ALBERT

Description: The operational numerical weather prediction model Lokalmodell LM with 7 km horizontal resolution was evaluated for simulations of the 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 speed 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: The heterogeneous reaction of N2O5 with mineral (Saharan) dust has been studied at T=298 K using a combination of Knudsen and DRIFTS cells for kinetic and product investigations, respectively. The initial uptake coefficient has been determined to be γ=(8.0±0.3)·10−2. This uptake slowly saturates into a steady state uptake of γ=(1.3±0.3)·10−2 suggesting that reaction of N2O5 with the mineral dust surface and hydrolysis of N2O5 on the surface take place simultaneously. Both uptake coefficients have been calculated on the basis of the geometric (projected) surface area of the sample and must therefore be regarded as upper limits. In addition, the product investigations show that N2O5 is irreversibly taken up to form nitrate on the surface. Recent model calculations suggest that the uptake rates of N2O5 on Saharan dust which we measured may be large enough to influence the photo-oxidant budget of the atmosphere.

Description: This study is devoted to the possible presence of cirrus clouds in the stratosphere. Three months of lidar data collected in the south of France (44° N) for detection of stratospheric cirrus are carefully analyzed. Most of the cirrus clouds appear to be located in the troposphere below the dynamical tropopause even when the cloud top is close to the thermal tropopause. Ten cirrus cases are found to be unambiguously located above the local dynamical tropopause according to high-resolution PV advection calculations. The highest cloud detected above the local tropopause (nearly 3 km above) is observed inside air masses that originate from the sub-tropical regions and are then transported rapidly to mid-latitudes through isentropic transport. The details of the air mass history is described with a 3-D trajectory model. The back-plumes indicate that the air mass, moist with respect to typical stratospheric air, was transported from the subtropical troposphere to the lowermost stratosphere in 4 days before detection above France. A continuous cooling of 5–10° along the trajectory took place during its transit. This cooling could have been partly responsible for the thin cirrus layer detected.

Description: Black carbon (BC) and polycyclic aromatic hydrocarbons (PAHs) are of concern due to their effects on climate and health. The main goal of this research is to provide the first estimate of emissions of BC and particle-phase PAHs (PPAHs) from motor vehicles in Mexico City. The emissions of other pollutants including carbon monoxide (CO), oxides of nitrogen (NOx), volatile organic compounds (VOCs), and particulate matter of diameter 2.5 μm and less (PM2.5) are also estimated. As a part of the Mexico City Metropolitan Area field campaign in April 2003 (MCMA-2003), a mobile laboratory was driven throughout the city. The laboratory was equipped with a comprehensive suite of gas and particle analyzers, including an aethalometer that measured BC and a photoionization aerosol sensor that measured PPAHs. While driving through traffic, the mobile lab continuously sampled exhaust plumes from the vehicles around it. We have developed a method of automatically identifying exhaust plumes, which are then used as the basis for calculation of fleet-average emissions. In the approximately 75 h of on-road sampling during the field campaign, we have identified ~30 000 exhaust measurement points that represent a variety of vehicle types and driving conditions. The large sample provides a basis for estimating fleet-average emission factors and thus the emission inventory. Motor vehicles in the Mexico City area are estimated to emit 1700±200 metric tons BC, 57±6 tons PPAHs, 1 190 000±40 000 tons CO, 120 000±3000 tons NOx, 240 000±50 000 tons VOCs, and 4400±400 tons PM2.5 per year, not including cold start emissions. The estimates for CO, NOx, and PPAHs may be low by up to 10% due to the slower response time of analyzers used to measure these species. Compared to the government's official motor vehicle emission inventory for the year 2002, the estimates for CO, NOx, VOCs, and PM2.5 are 38% lower, 23% lower, 27% higher, and 25% higher, respectively. The distributions of emission factors of BC, PPAHs, and PM2.5 are highly skewed, i.e. asymmetric, while those for benzene, measured as a surrogate for total VOCs, and NOx are less skewed. As a result, the total emissions of BC, PPAHs, and PM2.5 could be reduced by approximately 50% if the highest 20% of data points were removed, but "super polluters" are less influential on overall NOx and VOC emissions.

Description: Collections of samples were conducted for the determination of the size distributions of EC and OC during the intensive sampling campaigns of the POVA program, in two Alpine valleys of the French Alps, in summer and in winter. The comparison of concentrations obtained for samples collected in parallel with impactor- and filter-based methods is rather positive with slopes of 0.95 and 0.76 for OC and EC, respectively and correlations close to 1 (0.92 and 0.90 for OC and EC, respectively, n=26). This is an indication that the correction of pyrolysis seems to work for the impactor samples despite non even deposits. The size distributions of the concentrations of EC and OC present large evolutions between winter and summer, and between a suburban and a rural site. In winter, an overwhelming proportion of the mass fraction of both species is found in the droplet and accumulation modes, often (but not always) in association with sulfate and other chemical species resulting from secondary formation processes. Some indications of gas/particles exchanges can be found for the other parts of the size spectrum (the Aitken and super micron modes) in the case of the rural site. In summer, the changes are more drastic with, according to the case, a dominant droplet or accumulation mode. Particularly at the rural site, the large extent of processing of the aerosol due to gas/particles exchanges is evident for the Aitken and super micron modes, with increasing of the OC mass fractions in these size ranges. All of these observations give indications on the degree of internal vs. external mixing of the species investigated in the different modes.

Description: This paper presents the first global distributions of CO vertical profiles retrieved from a thermal infrared FTS working in the nadir geometry. It is based on the exploitation of the high resolution and high quality spectra measured by the Interferometric Monitor of Greenhouse gases (IMG) which flew onboard the Japanese ADEOS platform in 1996-1997. The retrievals are performed with an algorithm based on the Optimal Estimation Method (OEM) and are characterized in terms of vertical sensitivity and error budget. It is found that most of the IMG measurements contain between 1.5 and 2.2 independent pieces of information about the vertical distribution of CO from the lower troposphere to the upper troposphere-lower stratosphere (UTLS). The retrievals are validated against coincident NOAA/CMDL in situ surface measurements and NDSC/FTIR total columns measurements. The retrieved global distributions of CO are also found to be in good agreement with the distributions modeled by the GEOS-CHEM 3D CTM, highlighting the ability of IMG to capture the horizontal as well as the vertical structure of the CO distributions.

Description: Satellite-based measurements of Visible/NIR limb-scattered solar radiation are well suited for the detection and mapping of polar stratospheric clouds (PSCs). This publication describes a method to detect PCSs from limb scattering observations with the Scanning Imaging Absorption spectroMeter for Atmospheric CartograpHY (SCIAMACHY) on the European Space Agency's Envisat spacecraft. The method is based on a color-index approach and requires a priori knowledge of the stratospheric background aerosol loading in order to avoid false PSC identifications by stratospheric background aerosol. The method is applied to a sample data set including the 2003 PSC season in the Southern Hemisphere. The PSCs are correlated with coincident UKMO model temperature data, and with very few exceptions, the detected PSCs occur at temperatures below 195–198 K. Monthly averaged PSC descent rates are about 1.5 km/month for the −50° S to −75° S latitude range and assume a maximum between August and September with a value of about 2.5 km/month. The main cause of the PSC descent is the slow descent of the lower stratospheric temperature minimum.

Description: A series of 7-week sampling campaigns were conducted in urban background sites of six European cities as follows: Duisburg (autumn), Prague (winter), Amsterdam (winter), Helsinki (spring), Barcelona (spring) and Athens (summer). The campaigns were scheduled to include seasons of local public health concern due to high particulate concentrations or findings in previously conducted epidemiological studies. Aerosol samples were collected in parallel with two identical virtual impactors that divide air particles into fine (PM2.5) and coarse (PM2.5-10) size ranges. From the collected filter samples, elemental (EC) and organic (OC) carbon contents were analysed with a thermal-optical carbon analyser (TOA); total Ca, Ti, Fe, Si, Al and K by energy dispersive X-ray fluorescence (ED-XRF); As, Cu, Ni, V, and Zn by inductively coupled plasma mass spectrometry (ICP/MS); Ca2+, succinate, malonate and oxalate by ion chromatography (IC); and the sum of levoglucosan+galactosan+mannosan (∑MA) by liquid chromatography mass spectrometry (LC/MS). The campaign means of PM2.5 and PM2.5-10 were 8.3-29.6 µg m-3 and 5.4-28.7 µg m-3, respectively. The contribution of particulate organic matter (POM) to PM2.5 ranged from 21% in Barcelona to 54% in Prague, while that to PM2.5-10 ranged from 10% in Barcelona to 27% in Prague. The contribution of EC was higher to PM2.5 (5-9%) than to PM2.5-10 (1-6%) in all the six campaigns. Carbonate (C(CO3), that interferes with the TOA analysis, was detected in PM2.5-10 of Athens and Barcelona but not elsewhere. It was subtracted from the OC by a simple integration method that was validated. The CaCO3 accounted for 55% and 11% of PM2.5-10 in Athens and Barcelona, respectively. It was anticipated that combustion emissions from vehicle engines affected the POM content in PM2.5 of all the six sampling campaigns, but a comparison of mass concentration ratios of the selected inorganic and organic tracers of common sources of organic material to POM suggested also interesting differences in source dominance during the campaign periods: Prague (biomass and coal combustion), Barcelona (fuel oil combustion, secondary photochemical organics) and Athens (secondary photochemical organics). The on-going toxicological studies will clarify the health significance of these findings.

Description: In situ atmospheric observations of bromoform (CHBr3) made over a 2.5 year period at Mace Head, Ireland from May 2001- Dec 2003, including during the NAMBLEX (North Atlantic Marine Boundary Layer Experiment) campaign, show broad maxima from spring until autumn and winter minima, with mixing ratios of 5.3+1.0 pptv (mid March - mid October) and 1.8+0.8 pptv (December-February). This indicates that, unlike CHCl3, which has a summer minimum and winter maximum at Mace Head, local biological sources of CHBr3 have a greater influence on the atmospheric data than photochemical decay during long-range transport. The emission sources are predominantly macroalgal, but we find evidence for a small terrestrial flux from peatland ecosystems, which so far has not been accounted for in the CHBr3 budget. Sharp increases in CHCl3 and CHBr3 concentrations and decreases in O3 concentrations occurred at night when the wind direction switched from an ocean- to a land-based sector (land breeze) and the wind speed dropped to below 5 ms-1. These observations infer a shallow atmospheric boundary layer with increased O3 deposition and concentration of local emissions of both CHCl3 and CHBr3. The ratio of ΔCHCl3/ΔCHBr3 varied strongly according to the prevailing wind direction; from 0.60+0.15 in south-easterly (100-170° and northerly (340-20°) air to 2.5+0.4 in north-easterly (40-70°) air. Of these land-sectors, the south-easterly air masses are likely to be strongly influenced by macroalgal beds along the coast and the emission ratios probably reflect those from seaweeds in addition to land sources. The north-easterly airmasses however had an immediate fetch inland, which locally is comprised of coastal peatland ecosystems (peat bogs and coastal conifer plantations), previously identified as being strong sources of atmospheric CHCl3 under these conditions. Although we cannot entirely rule out other local land or coastal sources, our observations also suggest peatland ecosystem emissions of CHBr3. We use correlations between CHCl3 and CHBr3 during the north-easterly land breeze events in conjunction with previous estimates of local wetland CHCl3 release to tentatively deduce a global wetland CHBr3 source of 20.4(0.4-948) Gg yr-1, which is approximately 7% of the total global source.

Description: The IPCC has stressed the importance of producing unbiased estimates of the uncertainty in indirect aerosol forcing, in order to give policy makers as well as research managers an understanding of the most important aspects of climate change that require refinement. In this study, we use 3-D meteorological fields together with a radiative transfer model to examine the spatially-resolved uncertainty in estimates of the first indirect aerosol forcing. The global mean forcing calculated in the reference case is -1.30 Wm-2. Uncertainties in the indirect forcing associated with aerosol and aerosol precursor emissions, aerosol mass concentrations from different chemical transport models, aerosol size distributions, the cloud droplet parameterization, the representation of the in-cloud updraft velocity, the relationship between effective radius and volume mean radius, cloud liquid water content, cloud fraction, and the change in the cloud drop single scattering albedo due to the presence of black carbon are calculated. The aerosol burden calculated by chemical transport models and the cloud fraction are found to be the most important sources of uncertainty. Variations in these parameters cause an underestimation or overestimation of the indirect forcing compared to the base case by more than 0.6 Wm-2. Uncertainties associated with aerosol and aerosol precursor emissions, uncertainties in the representation of the aerosol size distribution (including the representation of the pre-industrial size distribution), and uncertainties in the representation of cloud droplet spectral dispersion effect cause uncertainties in the global mean forcing of 0.2~0.6 Wm-2. There are significant regional differences in the uncertainty associated with the first indirect forcing with the largest uncertainties in industrial regions (North America, Europe, East Asia) followed by those in the major biomass burning regions.

Description: Samples of atmospheric aerosol particles were collected in Valladolid, Spain, during the winter of 2003-2004. The measurements were made with a Dekati PM10 cascade impactor with four size stages: greater than 10 µm, between 2.5 to 10 µm, 1 to 2.5 µm and less than 1 µm. The size and shape of the particles were analyzed with a scanning electron microscope (SEM) and elemental analysis was done with an energy dispersive x-ray analysis (EDX). We present an evaluation by size, shape and composition of the major particulate species in the Valladolid urban atmosphere. The total aerosol concentration is very variable, ranging from 39.86 µg·m-3 to 184.88 µg·m-3 with the coarse particles as the dominant mass fraction. Emphasis was given to fine particles (

Description: A new cumulus convection parameterisation is presented in this paper. The parameterisation uses an explicit spectral approach and determines, unlike other convection schemes, for each convection event a new cloud distribution function regarding to the given vertical temperature and humidity profiles. This is done by using a one dimensional cloud model to create a spectrum of different clouds. The interaction between all non convective physical processes in the AGCM and all different clouds is taken into account to calculate a selfconsistent cloud spectrum. The model has been implemented in the ECHAM5 AGCM and tested against a large eddy simulation model. The representation of a shallow cumulus cloud field by the AGCM could be much improved. Diurnal cycle, cloud cover, liquid water path and the vertical structure of the mass flux, determined by the new convection scheme are close to the large eddy simulation, whereas the standard convection scheme failed in simulating this convection episode.

