tracer for biomass burning than for Saharan dust. The ratio of the two clear tracers for biomass burning, nss potassium and oxalate, was different in European and in African samples, suggesting that this ratio could be used as an indicator of biomass burning type. The concentrations of continent-related particles decreased exponentially with the distance from Africa. The shortest half-value distance, ~100 km, was for nss calcium. The half-value distance of particles that are mainly in the submicron particles was ~700±200 km. The MSA to nss sulfate ratio, R, increased faster than MSA concentration with decreasing anthropogenic influence, indicating that the R increase could largely be explained by the decrease of anthropogenic sulfate.

Description: Using an aerosol flow tube apparatus, we have studied the effects of aliphatic aldehydes (C3 to C10) and ketones (C3 and C9) on ice nucleation in sulfuric acid aerosols. Mixed aerosols were prepared by combining an organic vapor flow with a flow of sulfuric acid aerosols over a small mixing time (~60 s) at room temperature. No acid-catalyzed reactions were observed under these conditions, and physical uptake was responsible for the organic content of the sulfuric acid aerosols. In these experiments, aerosol organic content, determined by a Mie scattering analysis, was found to vary with the partial pressure of organic, the flow tube temperature, and the identity of the organic compound. The physical properties of the organic compounds (primarily the solubility and melting point) were found to play a dominant role in determining the inferred mode of nucleation (homogenous or heterogeneous) and the specific freezing temperatures observed. Overall, very soluble, low-melting organics, such as acetone and propanal, caused a decrease in aerosol ice nucleation temperatures when compared with aqueous sulfuric acid aerosol. In contrast, sulfuric acid particles exposed to organic compounds of eight carbons and greater, of much lower solubility and higher melting temperatures, nucleate ice at temperatures above aqueous sulfuric acid aerosols. Organic compounds of intermediate carbon chain length, C4-C7, (of intermediate solubility and melting temperatures) nucleated ice at the same temperature as aqueous sulfuric acid aerosols. Interpretations and implications of these results for cirrus cloud formation are discussed.

Description: A size dependent parameterization for the removal of aerosol particles by falling rain droplets is developed. Scavenging coefficients are calculated explicitly as a function of aerosol particle size and precipitation intensity including the full interaction of rain droplet size distribution and aerosol particles. The actual parameterization is a simple and accurate three-parameter fit through these pre-calculated scavenging coefficients. The parameterization is applied in the global chemistry transport model TM4 and the importance of below-cloud scavenging relative to other removal mechanisms is investigated for sea salt aerosol. For a full year run (year 2000), we find that below-cloud scavenging accounts for 12% of the total removal of super-micron aerosol. At mid-latitudes of both hemispheres the fractional contribution of below-cloud scavenging to the total removal of super-micron sea salt is about 30% with regional maxima exceeding 50%. Below-cloud scavenging reduces the global average super-micron aerosol lifetime from 2.47 to 2.16 days in our simulations. Despite large uncertainties in precipitation, relative humidity, and water uptake by aerosol particles, we conclude that below cloud scavenging is likely an important sink for super-micron sized sea salt aerosol particles that needs to be included in size-resolved aerosol models.

Description: First measurements from space of upper tropospheric and lower stratospheric methanol profiles within aged fire plumes are reported. Elevated levels of methanol at 0–45° S from 30 September to 3 November 2004 have been measured by the high resolution infrared spectrometer ACE-FTS onboard the SCISAT satellite. Methanol volume mixing ratios higher than 4000 pptv are detected and are strongly correlated with other fire products such as CO, C2H6, and HCN. A sensitivity study of the methanol retrieval, accounting for random and systematic contributions, shows that the retrieved methanol profile for a single occultation exceeds 100% error above 16.5 km, with an accuracy of about 20% for measurements inside polluted air masses. The upper tropospheric enhancement ratio of methanol with respect to CO is estimated from the correlation plot between methanol and CO for aged tropical biomass burning plumes. This ratio is in good agreement with the ratio measured in the free troposphere (up to 12 km) by recent aircraft studies and does not suggest any secondary production of methanol by oxidation in aged biomass burning plumes.

Description: Spectral aerosol light absorption is an important parameter for the assessment of the radiation budget of the atmosphere. Although on-line measurement techniques for aerosol light absorption, such as the Aethalometer and the Particle Soot Absorption Photometer (PSAP), have been available for two decades, they are limited in accuracy and spectral resolution because of the need to deposit the aerosol on a filter substrate before measurement. Recently, a 7-wavelength (λ) Aethalometer became commercially available, which covers the visible (VIS) to near-infrared (NIR) spectral range (λ=450–950 nm), and laboratory calibration studies improved the degree of confidence in these measurement techniques. However, the applicability of the laboratory calibration factors to ambient conditions has not been investigated thoroughly yet. As part of the LBA-SMOCC (Large scale Biosphere atmosphere experiment in Amazonia – SMOke aerosols, Clouds, rainfall and Climate) campaign from September to November 2002 in the Amazon basin we performed an extensive field calibration of a 1-λ PSAP and a 7-λ Aethalometer utilizing a photoacoustic spectrometer (PAS, 532 nm) as reference device. Especially during the dry period of the campaign, the aerosol population was dominated by pyrogenic emissions. The most pronounced artifact of integrating-plate type attenuation techniques (e.g. Aethalometer, PSAP) is due to multiple scattering effects within the filter matrix. For the PSAP, we essentially confirmed the laboratory calibration factor by Bond et al. (1999). On the other hand, for the Aethalometer we found a multiple scattering enhancement of 5.23 (or 4.55, if corrected for aerosol scattering), which is significantly larger than the factors previously reported (~2) for laboratory calibrations. While the exact reason for this discrepancy is unknown, the available data from the present and previous studies suggest aerosol mixing (internal versus external) as a likely cause. For Amazonian aerosol, we found no absorption enhancement due to hygroscopic particle growth in the relative humidity (RH) range between 40% and 80%. However, a substantial bias in PSAP sensitivity that correlated with both RH and temperature (T) was observed for 20%

Description: Reverse domain-filling trajectory calculations have been performed for the years 1993, 1995, 1996, 1997, and 2000 to calculate the spreading of ozone depleted air from the polar vortex to midlatitudes in spring. We find that for these years with massive Arctic ozone depletion the zonal mean total ozone column at midlatitudes is reduced with between 7 and 12 DU in the April-May period. The polar vortex and remnants have preferred locations which leads to longitudinal differences in the midlatitude ozone trends. Together with decadal variations in circulation the dilution of ozone depleted air may explain the major fraction of longitudinal differences in midlatitude ozone trends. For the period 1979–1997 the dilution may explain 50% of the longitudinal differences in ozone trends and for the period 1979–2002 it may explain 45%. The dilution also has a significant impact on the zonal mean ozone trends in the April-May period. Although uncertainties are large due to uncertainties in the ozone depletion values and neglect of ozone depletion in other years than 1993, 1995, 1996, 1997, and 2000 we have tried to calculate the size of this effect. We estimate that dilution may explain 29% of the trend in the period 1979–1997 and 33% of the trend in the period 1979–2002 as a lower limit.

Description: Nocturnal chemistry in the atmospheric boundary layer plays a key role in determining the initial chemical conditions for photochemistry during the following morning as well as influencing the budgets of O3 and NO2. Despite its importance, chemistry in the nocturnal boundary layer (NBL), especially in heavily polluted urban areas, has received little attention so far, which greatly limits the current understanding of the processes involved. In particular, the influence of vertical mixing on chemical processes gives rise to complex vertical profiles of various reactive trace gases and makes nocturnal chemistry altitude-dependent. The processing of pollutants is thus driven by a complicated, and not well quantified, interplay between chemistry and vertical mixing. In order to gain a better understanding of the altitude-dependent nocturnal chemistry in the polluted urban environment, a field study was carried out in the downtown area of Phoenix, AZ, in summer 2001. Vertical profiles of reactive species, such as O3, NO2, and NO3, were observed in the lowest 140 m of the troposphere throughout the night. The disappearance of these trace gas vertical gradients during the morning coincided with the morning transition from a stable NBL to a well-mixed convective layer. The vertical gradients of trace gas levels were found to be dependent on both surface NOx emission strength and the vertical stability of the NBL. The vertical gradients of Ox, the sum of O3 and NO2, were found to be much smaller than those of O3 and NO2, revealing the dominant role of NO emissions followed by the O3+NO reaction for the altitude-dependence of nocturnal chemistry in urban areas. Dry deposition, direct emissions, and other chemical production pathways of NO2 also play a role for the Ox distribution. Strong positive vertical gradients of NO3, that are predominantly determined by NO3 loss near the ground, were observed. The vertical profiles of NO3 and the calculated vertical profiles of its reservoir species (N2O5) confirm earlier model results suggesting complex vertical distributions of atmospheric denoxification processes during the night.

