ALBERT

Description: We assess the potential damage and smoke production associated with the detonation of small nuclear weapons in modern megacities. While the number of nuclear warheads in the world has fallen by about a factor of three since its peak in 1986, the number of nuclear weapons states is increasing and the potential exists for numerous regional nuclear arms races. Eight countries are known to have nuclear weapons, 2 are constructing them, and an additional 32 nations already have the fissile material needed to build substantial arsenals of low-yield (Hiroshima-sized) explosives. Population and economic activity worldwide are congregated to an increasing extent in megacities, which might be targeted in a nuclear conflict. Our analysis shows that, per kiloton of yield, low yield weapons can produce 100 times as many fatalities and 100 times as much smoke from fires as high-yield weapons, if they are targeted at city centers. A single "small'' nuclear detonation in an urban center could lead to more fatalities, in some cases by orders of magnitude, than have occurred in the major historical conflicts of many countries. We analyze the likely outcome of a regional nuclear exchange involving 100 15-kt explosions (less than 0.1% of the explosive yield of the current global nuclear arsenal). We find that such an exchange could produce direct fatalities comparable to all of those worldwide in World War II, or to those once estimated for a "counterforce'' nuclear war between the superpowers. Megacities exposed to atmospheric fallout of long-lived radionuclides would likely be abandoned indefinitely, with severe national and international implications. Our analysis shows that smoke from urban firestorms in a regional war would rise into the upper troposphere due to pyro-convection. Robock et al. (2006) show that the smoke would subsequently rise deep into the stratosphere due to atmospheric heating, and then might induce significant climatic anomalies on global scales.We also anticipate substantial perturbations of global ozone. While there are many uncertainties in the predictions we make here, the principal unknowns are the type and scale of conflict that might occur. The scope and severity of the hazards identified pose a significant threat to the global community. They deserve careful analysis by governments worldwide advised by a broad section of the world scientific community, as well as widespread public debate.

Description: We briefly present in this short paper a new SIze REsolved Aerosol Model (SIREAM) which simulates the evolution of atmospheric aerosol by solving the General Dynamic Equation (GDE). SIREAM segregates the aerosol size distribution into sections and solves the GDE by splitting coagulation and condensation/evaporation. A moving sectional approach is used to describe the size distribution change due to condensation/evaporation and a hybrid method has been developed to lower the computational burden. SIREAM uses the same physical parameterizations as those used in the Modal Aerosol Model, MAM sartelet05development. It is hosted in the modeling system POLYPHEMUS (Mallet et al., 2006) but can be linked to any other three-dimensional Chemistry-Transport Model.

Description: The results from three 45-year simulations of a coupled chemistry climate model are analysed for solar cycle influences on ozone and temperature. The simulations include UV forcing at the top of the atmosphere, which includes a generic 27-day solar rotation effect as well as the observed monthly values of the solar fluxes. The results are analysed for the 27-day and 11-year cycles in temperature and ozone. In accordance with previous results, the 27-day cycle results are in good qualitative agreement with observations, particularly for ozone. However, the results show significant variations, typically a factor of two or more in sensitivity to solar flux, depending on the solar cycle. We show for the first time good agreement also between the observed 11-year cycle and model results for the ozone vertical profile, which both indicate a minimum in solar response near 20 hPa. In comparison, simulations of the model with fixed solar phase (solar maximum/solar mean) and climatological sea surface temperatures lead to a poor simulation of the solar response in the ozone vertical profile. The results indicate the need for variable phase simulations in solar sensitivity experiments and the role of sea surface temperatures is discussed.

Description: The aerosol chemical mass closure is revisited and a simple and inexpensive methodology is proposed. This methodology relies on data obtained for aerosol mass, and concentration of the major ions and the two main carbon components, the organic carbon (OC) and the black carbon (BC). Atmospheric particles are separated into coarse (AD〉2µm) and fine (AD

Description: Knowledge of molecular photolysis cross sections is important for determining atmospheric lifetimes and fates of many species. A method and laser apparatus for measurement of these cross sections in the near-ultraviolet (UV) region is described. The technique is based on action spectroscopy, where the yield of a photodissociation product (in this case OH) is measured as a function of excitation energy. For compounds yielding OH, this method can be used to measure near-UV photodissociation cross section as low as 10−23 cm2 molecule−1. The method is applied to determine the photodissociation cross sections for methyl hydroperoxide (CH3OOH; MHP) and hydroxymethyl hydroperoxide (HOCH2OOH; HMHP) in the 305–365 nm wavelength range. The measured cross sections are in good agreement with previous measurements of absorption cross sections.