Description: Some of the meteorological approaches commonly considered in urban air pollution models do not take into account the importance of the smaller scales in the meteorology of complex-terrain coastal sites. The aim of this work is to estimate the impact of using the proper meteorological scales when simulating the behaviour of the pollutant concentrations emitted in the lower layers over coastal complex terrain areas. The availability of experimental measurements of a power plant plume near the Castellón conurbation (on the Spanish Mediterranean coast) has allowed us to use this plume as a tracer of opportunity of the lower atmosphere to check the results of a simulation exercise using the RAMS mesoscale model coupled to the HYPACT particle model. The results obtained show that in a complex-terrain coastal site, because of the strong effect of the meteorological interactions between the different scales on the integral advection and the turbulent dispersion of pollutants, using an inadequate scale to solve the meteorology can result in a very big gap in the simulation of lower-layer pollutant behaviour at urban scales.

Description: We explore the use of a fixed-lag Kalman smoother for sequential estimation of atmospheric carbon dioxide fluxes. This technique takes advantage of the fact that most of the information about the spatial distribution of sources and sinks is observable within a few months to half of a year of emission. After this period, the spatial structure of sources is diluted by transport and cannot significantly constrain flux estimates. We therefore describe an estimation technique that steps through the observations sequentially, using only the subset of observations and modeled transport fields that most strongly constrain the fluxes at a particular time step. Estimates of each set of fluxes are sequentially updated multiple times, using measurements taken at different times, and the estimates and their uncertainties are shown to quickly converge. Final flux estimates are incorporated into the background state of CO2 and transported forward in time, and the final flux uncertainties and covariances are taken into account when estimating the covariances of the fluxes still being estimated. The computational demands of this technique are greatly reduced in comparison to the standard Bayesian synthesis technique where all observations are used at once with transport fields spanning the entire period of the observations. It therefore becomes possible to solve larger inverse problems with more observations and for fluxes discretized at finer spatial scales. We also discuss the differences between running the inversion simultaneously with the transport model and running it entirely off-line with pre-calculated transport fields. We find that the latter can be done with minimal error if time series of transport fields of adequate length are pre-calculated.

Description: Stratospheric aerosols play an important role in a number of atmospheric issues such as midlatitude ozone depletion, atmospheric dynamics and the Earth radiative budget. Polar stratospheric clouds on the other hand are a crucial factor in the yearly Arctic and Antarctic ozone depletion. It is therefore important to quantify the stratospheric aerosol/PSC abundance. In orbit since March 2002, the GOMOS instrument onboard the European Envisat satellite has provided a vast aerosol extinction data set. In this paper we present aerosol/PSC zonal median values that were constructed from this data set, together with a discussion of the results.

Description: Atmospheric chloromethane (CH3Cl) plays an important role in stratospheric ozone destruction, but many uncertainties still exist regarding strengths of both sources and sinks and the processes leading to formation of this naturally occurring gas. Recent work has identified a novel chemical origin for CH3Cl, which can explain its production in a variety of terrestrial environments: the widespread structural component of plants, pectin, reacts readily with chloride ion to form CH3Cl at both ambient and elevated temperatures (Hamilton et al., 2003). It has been proposed that this abiotic chloride methylation process in terrestrial environments could be responsible for formation of a large proportion of atmospheric CH3Cl. However, more information is required to determine the global importance of this new source and its contribution to the atmospheric CH3Cl budget. A potentially powerful tool in studying the atmospheric CH3Cl budget is the use of stable carbon isotope ratios. In an accompanying paper it is reported that the reaction of CH3Cl with OH radical, the dominant sink for atmospheric CH3Cl, is accompanied by an unexpectedly large fractionation factor (Gola et al., 2005). Another recently published study shows that CH3Cl formed by the abiotic methylation process at ambient temperatures has a unique stable carbon isotope signature, extremely depleted in 13C, unequivocally distinguishing it from all other known sources (Keppler et al., 2004). Using these findings together with data existing in the literature, we here present three scenarios for an isotopic mass balance for atmospheric CH3Cl. Our calculations provide strong support for the proposal that the largest source of atmospheric CH3Cl (1800 to 2500 Gg yr-1) is the abiotic methylation of chloride in terrestrial ecosytems, primarily located in tropical and subtropical areas where turnover of biomass is highest. Furthermore our calculations also indicate that the microbial soil sink for CH3Cl is likely to be much larger (〉1000 Gg yr-1) than that previously assumed.

Description: Global stratospheric ozone columns derived from UV nadir spectra measured by SCIAMACHY (Scanning Imaging Spectrometer for Atmospheric Chartography; data ESA Versions 5.01 and 5.04) aboard the recently launched Environmental Satellite (ENVISAT) from January to June 2003 were compared to collocated total ozone data from GOME (Global Ozone Monitoring Experiment on ERS-2) retrieved using the weighting function DOAS algorithm (WFDOAS; Version 1.0) in order to assess the level-2 data (trace gas data) retrieval accuracy from SCIAMACHY. In addition, SCIAMACHY ozone columns retrieved with WFDOAS V1.0 were compared to GOME WFDOAS for some selected days in 2003 in order to separate data quality issues that either come from the optical performance of the instrument or algorithm implementation. Large numbers of collocated total ozone data from the two instruments, which are flying in the same orbit about 30 min apart, were spatially binned into regular 2.5° times 2.5° grids and then compared. Results of these satellite comparisons show that SCIAMACHY O3 vertical columns (ESA Version 5.01/5.04) are on average 1% (±2%) lower than GOME WFDOAS and scatter increases at solar zenith angles above 85° and at very low total ozone values. Results show dependencies on the solar zenith angle, latitudes, and total ozone amounts which are explained by the implementation of an outdated GOME algorithm based on GOME Data Processor (GDP) version 2.4 algorithms for the SCIAMACHY operational product. The reprocessing with an algorithm equivalent to GOME WFDOAS V1.0 shows that the offset and dependencies on solar zenith angle, latitude, and total ozone disappear and that SCIAMACHY WFDOAS data are within 1% of GOME WFDOAS. Since GOME lost its global coverage in July 2003 due to data rate limitation, continuation of the total ozone time series with SCIAMACHY is of highest importance for long-term trend monitoring. Since the beginning of its operation in March 2002 the SCIAMACHY instrument has performed stable. With the application of proper algorithms to retrieve total ozone, SCIAMACHY will be able to contribute to the global long term satellite total ozone record and it has the potential to achieve the high accuracy of GOME total ozone.

Description: Tropospheric NO2 column retrievals from the Global Ozone Monitoring Experiment (GOME) satellite spectrometer are used to quantify the source strength and 3-D distribution of lightning produced nitrogen oxides (NOx=NO+NO2). A sharp increase of NO2 is observed at convective cloud tops with increasing cloud top height, consistent with a power-law behaviour with power 5±2. Convective production of clouds with the same cloud height are found to produce NO2 with a ratio 1.6/1 for continents compared to oceans. This relation between cloud properties and NO2 is used to construct a 10:30 local time global lightning NO2 production map for 1997. An extensive statistical comparison is conducted to investigate the capability of the TM3 chemistry transport model to reproduce observed patterns of lightning NO2 in time and space. This comparison uses the averaging kernel to relate modelled profiles of NO2 to observed NO2 columns. It exploits a masking scheme to minimise the interference of other NOx sources on the observed total columns. Simulations are performed with two lightning parameterizations, one relating convective preciptation (CP scheme) to lightning flash distributions, and the other relating the fifth power of the cloud top height (H5 scheme) to lightning distributions. The satellite-retrieved NO2 fields show significant correlations with the simulated lightning contribution to the NO2 concentrations for both parameterizations. Over tropical continents modelled lightning NO2 shows remarkable quantitative agreement with observations. Over the oceans however, the two model lightning parameterizations overestimate the retrieved NO2 attributed to lightning. Possible explanations for these overestimations are discussed. The ratio between satellite-retrieved NO2 and modelled lightning NO2 is used to rescale the original modelled lightning NOx production. Eight estimates of the lightning NOx production in 1997 are obtained from spatial and temporal correlation methods, from cloud-free and cloud-covered observations, and from two different lightning parameterizations. Accounting for a wide variety of random and possible systematic errors, we estimate the global NOx production from lightning to be in the range 1.1–6.4 Tg N in 1997.

Description: We studied the sources, compositions and size distributions of aerosol particles during long-range transport (LRT) PM2.5 episodes which occurred on 12–15 August, 26–28 August and 5–6 September 2002 in Finland. Backward air mass trajectories, satellite detections of fire areas and dispersion modelling results indicate that emissions from wildfires in Russia and other Eastern European countries arrived in Finland during these episodes. Elemental analyses using scanning electron microscopy (SEM) coupled with energy dispersive X-ray microanalyses (EDX) showed that the proportions of S-rich particles and agglomerates (agglomeration was caused partly by the sampling method used) increased during the episodes, and they contained elevated fractions of K, indicating emissions from biomass burning. These aerosols were mixed with S-rich emissions from fossil fuel burning during transport since air masses came through polluted areas of Europe. Minor amounts of coarse Ca-rich particles were also brought by LRT during the episodes, and they probably originated from wildfires and/or from Estonian and Russian oil-shale-burning industrial areas. Ion chromatography analysis showed that concentrations of sulphate (SO42-), total nitrate (NO3-+HNO3(g)) and total ammonium (NH4++NH3(g)) increased during the episodes, but the ratio of the total amount of these ions to PM10 concentration decreased, indicating unusually high fractions of other chemical components. Particle number size distribution measurements with differential mobility particle sizer (DMPS) revealed that concentrations of particles 90–500 nm increased during the episodes, while concentrations of particles smaller than 90 nm decreased. The reduction of the smallest particles was caused by suppressed new particle formation due to vapour and molecular cluster uptake of LRT particles. Our results show that emissions from wildfires in Russian and other Eastern European countries deteriorated air quality of very large areas, even at distances of over 1000 km from the fire areas.

Description: The Indian summer monsoon rainfall (ISMR), which has a strong connection to agricultural food production, has been less predictable by conventional models in recent times. Two distinct years 2002 and 2003 with lower and higher July rainfall, respectively, are selected to help understand the natural and anthropogenic influences on ISMR. We show that heating gradients along the meridional monsoon circulation are reduced due to aerosol radiative forcing and the Indian Ocean Dipole in 2002. An increase in the dust and biomass-burning component of the aerosols through the zonal monsoon circulation resulted in reduction of cloud droplet growth in July 2002. These conditions were opposite to those in July 2003 which led to an above average ISMR. In this study, we have utilized NCEP/NCAR reanalyses for meteorological data (e.g. sea-surface temperature, horizontal winds, and precipitable water), NOAA interpolated outgoing long-wave radiation, IITM constructed all-India rainfall amounts, aerosol parameters as observed from the TOMS and MODIS satellites, and ATSR fire count maps. Based on this analysis, we suggest that monsoon rainfall prediction models should include synoptic as well as interannual variability in both atmospheric dynamics and chemical composition.

Description: Methane total-vertical column retrievals from ground-based solar FTIR measurements at the Permanent Ground-Truthing Station Zugspitze (47.42° N, 10.98° E, 2964m a.s.l.), Germany are used to validate column averaged methane retrieved from ENVISAT/SCIAMACHY spectra by WFM-DOAS (WFMD) version 0.4 and 0.41 for 153 days in 2003. Smoothing errors are estimated to be below 0.10% for FTIR and 0.14% for SCIAMACHY-WFMD retrievals and can be neglected for the assessment of observed bias and day-to-day-scatter. In order to minimize the altitude-difference effect, dry-air column averaged mixing ratios (XCH4) have been utilized. From the FTIR-time series of XCH4 an atmospheric day-to-day variability of 1% was found, and a sinusoidal annual cycle with a ≈1.6% amplitude. To obtain the WFMD bias, a polynomial fitted to the FTIR series was used as a reference. The result is WFMD v0.4/FTIR=1.008±0.019 and WFMD v0.41/FTIR=1.058±0.008. WFMD v0.41 was significantly improved by a time-dependent bias correction. It can still not capture the natural day-to-day variability, i.e., the standard deviation calculated from the daily-mean values is 2.4% using averages within a 2000-km radius, and 2.7% for a 1000-km radius. These numbers are dominated by a residual time-dependent bias in the order of 3%/month. The latter can be reduced, e.g., from 2.4% to 1.6% as shown by an empirical time-dependent bias correction. Standard deviations of the daily means, calculated from the individual measurements of each day, are excluding time-dependent biases, thus showing the potential precision of WFMD daily means, i.e., 0.3% for a 2000-km selection radius, and 0.6% for a 1000-km selection radius. Therefore, the annual cycle as well as possibly the day-to-day variability could be captured under the prerequisite of further advanced time-dependent bias corrections, or the use of other channels, where the icing issue is less prominent.

Description: We report on the vertical distributions of Saharan dust aerosols over the N.E. Mediterranean region, which were obtained during a typical dust outbreak on August 2000, by two lidar systems located in Athens and Thessaloniki, Greece, in the frame of the European EARLINET project. MODIS and ground sun spectrophotometric data, as well as air-mass backward trajectories confirmed the existence of Saharan dust in the case examined, which was also successfully forecasted by the DREAM dust model. The lidar data analysis for the period 2000-2002 made possible, for the first time, an estimation of the vertical extent of free tropospheric dust layers [mean values of the aerosol backscatter and extinction coefficients and the extinction-to-backscatter ratio (lidar ratio, LR) at 355 nm], as well as a seasonal distribution of Saharan dust outbreaks over Greece, under cloud-free conditions. A mean value of the lidar ratio at 355 nm was obtained over Athens (53±1 sr) and over Thessaloniki (44±2 sr) during the Saharan dust outbreaks. The corresponding aerosol optical thickness (AOT) at 355 nm, in the altitude range 0-5 km, was 0.69±0.12 and 0.65±0.10 for Athens and Thessaloniki, respectively (within the dust layer the AOT was 0.23 and 0.21, respectively). Air-mass back-trajectory analysis performed in the period 2000-2002 for all Saharan dust outbreaks over the N.E. Mediterranean indicated the main pathways followed by the dust aerosols.