Description: The three carbon gases carbon monoxide (CO), carbon dioxide (CO2), and methane (CH4) are important atmospheric constituents affecting air quality and climate. The near-infrared nadir spectra measured by SCIAMACHY on ENVISAT contain information on the vertical columns of these gases which we retrieve using a modified DOAS algorithm (WFM-DOAS or WFMD). Our main data products are CO vertical columns and dry-air column averaged mixing ratios of methane (CH4) and CO2 (denoted XCH4 and XCO2). For CO and CH4 we present new results for the year 2003 obtained with an improved version of WFM-DOAS (WFMDv0.5) retrieved from Level 1 version 4 (Lv1v4) spectra. This data set has recently been compared with a network of ground based FTIR stations. Here we describe the WFMDv0.5 algorithm, present global and regional maps, and comparisons with global reference data. We show that major problems of the previous versions (v0.4 and v0.41) related to the varying ice-layer on the SCIAMACHY channel 8 detector have been solved. Compared to MOPITT the SCIAMACHY CO columns are on average higher by about 10–20%. Regionally, however, especially over central South America, differences can be much larger. For methane we present global and regional maps which are compared to TM5 model simulations performed using standard methane emission inventories. We show that methane source regions can be clearly detected with SCIAMACHY. We also show that the methane data product can be significantly further improved using Lv1v5 spectra with improved calibration. For CO2 we present three years of SCIAMACHY CO2 measurements over Park Falls, Wisconsin, USA, retrieved from Lv1v5. We show that the quality of CO2 retrieved from these spectra is significantly higher compared to WFMDv0.4 XCO2 retrieved from Lv1v4.

Description: Measured Fluxes of nitrous acid at Browning Pass, Antarctica were very low, despite conditions that are generally understood as favorable for HONO emissions, including: acidic snow surfaces, an abundance of NO3- anions in the snow surface, and abundant UV light for NO3- photolysis. Photochemical modeling suggests noon time HONO fluxes of 5–10 nmol m-2 h-1; the measured fluxes, however, were close to zero throughout the campaign. The location and state of NO3- in snow is crucial to its reactivity. The analysis of soluble mineral ions in snow reveals that the NO3- ion is probably present in aged snows as NaNO3. This is peculiar to our study site, and we suggest that this may affect the photochemical reactivity of NO3-, by preventing the release of products, or providing a reactive medium for newly formed HONO. In fresh snow, the NO3- ion is probably present as dissolved or adsorbed HNO3 and yet, no HONO emissions were observed. We speculate that HONO formation from NO3- photolysis may involve electron transfer reactions of NO2 from photosensitized organics and that fresh snows at our site had insufficient concentrations of adequate organic compounds to favor this reaction.

Description: Two aircraft instruments for the measurement of total odd nitrogen (NOy) were compared side by side aboard a Learjet A35 in April 2003 during a campaign of the AFO2000 project SPURT (Spurengastransport in der Tropopausenregion). The instruments albeit employing the same measurement principle (gold converter and chemiluminescence) had different inlet configurations. The ECO-Physics instrument operated by ETH-Zürich in SPURT had the gold converter mounted outside the aircraft, whereas the instrument operated by FZ-Jülich in the European project MOZAIC III (Measurements of ozone, water vapour, carbon monoxide and nitrogen oxides aboard Airbus A340 in-service aircraft) employed a Rosemount probe with 80 cm of FEP-tubing connecting the inlet to the gold converter. The NOy concentrations during the flight ranged between 0.3 and 3 ppb. The two data sets were compared in a blind fashion and each team followed its normal operating procedures. On average, the measurements agreed within 7%, i.e. within the combined uncertainty of the two instruments. This puts an upper limit on potential losses of HNO3 in the Rosemount inlet of the MOZAIC instrument. Larger transient deviations were observed during periods after calibrations and when the aircraft entered the stratosphere. The time lag of the MOZAIC instrument observed in these instances is in accordance with the time constant of the MOZAIC inlet line determined in the laboratory for HNO3.

Description: This study presents the first laboratory observation of HNO3 uptake by airborne mineral dust particles. The model aerosols were generated by dry dispersion of Arizona Test Dust (ATD), SiO2, and by nebulizing a saturated solution of calcium carbonate. The uptake of 13N-labeled gaseous nitric acid was observed in a flow reactor on the 0.2–2 s reaction time scale at room temperature and atmospheric pressure. The amount of nitric acid appearing in the aerosol phase at the end of the flow tube was found to be a linear function of the aerosol surface area. SiO2 particles did not show any significant uptake, while the CaCO3 aerosol was found to be more reactive than ATD. Due to the smaller uncertainty associated with the reactive surface area in the case of suspended particles as compared to bulk powder samples, we believe that we provide an improved estimate of the rate of uptake of HNO3 to mineral dust. The fact that the rate of uptake was smaller at a concentration of 1012 than at 1011 was indicative of a complex uptake mechanism. The uptake coefficient averaged over the first 2 s of reaction time at a concentration of 1012 molecules cm-3 was found to increase with increasing relative humidity, from 0.022±0.007 at 12% RH to 0.113±0.017 at 73% RH , which was attributed to an increasing degree of solvation of the more basic minerals. The extended processing of the dust by higher concentrations of HNO3 at 85% RH led to a water soluble coating on the particles and enhanced their hygroscopicity.

Description: A parameterization for cloud processing is presented that calculates activation of aerosol particles to cloud drops, cloud drop size, and pH-dependent aqueous phase sulfur chemistry. The parameterization is implemented in the global aerosol-climate model ECHAM5-HAM. The cloud processing parameterization uses updraft speed, temperature, and aerosol size and chemical parameters simulated by ECHAM5-HAM to estimate the maximum supersaturation at the cloud base, and subsequently the cloud drop number concentration (CDNC) due to activation. In-cloud sulfate production occurs through oxidation of dissolved SO2 by ozone and hydrogen peroxide. The model simulates realistic distributions for annually averaged CDNC although it is underestimated especially in remote marine regions. On average, CDNC is dominated by cloud droplets growing on particles from the accumulation mode, with smaller contributions from the Aitken and coarse modes. The simulations indicate that in-cloud sulfate production is a potentially important source of accumulation mode sized cloud condensation nuclei, due to chemical growth of activated Aitken particles and to enhanced coalescence of processed particles. The strength of this source depends on the distribution of produced sulfate over the activated modes. This distribution is affected by uncertainties in many parameters that play a direct role in particle activation, such as the updraft velocity, the aerosol chemical composition and the organic solubility, and the simulated CDNC is found to be relatively sensitive to these uncertainties.

Description: The Berlin Ozone Experiment (BERLIOZ) was carried out in summer 1998. One of its purposes was the evaluation of Chemistry Transport Models (CTM). CTM KAMM/DRAIS was one of the models considered. The data of 20 July were selected for evaluation. On that day, a pronounced ozone plume developed downwind of the city. Evaluation showed that the KAMM/DRAIS model is able to reproduce the meteorological and ozone data observed, except at farther distances (60–80 km) downwind of the city. In that region, the DRAIS model underestimates the measured ozone concentrations by 10–15 ppb, approximately. Therefore, this study was conducted to detect possible reasons for this deviation. A comprehensive sensitivity analysis was carried out to determine the most relevant model parameters. The adjoint DRAIS model was developed for this purpose, because for this study the application of this model is the most effective method of calculating the sensitivities. The least squares of the measured and simulated ozone concentrations between 08:00 UTC and 16:00 UTC at two stations 30 km and 70 km downwind of the city centre were chosen as distance function. The model parameters considered in this study are the complete set of initial and boundary species concentrations, emissions, and reaction rates, respectively. A sensitivity ranking showing the relevance of the individual parameters in the set is determined for each parameter set. In order to find out which modification in the parameter sets most reduces the cost function, simplified 4-D data assimilation was carried out. The result of this data assimilation shows that modifications of the reaction rates provide the best agreement between the measured and the simulated ozone concentrations at both stations. However, the modified reaction rates seem to be unrealistic for the whole simulation period. Therefore, the good agreement should not be overestimated. The agreement is still acceptable when the parameters in the other sets are modified together. The investigation demonstrates that an analysis of this type can help to explain inconsistencies between observations and simulations. But in the case considered here the inconsistencies cannot be explained by an error in only one parameter set.

Description: Although reactive halogen species (X*=X•, •X2-, X2 and HOX, where X=Br, Cl, or I) are important environmental oxidants, relatively little is known about their kinetics in condensed phases such as seawater and sea-salt particles. Here we describe a new technique to determine reactive chlorine and bromine species in aqueous solutions by using allyl alcohol (CH2=CHCH2OH) as a chemical probe. This probe is combined with competition kinetics in order to determine steady state concentrations of X*(aq). In some cases the technique also can be used to determine the rates of formation and lifetimes of X* in aqueous solution. In a companion paper we reported the results of our method development for aqueous solutions containing only bromide (Br-). In this paper, we discuss method development for solutions containing chloride (Cl-) alone, and for solutions containing both bromide and chloride.