Description: We describe and begin to evaluate a parameterization to include the vertical transport of hot gases and particles emitted from biomass burning in low resolution atmospheric-chemistry transport models. This sub-grid transport mechanism is simulated by embedding a 1-D cloud-resolving model with appropriate lower boundary conditions in each column of the 3-D host model. Through assimilation of remote sensing fire products, we recognize which columns have fires. Using a land use dataset appropriate fire properties are selected. The host model provides the environmental conditions, allowing the plume rise to be simulated explicitly. The derived height of the plume is then used in the source emission field of the host model to determine the effective injection height, releasing the material emitted during the flaming phase at this height. Model results are compared with CO aircraft profiles from an Amazon basin field campaign and with satellite data, showing the huge impact that this mechanism has on model performance. We also show the relative role of each main vertical transport mechanisms, shallow and deep moist convection and the pyro-convection (dry or moist) induced by vegetation fires, on the distribution of biomass burning CO emissions in the troposphere.

Description: We use a modern climate model and new estimates of smoke generated by fires in contemporary cities to calculate the response of the climate system to a regional nuclear war between emerging third world nuclear powers using 100 Hiroshima-size bombs (less than 0.03% of the explosive yield of the current global nuclear arsenal) on cities in the subtropics. We find significant cooling and reductions of precipitation lasting years, which would impact the global food supply. The climate changes are large and long-lasting because the fuel loadings in modern cities are quite high and the subtropical solar insolation heats the resulting smoke cloud and lofts it into the high stratosphere, where removal mechanisms are slow. While the climate changes are less dramatic than found in previous "nuclear winter'' simulations of a massive nuclear exchange between the superpowers, because less smoke is emitted, the changes are more long-lasting because the older models did not adequately represent the stratospheric plume rise.

Description: Retrieved aerosol optical thickness (AOT) based on data obtained by the Sea viewing Wide Field Sensor (SeaWiFS) is combined with surface wind speed, obtained at the European Centre for Medium-Range Weather Forecasts (ECMWFs), over the North Pacific for September 2001. In this study a cloud screening approach is introduced in an attempt to exclude pixels partly or fully covered by clouds. The relatively broad swath width for which the nadir looking SeaWiFS instrument scanned over the North Pacific means that the AOT can be estimated according to relatively large range of wind speeds for each of the scenes analyzed. The sensitivity in AOT due to sea salt and hygroscopic growth of the marine aerosols has also been investigated. The validation of the results is based on previous parameterization in combination with the environmental quantities wind speed, RH and boundary layer height (BLH), estimated at the ECMWF. In this study a factor of 2 higher mean AOT is obtained for a wind speed up to about 13 m s−1 for September 2001 over remote ocean areas. Furthermore, a factor of 2 higher AOT is more or less supported by the validation of the results. Approximately, 50% of the enhancement seems to be due to hygroscopic growth of the marine aerosols and the remaining part due to increase in the sea salt particle mass concentrations, caused by a wind driven water vapor and sea salt flux, respectively. Reasonable agreement occurs also between satellites retrieved aerosol optical thickness and AOT observed at several AERONET (Aerosol Robotic NETwork) ground-based remote sensing stations. Finally, possible reasons why relatively large standard deviations occur around the mean values of AOT estimated for a single scene are discussed.