Description: During the 2003 SAGE (Stratospheric Aerosol and Gas Experiment) III Ozone Loss and Validation Experiment (SOLVE) II, the fourteen-channel NASA Ames Airborne Tracking Sunphotometer (AATS-14) was mounted on the NASA DC-8 aircraft and measured spectra of total and aerosol optical depth (TOD and AOD) during the sunlit portions of eight science flights. Values of ozone column content above the aircraft have been derived from the AATS-14 measurements by using a linear least squares method that exploits the differential ozone absorption in the seven AATS-14 channels located within the Chappuis band. We compare AATS-14 columnar ozone retrievals with temporally and spatially near-coincident measurements acquired by the SAGE III and the Polar Ozone and Aerosol Measurement (POAM) III satellite sensors during four solar occultation events observed by each satellite. RMS differences are 19 DU (7% of the AATS value) for AATS-SAGE and 10 DU (3% of the AATS value) for AATS-POAM. In these checks of consistency between AATS-14 and SAGE III or POAM III ozone results, the AATS-14 analyses use airmass factors derived from the relative vertical profiles of ozone and aerosol extinction obtained by SAGE III or POAM III. We also compare AATS-14 ozone retrievals for measurements obtained during three DC-8 flights that included extended horizontal transects with total column ozone data acquired by the Total Ozone Mapping Spectrometer (TOMS) and the Global Ozone Monitoring Experiment (GOME) satellite sensors. To enable these comparisons, the amount of ozone in the column below the aircraft is estimated either by assuming a climatological model or by combining SAGE and/or POAM data with high resolution in-situ ozone measurements acquired by the NASA Langley Research Center chemiluminescent ozone sensor, FASTOZ, during the aircraft vertical profile at the start or end of each flight. Resultant total column ozone values agree with corresponding TOMS and GOME measurements to within 10-15 DU (~3%) for AATS data acquired during two flights - a longitudinal transect from Sweden to Greenland on 21 January, and a latitudinal transect from 47° N to 35° N on 6 February. For the round trip DC-8 latitudinal transect between 34° N and 22° N on 19-20 December 2002, resultant AATS-14 ozone retrievals plus below-aircraft ozone estimates yield a latitudinal gradient that is similar in shape to that observed by TOMS and GOME, but resultant AATS values exceed the corresponding satellite values by up to 30 DU at certain latitudes. These differences are unexplained, but they are attributed to spatial and temporal variability that was associated with the dynamics near the subtropical jet but was unresolved by the satellite sensors. For selected cases, we also compare AATS-14 ozone retrievals with values derived from coincident measurements by the other two DC-8 based solar occultation instruments: the National Center for Atmospheric Research Direct beam Irradiance Airborne Spectrometer (DIAS) and the NASA Langley Research Center Gas and Aerosol Monitoring System (GAMS). AATS and DIAS retrievals agree to within RMS differences of 1% of the AATS values for the 21 January and 19-20 December flights, and 2.3% for the 6 February flight. Corresponding AATS-GAMS RMS differences are ~1.5% for the 21 January flight; GAMS data were not compared for the 6 February flight and were not available for the 19-20 December flight. Line of sight ozone retrievals from coincident measurements obtained by the three DC-8 solar occultation instruments during the SAGE III solar occultation event on 24 January yield RMS differences of 2.1% for AATS-DIAS and 0.5% for AATS-GAMS.

Description: MCMA-2003 was a major field campaign investigating the atmospheric chemistry of the Mexico City Metropolitan Area (MCMA) in April of 2003. This paper describes the wind circulation patterns during the campaign both within the Mexico City basin and on the regional scale. ''Time roses'' are introduced to concisely analyze the diurnal wind patterns. Three episode types were identified that explain the conditions encountered: ''O3-South'', ''Cold Surge'' and ''O3-North''. These can be diagnosed from a combination of synoptic and basin observations based on whether the day was predominantly cloudy, or whether the O3 peak was in the north or south of the basin. O3-South days have weak synoptic forcing due to an anti-cyclone over the eastern Pacific. Strong solar heating leads to northerly flows in the basin and an evening shift due to a gap flow from the south-east. Peak ozone concentrations are in the convergence zone in the south of the city. Cold Surge days are associated with ''El Norte'' events, with strong surface northerlies bringing cold moist air and rain. Stable conditions lead to high concentrations of primary pollutants and peak ozone in the city center. O3-North days occur when the sub-tropical jet is closer to Mexico City. With strong westerlies aloft, the circulation pattern is the same as O3-South days except for a wind shift in the mid-afternoon leading to ozone peaks in the north of the city. This classification is proposed as a means of understanding pollutant transport in the Mexico City basin and as a basis for future meteorological and chemical analysis. Furthermore, model evaluation and design of policy recommendations will need to take into account the three episode types.

Description: The chemical nature of a large mass fraction of ambient organic aerosol particles is not known. High molecular weight compounds (often named humic-like substances) have recently been detected by several authors and these compounds seem to account for a significant fraction of the total organic aerosol mass. Due to the unknown chemical structure of these compounds quantification as well as a determination of their molecular weight is difficult. In this paper we investigate water soluble humic-like substances in ambient urban aerosol using size exclusion chromatography-UV spectroscopy and laser desorption/ionization mass spectrometry (LDI-MS). LDI-MS was used for the first time to investigate HULIS from atmospheric aerosols. A careful evaluation of the two method shows that both methods complement each other and that both are needed to learn more about the molecular weight distribution and the concentration of humic-like substances. An upper molecular weight limit of humic-like substances of about 700 Da and a concentration of 0.3-1.6 µg/m3 air can be estimated, corresponding to 9-30% of the total organic carbon for an urban background site.

Description: CO, CH4, N2O and CO2 were retrieved from high resolution solar absorption spectra obtained during a ship cruise from Capetown to Bremerhaven in January/February 2003 by Fourier Transform Infrared (FTIR) spectroscopy. Precisions of better than 0.5% for the column averaged volume mixing ratios (VMR) of CH4 and CO2 are achieved using of O2 as a reference gas. Shipborne FTIR-measurements of CO and data from SCIAMACHY/ENVISAT retrieved by the Weighting Function Modified Differential Optical Absorption Spectroscopy (WFM-DOAS) retrieval algorithm show qualitatively the same latitudinal variations. WFM-DOAS data of CH4, N2O and CO2 measured over sea exhibit a great spread. The spread is significantly reduced for satellite measurements over land and a reasonable agreement can be obtained if the shipborne data are compared with the closest SCIAMACHY measurements over land. The number of comparisons is too small to draw conclusions. However, by including only WFM-DOAS data with small errors the shipborne and WFM-DOAS data compare within 5% for CH4 and CO2 and within 30% for N2O.

Description: A multi-column radiative transfer code is used to assess the direct radiative effect of biomass burning aerosols over the southern African region during September. The horizontal distribution of biomass smoke is estimated from two sources; i) General Circulation Model (GCM) simulations combined with measurements from the Aerosol Robotic Network (AERONET) of Sun photometers; ii) data from the Moderate resolution Imaging Spectrometer (MODIS) satellite. Aircraft and satellite measurements are used to constrain the cloud fields, aerosol optical properties, vertical structure, and land surface albedo included in the model. The net regional direct effect of the biomass smoke is -3.1 to -3.6 Wm-2 at the top of atmosphere, and -14.4 to -17.0 Wm-2 at the surface for the MODIS and GCM distributions of aerosol. The direct radiative effect is shown to be highly sensitive to the prescribed vertical profiles and aerosol optical properties. The diurnal cycle of clouds and the spectral dependency of surface albedo are also shown to play an important role.

Description: In September 2002, the first INSPECTRO campaign to study the influence of clouds on the spectral actinic flux in the lower troposphere was carried out in East Anglia, England. Measurements of the actinic flux, the irradiance and aerosol and cloud properties were made from four ground stations and by aircraft. The radiation measurements were modelled using the uvspec model and ancillary data. For cloudless conditions, the measurements of the actinic flux were reproduced by 1-D radiative transfer modelling within the measurement and model uncertainties of about ±10%. For overcast days, the ground-based and aircraft radiation measurements and the cloud microphysical property measurements are consistent within the framework of 1-D radiative transfer and within experimental uncertainties. Furthermore, the actinic flux is increased by between 60-100% above the cloud when compared to a cloudless sky, with the largest increase for the optically thickest cloud. Correspondingly, the below cloud actinic flux is decreased by about 55-65%. Just below the cloud top, the downwelling actinic flux has a maximum that is seen in both the measurements and the model results. For broken clouds the traditional cloud fraction approximation is not able to simultaneously reproduce the measured above-cloud enhancement and below-cloud reduction in the actinic flux.

Description: While water insoluble organics are prevalent in the atmosphere, it is not clear how the presence of such species alters the chemical and physical properties of atmospheric aerosols. Here we use a combination of FTIR spectroscopy, Transmission Electron Microscopy (TEM) and Aerosol Mass Spectrometry (AMS) to characterize ammonium sulfate particles coated with palmitic acid. Coated aerosols were generated by atomizing pure ammonium sulfate, mixing the particles with a heated flow of nitrogen with palmitic acid vapor, and then flowing the mixture through an in-line oven to create internally mixed particles. The mixing state of the particles was probed using the AMS data and images from the TEM. Both of these probes suggest that the particles were internally mixed. Water uptake by the mixed particles was then probed at 273 K. It was found that for ammonium sulfate containing ~20 wt% palmitic acid the deliquescence relative humidity (DRH) was the same as for pure ammonium sulfate (80±3% RH). For particles with ~50 wt% palmitic acid however, the mixed particles began to take up water at relative humidities as low at 69% and continued to slowly take up water to 85% RH without fully deliquescing. In addition to studies of water uptake, water loss was also investigated. Here coatings of up to 50 wt% had no impact on the efflorescence relative humidity. These studies suggest that even if insoluble substances coat salt particles in the atmosphere, there may be relatively little effect on the resulting water uptake and loss.

Description: Black carbon (BC) particles in the atmosphere have important impacts on climate. The amount of BC in the atmosphere must be carefully quantified to allow evaluation of the climate effects of this type of aerosol. In this study, we present the treatment of BC aerosol in the developmental version of the 4th generation Canadian Centre for Climate modelling and analysis (CCCma) atmospheric general circulation model (AGCM). The focus of this work is on the conversion of insoluble BC to soluble/mixed BC by physical and chemical ageing. Physical processes include the condensation of sulphuric and nitric acid onto the BC aerosol, and coagulation with more soluble aerosols such as sulphates and nitrates. Chemical processes that may age the BC aerosol include the oxidation of organic coatings by ozone. Four separate parameterizations of the ageing process are compared to a control simulation that assumes no ageing occurs. These simulations use 1) an exponential decay with a fixed 24h half-life, 2) a condensation and coagulation scheme, 3) an oxidative scheme, and 4) a linear combination of the latter two ageing treatments. Global BC burdens are 2.15, 0.15, 0.11, 0.21, and 0.11TgC for the control run, and four ageing schemes, respectively. The BC lifetimes are 98.1, 6.6, 5.0, 9.5, and 4.9 days, respectively. The sensitivity of modelled BC burdens, and concentrations to the factor of two uncertainty in the emissions inventory is shown to be greater than the sensitivity to the parameterization used to represent the BC ageing, except for the oxidation based parameterization. A computationally efficient parameterization that represents the processes of condensation, coagulation, and oxidation is shown to simulate BC ageing well in the CCCma AGCM. As opposed to the globally fixed ageing time scale, this treatment of BC ageing is responsive to varying atmospheric composition.

Description: Research during the past decades has outlined the importance of biogenic isoprene emission in tropospheric chemistry and regional ozone photo-oxidant pollution. The first part of this article focuses on the development and validation of a simple biogenic emission scheme designed for regional studies. Experimental data sets relative to Boreal, Tropical, Temperate and Mediterranean ecosystems are used to estimate the robustness of the scheme at the canopy scale, and over contrasted climatic and ecological conditions. A good agreement is generally found when comparing field measurements and simulated emission fluxes, encouraging us to consider the model suitable for regional application. Limitations of the scheme are nevertheless outlined as well as further on-going improvements. In the second part of the article, the emission scheme is used on line in the broader context of a meso-scale atmospheric chemistry model. Dynamically idealized simulations are carried out to study the chemical interactions of pollutant plumes with realistic isoprene emissions coming from a Mediterranean oak forest. Two types of anthropogenic sources, respectively representative of the Marseille (urban) and Martigues (industrial) French Mediterranean sites, and both characterized by different VOC/NOx are considered. For the Marseille scenario, the impact of biogenic emission on ozone production is larger when the forest is situated in a sub-urban configuration (i.e. downwind distance TOWN-FOREST

Description: Measurements of acetone, methanol, acetaldehyde and a range of non-methane hydrocarbons have been made in North Atlantic marine air at the Mace Head observatory. Under maritime conditions the combination of OVOCs (acetone, methanol and acetaldehyde) contributed up to 85% of the total mass of measured non methane organics in air and up to 80% of the OH radical organic sink, when compared with the sum of all other organic compounds including non-methane hydrocarbons, DMS and OH-reactive halocarbons (trichloromethane and tetrachloroethylene). The observations showed anomalies in the variance and abundance of acetaldehyde and acetone over that expected for species with a remote terrestrial emission source and OH controlled chemical lifetime. A detailed model incorporating an explicit chemical degradation mechanism indicated in situ formation during air mass transport was on timescales longer than the atmospheric lifetime of precursor hydrocarbons or primary emission. The period over which this process was significant was similar to that of airmass motion on intercontinental scales, and formation via this route may reproduce that of a widespread diffuse source. The model indicates that continued short chain OVOC formation occurs many days from the point of emission, via longer lived intermediates of oxidation such as organic peroxides and long chain alcohols.

Description: In this paper we present an extensive validation of calibrated SCIAMACHY nadir reflectance in the UV (240-400 nm) by comparison with spectra calculated with a fast radiative transfer model. We use operationally delivered near-real-time level 1 data, processed with standard calibration tools. A total of 9 months of data has been analysed. This is the first reflectance validation study incorporating such a large amount of data. It is shown that this method is a valuable tool for spotting spatial and temporal anomalies. We conclude that SCIAMACHY reflectance data in this wavelength range are stable over the investigated period. In addition, we show an example of an anomaly in the data due to an error in the processing chain that could be detected by our comparison. This validation method could be extremely useful too for validation of other satellite spectrometers, such as OMI and GOME-2.

Description: A transient simulation with the interactively coupled chemistry-climate model (CCM) E39/C has been carried out which covers the 40-year period between 1960 and 1999. Forcing of natural and anthropogenic origin is prescribed where the characteristics are sufficiently well known and the typical timescales are slow compared to synoptic timescale so that the simulated atmospheric chemistry and climate evolve under a "slowly" varying external forcing. Based on observations, sea surface temperature (SST) and ice cover are prescribed. The increase of greenhouse gas and chlorofluorocarbon concentrations, as well as nitrogen oxide emissions are taken into account. The 11-year solar cycle is considered in the calculation of heating rates and photolysis of chemical species. The three major volcanic eruptions during that time (Agung, 1963; El Chichon, 1982; Pinatubo, 1991) are considered. The quasi-biennial oscillation (QBO) is forced by linear relaxation, also known as nudging, of the equatorial zonal wind in the lower stratosphere towards observed zonal wind profiles. Beyond a reasonable reproduction of mean parameters and long-term variability characteristics there are many apparent features of episodic similarities between simulation and observation: In the years 1986 and 1988 the Antarctic ozone holes are smaller than in the other years of that decade. In mid-latitudes of the Southern Hemisphere ozone anomalies resemble the corresponding observations, especially in 1985, 1989, 1991/1992, and 1996. In the Northern Hemisphere, the episode between the late 1980s and the first half of the 1990s is dynamically quiet, in particular, no stratospheric warming is found between 1988 and 1993. As observed, volcanic eruptions strongly influence dynamics and chemistry, though only for few years. Obviously, planetary wave activity is strongly driven by the prescribed SST and modulated by the QBO. Preliminary evidence of realistic cause and effect relationships strongly suggests that detailed process-oriented studies will be a worthwhile endeavour.