Description: The effects of using three alternative gasoline fuel blends on regional air quality of the upper Rhine valley have been investigated. The first of the tested fuels is oxygenated by addition of ethyl-tertio-butyl ether (ETBE), the second is based on a reformulation of its composition and the third on is both oxygenated and reformulated. The upper Rhine valley is a very sensitive region for pollution episodes and several meteorological and air quality studies have already been performed. High temporal and spatial emission inventories are available allowing relevant and realistic modifications of the emission inventories. The calculation period, i.e., 11 May 1998, corresponds to a regional photochemical ozone pollution episode during which ozone concentrations exceeded several times the information threshold of the ozone directive of the European Union (180 μg m-3 as 1 hourly average). New emission inventories are set up using specific emission factors related to the alternative fuels by varying the fraction of gasoline passenger cars (from 50% to 100%) using the three fuel blends. Then air quality modeling simulations are performed using these emission inventories over the upper Rhine valley. The impact of alternative fuels on regional air quality is evaluated by comparing these simulations with the one using a reference emission inventory, e.g., where no modifications of the fuel composition are included. The results are analyzed by focusing on peak levels and daily averaged concentrations. The use of the alternative fuels leads to general reductions of ozone and volatile organic compounds (VOC) and increases of NOx levels. We found different behaviors related to the type of the area of concern i.e. rural or urban. The impacts on ozone are enhanced in urban areas where 15% reduction of the ozone peak and daily averaged concentrations can be reached. This behavior is similar for the NOx for which, in addition, an increase of the levels can be noted in urban plumes over rural areas. The most important decreases of the total VOC levels are mainly located over rural areas (more than 5% reduction of the levels except in urban plumes). By comparing these results with those from a local study related to the air quality of Strasbourg, we estimate that the regional contribution to the urban air quality of Strasbourg allows an enhancement of the results by using alternative fuel blends at the regional scale.

Description: A recently developed cloud retrieval algorithm for the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) is briefly presented and validated using independent and well tested cloud retrieval techniques based on the look-up-table approach for MODeration resolutIon Spectrometer (MODIS) data. The results of the cloud top height retrievals using measurements in the oxygen A-band by an airborne crossed Czerny-Turner spectrograph and the Global Ozone Monitoring Experiment (GOME) instrument are compared with those obtained from airborne dual photography and retrievals using data from Along Track Scanning Radiometer (ATSR-2), respectively.

Description: Levels of coarse (PM10-2.5) and fine (PM2.5) particles were determined between February 2004 and January 2005 in the city of Beirut, Lebanon. While low PM mass concentrations were measured in the rainy season, elevated levels were detected during sand storms originating from Arabian desert and/or Africa. Using ATR-FTIR and IC, it was shown that nitrate, sulfate, carbonate and chloride were the main anionic constituents of the coarse particles, whereas sulfate was mostly predominant in the fine particles in the form of (NH4)2SO4. Ammonium nitrate was not expected to be important because the medium was defined as ammonium poor. In parallel, the cations Ca2+ and Na+ dominated in the coarse, and NH4+, Ca2+ and Na+ in the fine particles. Coarse nitrate and sulfate ions resulted from the respective reactions of nitric and sulfuric acid with a relatively high amount of calcium carbonate. Both CaCO3 and Ca(NO3)2 crystals identified by ATR-FTIR in the coarse particles were found to be resistant to soaking in water for 24 h but became water soluble when they were formed in the fine particles suggesting, thereby, different growth and adsorption phenomena. The seasonal variational study showed that nitrate and sulfate ion concentrations increased in the summer due to the enhancement of photochemical reactions which facilitated the conversion of NO2 and SO2 gases into NO3- and SO42-, respectively. While nitrate was mainly due to local heavy traffic, sulfates were due to local and long-range transport phenomena. Using the air mass trajectory HYSPLIT model, it was found that the increase in the sulfate concentration correlated with wind vectors coming from Eastern and Central Europe. Chloride levels, on the other hand, were high when wind originated from the sea and low during sand storms. In addition to sea salt, elevated levels of chloride were also attributed to waste mass burning in proximity to the site. In comparison to other neighboring Mediterranean countries, relatively higher concentrations of calcium in Beirut were good indication of calcitic crustal abundance. Considering the importance of the health and climate impacts of aerosols locally and regionally, this study constitutes a point of reference for eastern Mediterranean transport modeling studies and local regulatory and policy makers.

Description: The first vertical profiles of stratospheric OClO retrieved from Odin/OSIRIS limb-scattered sunlight radiances are presented. The retrieval method is based on a two-step approach, using differential optical absorption spectroscopy combined with the maximum a posteriori estimator. The details of the spectral window selection, spectral corrections and inversion technique are discussed. The results show that OClO can be detected inside the South polar vortex region between about 14 and 22 km altitude with a 2–5 km height resolution and an estimated retrieval error better than 50% at the peak. OClO concentrations show the expected relation to the atmospheric conditions in the lower stratosphere in the austral spring 2002. This unique data set of OClO profiles is very promising to study the stratospheric chlorine activation in both polar regions.

Description: The organic fraction of atmospheric aerosols contains a multitude of compounds and usually only a small fraction can be identified and quantified. However, a limited number of representative organic compounds can be used to describe the water-soluble organic fraction. In this work, initiated within the EU 5FP project SMOCC, four mixtures containing various amounts of inorganic salts (ammonium sulfate, ammonium nitrate, and sodium chloride) and three model organic compounds (levoglucosan, succinic acid and fulvic acid) were studied. The interaction between water vapor and aerosol particles was studied at different relative humidities: at subsaturation using a hygroscopic tandem differential mobility analyzer (H-TDMA) and at supersaturation using a cloud condensation nuclei spectrometer (CCN spectrometer). Surface tensions as a function of carbon concentrations were measured using a bubble tensiometer. Parameterizations of water activity as a function of molality, based on hygroscopic growth, are given for the pure organic compounds and for the mixtures, indicating van't Hoff factors around 1 for the organics. The Zdanovskii-Stokes-Robinson (ZSR) mixing rule was tested on the hygroscopic growth of the mixtures and it was found to adequately explain the hygroscopic growth for 3 out of 4 mixtures, when the limited solubility of succinic acid is taken into account. One mixture containing sodium chloride was studied and showed a pronounced deviation from the ZSR mixing rule. Critical supersaturations calculated using the parameterizations of water activity and the measured surface tensions were compared with those determined experimentally.

Description: Aerosol light attenuation on quartz fibre filters has been measured since February 1989 at the Mace Head Atmospheric Research station near Carna, Co. Galway, Ireland, using an Aethalometer. The frequency of occurrence of the hourly averaged aerosol absorption data is found to be bimodally distributed. The two modes result from clean marine air and anthropogenically polluted continental air both being advected to the station dependent on the prevailing wind direction. The hourly averages of the marine portion of the aerosol light absorption are found to follow closely a lognormal distribution with a geometric mean of 0.310 Mm-1. The hourly averages of continental sector aerosol absorption are neither normally nor lognormally distributed and have an arithmetic mean of 6.36 Mm-1, indicating the presence of anthropogenic sources for BC east of the Mace Head station. The time series of the monthly averaged attenuation coefficient σatt of both marine and continental sector aerosol shows an increase from 1989 to 1997 and a levelling off thereafter. The monthly maximum of marine sector σatt is found in May. Trend and seasonal characteristics of the clean marine aerosol attenuation coefficients observed at Mace Head appear to be driven by meteorological factors, as indicated by rainfall data and by trends in the North Atlantic Oscillation (NAO) indices. The observed increasing trends of the continental sector σatt from 1989 up to 1997 are possibly related to changes in BC emissions over Ireland, calculated from UNSTAT (2002) fuel consumption data.

Description: The operational numerical weather prediction model Lokalmodell LM with 7 km horizontal resolution was evaluated for forecasting meteorological conditions during observed urban air pollution episodes. The resolution was increased to experimental 2.8 km and 1.1 km resolution by one-way interactive nesting without introducing urbanisation of physiographic parameters or parameterisations. The episodes examined are two severe winter inversion-induced episodes in Helsinki in December 1995 and Oslo in January 2003, three suspended dust episodes in spring and autumn in Helsinki and Oslo, and a late-summer photochemical episode in the Valencia area. The evaluation was basically performed against observations and radiosoundings and focused on the LM skill at forecasting the key meteorological parameters characteristic for the specific episodes. These included temperature inversions, atmospheric stability and low wind speeds for the Scandinavian episodes and the development of mesoscale recirculations in the Valencia area. LM forecasts often improved due to higher model resolution especially in mountainous areas like Oslo and Valencia where features depending on topography like temperature, wind fields and mesoscale valley circulations were better described. At coastal stations especially in Helsinki, forecast gains were due to the improved physiographic parameters (land fraction, soil type, or roughness length). The Helsinki and Oslo winter inversions with extreme nocturnal inversion strengths of 18°C were not sufficiently predicted with all LM resolutions. In Helsinki, overprediction of surface temperatures and low-level wind speeds basically led to underpredicted inversion strength. In the Oslo episode, the situation was more complex involving erroneous temperature advection and mountain-induced effects for the higher resolutions. Possible explanations include the influence of the LM treatment of snow cover, sea ice and stability-dependence of transfer and diffusion coefficients. The LM simulations distinctly improved for winter daytime and nocturnal spring and autumn inversions and showed good skill at forecasting further episode-relevant meteorological parameters. The evaluation of the photochemical Valencia episode concentrated on the dominating mesoscale circulation patterns and showed that the LM succeeds well in describing all the qualitative features observed in the region. LM performance in forecasting the examined episodes thus depends on the key episode characteristics and also the season of the year with a need to improve model performance in very stable inversion conditions not only for urban simulations.