Description: Improving the constraints on the atmospheric fate and depletion rates of acidic compounds persistently emitted by non-erupting (quiescent) volcanoes is important for quantitatively predicting the environmental impact of volcanic gas plumes. Here, we present new experimental data coupled with modelling studies to investigate the chemical processing of acidic volcanogenic species during tropospheric dispersion. Diffusive tube samplers were deployed at Mount Etna, a very active open-conduit basaltic volcano in eastern Sicily, and Vulcano Island, a closed-conduit quiescent volcano in the Aeolian Islands (northern Sicily). Sulphur dioxide (SO2), hydrogen sulphide (H2S), hydrogen chloride (HCl) and hydrogen fluoride (HF) concentrations in the volcanic plumes (typically several minutes to a few hours old) were repeatedly determined at distances from the summit vents ranging from 0.1 to ~10 km, and under different environmental conditions. At both volcanoes, acidic gas concentrations were found to decrease exponentially with distance from the summit vents (e.g., SO2 decreases from ~10 000 μg/m3 at 0.1 km from Etna's vents down to ~7 μg/m3 at ~10 km distance), reflecting the atmospheric dilution of the plume within the acid gas-free background troposphere. Conversely, SO2/HCl, SO2/HF, and SO2/H2S ratios in the plume showed no systematic changes with plume aging, and fit source compositions within analytical error. Assuming that SO2 losses by reaction are small during short-range atmospheric transport within quiescent (ash-free) volcanic plumes, our observations suggest that, for these short transport distances, atmospheric reactions for H2S and halogens are also negligible. The one-dimensional model MISTRA was used to simulate quantitatively the evolution of halogen and sulphur compounds in the plume of Mt. Etna. Model predictions support the hypothesis of minor HCl chemical processing during plume transport, at least in cloud-free conditions. Larger variations in the modelled SO2/HCl ratios were predicted under cloudy conditions, due to heterogeneous chlorine cycling in the aerosol phase. The modelled evolution of the SO2/H2S ratios is found to be substantially dependent on whether or not the interactions of H2S with halogens are included in the model. In the former case, H2S is assumed to be oxidized in the atmosphere mainly by OH, which results in minor chemical loss for H2S during plume aging and produces a fair match between modelled and measured SO2/H2S ratios. In the latter case, fast oxidation of H2S by Cl leads to H2S chemical lifetimes in the early plume of a few seconds, and thus SO2 to H2S ratios that increase sharply during plume transport. This disagreement between modelled and observed plume compositions suggests that more in-detail kinetic investigations are required for a proper evaluation of H2S chemical processing in volcanic plumes.

Description: The Active Tracer High-resolution Atmospheric Model (ATHAM) has been adopted to examine the aerosol indirect effect in contrasting clean and polluted cloudy boundary layers during the Second Aerosol Characterization Experiment (ACE-2). Model results are in good agreement with available in-situ observations, which provides confidence in the results of ATHAM. Sensitivity tests have been conducted to examine the response of the cloud fraction (CF), cloud liquid water path (LWP), and cloud optical depth (COD) to changes in aerosols in the clean and polluted cases. It is shown for two cases that CF and LWP would decrease or remain nearly constant with an increase in aerosols, a result which shows that the second aerosol indirect effect is positive or negligibly small in these cases. Further investigation indicates that the background meteorological conditions play a critical role in the response of CF and LWP to aerosols. When large-scale subsidence is weak as in the clean case, the dry overlying air above the cloud is more efficiently entrained into the cloud, and in so doing, removes cloud water more efficiently, and results in lower CF and LWP when aerosol burden increases. However, when the large-scale subsidence is strong as in the polluted case, the growth of the cloud top is suppressed and the entrainment drying makes no significant difference when aerosol burden increases. Therefore, the CF and LWP remain nearly constant. In both the clean and polluted cases, the COD tends to increase with aerosols, and the total aerosol indirect effect (AIE) is negative even when the CF and LWP decrease with an increase in aerosols. Therefore, the first AIE dominates the response of the cloud to aerosols.