Description: In order to investigate the variability of the secondary organic aerosol (SOA) distributions and budget and provide a measure for the robustness of the conclusions on human induced changes of SOA, a global 3-dimensional chemistry transport model describing both the gas and the particulate phase chemistry of the troposphere has been applied. The response of the global budget of SOA to temperature and moisture changes as well as to biogenic emission changes over a decade (1984-1993) has been evaluated. The considered emissions of biogenic non-methane volatile organic compounds (VOC) are driven by temperature, light and vegetation. They vary between 756 and 810 Tg Cy-1 and are therefore about 5.5 times higher than the anthropogenic VOC emissions. All secondary aerosols (sulphuric, nitrates and organics) are computed on-line together with the aerosol associated water. Over the studied decade, the computed natural variations (8%) in the chemical SOA production from biogenic VOC oxidation equal the chemical SOA production from anthropogenic VOC oxidation. Maximum values are calculated for 1990 (warmer and drier) and minimum values for 1986 (colder and wetter). The SOA computed variability results from a 7% increase in biogenic VOC emissions from 1986 to 1990 combined with 8.5% and 6% increases in the wet and dry deposition of SOA and leads to about 11.5% increase in the SOA burden of biogenic origin. The present study also demonstrates the importance of the hydrological cycle in determining the built up and fate of SOA in the atmosphere. It also reveals the existence of significant positive and negative feedback mechanisms in the atmosphere responsible for the non linear relationship between emissions of biogenic VOC and SOA burden.

Description: A regression method was developed to retrieve upper tropospheric water vapor (UTWV in kg/m2) and upper tropospheric humidity (UTH in % RH) from radiances measured by the Advanced Microwave Sounding Unit (AMSU). In contrast to other UTH retrieval methods, UTH is defined as the average relative humidity between 500 and 200hPa, not as a Jacobian weighted average, which has the advantage that the UTH altitude does not depend on the atmospheric conditions. The method uses AMSU channels 6-10, 18, and 19, and should achieve an accuracy of 0.48 kg/m2 for UTWV and 6.3% RH for UTH, according to a test against an independent synthetic data set. This performance was confirmed for northern mid-latitudes by a comparison against radiosonde data from station Lindenberg in Germany, which yielded errors of 0.23 kg/m2 for UTWV and 6.1% RH for UTH.

Description: A first validation of water vapour total column amounts derived from measurements of the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) in the visible spectral region has been performed. For this purpose, SCIAMACHY water vapour data have been determined for the year 2003 using an extended version of the Differential Optical Absorption Spectroscopy (DOAS) method, called Air Mass Corrected (AMC-DOAS). The SCIAMACHY results are compared with corresponding water vapour measurements by the Special Sensor Microwave Imager (SSM/I) and with model data from the European Centre for Medium-Range Weather Forecasts (ECMWF). In confirmation of previous results it could be shown that SCIAMACHY derived water vapour columns are typically slightly lower than both SSM/I and ECMWF data, especially over ocean areas. However, these deviations are much smaller than the observed scatter of the data which is caused by the different temporal and spatial sampling and resolution of the data sets. For example, the overall difference with ECMWF data is only -0.05 g/cm2 whereas the typical scatter is in the order of 0.5 g/cm2. Both values show almost no variation over the year. In addition, first monthly means of SCIAMACHY water vapour data have been computed. The quality of these monthly means is currently limited by the availability of calibrated SCIAMACHY spectra. Nevertheless, first comparisons with ECMWF data show that SCIAMACHY (and similar instruments) are able to provide a new independent global water vapour data set.

Description: The libRadtran software package is a suite of tools for radiative transfer calculations in the Earth's atmosphere. Its main tool is the uvspec program. It may be used to compute radiances, irradiances and actinic fluxes in the solar and terrestrial part of the spectrum. The design of uvspec allows simple problems to be easily solved using defaults and included data, hence making it suitable for educational purposes. At the same time the flexibility in how and what input may be specified makes it a powerful and versatile tool for research tasks. The uvspec tool and additional tools included with libRadtran are described and realistic examples of their use are given. The libRadtran software package is available from http://www.libradtran.org.

Description: Combustion of elemental carbon (EC) and organic carbon (OC) contained in ambient aerosol matter was explored using scanning electron microscopy (SEM) in combination with energy dispersive X-ray analysis (EDX). To ease identification of the particles of interest and to avoid or at least reduce interaction with simultaneously sampled inorganic oxides and salts, the approach used in this work differed in two ways from commonly applied procedures. First, rather than using a mixture of particles of vastly different sizes, as in PM10 or PM2.5, aerosol matter was collected in a 5-stage impactor. Second, the water soluble fraction of the collected matter was removed prior to analysis. Diesel soot particles, which appeared in the well-known form of chain-type aggregates, constituted the major fraction of EC. In contrast, OC containing particles were observed in a variety of shapes, including a sizable amount of bioaerosol matter appearing mostly in the size range above about 1 µm. During heating in ambient air for 1h, diesel soot particles were found to be stable up to 470°C, but complete combustion occurred in a narrow temperature interval between about 480 and 510°C. After diesel soot combustion, minute quantities of "ash" were observed in the form of aggregated tiny particles with sizes less than 10 nm. These particles could be due to elemental or oxidic contaminants of diesel soot. Combustion of OC was observed over a wide range of temperatures, from well below 200°C to at least 500°C. Incompletely burnt bioaerosol matter was still found after heating to 600°C. The results imply that the EC fraction in aerosol matter can be overestimated significantly if the contribution of OC to a thermogram is not well separated.

Description: A decadal-scale trend in the tropical radiative energy budget has been observed recently by satellites, which however is not reproduced by climate models. In the present study, we have computed the outgoing shortwave radiation (OSR) at the top of atmosphere (TOA) at 2.5° longitude-latitude resolution and on a mean monthly basis for the 17-year period 1984-2000, by using a deterministic solar radiative transfer model and cloud climatological data from the International Satellite Cloud Climatology Project (ISCCP) D2 database. Anomaly time series for the mean monthly pixel-level OSR fluxes, as well as for the key physical parameters, were constructed. A significant decreasing trend in OSR anomalies, starting mainly from the late 1980s, was found in tropical and subtropical regions (30° S-30° N), indicating a decadal increase in solar planetary heating equal to 1.9±0.3Wm-2/decade, reproducing well the features recorded by satellite observations, in contrast to climate model results. This increase in solar planetary heating, however, is accompanied by a similar increase in planetary cooling, due to increased outgoing longwave radiation, so that there is no change in net radiation. The model computed OSR trend is in good agreement with the corresponding linear decadal decrease of 2.5±0.4Wm-2/decade in tropical mean OSR anomalies derived from ERBE S-10N non-scanner data (edition 2). An attempt was made to identify the physical processes responsible for the decreasing trend in tropical mean OSR. A detailed correlation analysis using pixel-level anomalies of model computed OSR flux and ISCCP cloud cover over the entire tropical and subtropical region (30° S-30° N), gave a correlation coefficient of 0.79, indicating that decreasing cloud cover is the main reason for the tropical OSR trend. According to the ISCCP-D2 data derived from the combined visible/infrared (VIS/IR) analysis, the tropical cloud cover has decreased by 6.6±0.2% per decade, in relative terms. A detailed analysis of the inter-annual and long-term variability of the various parameters determining the OSR at TOA, has shown that the most important contribution to the observed OSR trend comes from a decrease in low-level cloud cover over the period 1984-2000, followed by decreases in middle and high-level cloud cover. Note, however, that there still remain some uncertainties associated with the existence and magnitude of trends in ISCCP-D2 cloud amounts. Opposite but small trends are introduced by increases in cloud scattering optical depth of low and middle clouds.

Description: Understanding the impact of atmospheric dynamical variability on observed changes in stratospheric O3 is a key to understanding how O3 will change with future climate dynamics and trace gas abundances. In this paper we examine the linkage between interannual variability in total column O3 at northern high latitudes in March and lower-to-mid stratospheric vortex O3 in the prior November. We find that these two quantities are significantly correlated in the years available from TOMS, SBUV, and POAM data (1978-2004). Additionally, we find that the increase in March O3 variability from the 1980s to years post-1990 is also seen in the November vortex O3, i.e., interannual variability in both quantities is much larger in the later years. The cause of this correlation is not clear, however. Interannual variations in March total O3 are known to correspond closely with variations in winter stratospheric wave driving consistent with the effects of varying residual circulation, temperature, and chemical loss. Variation in November vortex O3 may also depend on dynamical wave activity, but the dynamics in fall are less variable than in winter and spring. We do not find significant correlations of dynamic indicators for November such as temperature, heat flux, or polar average total O3 with the November vortex O3, nor with dynamical indicators later in winter and spring that might lead to a connection to March. We discuss several potential hypotheses for the observed correlation but do not find strong evidence for any considered mechanism. We present the observations as a phenomenon whose understanding may improve our ability to predict the dependence of O3 on changing dynamics and chemistry.

Description: The Optimal Estimation Method is used to retrieve temperature and water vapor profiles from simulated radio occultation measurements in order to assess how different retrieval schemes may affect the assimilation of this data. High resolution ECMWF global fields are used by a state-of-the-art radio occultation simulator to provide quasi-realistic bending angle and refractivity profiles. Both types of profiles are used in the retrieval process to assess their advantages and disadvantages. The impact of the GPS measurement is expressed as an improvement over the a priori knowledge (taken from a 24h old analysis). Large improvements are found for temperature in the upper troposphere and lower stratosphere. Only very small improvements are found in the lower troposphere, where water vapor is present. Water vapor improvements are only significant between about 1 km to 7 km. No pronounced difference is found between retrievals based upon bending angles or refractivity. Results are compared to idealized retrievals, where the atmosphere is spherically symmetric and instrument noise is not included. Comparing idealized to quasi-realistic calculations shows that the main impact of a ray tracing algorithm can be expected for low latitude water vapor, where the horizontal variability is high. We also address the effect of altitude correlations in the temperature and water vapor. Overall, we find that water vapor and temperature retrievals using bending angle profiles are more CPU intensive than refractivity profiles, but that they do not provide significantly better results.

Description: In this study the global lapse-rate tropopause (LRT) pressure, temperature, potential temperature, and sharpness are discussed based on Global Positioning System (GPS) radio occultations (RO) from the German CHAMP (CHAllenging Minisatellite Payload) and the U.S.-Argentinian SAC-C (Satelite de Aplicaciones Cientificas-C) satellite missions. Results with respect to seasonal variations are compared with operational radiosonde data and ECMWF (European Centre for Medium-Range Weather Forecast) operational analyses. Results on the tropical quasi-biennial oscillation (QBO) are updated from an earlier study. CHAMP RO data are available continuously since May 2001 with on average 150 high resolution temperature profiles per day. SAC-C data are available for several periods in 2001 and 2002. In this study temperature data from CHAMP for the period May 2001-December 2004 and SAC-C data from August 2001-October 2001 and March 2002-November 2002 were used, respectively. The bias between GPS RO temperature profiles and radiosonde data was found to be less than 1.5K between 300 and 10hPa with a standard deviation of 2-3K. Between 200-20hPa the bias is even less than 0.5K (2K standard deviation). The mean deviations based on 167699 comparisons between CHAMP/SAC-C and ECMWF LRT parameters are (-2.1±37.1)hPa for pressure and (0.1±4.2)K for temperature. Comparisons of LRT pressure and temperature between CHAMP and nearby radiosondes (13230) resulted in (5.8±19.8)hPa and (-0.1±3.3)K, respectively. The comparisons between CHAMP/SAC-C and ECMWF show on average the largest differences in the vicinity of the jet streams with up to 700m in LRT altitude and 3K in LRT temperature, respectively. The CHAMP mission generates the first long-term RO data set. Other satellite missions will follow (GRACE, COSMIC, MetOp, TerraSAR-X, EQUARS) generating together some thousand temperature profiles daily.

Description: A novel light-weight, elevation scanning and absolutely calibrated UV/vis spectrometer and its application to balloon-borne limb radiance and trace gas profile measurements is described. Its performance and the novel method of balloon-borne UV/vis limb trace gas measurements has been tested against simultaneous observations of the same atmospheric parameters available from either (a) in-situ instrumentation (cf., by an electrochemical cell (ECC) ozone sonde also deployed aboard the gondola) or (b) trace gas profiles inferred from UV/vis/near IR solar occultation measurements performed on the same payload. The novel technique is also cross validated with radiative transfer modeling. Reasonable agreement is found (a) between measured and simulated limb radiances and (b) inferred limb O3, NO2, and BrO and correlative profile measurements when properly accounting for all relevant atmospheric parameters (temperature, pressure, aerosol extinction, and major absorbers).

Description: The volatile organic compound (VOC) emission rates of Scots pine (Pinus sylvestris L.) were measured from trees growing in a natural forest environment at two locations in Finland. The observed total VOC emission rates varied between 21 and 874 ngg-1 h-1 and 268 and 1670 ngg-1 h-1 in southern and northern Finland, respectively. A clear seasonal cycle was detected with high emission rates in early spring, a decrease of the emissions in late spring and early summer, high emissions again in late summer, and a gradual decrease in autumn. The main emitted compounds were Δ3-carene (southern Finland) and α- and β-pinene (northern Finland), with approximate relative contributions of 60–70% and 60–85% of the total observed monoterpene emission rates, respectively. Sesquiterpene (β-caryophyllene) and 2-methyl-3-buten-2-ol (MBO) emissions were initiated in early summer at both sites. The observed MBO emission rates were between 1 and 3.5% of the total monoterpene emission rates. The sesquiterpene emission rates varied between 2 and 5% of the total monoterpene emission rates in southern Finland, but were high (40%) in northern Finland in spring. Most of the measured emission rates were found to be well described by the temperature dependent emission algorithm. The calculated standard emission potentials were high in spring and early summer, decreased somewhat in late summer, and were high again towards autumn. The experimental coefficient β ranged from 0.025 to 0.19 (average 0.10) in southern Finland, with strongest temperature dependence in spring and weakest in late summer. Only the emission rates of 1,8-cineole were found to be both light and temperature dependent.