Description: This study describes the atmospheric aerosol load encountered during the large-scale pollution episode that occurred in August 2003, by means of the aerosol optical thicknesses (AOTs) measured at 865 nm by the Polarization and Directionality of the Earth's Reflectances (POLDER) sensor and the simulation by the CHIMERE chemistry-transport model. During this period many processes (stagnation, photochemistry, forest fires) led to unusually high particle concentrations and optical thicknesses. The observed/simulated AOT comparison helps understanding the ability of the model to reproduce most of the gross AOT features observed in satellite data, with a general agreement within a factor 2 and correlations in the 0.4–0.6 range. However some important aerosol features are missed when using regular anthropogenic sources. Additional simulations including emissions and high-altitude transport of smoke from wildfires that occurred in Portugal indicate that these processes could dominate the AOT signal in some areas. Our results also highlight the difficulties of comparing simulated and POLDER-derived AOTs due to large uncertainties in both cases. Observed AOT values are significantly lower than the simulated ones (30–50%). Their comparison with the ground-based Sun photometer Aerosol Robotic Network (AERONET) measurements suggests, for the European sites considered here, an underestimation of POLDER-derived aerosol levels with a factor between 1 and 2. AERONET AOTs compare better with simulations (no particular bias) than POLDER AOTs.

Description: Gas and aerosol samples were taken using a wet effluent diffusion denuder/aerosol collector (WEDD/AC) coupled to ion chromatography (IC) in the city of Zurich, Switzerland from August to September 2002 and in March 2003. Major water soluble inorganic ions; nitrate, sulfate, and nitrite were analyzed online with a time resolution of two hours for the gas and aerosol phase. The fraction of water soluble inorganic anions in PM10 varied from 15% in August to about 38% in March. Seasonal and diurnal variations of nitrate in the gas and aerosol phase were observed with more than 50% of the total nitrate in the gas phase during August and more than 80% of nitrate in the aerosol phase during March exceeding the concentration of sulfate by a factor of 2. Aerosol sulfate, on the other hand, did not show significant variability with season. However, in the gas phase, the SO2 concentration was 6.5 times higher in winter than in summer. Nitrous acid (HONO) also showed a diurnal variation in both the gas and aerosol phase with the lowest concentration (0.2–0.6 µg/m3) in the afternoon. The primary pollutants, NO, CO and SO2 mixing ratios were often at their highest between 04:00–10:00 local time due to the build up of fresh vehicle emission under a nocturnal inversion.

Description: The AeroCom exercise diagnoses multi-component aerosol modules in global modeling. In an initial assessment simulated global distributions for mass and mid-visible aerosol optical thickness (aot) were compared among 20 different modules. Model diversity was also explored in the context of previous comparisons. For the component combined aot general agreement has improved for the annual global mean. At 0.11 to 0.14, simulated aot values are at the lower end of global averages suggested by remote sensing from ground (AERONET ca. 0.135) and space (satellite composite ca. 0.15). More detailed comparisons, however, reveal that larger differences in regional distribution and significant differences in compositional mixture remain. Of particular concern are large model diversities for contributions by dust and carbonaceous aerosol, because they lead to significant uncertainty in aerosol absorption (aab). Since aot and aab, both, influence the aerosol impact on the radiative energy-balance, the aerosol (direct) forcing uncertainty in modeling is larger than differences in aot might suggest. New diagnostic approaches are proposed to trace model differences in terms of aerosol processing and transport: These include the prescription of common input (e.g. amount, size and injection of aerosol component emissions) and the use of observational capabilities from ground (e.g. measurements networks) or space (e.g. correlations between aerosol and clouds).

Description: In late May 2005 unusual high levels of solar ultraviolet radiation were observed over central Europe. In Northern Germany the measured irradiance of erythemally effective radiation exceeded the climatological mean by more than about 20%. An extreme low ozone event for the season coincided with high solar elevation angles and high pressure induced clear sky conditions leading to the highest value of erythemal UV-radiation ever observed over this location in May since 1994. This hereafter called "ozone mini-hole" was caused by an elevation of tropopause height accompanied with a poleward advection of ozone-poor air from the tropics. The resultant increase in UV-radiation is of particular significance for human health. Dynamically induced low ozone episodes that happen in late spring can considerably enhance the solar UV-radiation in mid latitudes and therefore contribute to the UV-burden of people living in these regions.

Description: Simulation results of global aerosol models have been assembled in the framework of the AeroCom intercomparison exercise. In this paper, we analyze the life cycles of dust, sea salt, sulfate, black carbon and particulate organic matter as simulated by sixteen global aerosol models. The differences among the results (model diversities) for sources and sinks, burdens, particle sizes, water uptakes, and spatial dispersals have been established. These diversities have large consequences for the calculated radiative forcing and the aerosol concentrations at the surface. Processes and parameters are identified which deserve further research. The AeroCom all-models-average emissions are dominated by the mass of sea salt (SS), followed by dust (DU), sulfate (SO4), particulate organic matter (POM), and finally black carbon (BC). Interactive parameterizations of the emissions and contrasting particles sizes of SS and DU lead generally to higher diversities of these species, and for total aerosol. The lower diversity of the emissions of the fine aerosols, BC, POM, and SO4, is due to the use of similar emission inventories, and does therefore not necessarily indicate a better understanding of their sources. The diversity of SO4-sources is mainly caused by the disagreement on depositional loss of precursor gases and on chemical production. The diversities of the emissions are passed on to the burdens, but the latter are also strongly affected by the model-specific treatments of transport and aerosol processes. The burdens of dry masses decrease from largest to smallest: DU, SS, SO4, POM, and BC. The all-models-average residence time is shortest for SS with about half a day, followed by SO4 and DU with four days, and POM and BC with six and seven days, respectively. The wet deposition rate is controlled by the solubility and increases from DU, BC, POM to SO4 and SS. It is the dominant sink for SO4, BC, and POM, and contributes about one third to the total removal of SS and DU species. For SS and DU we find high diversities for the removal rate coefficients and deposition pathways. Models do neither agree on the split between wet and dry deposition, nor on that between sedimentation and other dry deposition processes. We diagnose an extremely high diversity for the uptake of ambient water vapor that influences the particle size and thus the sink rate coefficients. Furthermore, we find little agreement among the model results for the partitioning of wet removal into scavenging by convective and stratiform rain. Large differences exist for aerosol dispersal both in the vertical and in the horizontal direction. In some models, a minimum of total aerosol concentration is simulated at the surface. Aerosol dispersal is most pronounced for SO4 and BC and lowest for SS. Diversities are higher for meridional than for vertical dispersal, they are similar for the individual species and highest for SS and DU. For these two components we do not find a correlation between vertical and meridional aerosol dispersal. In addition the degree of dispersals of SS and DU is not related to their residence times. SO4, BC, and POM, however, show increased meridional dispersal in models with larger vertical dispersal, and dispersal is larger for longer simulated residence times.

Description: Extensive ozone measurements were made during the second SAGE III Ozone Loss and Validation Experiment (SOLVE II). We compare high-latitude line-of-sight (LOS) slant column ozone measurements from the NASA DC-8 to ozone simulated by forward integration of measurement-derived ozone fields constructed both with and without the assumption of horizontal homogeneity. The average bias and rms error of the simulations assuming homogeneity are relatively small (−6 and 10%, respectively) in comparison to the LOS measurements. The comparison improves significantly (−2% bias; 8% rms error) using forward integrations of three-dimensional proxy ozone fields reconstructed from potential vorticity-O3 correlations. The comparisons provide additional verification of the proxy fields and quantify the influence of large-scale ozone inhomogeneity. The spatial inhomogeneity of the atmosphere is a source of error in the retrieval of trace gas vertical profiles and column abundance from LOS measurements, as well as a complicating factor in intercomparisons that include LOS measurements at large solar zenith angles.

Description: Recent observations have detected surface active organics in atmospheric aerosols. We have studied the reaction of N2O5 on aqueous natural seawater and NaCl aerosols as a function of sodium dodecyl sulfate (SDS) concentration to test the effect of varying levels of surfactant on gas-aerosol reaction rates. SDS was chosen as a proxy for naturally occurring long chain monocarboxylic acid molecules, such as palmitic or stearic acid, because of its solubility in water and well-characterized surface properties. Experiments were performed using a newly constructed aerosol flow tube coupled to a chemical ionization mass spectrometer for monitoring the gas phase, and a differential mobility analyzer/condensation particle counter for determining aerosol surface area. We find that the presence of ~3.5wt% SDS in the aerosol, which corresponds to a monolayer surface coverage of ~2×1014 molecules cm-2, suppresses the N2O5 reaction probability, γN2O5, by approximately a factor of ten, independent of relative humidity. Consistent with this observation is a similar reduction in the rate of ClNO2 product generation measured simultaneously. However, the product yield remains nearly constant under all conditions. The degree of suppression is strongly dependent on SDS content in the aerosol, with no discernable effect at 0.1wt% SDS, but significant suppression at what we predict to be submonolayer coverages with 0.3–0.6wt% SDS on NaCl and natural seawater aerosols, respectively.