Description: We use a global chemical transport model (GEOS-Chem) to evaluate the consistency of satellite measurements of lightning flashes and ozone precursors with in situ measurements of tropical tropospheric ozone. The measurements are tropospheric O3, NO2, and HCHO columns from the GOME satellite instrument, lightning flashes from the OTD and LIS instruments, profiles of O3, CO, and relative humidity from the MOZAIC aircraft program, and profiles of O3 from the SHADOZ ozonesonde network. We interpret these multiple data sources with our model to better understand what controls tropical tropospheric ozone. Tropical tropospheric ozone is mainly affected by lightning and convection in the upper troposphere and by surface emissions in the lower troposphere. Scaling the spatial distribution of lightning in the model to the observed flash counts improves the simulation of O3 in the upper troposphere by 5–20 ppbv versus in situ observations and by 1–4 Dobson Units versus GOME retrievals of tropospheric O3 columns. A lightning source strength of 5±2 Tg N/yr best represents in situ observations from aircraft and ozonesonde. Tropospheric NO2 and HCHO columns from GOME are applied to provide top-down constraints on emission inventories of NOx (biomass burning and soils) and VOCs (biomass burning). The top-down biomass burning inventory is larger by a factor of 2 for HCHO and alkenes, and by 2.6 for NOx over northern equatorial Africa. These emissions increase lower tropospheric O3 by 5–20 ppbv, improving the simulation versus aircraft observations, and by 4 Dobson Units versus GOME observations of tropospheric O3 columns. Emission factors in the a posteriori inventory are more consistent with a recent compilation from in situ measurements. The ozone simulation using two different dynamical schemes (GEOS-3 and GEOS-4) is evaluated versus observations; GEOS-4 better represents O3 observations by 5–15 ppbv due to enhanced convective detrainment in the upper troposphere. Heterogeneous uptake of HNO3 on aerosols reduces simulated O3 by 5–7 ppbv, reducing a model bias versus in situ observations over and downwind of deserts. Exclusion of HO2 uptake on aerosols improves O3 by 5 ppbv in biomass burning regions.

Description: The mechanisms responsible for the extreme dryness of the stratosphere have been debated for decades. A key difficulty has been the lack of models which are able to reproduce the observations. Here we examine results from a new atmospheric chemistry general circulation model (ECHAM5/MESSy1) together with satellite observations. Our model results match observed temperatures in the tropical lower stratosphere and realistically represent recurrent features such as the semi-annual oscillation (SAO) and the quasi-biennual oscillation (QBO), indicating that dynamical and radiation processes are simulated accurately. The model reproduces the very low water vapor mixing ratios (1–2 ppmv) periodically observed at the tropical tropopause near 100 hPa, as well as the characteristic tape recorder signal up to about 10 hPa, providing evidence that the dehydration mechanism is well-captured, albeit that the model underestimates convective overshooting and consequent moistening events. Our results show that the entry of tropospheric air into the stratosphere at low latitudes is forced by large-scale wave dynamics; however, radiative cooling can regionally limit the upwelling or even cause downwelling. In the cold air above cumulonimbus anvils thin cirrus desiccates the air through the sedimentation of ice particles, similar to polar stratospheric clouds. Transport deeper into the stratosphere occurs in regions where radiative heating becomes dominant, to a large extent in the subtropics. During summer the stratosphere is moistened by the monsoon, most strongly over Southeast Asia.

Description: Spores and related chemical compounds from actively spore-discharging Ascomycota (AAM) and actively spore-discharging Basidiomycota (ABM) are primary biogenic components of air particulate matter (characteristic size range 1–10 μm). Measurement results and budget calculations based on investigations in Amazonia (Balbina, Brazil, July 2001) indicate that the forcible discharge of fungal spores may account for a large proportion of coarse air particulate matter in tropical rainforest regions during the wet season. For the particle diameter range of 1–10 μm, the estimated proportions are ~25% during day-time, ~45% at night, and ~35% on average. For the sugar alcohol, mannitol, the budget calculations indicate that it is suitable for use as a molecular tracer for actively discharged basidiospores (ABS), and that the literature-derived emission ratio of about 5 pg per ABS may be taken as a representative average. ABM emissions may account for most of the atmospheric abundance of mannitol, and can explain the observed diurnal cycle (higher abundance at night). ABM emissions of hexose carbohydrates might also account for a significant proportion of glucose and fructose in air particulate matter, but the literature-derived ratios are not consistent with the observed diurnal cycle (lower abundance at night). AAM emissions appear to account for a large proportion of potassium in air particulate matter over tropical rainforest regions during the wet season, and they can also explain the observed diurnal cycle (higher abundance at night). The results of our investigations and budget calculations for tropical rainforest aerosols are consistent with measurements performed at other locations. Based on the average abundance of mannitol in particulate matter, which is consistent with the above emission ratio and the observed abundance of ABS, we have also calculated a value of ~17 Tg yr−1 as a first estimate for the global average emission rate of ABS over land surfaces. Comparisons with estimated rates of emission and formation of other major types of organic aerosol (~47 Tg yr−1 of anthropogenic primary organic aerosol; 12–70 Tg yr−1 of secondary organic aerosol) indicate that emissions from actively spore-discharging fungi should be taken into account as a significant source of organic aerosol. Their effects might be particularly important in tropical regions, where both physicochemical processes in the atmosphere and biological activity at the Earth's surface are particularly intense, and where the abundance of fungal spores and related chemical compounds are typically higher than in extratropical regions.