Description: Particulate matter and photo-oxidant processes in the Eastern Mediterranean have been studied using the UAM-AERO mesoscale air quality model in conjunction with the NILU-CTM regional model. Meteorological data were obtained from the RAMS prognostic meteorological model. The modeling domain includes the eastern Mediterranean area between the Greek mainland and the island of Crete. The modeling system is applied to study the atmospheric processes in three periods, i.e. 13–16 July 2000, 26–30 July 2000 and 7–14 January 2001. The spatial and temporal distributions of both gaseous and particulate matter pollutants have been extensively studied together with the identification of major emission sources in the area. The modeling results were compared with field data obtained in the same period. The objective of the current modeling work was mainly to apply the UAM-AERO mesoscale model in the eastern Mediterranean in order to assess the performed field campaigns and determine that the applied mesoscale model is fit for this purpose. Comparison of the modeling results with measured data was performed for a number of gaseous and aerosol species. The UAM-AERO model underestimates the PM10 measured concentrations during summer and winter campaigns. Discrepancies between modeled and measured data are attributed to unresolved particulate matter emissions. Particulate matter in the area is mainly composed by sulphate, sea salt and crustal materials, and with significant amounts of nitrate, ammonium and organics. During winter the particulate matter and oxidant concentrations were lower than the summer values.

Description: The present paper reviews existing knowledge with regard to Organic Aerosol (OA) of importance for global climate modelling and defines critical gaps needed to reduce the involved uncertainties. All pieces required for the representation of OA in a global climate model are sketched out with special attention to Secondary Organic Aerosol (SOA): The emission estimates of primary carbonaceous particles and SOA precursor gases are summarized. The up-to-date understanding of the chemical formation and transformation of condensable organic material is outlined. Knowledge on the hygroscopicity of OA and measurements of optical properties of the organic aerosol constituents are summarized. The mechanisms of interactions of OA with clouds and dry and wet removal processes parameterisations in global models are outlined. This information is synthesized to provide a continuous analysis of the flow from the emitted material to the atmosphere up to the point of the climate impact of the produced organic aerosol. The sources of uncertainties at each step of this process are highlighted as areas that require further studies.

Description: The remote sensing of the atmospheric greenhouse gases methane (CH4) and carbon dioxide (CO2) in the troposphere from instrumentation aboard satellites is a new area of research. In this manuscript, results obtained from observations of the up-welling radiation in the near-infrared by SCIAMACHY on board ENVISAT are presented. Vertical columns of CH4, CO2 and oxygen (O2) have been retrieved and the (air or) O2-normalised CH4 and CO2 column amounts, the dry air column averaged mixing ratios XCH4 and XCO2 derived. In this manuscript the first results, obtained by using the version 0.4 of the Weighting Function Modified (WFM) DOAS retrieval algorithm applied to SCIAMACHY data, are described and compared with global models. For the set of individual cloud free measurements over land the standard deviation of the difference with respect to the models is in the range ~100–200 ppbv (5–10%) for XCH4 and ~14–32 ppmv (4–9%) for XCO2. The inter-hemispheric difference of the methane mixing ratio, as determined from single day data, is in the range 30–110 ppbv and in reasonable agreement with the corresponding model data (48–71 ppbv). The weak inter-hemispheric difference of the CO2 mixing ratio can also be detected with single day data. The spatiotemporal pattern of the measured and the modelled XCO2 are in reasonable agreement. However, the amplitude of the difference between the maximum and the minimum for SCIAMACHY XCO2 is about ±20 ppmv which is about a factor of four larger than the variability of the model data which is about ±5 ppmv. More studies are needed to explain the observed differences. The XCO2 model field shows low CO2 concentrations beginning of January 2003 over a spatially extended CO2 sink region located in southern tropical/sub-tropical Africa. The SCIAMACHY data also show low CO2 mixing ratios over this area. According to the model the sink region becomes a source region about six months later and exhibits higher mixing ratios. The SCIAMACHY and the model data over this region show a similar time dependence over the period from January to October 2003. These results indicate that for the first time a regional CO2 surface source/sink region has been detected by measurements from space. The interpretation of the SCIAMACHY CO2 and CH4 measurements is difficult, e.g., because the error analysis of the currently implemented retrieval algorithm indicates that the retrieval errors are on the same order as the small greenhouse gas mixing ratio changes that are to be detected.

Description: Because of its wide coverage over much of the globe, biomass burning has been widely studied in the context of direct radiative forcing. Such study is warranted as smoke particles scatter and at times absorb solar radiation efficiently. Further, as much of what is known about smoke transport and impacts is based on remote sensing measurements, the optical properties of smoke particles have far reaching effects into numerous aspects of biomass burning studies. Global estimates of direct forcing have been widely varying, ranging from near zero to −1 W m-2. A significant part of this difference can be traced to varying assumptions on the optical properties of smoke. This manuscript is the third part of four examining biomass-burning emissions. Here we review and discuss the literature concerning measurement and modeling of optical properties of biomass-burning particles. These include available data from published sensitivity studies, field campaigns, and inversions from the Aerosol Robotic Network (AERONET) of Sun photometer sites. As a whole, optical properties reported in the literature are varied, reflecting both the dynamic nature of fires, variations in smoke aging processes and differences in measurement technique. We find that forward modeling or ''internal closure'' studies ultimately are of little help in resolving outstanding measurement issues due to the high degree of degeneracy in solutions when using ''reasonable'' input parameters. This is particularly notable with respect to index of refraction and the treatment of black carbon. Consequently, previous claims of column closure may in fact be more ambiguous. Differences between in situ and retrieved ωo values have implications for estimates of mass scattering and mass absorption efficiencies. In this manuscript we review and discuss this community dataset. Strengths and lapses are pointed out, future research topics are prioritized, and best estimates and uncertainties of key smoke particle parameters are provided.

Description: The simulation chamber SAPHIR at Forschungszentrum Jülich has UV permeable teflon walls facilitating atmospheric photochemistry studies under the influence of natural sunlight. Because the internal radiation field is strongly affected by construction elements, we use external, radiometric measurements of spectral actinic flux and a model to calculate mean photolysis frequencies for the chamber volume Bohn04B. In this work we determine NO2 photolysis frequencies j(NO2) within SAPHIR using chemical actinometry by injecting NO2 and observing the chemical composition during illumination under various external conditions. In addition to a photo-stationary approach, a time-dependent method was developed to analyse the data. These measurements had two purposes. Firstly, to check the model predictions with respect to diurnal and seasonal variations in the presence of direct sunlight and secondly to obtain an absolute calibration factor for the combined radiometry-model approach. We obtain a linear correlation between calculated and actinometric j(NO2). A calibration factor of 1.34±0.10 is determined, independent of conditions in good approximation. This factor is in line with expectations and can be rationalised by internal reflections within the chamber. Taking into account the uncertainty of the actinometric j(NO2), an accuracy of 13% is estimated for the determination of j(NO2) in SAPHIR. In separate dark experiments a rate constant of (1.93±0.12)x10-14 cm3 s-1 was determined for the NO+O3 reaction at 298K using analytical and numerical methods of data analysis.

Description: We report in situ measurements of N2O5, NO2, and O3 in Contra Costa County, California during January 2004. Mixing ratios of N2O5, an intermediate compound in the atmosphere's nocturnal cleansing process, ranged up to 200pmol/mol at night. The highest N2O5 concentrations were correlated with low O3 and high NO2 concentrations. The calculated steady state lifetime for N2O5 ranged from 5 to 30min. The total HNO3 produced by N2O5 hydrolysis over a 14h night was comparable to ambient NO2 concentrations, and is estimated to be a factor of nine bigger than the HNO3 produced during the day.

Description: The mass accommodation coefficient of water is a quantity for which different experimental techniques have yielded conflicting values in the range 0.04-1. From the viewpoint of cloud modelling, this is an unfortunate situation, since the value of the mass accommodation coefficient affects the model results, e.g. the number concentration of activated cloud droplets. In this commentary we note that in cloud modelling, the primary quantity of interest is the droplet growth rate rather than the mass accommodation coefficient, and that experimental investigations of droplet growth rates provide more direct verification of cloud models than do measurements of the mass accommodation coefficient. Furthermore, we argue that the droplet growth rates calculated in cloud model studies are consistent with experimental results obtained so far only if a mass accommodation coefficient of unity is applied.

Description: The measurement of atmospheric concentrations by a monitoring network is a promising tool for the identification of the widespread sources of trace species. The paper addresses the case of the species scattered linearly by a known meteorology. The question is classical: what can be said about the source from a set of measurements? Is it possible to guess from the values observed by the measurements that the source is spread close to the detectors, or that the tracer comes from a remote region? And, if the source was a point source, would it be possible to understand it by just considering these values? A part of the answers is a matter of practical sense: the resolution with which an emission can be retrieved will always be limited and probably lower for a remote region, even if the detectors and dispersion model are error free. The paper proposes a linear strategy of inference: to any set of values taken by the observed concentrations is associated linearly an estimate of the source. Doubled values lead to a doubled estimate. The method, based on adjoint techniques, is intended to optimise the resolution by quantifying, with the concept of illumination, which regions are well, poorly or not seen at all. The illumination tied to ordinary adjoint functions becomes excessive close to the detectors thus leading to inversion artefacts. This may be corrected by attributing each point of the space time domain a geometric and statistical weight. The adjoint functions are transformed. The choice of this renormalising function is constrained by an unambiguous entropic criterion preventing any overestimation of the available information that would lead to artefacts. It amounts to evenly distribute the information between the points organised with their weights as a "known domain". The theory is illustrated by calculations performed with the experimental source ETEX1.

Description: The role of halogens in both the marine boundary layer and the stratosphere has long been recognized, while their role in the free troposphere is often not considered in global chemical models. However, a careful examination of free-tropospheric chemistry constrained by observations using a full chemical data assimilation system shows that halogens do play a significant role in the free troposphere. In particular, the chlorine initiation of methane oxidation in the free troposphere can contribute more than 10%, and in some regions up to 50%, of the total rate of initiation. The initiation of methane oxidation by chlorine is particularly important below the polar vortex and in northern mid-latitudes. Likewise, the hydrolysis of alone can contribute more than 35% of the production rate in the free-troposphere.

Description: In-situ measurements of ClO and its dimer carried out during the SOLVE II/VINTERSOL-EUPLEX and ENVISAT Validation campaigns in the Arctic winter 2003 suggest that the thermal equilibrium between the dimer formation and dissociation is shifted significantly towards the monomer compared to the current JPL 2002 recommendation. Detailed analysis of observations made in thermal equilibrium allowed to re-evaluate the magnitude and temperature dependence of the equilibrium constant. A fit of the JPL format for equilibrium constants yields KEQ=3.61x10-27exp(8167/T), but to reconcile the observations made at low temperatures with the existing laboratory studies at room temperature, a modified equation, KEQ=5.47x10-25(T/300)-2.29exp(6969/T), is required. This format can be rationalised by a strong temperature dependence of the reaction enthalpy possibly induced by Cl2O2 isomerism effects. At stratospheric temperatures, both equations are practically equivalent. Using the equilibrium constant reported here rather than the JPL 2002 recommendation in atmospheric models does not have a large impact on simulated ozone loss. Solely at large zenith angles after sunrise, a small decrease of the ozone loss rate due to the ClO dimer cycle and an increase due to the ClO-BrO cycle (attributed to the enhanced equilibrium ClO concentrations) is observed, the net effect being a slightly stronger ozone loss rate.

Description: A small system for the unattended measurement of total odd nitrogen (NOy, i.e., the sum of NO and its atmospheric oxidation products) aboard civil in-service aircraft in the framework of MOZAIC is described. The instrument employs the detection of NO by its chemiluminescence with O3 in combination with catalytic conversion of the other NOy compounds to NO at 300°C on a gold surface in the presence of H2. The instrument has a sensitivity of 0.4-0.7cps/ppt and is designed for unattended operation during 1-2 service cycles of the aircraft (400-800 flight hours). The total weight is 50kg, including calibration system, compressed gases, mounting, and safety measures. The layout and inlet configuration are governed by requirements due to the certification for passenger aircraft. Laboratory tests are described regarding the conversion efficiency for NO2 and HNO3 (both 〉98%). Interference by non-NOy species is

Description: A modified version of an operational 3-dimensional, non-hydrostatic, limited-area atmospheric model (MM5) was used to perform high-resolution, idealized simulations of the interaction of an infinitely long single ridge with a steady, lateral large-scale wind field. The effect of different mountain ridge dimensions, wind speeds and patterns and moisture profiles on the quantity and distribution of orographic rainfall was investigated. The simulations demonstrated a number of commonly observed mountain flow features like formation of cap clouds, foehn wall, convective break-out associated with mountain topography, interaction of downslope winds with sea breeze, and different stages of cumulus development. It was found that the rainfall maxima associated with the mountain always occur upstream of the ridge peak. Changing mountain dimensions, wind speeds and patterns and moisture profile had clear effects on amount and pattern of accumulated rainfall. Low wind speeds resulted the maximum accumulated rainfall to occur considerable distance upstream of ridge peak. Reversal of wind directions in upper atmosphere caused rainfall to be largely restricted to the wind-side of the peak. The observed rainfall patterns are explained by the different flow patterns observed in the model output.

Description: The SLIMCAT three-dimensional chemical transport model (CTM) is used to infer chemical ozone loss from Polar Ozone and Aerosol Measurement (POAM) III observations of stratospheric ozone during the Arctic winter of 2002-2003. Inferring chemical ozone loss from satellite data requires quantifying ozone variations due to dynamical processes. To accomplish this, the SLIMCAT model was run in a "passive" mode from early December until the middle of March. In these runs, ozone is treated as an inert, dynamical tracer. Chemical ozone loss is inferred by subtracting the model passive ozone, evaluated at the time and location of the POAM observations, from the POAM measurements themselves. This "CTM Passive Subtraction" technique relies on accurate initialization of the CTM and a realistic description of vertical/horizontal transport, both of which are explored in this work. The analysis suggests that chemical ozone loss during the 2002-2003 winter began in late December. This loss followed a prolonged period in which many polar stratospheric clouds were detected, and during which vortex air had been transported to sunlit latitudes. A series of stratospheric warming events starting in January hindered chemical ozone loss later in the winter of 2003. Nevertheless, by 15 March, the final date of the analysis, ozone loss maximized at 425K at a value of about 1.2ppmv, a moderate amount of loss compared to loss during the unusually cold winters in the late-1990s. SLIMCAT was also run with a detailed stratospheric chemistry scheme to obtain the model-predicted loss. The SLIMCAT model simulation also shows a maximum ozone loss of 1.2ppmv at 425K, and the morphology of the loss calculated by SLIMCAT was similar to that inferred from the POAM data. These results from the recently updated version of SLIMCAT therefore give a much better quantitative description of polar chemical ozone loss than older versions of the same model. Both the inferred and modeled loss calculations show the early destruction in late December and the region of maximum loss descending in altitude through the remainder of the winter and early spring.