Description: The removal of molecular hydrogen (H2) from the atmosphere is dominated by the uptake in soils. Notwithstanding, estimates of the magnitude of this important process on a global scale are highly uncertain. The CARIBIC aircraft observations of the seasonal variations of H2 and its D/H isotopic ratio in the Northern Hemisphere allow an independent, better constrained estimate. We derive that 82% of the annual turnover of tropospheric H2 is due to soil uptake, equaling 88 (±11)Tg a-1, of which the Northern Hemisphere alone accounts for 62 (±10)Tg a-1. Our calculations further show that tropospheric H2 has a lifetime of only 1.4 (±0.2) years – significantly shorter than the recent estimate of ~2 years – which is expected to decrease in the future. In addition, our independent top-down approach, confined by the global and hemispheric sinks of H2, indicates 64 (±12)Tg a-1 emissions from various sources of volatile organic compounds by photochemical oxidation in the atmosphere. This estimate is as much as up to 60% larger than the previous estimates. This large airborne production of H2 helps to explain the fairly homogeneous distribution of H2 in the troposphere.

Description: The recent important developments in satellite measurements of the composition of the lower atmosphere open the challenging perspective to use such measurements as independent information on sources and sinks of atmospheric pollutants. This study explores the possibility to improve estimates of gridded NOx emissions used in a continental scale chemistry transport model (CTM), CHIMERE, by employing measurements performed by the GOME and SCIAMACHY instruments. We set-up an original inverse modelling scheme that not only enables a computationally efficient optimisation of the spatial distribution of seasonally averaged NOx emissions (during summertime), but also allows estimating uncertainties in input data and a priori emissions. The key features of our method are (i) replacement of the CTM by a set of empirical models describing the relationships between tropospheric NO2 columns and NOx emissions with sufficient accuracy, (ii) combination of satellite data for tropospheric NO2 columns with ground based measurements of near surface NO2 concentrations, and (iii) evaluation of uncertainties in a posteriori emissions by means of a special Bayesian Monte-Carlo experiment which is based on random sampling of errors of both NO2 columns and emission rates. We have estimated the uncertainty in a priori emissions based on the EMEP emission inventory to be about 1.9 (in terms of geometric standard deviation) and found the uncertainty in a posteriori emissions obtained from our inverse modelling scheme to be significantly lower (about 1.4). It is found also that a priori NOx emission estimates are probable to be persistently biased in many regions of Western Europe, and that the use of a posteriori emissions in the CTM improves the agreement between the modelled and measured data.

Description: Understanding sources, concentrations, and transformations of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere is important because of their potent mutagenicity and carcinogenicity. The measurement of particle-bound PAHs by three different methods during the Mexico City Metropolitan Area field campaign in April 2003 presents a unique opportunity for characterization of these compounds and intercomparison of the methods. The three methods are (1) collection and analysis of bulk samples for time-integrated gas- and particle-phase speciation by gas chromatography/mass spectrometry; (2) aerosol photoionization for fast detection of PAHs on particles' surfaces; and (3) aerosol mass spectrometry for fast analysis of size and chemical composition. This research represents the first time aerosol mass spectrometry has been used to measure ambient PAH concentrations and the first time that fast, real-time methods have been used to quantify PAHs alongside traditional filter-based measurements in an extended field campaign. Speciated PAH measurements suggest that motor vehicles and garbage and wood burning are important sources in Mexico City. The diurnal concentration patterns captured by aerosol photoionization and aerosol mass spectrometry are generally consistent. Ambient concentrations of particle-phase PAHs typically peak at ~110 ng m-3 during the morning rush hour and rapidly decay due to changes in source activity patterns and dilution as the boundary layer rises, although surface-bound PAH concentrations decay faster. The more rapid decrease in surface versus bulk PAH concentrations during the late morning suggests that freshly emitted combustion-related particles are quickly coated by secondary aerosol material in Mexico City's atmosphere and may also be transformed by heterogeneous reactions.

Description: The largest uncertainty in the radiative forcing of climate change over the industrial era is that due to aerosols, a substantial fraction of which is the uncertainty associated with scattering and absorption of shortwave (solar) radiation by anthropogenic aerosols in cloud-free conditions (IPCC, 2001). Quantifying and reducing the uncertainty in aerosol influences on climate is critical to understanding climate change over the industrial period and to improving predictions of future climate change for assumed emission scenarios. Measurements of aerosol properties during major field campaigns in several regions of the globe during the past decade are contributing to an enhanced understanding of atmospheric aerosols and their effects on light scattering and climate. The present study, which focuses on three regions downwind of major urban/population centers (North Indian Ocean (NIO) during INDOEX, the Northwest Pacific Ocean (NWP) during ACE-Asia, and the Northwest Atlantic Ocean (NWA) during ICARTT), incorporates understanding gained from field observations of aerosol distributions and properties into calculations of perturbations in radiative fluxes due to these aerosols. This study evaluates the current state of observations and of two chemical transport models (STEM and MOZART). Measurements of burdens, extinction optical depth (AOD), and direct radiative effect of aerosols (DRE – change in radiative flux due to total aerosols) are used as measurement-model check points to assess uncertainties. In-situ measured and remotely sensed aerosol properties for each region (mixing state, mass scattering efficiency, single scattering albedo, and angular scattering properties and their dependences on relative humidity) are used as input parameters to two radiative transfer models (GFDL and University of Michigan) to constrain estimates of aerosol radiative effects, with uncertainties in each step propagated through the analysis. Constraining the radiative transfer calculations by observational inputs increases the clear-sky, 24-h averaged AOD (34±8%), top of atmosphere (TOA) DRE (32±12%), and TOA direct climate forcing of aerosols (DCF – change in radiative flux due to anthropogenic aerosols) (37±7%) relative to values obtained with "a priori" parameterizations of aerosol loadings and properties (GFDL RTM). The resulting constrained clear-sky TOA DCF is −3.3±0.47, −14±2.6, −6.4±2.1 Wm−2 for the NIO, NWP, and NWA, respectively. With the use of constrained quantities (extensive and intensive parameters) the calculated uncertainty in DCF was 25% less than the "structural uncertainties" used in the IPCC-2001 global estimates of direct aerosol climate forcing. Such comparisons with observations and resultant reductions in uncertainties are essential for improving and developing confidence in climate model calculations incorporating aerosol forcing.

Description: Biomass burning activities emit high concentrations of aerosol particles to the atmosphere. Such particles can interact with solar radiation, decreasing the amount of light reaching the surface and increasing the fraction of diffuse radiation through scattering processes, and thus has implications for photosynthesis within plant canopies. This work reports results from photosynthetically active radiation (PAR) and aerosol optical depth (AOD) measurements conducted simultaneously at Reserva Biológica do Jaru (Rondonia State, Brazil) during LBA/SMOCC (Large-Scale Biosphere-Atmosphere Experiment in Amazonia/ Smoke, Aerosols, Clouds, Rainfall, and Climate) and RaCCI (Radiation, Cloud, and Climate Interactions in the Amazon during the Dry-to-Wet Transition Season) field experiments from 15 September to 15 November 2002. AOD values were retrieved from an AERONET (Aerosol Robotic Network) radiometer, MODIS (Moderate Resolution Spectroradiometer) and a portable sunphotometer from the United States Department of Agriculture – Forest Service. Significant reduction of PAR irradiance at the top of the canopy was observed due to the smoke aerosol particles layer. This radiation reduction affected turbulent fluxes of sensible and latent heats. The increase of AOD also enhanced the transmission of PAR inside the canopy. As a consequence, the availability of diffuse radiation was enhanced due to light scattering by the aerosol particles. A complex relationship was identified between light availability inside the canopy and net ecosystem exchange (NEE). The results showed that the increase of aerosol optical depth corresponded to an increase of CO2 uptake by the vegetation. However, for even higher AOD values, the corresponding NEE was lower than for intermediate values. As expected, water vapor pressure deficit (VPD), retrieved at 28m height inside the canopy, can also affect photosynthesis. A decrease in NEE was observed as VPD increased. Further studies are needed to better understand these findings, which were reported for the first time for the Amazon region under smoky conditions.

Description: Highest atmospheric ozone production rates can be found at around 30 km in the tropical stratosphere, leading to ozone mixing ratios of about 10 ppmv. Those stratospheric air masses are then transported to extra-tropical latitudes via the Brewer-Dobson circulation. This is considered the main mechanism to generate mid- and high latitude ozone. By applying the climate-chemistry models E39/C and MAECHAM4/CHEM, this view is investigated in more detail. The origin of ozone in the troposphere and stratosphere is analysed, by incorporating a diagnostics ("marked ozone origin tracers") into the models, which allows to identify the origin of ozone. In most regions the simulated local ozone concentration is dominated by local ozone production, i.e. less than 50% of the ozone at higher latitudes of the stratosphere is produced in the tropics, which conflicts with the idea that the tropics are the global source for stratospheric ozone. Although episodic stratospheric intrusions occur basically everywhere, the main ozone stratosphere-to-troposphere exchange is connected to exchange processes at the sub-tropical jet-stream. The simulated tropospheric influx of ozone amounts to 420 Tg per year, and originates in the Northern Hemisphere from the extra-tropical stratosphere, whereas in the Southern Hemisphere a re-circulation of tropical tropospheric ozone contributes most to the influx of ozone into the troposphere. In the model E39/C, the upper troposphere of both hemispheres is clearly dominated by tropical tropospheric ozone (40%–50%) except for northern summer hemisphere, where the tropospheric contribution (from the tropics as well as from the Northern Hemisphere) does not exceed 20%.