Description: The upwelling planetary wave activity (PW) from the troposphere controls the intensity of the equator to pole transport of stratospheric ozone by the Brewer-Dobson circulation and thereby modulates the total ozone content at mid- and high-latitudes. Rayleigh lidar temperature data obtained from 1981 to 2001 at mid-latitude were used to study the interannual variability of PW activity in winter (October to April). The spectrum of stratospheric temperature fluctuations exhibits 2 peaks corresponding to 2 dominant modes of free travelling Rossby waves known as 16 day- and 12 day-waves. The 12 day-wave activity is shown to be anticorrelated with the equatorial QBO wind at 40 hPa. During the period 1981–2000 the global PW activity shows a negative trend for months October to January and a positive trend in March and April.

Description: The use of SAGE III multiwavelength aerosol extinction coefficient measurements to infer PSC type is contingent on the robustness of both the extinction magnitude and its spectral variation. Past validation with SAGE II and other similar measurements has shown that the SAGE III extinction coefficient measurements are reliable though the comparisons have been greatly weighted toward measurements made at mid-latitudes. Some aerosol comparisons made in the Arctic winter as a part of SOLVE II suggested that SAGE III values, particularly at longer wavelengths, are too small with the implication that both the magnitude and the wavelength dependence are not reliable. Comparisons with POAM III have also suggested a similar discrepancy. Herein, we use SAGE II data as a common standard for comparison of SAGE III and POAM III measurements in the Arctic winters of 2002/2003 through 2004/2005. During the winter, SAGE II measurements are made infrequently at the same latitudes as these instruments. We have mitigated this problem through the use potential vorticity as a spatial coordinate and thus greatly increased the number of coincident events. We find that SAGE II and III extinction coefficient measurements show a high degree of compatibility at both 1020 nm and 450 nm except a 10–20% bias at both wavelengths. In addition, the 452 to 1020 nm extinction ratio shows a consistent bias of ~30% throughout the lower stratosphere. We also find that SAGE II and POAM III are on average consistent though the comparisons show a much higher variability and larger bias than SAGE II/III comparisons. In addition, we find that the two data sets are not well correlated below 18 km. Overall, we find both the extinction values and the spectral dependence from SAGE III are robust and we find no evidence of a significant defect within the Arctic vortex.

Description: In this paper, we study the transport of air mass to San Pietro Capofiume (SPC) in Po Valley, Italy, by means of back trajectory analysis. Our main aim is to investigate whether air masses originate from different regions on nucleation event days and on nonevent days, during three years when nucleation events have been continuously recorded at SPC. The results indicate that nucleation events occur frequently in air masses arriving form Central Europe, whereas event frequency is much lower in air transported from southern directions and from the Atlantic Ocean. We also analyzed the behaviour of meteorological parameters during 96 h transport to SPC, and found that on average, event trajectories undergo stronger subsidence during the last 12 h before the arrival at SPC than nonevent trajectories. This causes a reversal in the temperature and relative humidity (RH) differences between event and nonevent trajectories: between 96 and 12 h back time, temperatures are lower and RH's higher for event than nonevent trajectories and between 12 and 0 h vice versa. Boundary layer mixing is stronger along the event trajectories compared to nonevent trajectories. The absolute humidity (AH) is similar for the event and nonevent trajectories between about 96 h and about 60 h back time, but after that, the event trajectories AH becomes lower due to stronger rain. We also studied transport of SO2 to SPC, and conclude that although sources in Po Valley most probably dominate the measured concentrations, certain Central and Eastern European sources can also have a non-negligible contribution.

Description: Reactive halogens are responsible for boundary-layer ozone depletion and mercury deposition in Polar Regions during springtime. To investigate the source of reactive halogens in the air arriving at Barrow, Alaska, we measured BrO, a marker of reactive halogen chemistry, and correlated its abundance with airmass histories derived from meteorological back trajectories and remotely sensed sea ice properties. The BrO is found to be positively correlated to first-year sea-ice contact (R2=0.55), and weakly negatively correlated to potential frost flower (PFF) contact (R2=0.04). These data indicate that snow contaminated with sea salts on first-year sea ice is a more probable bromine source than are frost flowers. Recent climate-driven changes in Arctic sea ice are likely to alter frost flower and first year sea ice prevalence, suggesting a significant change in reactive halogen abundance, which will alter the chemistry of the overlying Arctic atmosphere.