Description: Motivated by the strong evidence that the state of the northern hemisphere vortex in boreal winter influences tropospheric variability, teleconnection patterns over the North Atlantic are defined separately for winter episodes where the zonal wind at 50hPa and 65° N is above or below the critical velocity for vertical propagation of zonal planetary wave 1. We argue that the teleconnection structure in the middle and upper troposphere differs considerably between the two regimes of the polar vortex, while this is not the case at sea level. If the polar vortex is strong, there exists one meridional dipole structure of geopotential height in the upper and middle troposphere, which is situated in the central North Atlantic. If the polar vortex is weak, there exist two such dipoles, one over the western and one over the eastern North Atlantic. Storm tracks (and precipitation related with these) are determined by mid and upper tropospheric conditions and we find significant differences of these parameters between the stratospheric regimes. For the strong polar vortex regime, in case of a negative upper tropospheric "NAO" index we find a blocking height situation over the Northeast Atlantic and the strongest storm track of all. It is reaching far north into the Arctic Ocean and has a secondary maximum over the Denmark Strait. Such storm track is not found in composites based on a classic NAO defined by surface pressure differences between the Icelandic Low and the Azores High. Our results suggest that it is important to include the state of the polar vortex strength in any study of the variability over the North Atlantic.

Description: Following the Cretaceous/Tertiary (K/T) meteoritic impact some 65Myr ago, large portions of aboveground terrestrial biomass were burned. As a result, large amounts of various trace gases were injected to the atmosphere, inducing a wide range of effects on climate and ecosystems. Here, it is commented on the previously unaccounted for emission to the atmosphere of methyl bromide (CH3Br) and methyl chloride (CH3Cl) from extensive biomass burning that followed the impact. Based on reported biomass burning emission rates of the above organohalogens relative to CO2, it is estimated that their emissions from global fires resulted in tropospheric mixing ratios of around 20-65.8ppbv organic Cl and 110-390pptv organic Br. The above calculated mixing ratios of organic chlorine and bromine are more than an order of magnitude greater than their present, anthropogenically perturbed level and, although the ocean ultimately might absorb them, we argue here that they could still remain in the atmosphere for many years, and a substantial fraction could be transported to the stratosphere, thus substantially affecting the ozone layer. This would have led to very serious increases in short wavelength UV radiation reaching the lowermost atmosphere.

Description: In this work diurnal and seasonal variations of mean photolysis frequencies for the atmosphere simulation chamber SAPHIR at Forschungszentrum Jülich are calculated. SAPHIR has a complex construction with UV permeable teflon walls allowing natural sunlight to enter the reactor volume. The calculations are based on external measurements of solar spectral actinic flux and a model considering the time-dependent impact of shadows from construction elements as well as the influence of the teflon walls. Overcast and clear-sky conditions are treated in a consistent way and different assumptions concerning diffuse sky radiance distributions are tested. Radiometric measurements inside the chamber are used for an inspection of model predictions. Under overcast conditions we obtain fractions of 0.74 and 0.67 of external values for photolysis frequencies j(NO2) (NO2+hν→NO+O(3P)) and j(O1D) (O3+hν→O2+O(1D)), respectively. On a clear sky summer day these values are time-dependent within ranges 0.65-0.86 and 0.60-0.73, for j(NO2) and j(O1D), respectively. A succeeding paper (Bohn et al., 2004) is dealing with an on-road test of the model approach by comparison with photolysis frequencies from chemical actinometry experiments within SAPHIR.

Description: Measurements of the C-H overtone transition strengths combined with estimates of the photodissociation cross sections for these transitions suggest that near-IR photodissociation of peroxy acetyl nitrate (PAN) is less significant (Jnear-IR≈3x10-8s-1 at noon) in the lower atmosphere than competing sinks resulting from unimolecular decomposition and ultraviolet photolysis. This is in contrast to the photochemical behavior of a related peroxy nitrate, pernitric acid (PNA), that undergoes rapid near-IR photolysis in the atmosphere with Jnear-IR≈10-5s-1 at noon (Roehl et al., 2002). This difference is attributed to the larger binding energy and larger number of vibrational degrees of freedom in PAN, which make 4νCH the lowest overtone excitation with a high photodissociation yield (as opposed to 2νOH in PNA).

Description: The growth properties of nucleation mode particles were investigated. The variation of source rates of condensable vapors in different locations and environmental conditions was analyzed. The measurements were performed in background stations in Antarctica, in Finnish Lapland and Boreal Forest stations (SMEAR I and SMEAR II) as well as in polluted urban sites in Athens, Marseille and New Delhi. Taking advantage of only the measured spectral evolution of aerosol particles as a function of time the formation and growth properties of nucleation mode aerosols were evaluated. The diameter growth-rate and condensation sink were obtained from the measured size distribution dynamics. Using this growth rate and condensation sink, the concentration of condensable vapors and their source rate were estimated. The growth rates and condensation sinks ranged between 0.3-20nmh-1 and 10-4-0.07s-1, respectively. The corresponding source rate of condensable vapors varied more than 4 orders of magnitude from 103 to over 107cm-1s-1. The highest condensation sink and source rate values were observed in New Delhi and the smallest values in Antarctica.

Description: A total ozone depletion of 68±7 Dobson units between 380 and 525K from 10 December 2002 to 10 March 2003 is derived from ozone sonde data by the vortex-average method, taking into account both diabatic descent of the air masses and transport of air into the vortex. When the vortex is divided into three equal-area regions, the results are 85±9DU for the collar region (closest to the edge), 52±5DU for the vortex centre and 68±7DU for the middle region in between centre and collar. Our results compare well with other studies: We find good agreement with ozone loss deduced from SAOZ data, with results inferred from POAM III observations and with results from tracer-tracer correlations using HF as the long-lived tracer. We find a higher ozone loss than that deduced by tracer-tracer correlations using CH4. We have made a careful comparison with Match results: The results were recalculated using a common time period, vortex edge definition and height interval. The two methods generally compare very well, except at the 475K level which exhibits an unexplained discrepancy.

Description: We have used the SLIMCAT 3-D off-line chemical transport model (CTM) to quantify the Arctic chemical ozone loss in the year 2002/2003 and compare it with similar calculations for the winters 1999/2000 and 2003/2004. Recent changes to the CTM have improved the model's ability to reproduce polar chemical and dynamical processes. The updated CTM uses σ-θ as a vertical coordinate which allows it to extend down to the surface. The CTM has a detailed stratospheric chemistry scheme and now includes a simple NAT-based denitrification scheme in the stratosphere. In the model runs presented here the model was forced by ECMWF ERA40 and operational analyses. The model used 24 levels extending from the surface to ~55km and a horizontal resolution of either 7.5° x 7.5° or 2.8° x 2.8°. Two different radiation schemes, MIDRAD and the CCM scheme, were used to diagnose the vertical motion in the stratosphere. Based on tracer observations from balloons and aircraft, the more sophisticated CCM scheme gives a better representation of the vertical transport in this model which includes the troposphere. The higher resolution model generally produces larger chemical O3 depletion, which agrees better with observations. The CTM results show that very early chemical ozone loss occurred in December 2002 due to extremely low temperatures and early chlorine activation in the lower stratosphere. Thus, chemical loss in this winter started earlier than in the other two winters studied here. In 2002/2003 the local polar ozone loss in the lower stratosphere was ~40% before the stratospheric final warming. Larger ozone loss occurred in the cold year 1999/2000 which had a persistently cold and stable vortex during most of the winter. For this winter the current model, at a resolution of 2.8° x 2.8°, can reproduce the observed loss of over 70% locally. In the warm and more disturbed winter 2003/2004 the chemical O3 loss was generally much smaller, except above 620K where large losses occurred due to a period of very low minimum temperatures at these altitudes.

Description: We present the results of a first comparison of the tropospheric NO2 column amounts derived from the measurements of the Global Ozone Monitoring Experiment (GOME) with the simulated data from a European scale chemistry transport model (CTM) which is distinct from existing global scale CTMs in higher horizontal resolution and more detailed description of the boundary layer processes and emissions. We employ, on the one hand, the newly developed extended version of the CHIMERE CTM, which covers both Western and Eastern Europe, and, on the other hand, the most recent version (Version 2) of GOME measurement based data-products, developed at the University of Bremen. We evaluate our model with the data from ground based monitoring of ozone and verify that it has a sufficiently high level of performance, which is expected for a state-of-the-art continental scale CTM. The major focus of the study is on a systematic statistical analysis and a comparison of spatial variability of the tropospheric NO2 columns simulated with CHIMERE and derived from GOME measurements. The analysis is performed separately for Western and Eastern Europe using the data for summer months of 1997 and 2001. In this way, we obtain useful information on the nature and magnitudes of uncertainties of spatial distributions of the considered data. Specifically, for Western Europe, it is found that the uncertainties of NO2 columns from GOME and CHIMERE are predominantly of the multiplicative character, and that the mean relative random (multiplicative) errors of the GOME measurement derived and simulated data averaged over the summer seasons considered do not exceed 23% and 32%, respectively. The mean absolute (additive) errors of both kinds of the data are estimated to be less than 3x1014mol/cm2. In Eastern Europe, the uncertainties have more complex character, and the separation between their multiplicative and additive parts is not sufficiently unambiguous. It is found, however, that the total random errors of NO2 columns from both GOME and CHIMERE over Eastern Europe are not, on the average, larger than the errors of the NO2 columns with similar magnitudes over Western Europe.

Description: The purpose of this study is to investigate horizontal transport processes in the winter stratosphere using data with a resolution relevant for chemistry and climate modeling. For this reason the Freie Universität Berlin Climate Middle Atmosphere Model (FUB-CMAM) with its model top at 83 km altitude, increased horizontal resolution T42 and the semi-Lagrangian transport scheme for advecting passive tracers is used. A new approach of this paper is the classification of specific transport phenomena within the stratosphere into tropical-subtropical streamers (e.g. Offermann et al., 1999) and polar vortex extrusions hereafter called polar vortex streamers. To investigate the role played by these large-scale structures on the inter-annual and seasonal variability of transport processes in northern mid-latitudes, the global occurrence of such streamers was calculated based on a 10-year model climatology, concentrating on the existence of the Arctic polar vortex. For the identification and counting of streamers, the new method of zonal anomaly was chosen. The analysis of the months October-May yielded a maximum occurrence of tropical-subtropical streamers during Arctic winter and spring in the middle and upper stratosphere. Synoptic maps revealed highest intensities in the subtropics over East Asia with a secondary maximum over the Atlantic in the northern hemisphere. Furthermore, tropical-subtropical streamers exhibited a higher occurrence than polar vortex streamers, indicating that the subtropical barrier is more permeable than the polar vortex barrier (edge) in the model, which is in good correspondence with observations (e.g. Plumb, 2002; Neu et al., 2003). Interesting for the total ozone decrease in mid-latitudes is the consideration of the lower stratosphere for tropical-subtropical streamers and the stratosphere above ~20 km altitude for polar vortex streamers, where strongest ozone depletion is observed at polar latitudes (WMO, 2003). In the lower stratosphere the FUB-CMAM simulated a climatological maximum of 10% occurrence of tropical-subtropical streamers over East-Asia/West Pacific and the Atlantic during early- and mid-winter. The results of this paper demonstrate that stratospheric streamers e.g. large-scale, tongue-like structures transporting tropical-subtropical and polar vortex air masses into mid-latitudes occur frequently during Arctic winter. They can therefore play a significant role on the strength and variability of the observed total ozone decrease at mid-latitudes and should not be neglected in future climate change studies.

Description: During the CRISTA-1 mission three pronounced fingerlike structures reaching from the lower latitudes to the mid-latitudes, so-called streamers, were observed in the measurements of several trace gases in early November 1994. A simulation of these streamers in previous studies employing the KASIMA (Karlsruhe Simulation Model of the Middle Atmosphere) and ROSE (Research on Ozone in the Stratosphere and its Evolution) model, both being Eulerian models, show that their formation is due to adiabatic transport processes. Here, the impact of mixing on the development of these streamers is investigated. These streamers were simulated with the CLaMS model (Chemical Lagrangian Model of the Stratosphere), a Lagrangian model, using N2O as long-lived tracer. Using several different initialisations the results were compared to the KASIMA simulations and CRISTA (Cryogenic Infrared Spectrometer and Telescope for the Atmosphere) observations. Further, since the KASIMA model was employed to derive a 9-year climatology, the quality of the reproduction of streamers from such a study was tested by the comparison of the KASIMA results with CLaMS and CRISTA. The streamers are reproduced well for the Northern Hemisphere in the simulations of CLaMS and KASIMA for the 6 November 1994. However, in the CLaMS simulation a stronger filamentation is found while larger discrepancies between KASIMA and CRISTA were found especially for the Southern Hemisphere. Further, compared to the CRISTA observations the mixing ratios of N2O are in general underestimated in the KASIMA simulations. An improvement of the simulations with KASIMA was obtained for a simulation time according to the length of the CLaMS simulation. To quantify the differences between the simulations with CLaMS and KASIMA, and the CRISTA observations, the probability density function technique (PDF) is used to interpret the tracer distributions. While in the PDF of the KASIMA simulation the small scale structures observed by CRISTA are smoothed out due to the numerical diffusion in the model, the PDFs derived from CRISTA observations can be reproduced by CLaMS by optimising the mixing parameterisation. Further, this procedure gives information on small-scale variabilities not resolved by the CRISTA observations.

Description: In the past, differential optical absorption spectroscopy (DOAS) has mostly been employed for atmospheric trace gas retrieval in the UV/Vis spectral region. New spectrometers such as SCIAMACHY onboard ENVISAT also provide near infrared channels and thus allow for the detection of greenhouse gases like CH4, CO2, or N2O. However, modifications of the classical DOAS algorithm are necessary to account for the idiosyncrasies of this spectral region, i.e. the temperature and pressure dependence of the high resolution absorption lines. Furthermore, understanding the sensitivity of the measurement of these high resolution, strong absorption lines by means of a non-ideal device, i.e. having finite spectral resolution, is of special importance. This applies not only in the NIR, but can also prove to be an issue for the UV/Vis spectral region. This paper presents a modified iterative maximum a posteriori-DOAS (IMAP-DOAS) algorithm based on optimal estimation theory introduced to the remote sensing community by rodgers76. This method directly iterates the vertical column densities of the absorbers of interest until the modeled total optical density fits the measurement. Although the discussion in this paper lays emphasis on satellite retrieval, the basic principles of the algorithm also hold for arbitrary measurement geometries. This new approach is applied to modeled spectra based on a comprehensive set of atmospheric temperature and pressure profiles. This analysis reveals that the sensitivity of measurement strongly depends on the prevailing pressure-height. The IMAP-DOAS algorithm properly accounts for the sensitivity of measurement on pressure due to pressure broadening of the absorption lines. Thus, biases in the retrieved vertical columns that would arise in classical algorithms, are obviated. Here, we analyse and quantify these systematic biases as well as errors due to variations in the temperature and pressure profiles, which is indispensable for the understanding of measurement precision and accuracy in the near infrared as well as for future intercomparisons of retrieval algorithms.