Description: OH and HO2 concentrations were measured simultaneously at the Mace Head Atmospheric Research Station in the summer of 2002 during the NAMBLEX (North Atlantic Marine Boundary Layer EXperiment) field campaign. OH was measured by laser-induced fluorescence employing the FAGE (Fluorescence Assay by Gas Expansion) technique, with a mean daytime detection limit of 2.7×105 molecule cm−3 (5 min acquisition period; signal-to-noise ratio = 1). HO2 was detected as OH following its chemical conversion through addition of NO, with a mean detection limit of 4.4×106 molecule cm−3. The diurnal variation of OH was measured on 24 days, and that of HO2 on 17 days. The local solar noon OH concentrations ranged between (3–8)×106 molecule cm−3, with a 24 h mean concentration of 9.1×105 molecule cm−3. The local solar noon HO2 concentrations were (0.9–2.1)×108 molecule cm−3 (3.5–8.2 pptv), with a 24 h mean concentration of 4.2×107 molecule cm−3 (1.6 pptv). HO2 radicals in the range (2–3)×107 molecule cm−3 were observed at night. During NAMBLEX, a comprehensive suite of supporting measurements enabled a detailed study of the behaviour of HOx radicals under primarily clean marine conditions. Steady state expressions are used to calculate OH and HO2 concentrations and to evaluate the effect of different free-radical sources and sinks. The diurnally averaged calculated to measured OH ratio was 1.04±0.36, but the ratio displays a distinct diurnal variation, being less than 1 during the early morning and late afternoon/evening, and greater than 1 in the middle of the day. For HO2 there was an overprediction, with the agreement between calculated and measured concentrations improved by including reaction with measured IO and BrO radicals and uptake to aerosols. Increasing the concentration of IO radicals included in the calculations to above that measured by a DOAS instrument with an absorption path located mainly over the ocean, reflecting the domination of the inter-tidal region as an iodine source at Mace Head, led to further improvement. The results are compared with previous measurements at Mace Head, and elsewhere in the remote marine boundary layer.

Description: Mesoscale meteorological modelling is an important tool to help understand air pollution and heat island effects in urban areas. Accurate wind simulations are difficult to obtain in areas of weak synoptic forcing. Local factors have a dominant role in the circulation and include land surface parameters and their interaction with the atmosphere. This paper examines an episode during the MCMA-2003 field campaign held in the Mexico City Metropolitan Area (MCMA) in April of 2003. Because the episode has weak synoptic forcing, there is the potential for the surface heat budget to influence the local meteorology. High resolution satellite observations are used to specify the land use, vegetation fraction, albedo and surface temperature in the MM5 model. Making use of these readily available data leads to improved meteorological simulations in the MCMA, both for the wind circulation patterns and the urban heat island. Replacing values previously obtained from land-use tables with actual measurements removes the number of unknowns in the model and increases the accuracy of the energy budget. In addition to improving the understanding of local meteorology, this sets the stage for the use of advanced urban modules.

Description: 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 20 K above the local tropopause in spring, up to 30 K in summer, and up to 40 K in autumn. Above these heights, and in winter, net ozone production is negative.

Description: Mexico City lies in a high altitude basin where air quality and pollutant fate is strongly influenced by local winds. The combination of high terrain with weak synoptic forcing leads to weak and variable winds with complex circulation patterns. A gap wind entering the basin in the afternoon leads to very different wind convergence lines over the city depending on the meteorological conditions. Surface and upper-air meteorological observations are analysed during the MCMA-2003 field campaign to establish the meteorological conditions and obtain an index of the strength and timing of the gap wind. A mesoscale meteorological model (MM5) is used in combination with high-resolution satellite data for the land surface parameters and soil moisture maps derived from diurnal ground temperature range. A simple method to map the lines of wind convergence both in the basin and on the regional scale is used to show the different convergence patterns according to episode types. The gap wind is found to occur on most days of the campaign and is the result of a temperature gradient across the southern basin rim which is very similar from day to day. Momentum mixing from winds aloft into the surface layer is much more variable and can determine both the strength of the flow and the pattern of the convergence zones. Northerly flows aloft lead to a weak jet with an east-west convergence line that progresses northwards in the late afternoon and early evening. Westerlies aloft lead to both stronger gap flows due to channelling and winds over the southern and western basin rim. This results in a north-south convergence line through the middle of the basin starting in the early afternoon. Improved understanding of basin meteorology will lead to better air quality forecasts for the city and better understanding of the chemical regimes in the urban atmosphere.

Description: Number fractions of externally mixed particles of four different sizes (30, 50, 80, and 150 nm in diameter) were measured using a Volatility Tandem DMA. The system was operated in a street canyon (Eisenbahnstrasse, EI) and at an urban background site (Institute for Tropospheric Research, IfT), both in the city of Leipzig, Germany as well as at a rural site (Melpitz (ME), a village near Leipzig). Intensive campaigns of 3–5 weeks each took place in summer 2003 as well as in winter 2003/04. The data set thus obtained provides mean number fractions of externally mixed soot particles of atmospheric aerosols in differently polluted areas and different seasons (e.g. at 80 nm on working days, 60% (EI), 22% (IfT), and 6% (ME) in summer and 26% (IfT), and 13% (ME) in winter). Furthermore, a new method is used to calculate the size distribution of these externally mixed soot particles from parallel number size distribution measurements. A decrease of the externally mixed soot fraction with decreasing urbanity and a diurnal variation linked to the daily traffic changes demonstrate, that the traffic emissions have a significant impact on the soot fraction in urban areas. This influence becomes less in rural areas, due to atmospheric mixing and transformation processes. For estimating the source strength of soot particles emitted by vehicles (veh), soot particle emission factors were calculated using the Operational Street Pollution Model (OSPM). The emission factor for an average vehicle was found to be (1.5±0.4)·1014 #(km·veh). The separation of the emission factor into passenger cars ((5.8±2)·1013} #(km·veh)) and trucks ((2.5±0.9)·1015 #(km·veh)) yielded in a 40-times higher emission factor for trucks compared to passenger cars.

Description: Several thousands of ozone vertical profiles collected in the course of the MOZAIC programme (Measurements of Ozone, Water Vapour, Carbon Monoxide and Nitrogen Oxides by In-Service Airbus Aircraft) from August 1994 to February 2002 are investigated to bring out climatological and interannual variability aspects. The study is centred on the most frequently visited MOZAIC airports, i.e. Frankfurt (Germany), Paris (France), New York (USA) and the cluster of Tokyo, Nagoya and Osaka (Japan). The analysis focuses on the vertical integration of ozone from the ground to the dynamical tropopause and the vertical integration of stratospheric-origin ozone throughout the troposphere. The characteristics of the MOZAIC profiles: frequency of flights, accuracy, precision, and depth of the troposphere observed, are presented. The climatological analysis shows that the Tropospheric Ozone Column (TOC) seasonal cycle ranges from a wintertime minimum at all four stations to a spring-summer maximum in Frankfurt, Paris, and New York. Over Japan, the maximum occurs in spring presumably because of the earlier springtime sun. The incursion of monsoon air masses into the boundary layer and into the mid troposphere then steeply diminishes the summertime value. Boundary layer contributions to the TOC are 10% higher in New York than in Frankfurt and Paris during spring and summer, and are 10% higher in Japan than in New York, Frankfurt and Paris during autumn and early spring. Local and remote anthropogenic emissions, and biomass burning over upstream regions of Asia may be responsible for the larger low- and mid-tropospheric contributions to the tropospheric ozone column over Japan throughout the year except during the summer-monsoon season. A simple Lagrangian analysis has shown that a minimum of 10% of the TOC is of stratospheric-origin throughout the year. Investigation of the short-term trends of the TOC over the period 1995–2001 shows a linear increase 0.7%/year in Frankfurt, 0.8%/year in Japan, 1.1%/year in New York and 1.6%/year in Paris for the reduced 1995–1999 period. Dominant ingredients of these positive short-term trends are the continuous increase of wintertime tropospheric ozone columns from 1996 to 1999 and the positive contributions of the mid troposphere whatever the season.