Description: Systematic analyses of interannual and seasonal variations of tropospheric NO2 vertical column densities (VCDs) based on GOME satellite data and the regional scale chemical transport model (CTM), Community Multi-scale Air Quality (CMAQ), are presented over eastern Asia between 1996 and June 2003. A newly developed year-by-year emission inventory (REAS) was used in CMAQ. The horizontal distribution of annual averaged GOME NO2 VCDs generally agrees well with the CMAQ results. However, CMAQ/REAS results underestimate the GOME retrievals with factors of 2–4 over polluted industrial regions such as Central East China (CEC), a major part of Korea, Hong Kong, and central and western Japan. For the Japan region, GOME and CMAQ NO2 data show good agreement with respect to interannual variation and show no clear increasing trend. For CEC, GOME and CMAQ NO2 data show good agreement and indicate a very rapid increasing trend from 2000. Analyses of the seasonal cycle of NO2 VCDs show that GOME data have systematically larger dips than CMAQ NO2 during February–April and September–November. Sensitivity experiments with fixed emission intensity reveal that the detection of emission trends from satellite in fall or winter have a larger error caused by the variability of meteorology. Examination during summer time and annual averaged NO2 VCDs are robust with respect to variability of meteorology and are therefore more suitable for analyses of emission trends. Analysis of recent trends of annual emissions in China shows that the increasing trends of 1996–1998 and 2000–2002 for GOME and CMAQ/REAS show good agreement, but the rate of increase by GOME is approximately 10–11% yr−1 after 2000; it is slightly steeper than CMAQ/REAS (8–9% yr−1). The greatest difference was apparent between the years 1998 and 2000: CMAQ/REAS only shows a few percentage points of increase, whereas GOME gives a greater than 8% yr−1 increase. The exact reason remains unclear, but the most likely explanation is that the emission trend based on the Chinese emission related statistics underestimates the rapid growth of emissions.

Description: The heterogeneous processing of organic aerosols by trace oxidants has many implications to atmospheric chemistry and climate regulation. This review covers a model heterogeneous reaction system (HRS): the oleic acid-ozone HRS and other reaction systems featuring fatty acids, and their derivatives. The analysis of the primary products of ozonolysis (azelaic acid, nonanoic acid, 9-oxononanoic acid, nonanal) is described. Anomalies in the relative product yields are noted and explained by the observation of secondary chemical reactions. The secondary reaction products arising from reactive Criegee intermediates are mainly peroxidic, notably secondary ozonides and α-acyloxyalkyl hydroperoxide polymers. These highly oxygenated products are of low volatility and hydrophilic which may enhance the ability of particles to act as cloud condensation nuclei. The kinetic description of this HRS is critically reviewed. Most kinetic studies suggest this oxidative processing is either a near surface reaction that is limited by the diffusion of ozone or a surface based reaction. Internally mixed particles and coatings represent the next stage in the progression towards more realistic proxies of tropospheric organic aerosols and a description of the products and the kinetics resulting from the ozonolysis of these proxies, which are based on fatty acids or their derivatives, is presented. Finally, a series of atmospheric implications of oxidative processing of particulate containing fatty acids is presented. These implications include the extended lifetime of unsaturated species in the troposphere facilitated by the presence of solids, semisolids or viscous phases, and an enhanced rate of ozone uptake by particulate unsaturates compared to corresponding gas phase organics. Ozonolysis of oleic acid enhances its CCN activity, which implies that oxidatively processed particulate may contribute to indirect forcing of radiation. Other effects, including the potential role of aldehydic products of ozonolysis in increasing the oxidative capacity of the troposphere, are also discussed.