Description: Airborne measurements of acetone, methanol, PAN, acetonitrile (by Proton Transfer Reaction Mass Spectrometry), and CO (by Tunable Diode Laser Absorption Spectroscopy) have been performed during the Mediterranean Intensive Oxidants Study (MINOS August 2001). We have identified ten biomass burning plumes from strongly elevated acetonitrile mixing ratios. The characteristic biomass burning signatures obtained from these plumes reveal secondary production of acetone and methanol, while CO photochemically declines in the plumes. Mean excess mixing ratios - normalized to CO - of 1.8%, 0.20%, 3.8%, and 0.65% for acetone, acetonitrile, methanol, and PAN, respectively, were found. By scaling to an assumed global annual source of 663-807Tg CO, biomass burning emissions of 25-31 and 29-35 Tg/yr for acetone and methanol are estimated, respectively. Our measurements suggest that the present biomass burning contributions of acetone and methanol are significantly underestimated due to the neglect of secondary formation within the plume. Median acetonitrile mixing ratios throughout the troposphere were around 150pmol/mol, in accord with current biomass burning inventories and an atmospheric lifetime of ~6 months.

Description: SCIAMACHY CO2 measurements show a large variability in total column CO2 over the Sahara desert of up to 10%, which is not anticipated from in situ measurements and cannot be explained by results of atmospheric models. Comparisons with colocated aerosol measurements by TOMS and MISR over the Sahara indicate that the seasonal variation of SCIAMACHY-observed CO2 strongly resembles seasonal variations of windblown dust. Correlation coefficients of monthly datasets of colocated MISR aerosol optical depth and SCIAMACHY CO2 vary between 0.6 and 0.8, indicating that about half of the CO2 variance is explained by aerosol optical depth. Radiative transfer model calculations confirm the role of dust and can explain the size of the errors. Sensitivity tests suggest that the remaining variance may largely be explained by variations in the vertical distribution of dust. Further calculations for a few typical aerosol classes and a broad range of atmospheric conditions show that the impact of aerosols on SCIAMACHY retrieved CO2 is by far the largest over the Sahara, but may also reach significant levels elsewhere. Over the continents, aerosols lead mostly to overestimated CO2 columns with the exception of biomass burning plumes and dark coniferous forests. Inverse modelling calculations confirm that aerosol correction of SCIAMACHY CO2 measurements is needed to derive meaningful source and sink estimates. Methods for correcting aerosol-induced errors exist, but so far mainly on the basis of theoretical considerations. As demonstrated by this study, SCIAMACHY may contribute to a verification of such methods using real data.

Description: Thermal/optical methods have been widely used for quantifying total carbon (TC), organic carbon (OC), and elemental carbon (EC) in ambient and source particulate samples. Thermally defined carbon fractions have been used for source identification. Temperature precision in thermal carbon analysis is critical to the allocation of carbon fractions. The sample temperature is determined by a thermocouple, which is usually located in the oven near the sample. Sample and thermocouple temperature may differ owing to different thermal properties between the sample filter punch and the thermocouple, or inhomogeneities in the heating zone. Quick-drying temperature-indicating liquids (Tempil Inc., South Plainfield, NJ) of different liquefying points are used as temperature calibration standards. These consist of chemicals that change their appearance at specific temperatures and can be optically monitored to determine the sample temperature. Temperature measures were evaluated for three different models of carbon analyzers. Sample temperatures were found to differ from sensor temperatures by 10 to 50°C. Temperature biases of 14 to 22°C during thermal analysis were found to change carbon fraction measurements. The temperature indicators allow calibration curves to be constructed that relate the sample temperature to the temperature measured by a thermocouple.

Description: A medium frequency spaced-antenna radar has been operating at Rothera station, Antarctica (67° S, 68° W) for two periods, between 1997-1998 and since 2002, measuring winds in the mesosphere and lower thermosphere. In this paper monthly mean winds are derived and presented along with three years of radiosonde balloon data for comparison with the HWM-93 model atmosphere and other high latitude southern hemisphere sites. The observed meridional winds are slightly more northwards than those predicted by the model above 80 km in the winter months and below 80 km in summer. In addition, the altitude of the summer time zero crossing of the zonal winds above the westward jet is overestimated by the model by up to 8 km. These data are then merged with the wind climatology obtained from falling sphere measurements made during the PORTA campaign at Rothera in early 1998 and the HWM-93 model atmosphere to generate a complete zonal wind climatology between 0 and 100 km as a benchmark for future studies at Rothera. A westwards (eastwards) maximum of 44 ms-1 at 67 km altitude occurs in mid December (62 ms-1 at 37 km in mid July). The 0 ms-1 wind contour reaches a maximum altitude of 90 km in mid November and a minimum altitude of 18 km in January extending into mid March at 75 km and early October at 76 km.

Description: We use the new GLOMAP model of global aerosol microphysics to investigate the sensitivity of modelled sulfate and sea salt aerosol properties to uncertainties in the driving microphysical processes and compare these uncertainties with those associated with aerosol and precursor gas emissions. Overall, we conclude that uncertainties in microphysical processes have a larger effect on global sulfate and sea salt derived condensation nuclei (CN) and cloud condensation nuclei (CCN) concentrations than uncertainties in present-day sulfur emissions. Our simulations suggest that uncertainties in predicted sulfate and sea salt CCN abundances due to poorly constrained microphysical processes are likely to be of a similar magnitude to long-term changes in sulfate and sea salt CCN due to changes in anthropogenic emissions. A microphysical treatment of the global sulfate aerosol allows the uncertainty in climate-relevant aerosol properties to be attributed to specific processes in a way that has not been possible with simpler aerosol schemes. In particular we conclude that: (1) changes in the binary H2SO4-H2O nucleation rate and condensation rate of gaseous H2SO4 cause a shift in the vertical location of the upper tropospheric CN layer by as much as 3 km, while the shape of the CN profile is essentially pre-served (2) uncertainties in the binary H2SO4-H2O nucleation rate have a relatively insignificant effect on marine boundary layer (MBL) aerosol properties; (3) emitting a fraction of anthropogenic SO2 as particulates (to represent production of sulfate particles in power plant plumes below the scale of the model grid (which is of the order of 300 km)) has the potential to change the global mean MBL sulfate-derived CN concentrations by up to 72%, and changes of up to a factor 20 can occur in polluted continental regions; (4) predicted global mean MBL sulfate and sea salt CCN concentrations change by 10 to 60% when several microphysical processes are changed within reasonable uncertainty ranges; (5) sulfate and sea salt derived CCN concentrations are particularly sensitive to primary particle emissions, with global mean MBL sulfate and sea salt CCN changing by up to 27% and local concentrations over continental regions changing by more than 100% when the percentage of anthropogenic SO2 emitted as particulates is changed from 0 to 5%; (6) large changes in sea spray flux have insignificant effects on global sulfate aerosol except when the mass accommodation coefficient of sulfuric acid on the salt particles is set unrealistically low.

Description: Laboratory absorption spectra of peroxyacetyl nitrate (PAN, CH3C(O)OONO2) vapour have been measured in the mid-infrared range 550 cm-1 to 1400 cm-1 (18.2 to 7.14 µm) at both 250 K and 273 K, using a Fourier transform infrared spectrometer at a nominal spectral resolution of 0.25 cm-1 (unapodised). In addition, the 1600 cm-1 to 2200 cm-1 (6.25 to 4.54 µm) spectral region has been measured at 250 K. Cross-sectional data at each temperature, as well as integrated band intensities and peak infrared absorptivities for nine absorption bands of PAN in this spectral range, have been derived from a total of twelve separately measured PAN transmission spectra. A general increase in the peak absorption cross-section for all bands is noted with decreasing temperature, with cross-sectional increases in the range 6% (for the 1842 cm-1 band) and 30% (for the 991 cm-1 band) at 250K, relative to those previously reported at 295K. Differences in integrated band intensities range from -22% to +16% for the 1741 cm-1 and 991 cm-1 bands respectively over the same temperature range. These new absorption cross-sections for PAN are the first to be reported at temperatures below 295 K, allowing the possibility of improved retrievals of the atmospherically important PAN species from remotely sensed infrared spectra of the cold upper troposphere. These new cross-sectional data accompany this paper as an electronic supplement.

Description: The distribution and evolution of reactive species in a boundary layer characterized by the presence of shallow cumulus over land is studied by means of two large-eddy simulation models: the NCAR and WUR codes. The study focuses on two physical processes that can influence the chemistry: the enhancement of the vertical transport by the buoyant convection associated with cloud formation and the perturbation of the photolysis rates below, in and above the clouds. It is shown that the dilution of the reactant mixing ratio caused by the deepening of the atmospheric boundary layer is an important process and that it can decrease reactant mixing ratios by 10 to 50 percent compared to very similar conditions but with no cloud formation. Additionally, clouds transport chemical species to higher elevations in the boundary layer compared to the case with no clouds which influences the reactant mixing ratios of the nocturnal residual layers following the collapse of the daytime boundary layer. Estimates of the rate of reactant transport based on the calculation of the integrated flux divergence range from to −0.2 ppb hr-1 to −1 ppb hr-1, indicating a net loss of sub-cloud layer air transported into the cloud layer. A comparison of this flux to a parameterized mass flux shows good agreement in mid-cloud, but at cloud base the parameterization underestimates the mass flux. Scattering of radiation by cloud drops perturbs photolysis rates. It is found that these perturbed photolysis rates substantially (10–40%) affect mixing ratios locally (spatially and temporally), but have little effect on mixing ratios averaged over space and time. We find that the ultraviolet radiance perturbation becomes more important for chemical transformations that react with a similar order time scale as the turbulent transport in clouds. Finally, the detailed intercomparison of the LES results shows very good agreement between the two codes when considering the evolution of the reactant mean, flux and (co-)variance vertical profiles.

Description: The wintertime ozone buildup over the Northern Hemisphere (NH) midlatitudes and its connection with the mean meridional circulation in the stratosphere are examined statistically on a monthly basis from October to March (1980–2002). The ozone buildup begins locally in October with positive total ozone tendencies over the North Pacific, which spread eastward and westward in November and finally cover all midlatitudes in December. The local onset of the buildup in October is not evident in zonal mean ozone tendency, which is close to zero. From November to March, zonal mean total ozone tendency (50°–60° N) shows a strong correlation (|r|=0.7) with several zonal mean parameters associated to the mean meridional circulation, namely: eddy heat flux, temperature tendency, the vertical residual velocity and the residual streamfunction. At the same time, on the latitude-altitude cross section, correlation patterns between ozone tendency and widely used eddy heat flux are not uniform during winter. The strongest correlations are located equatorward (almost throughout the stratosphere) or poleward (only in the lower stratosphere) of the edge of the polar vortex. Such distribution may depend on the existence of the midlatitude and polar waveguides which defined refraction of upward propagating waves from the troposphere either to the midlatitude stratosphere or to the polar stratosphere. As a consequence of the nonuniform correlation patterns, heat flux averaged over the common region 45°–75° N, 100 hPa is not always an optimum proxy for statistical models describing total ozone variability in midlatitudes. Other parameters approximating the strength of the mean meridional circulation have more uniform and stable correlation patterns with ozone tendency during winter. We show that the NH midlatitude ozone buildup has a stable statistical relationship with the mean meridional circulation in all months from October to March and half of the interannual variability in monthly ozone tendencies can be explained by applying different proxies of the mean meridional circulation.

Description: The Lagrangian particle dispersion model FLEXPART was originally (about 8 years ago) designed for calculating the long-range and mesoscale dispersion of air pollutants from point sources, such as after an accident in a nuclear power plant. In the meantime FLEXPART has evolved into a comprehensive tool for atmospheric transport modeling and analysis. Its application fields were extended from air pollution studies to other topics where atmospheric transport plays a role (e.g., exchange between the stratosphere and troposphere, or the global water cycle). It has evolved into a true community model that is now being used by at least 25 groups from 14 different countries and is seeing both operational and research applications. A user manual has been kept actual over the years and was distributed over an internet page along with the model's source code. In this note we provide a citeable technical description of FLEXPART's latest version (6.2).

Description: Verification of modeled rainfall with precipitation observed by a rain gauge network has been performed in a case study over the Cyprus Island. Cyprus has a relatively dense rain gauge network. The applied verification method is the Contiguous Rain Area (CRA) analysis. Some drawbacks of the CRA method are pointed out when it is applied to such a case study. Impact on the CRA results, when considering different dimensions of the verification sub-domain and different types of indicators (correlation and mean square error) used in the comparison, are discussed. Results indicate that care should be taken when verification of modeled rainfall is performed over a domain smaller than the model one.

Description: Ozone profiles retrieved from limb scattering measurements of the SCIAMACHY instrument based on the satellite ENVISAT are compared to ground-based low altitude resolution remote sensors. All profiles are retrieved using optimal estimation. Following the work of Rodgers and Connor (2003) the retrievals of the ground-based instruments are simulated using the SCIAMACHY retrieval. The SCIAMACHY results and the results of the ground-based microwave radiometer in Bremen and Ny Ålesund agree within the expected covariance of the intercomparison.

Description: We introduce an alternative method for the retrieval of polarisation in the ultraviolet by the satellite spectrometer SCIAMACHY. Unlike the operational polarisation retrieval algorithm, this method does not use the Polarisation Measurement Devices (PMDs) onboard SCIAMACHY, but only requires the reflectance signal. This makes the algorithm more robust and less sensitive to calibration errors caused by either improper characterisation of the instrument's response functions (key data) or degradation of the optical components. The alternative polarisation retrieval is able to retrieve the full state of atmospheric polarisation in the wavelength range between 330 and 400 nm, which is essentially the wavelength region covered by SCIAMACHY's PMD 1. This allows a direct comparison with the current operational product. When we compare the alternative polarisation algorithm with the operational algorithm, we find in some cases agreement, but not in other cases. The alternative algorithm compares well with an analytical model of the polarisation of a cloud-free scene. Using the alternative algorithm the polarisation-sensitive feature in the SCIAMACHY reflectance around 350 nm is automatically corrected for.