Description: Three-dimensional, nested tracer simulations of a pollution plume originating from the Indian sub-continent over the Indian Ocean, in the framework of the Indian Ocean Experiment (INDOEX), between 5 and 9 March 1999, were performed with the Regional Atmospheric Modeling System (RAMS), to provide insight into the transport patterns of the pollutants, as well as to investigate the dynamical mechanisms controlling the vertical structure of the plume and its evolution in the vicinity of the Maldives Islands. Airborne and ground-based LIDAR observations of the structure of the haze plume made on 7 March 1999 were used to assess the quality of the simulations, as well as the impact of grid resolution on the vertical structure of the simulated plume. It is shown that, over the Arabian Sea, in the vicinity of the Maldives Islands, the pollutants composing the plume observed by the airborne LIDAR essentially originated from the city of Madras and that the vertical structure of the plume was controlled by the diurnal cycle of the continental boundary layer depth. A combination of tracer simulations and remote sensing observations (airborne LIDAR, ship-borne photometer, ground-based LIDAR in Goa) was used to analyse the diurnal evolution of the haze plume over the sea. We find evidence that the sea breeze circulation and orographic lifting taking place in the southern part of the Indian sub-continent during the daytime play a crucial role in the modulation of the continental boundary layer depth, and in turn, the haze plume depth. The eastward shift of the subtropical high from central India to the Bay of Bengal after 6 March lead to an increase in the tracer concentrations simulated over the Arabian Sea, in the region of intensive observations north of the Maldives, as transport pathways form Hyderabad and Madras were modified significantly. The nesting of a high horizontal resolution domain (5 km, with 39 vertical levels below 4000 m above mean seal level) allows for a better representation of local dynamics, the circulation of sea and mountains breezes, and therefore a noticeable improvement in the representation of the pollutants' plume in the simulation.

Description: The quality of global sea level pressure patterns has been assessed for simulations by 23 coupled climate models. Most models showed high pattern correlations. With respect to the explained spatial variance, many models showed serious large-scale deficiencies, especially at mid-latitudes. Five models performed well at all latitudes and for each month of the year. Three models had a reasonable skill. We selected the five models with the best pressure patterns for a more detailed assessment of their simulations of the climate in Central Europe. We analysed observations and simulations of monthly mean geostrophic flow indices and of monthly mean temperature and precipitation. We used three geostrophic flow indices: the west component and south component of the geostrophic wind at the surface and the geostrophic vorticity. We found that circulation biases were important, and affected precipitation in particular. Apart from these circulation biases, the models showed other biases in temperature and precipitation, which were for some models larger than the circulation induced biases. For the 21st century the five models simulated quite different changes in circulation, precipitation and temperature. Precipitation changes appear to be primarily caused by circulation changes. Since the models show widely different circulation changes, especially in late summer, precipitation changes vary widely between the models as well. Some models simulate severe drying in late summer, while one model simulates significant precipitation increases in late summer. With respect to the mean temperature the circulation changes were important, but not dominant. However, changes in the distribution of monthly mean temperatures, do show large indirect influences of circulation changes. Especially in late summer, two models simulate very strong warming of warm months, which can be attributed to severe summer drying in the simulations by these models. The models differ also significantly in the simulated warming of cold winter months. Finally, the models simulate rather different changes in North Atlantic sea surface temperature, which is likely to impact on changes in temperature and precipitation. These results imply that several important aspects of climate change in Central Europe are highly uncertain. Other aspects of the simulated climate change appear to be more robust. All models simulate significant warming all year round and an increase in precipitation in the winter half-year.

Description: In this study, we theoretically investigate the reconstruction of 2-D cross sections through Gaussian concentration distributions, e.g. emission plumes, from long path DOAS measurements along a limited number of light paths. This is done systematically with respect to the extension of the up to four peaks and for six different measurement setups with 2-4 telescopes and 36 light paths each. We distinguish between cases with and without additional background concentrations. Our approach parametrises the unknown distribution by local piecewise constant or linear functions on a regular grid and solves the resulting discrete, linear system by a least squares minimum norm principle. We show that the linear parametrisation not only allows better representation of the distributions in terms of discretisation errors, but also better inversion of the system. We calculate area integrals of the concentration field (i.e. total emissions rates for non-vanishing perpendicular wind speed components) and show that reconstruction errors and reconstructed area integrals within the peaks for narrow distributions crucially depend on the resolution of the reconstruction grid. A recently suggested grid translation method for the piecewise constant basis functions, combining reconstructions from several shifted grids, is modified for the linear basis functions and proven to reduce overall reconstruction errors, but not the uncertainty of concentration integrals. We suggest a procedure to subtract additional background concentration fields before inversion. We find large differences in reconstruction quality between the geometries and conclude that, in general, for a constant number of light paths increasing the number of telescopes leads to better reconstruction results. It appears that geometries that give better results for negligible measurement errors and parts of the geometry that are better resolved are also less sensitive to increasing measurement errors.

Description: The Empirical Orthogonal Function (EOF) retrieval technique consists of calculating the eigenvectors of the spectra to later perform a linear regression between these and the atmospheric states, this first step is known as training. At a later stage, known as performing the retrievals, atmospheric profiles are derived from measured atmospheric radiances. When EOF retrievals are trained with a statistically different data set than the one used for retrievals two basic problems arise: significant biases appear in the retrievals and differences between the covariances of the training data set and the measured data set degrade them. The retrieved profiles will show a bias with respect to the real profiles which comes from the combined effect of the mean difference between the training and the real spectra projected into the atmospheric state space and the mean difference between the training and the atmospheric profiles. The standard deviations of the difference between the retrieved profiles and the real ones show different behavior depending on whether the covariance of the training spectra is bigger, equal or smaller than the covariance of the measured spectra with which the retrievals are performed. The procedure to correct for these effects is shown both analytically and with a measured example. It consists of first calculating the average and standard deviation of the difference between real observed spectra and the calculated spectra obtained from the real atmospheric state and the radiative transfer model used to create the training spectra. In a later step, measured spectra must be bias corrected with this average before performing the retrievals and the linear regression of the training must be performed adding noise to the spectra corresponding to the aforementioned calculated standard deviation. This procedure is optimal in the sense that to improve the retrievals one must resort to using a different training data set or a different algorithm.

Description: The sensitivity of ground-based instruments measuring in the infrared with respect to tropospheric water vapour content is generally limited to the lower and middle troposphere. The large vertical gradients and variabilities avoid a better sensitivity for the upper troposphere/lower stratosphere (UT/LS) region. In this work an optimised retrieval is presented and it is demonstrated that compared to a commonly applied method, it improves the performance of the FTIR technique. The reasons for this improvement and the possible deficiencies of the method are discussed. Only by applying the method proposed here and using measurements performed at mountain observatories can water vapour variabilities in the UT/LS be detected in a self-consistent manner. The precision, expressed as noise to signal ratio, is estimated at 45%. In the middle and lower troposphere, precisions of 22% are achieved. These estimations are confirmed by a comparison of retrieval results based on real FTIR measurements with coinciding measurements of synoptical meteorological radiosondes.

Description: According to atmospheric observations new particle formation seems to be a function of sulphuric acid concentration to the power from one to two. The nucleation theorem then predicts that the critical cluster contains one to two sulphuric acid molecules. However, existing nucleation theories predicts that the power is more (or equal) than 2. Here we present an activation theory, which can explain the observed slope. In cluster activation the clusters containing one sulphuric acid molecule will activate for further growth due to heterogeneous nucleation, heterogeneous chemical reactions including polymerization or activation of soluble clusters. In the activation process organic vapours are typically needed as condensing agents.

Description: During the Arctic winter of 2000/01, ground-based FTIR and millimetre-wave measurements revealed significant amounts of ClO over Kiruna after the final warming in February 2001. In fact, column amounts of ClO were still increased in March 2001 when temperatures were about 20K above the PSC (Polar Stratospheric Clouds) threshold. At these temperatures, chlorine activation due to heterogeneous processes on PSCs is not possible even in the presence of strong lee wave effects. In order to discuss possible reasons of this feature, time series of other chemical species will be presented and discussed, too. Measurements of HF and COF2 indicated that vortex air was still observed in mid-March 2001. Since the time series of HNO3 column amounts do not give any evidence of a denitrification later than 11 February, chlorine activation persisting for several weeks after the presence of PSCs due to denitrification is rather unlikely. The photolysis of ClONO2-rich air which had been formed at the end of February and beginning of March 2001 as well as chlorine activation due to the presence of an unusual aerosol layer are discussed as possible causes of the increased ClO column amounts after the final warming.

Description: An Aerodyne Aerosol Mass Spectrometer (AMS) was deployed at the CENICA Supersite, during the Mexico City Metropolitan Area field study (MCMA-2003) from 31 March-4 May 2003 to investigate particle concentrations, sources, and processes. The AMS provides real time information on mass concentration and composition of the non-refractory species in particulate matter less than 1 µm (NR-PM1) with high time and size-resolution. In order to account for the refractory material in the aerosol, we also present estimates of Black Carbon (BC) using an aethalometer and an estimate of the aerosol soil component obtained from Proton-Induced X-ray Emission Spectrometry (PIXE) analysis of impactor substrates. Comparisons of AMS + BC + soil mass concentration with other collocated particle instruments (a LASAIR Optical Particle Counter, a PM2.5 Tapered Element Oscillating Microbalance (TEOM), and a PM2.5 DustTrak Aerosol Monitor) show that the AMS + BC + soil mass concentration is consistent with the total PM2.5 mass concentration during MCMA-2003 within the combined uncertainties. In Mexico City, the organic fraction of the estimated PM2.5 at CENICA represents, on average, 54.6% (standard deviation σ=10%) of the mass, with the rest consisting of inorganic compounds (mainly ammonium nitrate and sulfate/ammonium salts), BC, and soil. Inorganic compounds represent 27.5% of PM2.5 (σ=10%); BC mass concentration is about 11% (σ=4%); while soil represents about 6.9% (σ=4%). Size distributions are presented for the AMS species; they show an accumulation mode that contains mainly oxygenated organic and secondary inorganic compounds. The organic size distributions also contain a small organic particle mode that is likely indicative of fresh traffic emissions; small particle modes exist for the inorganic species as well. Evidence suggests that the organic and inorganic species are not always internally mixed, especially in the small modes. The aerosol seems to be neutralized most of the time; however, there were some periods when there was not enough ammonium to completely neutralize the nitrate, chloride and sulfate present. The diurnal cycle and size distributions of nitrate suggest local photochemical production. On the other hand, sulfate appears to be produced on a regional scale. There are indications of new particle formation and growth events when concentrations of SO2 were high. Although the sources of chloride are not clear, this species seems to condense as ammonium chloride early in the morning and to evaporate as the temperature increases and RH decreases. The total and speciated mass concentrations and diurnal cycles measured during MCMA-2003 are similar to measurements during a previous field campaign at a nearby location.