Description: The speciation of iodine in atmospheric aerosol is currently poorly understood. Models predict negligible iodide concentrations and accumulation of iodate in aerosol, both of which is not confirmed by recent measurements. We present an updated aqueous phase iodine chemistry scheme for use in atmospheric chemistry models and discuss sensitivity studies with the marine boundary layer model MISTRA. These studies show that iodate can be reduced in acidic aerosol by inorganic reactions, i.e., iodate does not necessarily accumulate in particles. Furthermore, the transformation of particulate iodide to volatile iodine species likely has been overestimated in previous model studies due to negligence of collision-induced upper limits for the reaction rates. However, inorganic reaction cycles still do not seem to be sufficient to reproduce the observed range of iodide – iodate speciation in atmospheric aerosol. Therefore, we also investigate the effects of the recently suggested reaction of HOI with dissolved organic matter to produce iodide. If this reaction is fast enough to compete with the inorganic mechanism, it would not only directly lead to enhanced iodide concentrations but, indirectly via speed-up of the inorganic iodate reduction cycles, also to a decrease in iodate concentrations. Hence, according to our model studies, organic iodine chemistry, combined with inorganic reaction cycles, is able to reproduce observations. The presented chemistry cycles are highly dependent on pH and thus offer an explanation for the large observed variability of the iodide – iodate speciation in atmospheric aerosol.

Description: In order to improve the representation of the shortwave radiative transfer in the MAECHAM5 general circulation model, the spectral resolution of the shortwave radiation parameterization used in the model has been increased and extended in the UV-B and UV-C bands. The upgraded shortwave parameterization is first validated offline with a 4 stream discrete-ordinate line-by-line model. Thereafter, two 20-years simulations with the MAECHAM5 middle atmosphere general circulation model are performed to evaluate the temperature changes and the dynamical feedbacks arising from the newly introduced parameterization. The offline clear-sky comparison of the standard and upgraded parameterizations with the discrete ordinate model shows considerable improvement for the upgraded parameterization in terms of shortwave fluxes and heating rates. In the simulation with the upgraded ratiation parameterization, we report a significant warming of almost the entire atmosphere, largest at 1 hPa at the stratopause, and stronger zonal mean zonal winds in the middle atmosphere. The warming at the summer stratopause alleviates the cold bias present in the model when the standard radiation scheme is used. The stronger zonal mean zonal winds induce a dynamical feedback that results in a dynamical warming (cooling) of the polar winter (summer) mesosphere, caused by an increased downward (upward) circulation in the winter (summer) hemisphere. In the troposphere, the changes in the spectral resolution and the associated changes in the cloud optical parameters introduce a relatively small warming and, consistenly, a moisteneing. The warming occurs mostly in the upper troposphere and can contribute to a possible improvement of the model temperature climatology.

Description: This study investigates the connections between atmospheric sulphuric acid and new particle formation during QUEST III and BACCI/QUEST IV campaigns. The campaigns have been conducted in Heidelberg (2004) and Hyytiälä (2005), the first representing a polluted site surrounded by deciduous forest, and the second a rural site in a boreal forest environment. We have studied the role of sulphuric acid in particle formation and growth by determining 1) the power-law dependencies between sulphuric acid ([H2SO4]), and particle concentrations (N3–6) or formation rates at 1 nm and 3 nm (J1 and J3; 2) the time delays between [H2SO4] and N3–6 or J3, and the growth rates for 1–3 nm particles; 3) the empirical nucleation coefficients A and K in relations J1=A[H2SO4] and J1=K[H2SO4]2, respectively; 4) theoretical predictions for J1 and J3 for the days when no significant particle formation is observed, based on the observed sulphuric acid concentrations and condensation sinks. In both environments, N3–6 or J3 and [H2SO4] were linked via a power-law relation with exponents typically ranging from 1 to 2. The result suggests that the cluster activation theory and kinetic nucleation have the potential to explain the observed particle formation. However, some differences between the sites existed: The 1–3 nm growth rates were slightly higher and the nucleation coefficients about an order of magnitude greater in Heidelberg than in Hyytiälä conditions. The time lags between J3 and [H2SO4] were consistently lower than the corresponding delays between N3–6 and [H2SO4]. The exponents in the J3∝[H2SO4]nJ3-connection were consistently higher than or equal to the exponents in the relation N3–6∝[H2SO4]nN36. In the J1 values, no significant differences were found between the observed rates on particle formation event days and the predictions on non-event days. The J3 values predicted by the cluster activation or kinetic nucleation hypotheses, on the other hand, were considerably lower on non-event days than the rates observed on particle formation event days. This study provides clear evidence implying that the main process limiting the observable particle formation is the competition between the growth of the freshly formed particles and their loss by scavenging, rather than the initial particle production by nucleation of sulphuric acid. In general, it can be concluded that the simple models based on sulphuric acid concentrations and particle formation by cluster activation or kinetic nucleation can predict the occurence of atmospheric particle formation and growth well, if the particle scavenging is accurately accounted for.