Description: A method to compare upper tropospheric humidity (UTH) from satellite and radiosonde data has been applied to the European radiosonde stations. The method uses microwave data as a benchmark for monitoring the performance of the stations. The present study utilizes three years (2001-2003) of data from channel 18 (183.31±1.00 GHz) of the Advanced Microwave Sounding Unit-B (AMSU-B) aboard the satellites NOAA-15 and NOAA-16. The comparison is done in the radiance space, the radiosonde data were transformed to the channel radiances using a radiative transfer model. The comparison results confirm that there is a dry bias in the UTH measured by the radiosondes. This bias is highly variable among the stations and the years. This variability is attributed mainly to the differences in the radiosonde humidity measurements. The analysis also shows a difference between daytime and nighttime soundings which is attributed to radiation error in the radiosonde data. The dry bias due to this error alone correspond to approximately 11% relative error in the UTH measurements.

Description: To explore the relationship between tropospheric ozone and radiative forcing with changing emissions, we compiled two sets of global scenarios for the emissions of the ozone precursors methane (CH4), carbon monoxide (CO), non-methane volatile organic compounds (NMVOC) and nitrogen oxides (NOx) up to the year 2030 and implemented them in two global Chemistry Transport Models. The "Current Legislation" (CLE) scenario reflects the current perspectives of individual countries on future economic development and takes the anticipated effects of presently decided emission control legislation in the individual countries into account. In addition, we developed a "Maximum technically Feasible Reduction" (MFR) scenario that outlines the scope for emission reductions offered by full implementation of the presently available emission control technologies, while maintaining the projected levels of anthropogenic activities. Whereas the resulting projections of methane emissions lie within the range suggested by other greenhouse gas projections, the recent pollution control legislation of many Asian countries, requiring introduction of catalytic converters for vehicles, leads to significantly lower growth in emissions of the air pollutants NOx, NMVOC and CO than was suggested by the widely used and more pessimistic IPCC (Intergovernmental Panel on Climate Change) SRES (Special Report on Emission Scenarios) scenarios (Nakicenovic et al., 2000), which made Business-as-Usual assumptions regarding emission control technology. With the TM3 and STOCHEM models we performed several long-term integrations (1990-2030) to assess global, hemispheric and regional changes in CH4, CO, hydroxyl radicals, ozone and the radiative climate forcings resulting from these two emission scenarios. Both models reproduce broadly the observed trends in CO, and CH4 concentrations from 1990 to 2002. For the "current legislation" case, both models indicate an increase of the annual average ozone levels in the Northern Hemisphere by 5ppbv, and up to 15ppbv over the Indian sub-continent, comparing the 2020s (2020-2030) with the 1990s (1990-2000). The corresponding higher ozone and methane burdens in the atmosphere increase radiative forcing by approximately 0.2 Wm-2. Full application of today's emissions control technologies, however, would bring down ozone below the levels experienced in the 1990s and would reduce the radiative forcing of ozone and methane to approximately -0.1 Wm-2. This can be compared to the 0.14-0.47 Wm-2 increase of methane and ozone radiative forcings associated with the SRES scenarios. While methane reductions lead to lower ozone burdens and to less radiative forcing, further reductions of the air pollutants NOx and NMVOC result in lower ozone, but at the same time increase the lifetime of methane. Control of methane emissions appears an efficient option to reduce tropospheric ozone as well as radiative forcing.

Description: Monthly mean aerosol optical depth (AOD) over ocean is compared from a total of 9 aerosol retrievals during a 40 months period. Comparisons of AOD have been made both for the entire period and sub periods. We identify regions where there is large disagreement and good agreement between the aerosol satellite retrievals. Significant differences in AOD have been identified in most of the oceanic regions. Several analyses are performed including spatial correlation between the retrievals as well as comparison with AERONET data. During the 40 months period studied there have been several major aerosol field campaigns as well as events of high aerosol content. It is studied how the aerosol retrievals compare during such circumstances. The differences found in this study are larger than found in a previous study where 5 aerosol retrievals over an 8 months period were compared. Part of the differences can be explained by limitations and deficiencies in some of the aerosol retrievals. In particular, results in coastal regions are promising especially for aerosol retrievals from satellite instruments particularly suited for aerosol research. In depth analyses explaining the differences between AOD obtained in different retrievals are clearly needed. We limit this study to identifying differences and similarities and indicating possible sources that affect the quality of the retrievals. This is a necessary first step towards understanding the differences and improving the retrievals.

Description: Phenols are a major class of volatile organic compounds (VOC) whose reaction within, and partitioning between, the gas and liquid phases affects their lifetime within the atmosphere, the local oxidising capacity, and the extent of production of nitrophenols, which are toxic chemicals. In this work, a zero-dimension box model was constructed to quantify the relative importance of different nitration pathways, and partitioning into the liquid phase, of mono-aromatic compounds in order to help elucidate the formation pathways of 2- and 4-nitrophenol in the troposphere. The liquid phase contributed significantly to the production of nitrophenols for liquid water content (Lc) values exceeding 3x10-9, and for a range of assumed liquid droplet diameter, even though the resultant equilibrium partitioning to the liquid phase was much lower. For example, in a "typical" model scenario, with Lc=3x10-7, 58% of nitrophenol production occurred in the liquid phase but only 2% of nitrophenol remained there, i.e. a significant proportion of nitrophenol observed in the gas phase may actually be produced via the liquid phase. The importance of the liquid phase was enhanced at lower temperatures, by a factor ~1.5-2 at 278K c.f. 298K. The model showed that nitrophenol production was particularly sensitive to the values of the rate coefficients for the liquid phase reactions between phenol and OH or NO3 reactions, but insensitive to the rate coefficient for the reaction between benzene and OH, thus identifying where further experimental data are required.

Description: An intensive field measurement campaign was performed in July/August 2002 at the Global Atmospheric Watch station Izaña on Tenerife to study the interaction of mineral dust aerosol and tropospheric chemistry (MINATROC). A dense Saharan dust plume, with aerosol masses exceeding 500 µg m-3, persisted for three days. During this dust event strongly reduced mixing ratios of ROx (HO2, CH3O2 and higher organic peroxy radicals), H2O2, NOx (NO and NO2) and O3 were observed. A chemistry boxmodel, constrained by the measurements, has been used to study gas phase and heterogeneous chemistry. It appeared to be difficult to reproduce the observed HCHO mixing ratios with the model, possibly related to the representation of precursor gas concentrations or the absence of dry deposition. The model calculations indicate that the reduced H2O2 mixing ratios in the dust plume can be explained by including the heterogeneous removal reaction of HO2 with an uptake coefficient of 0.2, or by assuming heterogeneous removal of H2O2 with an accommodation coefficient of 5x10-4. However, these heterogeneous reactions cannot explain the low ROx mixing ratios observed during the dust event. Whereas a mean daytime net ozone production rate (NOP) of 1.06 ppbv/hr occurred throughout the campaign, the reduced ROx and NOx mixing ratios in the Saharan dust plume contributed to a reduced NOP of 0.14-0.33 ppbv/hr, which likely explains the relatively low ozone mixing ratios observed during this event.

Description: Atmospheric gaseous sulphuric acid was measured and its influence on particle formation and growth was investigated building on aerosol data. The measurements were part of the EU-project QUEST and took place at two different measurement sites in Northern and Central Europe (Hyytiälä, Finland, March-April 2003 and Heidelberg, Germany, March-April 2004). From a comprehensive data set including sulphuric acid, particle number size distributions and meteorological data, particle growth rates, particle formation rates and source rates of condensable vapors were inferred. Growth rates were determined in two different ways, from particle size distributions as well as from a so-called timeshift analysis. Moreover, correlations between sulphuric acid and particle number concentration between 3 and 6 nm were examined and the influence of air masses of different origin was investigated. Measured maximum concentrations of sulphuric acid were in the range from 1x106 to 16x106cm-3. The gaseous sulphuric acid lifetime with respect to condensation on aerosol particles ranged from 2 to 33min in Hyytiälä and from 0.5 to 8 min in Heidelberg. Most calculated values (growth rates, formation rates, vapor source rates) were considerably higher in Central Europe (Heidelberg), due to the more polluted air and higher preexistent aerosol concentrations. Close correlations between H2SO4 and nucleation mode particles (size range: 3-6 nm) were found on most days at both sites. The percentage contribution of sulphuric acid to particle growth was below 10% at both places and to initial growth below 20%. An air mass analysis indicated that at Heidelberg new particles were formed predominantly in air advected from southwesterly directions.

Description: An empirical approach for the retrieval of nitrogen dioxide (NO2) and formaldehyde (HCHO) photolysis frequencies from measurements of global irradiance is presented in this work. Four months of synchronous measurements of actinic flux and global irradiance performed in Thessaloniki, Greece by a Bentham spectroradiometer were used to extract polynomials for the conversion of global irradiance to photolysis frequencies [J(NO2) and J(HCHO)]. The comparison of these photolysis frequency values to the corresponding values calculated by spectral actinic flux measurements, showed a ratio very close to unity for all J's with a standard deviation of 12% (2σ) for J(NO2) and 6% (2σ) for J(HCHO). Additional sets of polynomials were also extracted to allow determination of J(NO2) by spectroradiometers with lower upper wavelength limits such as single and double Brewer spectroradiometers within acceptable uncertainty (corresponding ratio was 1 and standard deviation was 12% (2σ) for the method that can be used with double Brewers and 20% for the method that can be used for single Brewers). The validity of the method under different atmospheric conditions was also examined by applying the polynomials to another set of actinic flux and global irradiance measurements performed in May 2004, in Buchhofen, Germany. In this case, comparing J values extracted from the polynomials to those calculated from actinic flux, showed equivalent results, demonstrating that the method can also be applied to other measurement sites.

Description: Chlorine monoxide (ClO) plays a key role in stratospheric ozone loss processes at midlatitudes. We present two balloon-borne in situ measurements of ClO conducted in northern hemisphere midlatitudes during the period of the maximum of total inorganic chlorine loading in the atmosphere. Both ClO measurements were conducted on board the TRIPLE balloon payload, launched in November 1996 in León, Spain, and in May 1999 in Aire sur l'Adour, France. For both flights a ClO daylight and night-time vertical profile was derived over an altitude range of approximately 15-35 km. ClO mixing ratios are compared to model simulations performed with the photochemical box model version of the Chemical Lagrangian Model of the Stratosphere (CLaMS). Simulations along 24-hour backward trajectories were performed to study the diurnal variation of ClO in the midlatitude lower stratosphere. Model simulations for the flight launched in Aire sur l'Adour 1999 show an excellent agreement with the ClO measurements. For the flight launched in León 1996, an overall good agreement is found, whereas the flight is characterized by a more complex dynamical situation due to a possible mixture of vortex and non-vortex air. We note that for both flights at solar zenith angles greater than 86°-87° simulated ClO mixing ratios are higher than observed ClO mixing ratios. However, the present findings indicate that no substantial uncertainties exist in midlatitude chlorine chemistry of the stratosphere.

Description: Within the framework of the ENVISAT/-SCIAMACHY satellite validation, solar irradiance spectra are absolutely measured at moderate resolution in the UV/visible spectral range (in the UV from 316.7-418 nm and the visible from 400-652 nm at a full width half maximum resolution of 0.55 nm and 1.48 nm, respectively) from aboard the azimuth-controlled LPMA/DOAS balloon gondola at around 32 km balloon float altitude. After accounting for the atmospheric extinction due to Rayleigh scattering and gaseous absorption (O3 and NO2), the measured solar spectra are compared with previous observations. Our solar irradiance spectrum perfectly agrees within +0.03% with the re-calibrated Kurucz et al. (1984) solar spectrum (Fontenla et al., 1999, called MODTRAN 3.7) in the visible spectral range (415-650 nm), but it is +2.1% larger in the (370-415 nm) wavelength interval, and -4% smaller in the UV-A spectral range (316.7-370 nm), when the Kurucz spectrum is convolved to the spectral resolution of our instrument. Similar comparisons of the SOLSPEC (Thuillier et al., 1997, 1998a, b) and SORCE/SIM (Harder et al., 2000) solar spectra with MODTRAN 3.7 confirms our findings with the values being -0.5%, +2%, and -1.4% for SOLSPEC -0.33%, -0.47%, and -6.2% for SORCE/SIM, respectively. Comparison of the SCIAMACHY solar spectrum from channels 1 to 4 (- re-calibrated by the University of Bremen -) with MODTRAN 3.7 indicates an agreement within -0.4% in the visible spectral range (415-585 nm), -1.6% within the 370-415 nm, and -5.7% within 325-370 nm wavelength interval, in agreement with the results of the other sensors. In agreement with findings of Skupin et al. (2002) our study emphasizes that the present ESA SCIAMACHY level 1 calibration is systematically +15% larger in the considered wavelength intervals when compared to all available other solar irradiance measurements.

Description: Ozone and nitrous oxide are measured at high spatial and temporal resolution by instruments flying on the ER-2 NASA research aircraft. Comparing the airborne transects to reconstructions by ensemble of diffusive backward trajectories allows estimation of the average vertical Lagrangian turbulent diffusion experienced by the air parcels. The resulting estimates show large Lagrangian diffusion of the order of 0.1in the surf zone outside the polar vortex and smaller values of the order of 0.01 inside. Locally, large variation of Lagrangian diffusion occurs over mesoscale distances. It is found that high temporal resolution (3h or less) is required for off-line transport calculations and that the reconstructions are sensitive to spurious motion in standard analysed winds.

Description: Balloon-borne measurements of CFC11 (from the DIRAC in situ gas chromatograph and the DESCARTES grab sampler), ClO and O3 were made during the 1999/2000 Arctic winter as part of the SOLVE-THESEO 2000 campaign, based in Kiruna (Sweden). Here we present the CFC11 data from nine flights and compare them first with data from other instruments which flew during the campaign and then with the vertical distributions calculated by the SLIMCAT 3D CTM. We calculate ozone loss inside the Arctic vortex between late January and early March using the relation between CFC11 and O3 measured on the flights. The peak ozone loss (~1200ppbv) occurs in the 440-470K region in early March in reasonable agreement with other published empirical estimates. There is also a good agreement between ozone losses derived from three balloon tracer data sets used here. The magnitude and vertical distribution of the loss derived from the measurements is in good agreement with the loss calculated from SLIMCAT over Kiruna for the same days.

Description: A method is described that uses particle hygroscopicity measurements, made with a humidified tandem differential mobility analyzer (HTDMA), to determine solution water activity as a function of composition. The use of derived water activity data in computations determining the ability of aerosols to serve as cloud condensation nuclei (CCN) is explored. Results for sodium chloride and ammonium sulfate are shown in Part I. The methodology yields solution water activities and critical dry diameters for ammonium sulfate and sodium chloride in good agreement with previously published data. The approach avoids the assumptions required for application of simplified and modified Köhler equations to predict CCN activity, most importantly, knowledge of the molecular weight and the degree of dissociation of the soluble species. Predictions of the dependence of water activity on the mass fraction of aerosol species are sensitive to the assumed dry density, but predicted critical dry diameters are not.