Description: The phase transitions and hygroscopic growth of two humic acid aerosols (Aldrich sodium salt and Leonardite Standard (IHSS)) and their mixtures with ammonium sulphate have been investigated using a combination of two techniques, Fourier transform infra-red (FTIR) spectroscopy and tandem differential mobility analysis (TDMA). A growth factor of 1.16 at 85% relative humidity (RH) was found for the Aldrich humic acid which can be regarded as an upper limit for growth factors of humic-like substances (HULIS) found in atmospheric aerosol and is significantly smaller than that of typical atmospheric inorganics. We find that the humic acid aerosols exhibit water uptake over all relative humidities with no apparent phase changes, suggesting that these aerosols readily form supersaturated droplets. In the mixed particles, the humic acid component decreases the deliquescence relative humidity (DRH) and increases the efflorescence relative humidity (ERH) of the ammonium sulphate component, and there is some degree of water uptake prior to ammonium sulphate deliquescence. In addition, at low RH, the FTIR spectra show that the ammonium is present in a different chemical environment in the mixed aerosols than in crystalline ammonium sulphate, perhaps existing as a complex with the humic materials. The growth factors of the mixed aerosols are intermediate between those of the single-component aerosols and can be predicted assuming that the inorganic and organic fractions take up water independently.

Description: A class of organic molecules extracted from atmospheric aerosol particles and isolated from fog and cloud water has been termed HUmic-LIke Substances (HULIS) due to a certain resemblance to terrestrial and aquatic humic and fulvic acids. In light of the interest that this class of atmospheric compounds currently attracts, we comprehensively review HULIS properties, as well as laboratory and field investigations concerning their formation and characterization in atmospheric samples. While sharing some important features such as polyacidic nature, accumulating evidence suggests that atmospheric HULIS differ substantially from terrestrial and aquatic humic substances. Major differences between HULIS and humic substances, including smaller average molecular weight, lower aromatic moiety content, greater surface activity, better droplet activation ability, as well as others, are highlighted. Several alternatives are proposed that may explain such differences: (1) the possibility that mono- and di-carboxylic acids and mineral acids abundant in the atmosphere prevent the formation of large humic "supramolecular associations"; (2) that large humic macromolecules are destroyed in the atmosphere by UV radiation, O3, and OH- radicals; (3) that "HULIS" actually consists of a complex, unresolved mixture of relatively small molecules rather than macromolecular entities; and (4) that HULIS formed via abiotic and short-lived oxidative reaction pathways differ substantially from humic substances formed over long time periods via biologically-mediated reactions. It should also be recalled that the vast majority of studies of HULIS relate to the water soluble fraction, which would include only the fulvic acid fraction of humic substances, and exclude the humic acid (base-soluble) and humin (insoluble) fractions of humic substances. A significant effort towards adopting standard extraction and characterization methods is required to develop a better and meaningful comparison between different HULIS samples.

Description: Aerosol optical properties were retrieved from direct and diffuse spectral irradiance measurements made by a multi-filter rotating shadowband radiometer (MFRSR) at the island of Lampedusa (35.5° N, 12.6° E), in the Central Mediterranean, in the period July 2001–September 2003. In a companion paper (Pace et al., 2006) the aerosol optical depth (AOD) and Ångström exponent were used together with airmass backward trajectories to identify and classify different aerosol types. The MFRSR diffuse-to-direct ratio (DDR) at 415.6 nm and 868.7 nm for aerosol classified as "biomass burning-urban/industrial", originating primarily from the European continent, and desert dust, originating from the Sahara, is used in this study to estimate the aerosol single scattering albedo (SSA). A detailed radiative transfer model is initialised with the measured aerosol optical depth; calculations are performed at the two wavelengths varying the SSA values until the modelled DDR matches the MFRSR observations. Sensitivity studies are performed to estimate how uncertainties on AOD, DDR, asymmetry factor (g), and surface albedo influence the retrieved SSA values. The results show that a 3% variation of AOD or DDR produce a change of about 0.02 in the retrieved SSA value at 415.6 and 868.7 nm; a ±0.06 variation of the asymmetry factor g produces a change of the estimated SSA of

Description: In this paper, we introduce a statistical method for examining and adjusting chemical-transport models. We illustrate the findings with total column ozone predictions, based on the University of Illinois at Urbana-Champaign 2-D (UIUC 2-D) chemical-transport model of the global atmosphere. We propose a general diagnostic procedure for the model outputs in total ozone over the latitudes ranging from 60° South to 60° North to see if the model captures some typical patterns in the data. The method proceeds in two steps to avoid possible collinearity issues. First, we regress the measurements given by a cohesive data set from the SBUV(/2) satellite system on the model outputs with an autoregressive noise component. Second, we regress the residuals of this first regression on the solar flux, the annual cycle, the Antarctic or Arctic Oscillation, and the Quasi Biennial Oscillation. If the coefficients from this second regression are statistically significant, then they mean that the model did not simulate properly the pattern associated with these factors. Systematic anomalies of the model are identified using data from 1979 to 1995, and statistically corrected afterwards. The 1996–2003 validation sample confirms that the combined approach yields better predictions than the direct UIUC 2-D outputs.

Description: Aerosols affect the Earth's energy budget directly by scattering and absorbing radiation and indirectly by acting as cloud condensation nuclei and, thereby, affecting cloud properties. However, large uncertainties exist in current estimates of aerosol forcing because of incomplete knowledge concerning the distribution and the physical and chemical properties of aerosols as well as aerosol-cloud interactions. In recent years, a great deal of effort has gone into improving measurements and datasets. It is thus feasible to shift the estimates of aerosol forcing from largely model-based to increasingly measurement-based. Our goal is to assess current observational capabilities and identify uncertainties in the aerosol direct forcing through comparisons of different methods with independent sources of uncertainties. Here we assess the aerosol optical depth (τ), direct radiative effect (DRE) by natural and anthropogenic aerosols, and direct climate forcing (DCF) by anthropogenic aerosols, focusing on satellite and ground-based measurements supplemented by global chemical transport model (CTM) simulations. The multi-spectral MODIS measures global distributions of aerosol optical depth (τ) on a daily scale, with a high accuracy of ±0.03±0.05τ over ocean. The annual average τ is about 0.14 over global ocean, of which about 21%±7% is contributed by human activities, as estimated by MODIS fine-mode fraction. The multi-angle MISR derives an annual average AOD of 0.23 over global land with an uncertainty of ~20% or ±0.05. These high-accuracy aerosol products and broadband flux measurements from CERES make it feasible to obtain observational constraints for the aerosol direct effect, especially over global the ocean. A number of measurement-based approaches estimate the clear-sky DRE (on solar radiation) at the top-of-atmosphere (TOA) to be about -5.5±0.2 Wm-2 (median ± standard error from various methods) over the global ocean. Accounting for thin cirrus contamination of the satellite derived aerosol field will reduce the TOA DRE to -5.0 Wm-2. Because of a lack of measurements of aerosol absorption and difficulty in characterizing land surface reflection, estimates of DRE over land and at the ocean surface are currently realized through a combination of satellite retrievals, surface measurements, and model simulations, and are less constrained. Over the oceans the surface DRE is estimated to be -8.8±0.7 Wm-2. Over land, an integration of satellite retrievals and model simulations derives a DRE of -4.9±0.7 Wm-2 and -11.8±1.9 Wm-2 at the TOA and surface, respectively. CTM simulations derive a wide range of DRE estimates that on average are smaller than the measurement-based DRE by about 30-40%, even after accounting for thin cirrus and cloud contamination. A number of issues remain. Current estimates of the aerosol direct effect over land are poorly constrained. Uncertainties of DRE estimates are also larger on regional scales than on a global scale and large discrepancies exist between different approaches. The characterization of aerosol absorption and vertical distribution remains challenging. The aerosol direct effect in the thermal infrared range and in cloudy conditions remains relatively unexplored and quite uncertain, because of a lack of global systematic aerosol vertical profile measurements. A coordinated research strategy needs to be developed for integration and assimilation of satellite measurements into models to constrain model simulations. Enhanced measurement capabilities in the next few years and high-level scientific cooperation will further advance our knowledge.