Description: Atmospheric cloud condensation nuclei (CCN) concentrations are a key uncertainty in the assessment of the effect of anthropogenic aerosols on clouds and climate. The ability of new ultrafine particles to grow to become CCN varies throughout the atmosphere and must be understood in order to understand CCN formation. We have developed the Probability of Ultrafine particle Growth (PUG) model to answer questions regarding which growth and sink mechanisms control this growth, how the growth varies between different parts of the atmosphere and how uncertainties with respect to the magnitude and size distribution of ultrafine emissions translates into uncertainty in CCN generation. It was found in most cases that condensation is the dominant growth mechanism and coagulation with larger particles is the dominant sink mechanism for ultrafine particles. In this work we found that the probability of a new ultrafine particle generating a CCN varies from 90% in different parts of the atmosphere, though in the boundary layer a large fraction of ultrafine particles have a probability between 5% and 40%. Some regions, such as the tropical free troposphere, are areas with high probabilities; however, variability within regions makes it difficult to predict which regions of the atmosphere are most efficient for generating CCN from ultrafine particles. For a given mass of primary ultrafine aerosol, an uncertainty of a factor of two in the modal diameter can lead to an uncertainty in the number of CCN generated as high as a factor for eight. It was found that no single moment of the primary aerosol size distribution, such as total mass or number, is a robust predictor of the number of CCN ultimately generated. Therefore, a complete description of the size distribution is generally required for global aerosol microphysics models.

Description: Long-range atmospheric transport to Svalbard has been studied with a compilation of 4 years of daily trajectories to determine how the atmospheric flow patterns influence the observed methane (CH4) at Mt. Zeppelin station (475 m.a.s.l.) in Ny-Ålesund (78°54' N, 11°53' E). The flow patterns were determined through cluster analysis of 5-day back-trajectories arriving at Ny-Ålesund twice a day (00:00 and 12:00 UTC) for the period 2000–2003. Eight cluster patterns were obtained and used in the analysis of the continuous methane measurements at Mt. Zeppelin station. The analysis shows a shift in frequencies eastward into the Arctic compared to identical studies of transport for 1992–2001. Higher concentrations of methane are mainly seen in clusters with transport from Europe and Russia in contrast to air following transport pathways within the Arctic Basin. The vertical motion of the trajectories has been investigated and shows that it has an effect on the methane concentration at the Mt. Zeppelin station. This is consistent with previous similar studies of CO2 and of other anthropogenic species. Seasonal variation in trajectory frequency can be seen, like for instance more trajectories from Europe and Siberia during winter, and short trajectories from the Arctic region in summer. The identified seasonal and indications of decadal shifts in transport pathways translate into shifts in source areas sampled by a single station. To determine shifts in regional source (and sink) strengths it is necessary to correct for transport pathway shifts when interpreting time series data.

Description: An intercomparison of three Fourier transform spectrometers (FTSs) with significantly different resolutions is presented. The highest-resolution instrument has a maximum optical path difference of 250 cm, and the two lower-resolution instruments have maximum optical path differences of 50 cm and 25 cm. The results indicate that the two lower-resolution instruments can retrieve total column amounts of O3, HCl, N2O and CH4 using the SFIT2 retrieval code with percent differences from the high-resolution instrument generally better than 3%, with respect to the high-resolution FTS. Total column amounts of the stratospheric species (O3 and HCl) have larger differences than those of the tropospheric species (N2O and CH4). Instrument line shape (ILS) information is found to be of critical importance when retrieving total columns of stratospheric gases from the lower-resolution instruments. Including the ILS information in the retrievals significantly reduces the difference in total column amounts between the three instruments. The remaining errors for stratospheric species total column amounts can be attributed to the lower sensitivity of the lower-resolution FTSs to the stratosphere.

Description: There is increasing evidence that there exist interstellar-terrestrial relations and that the heliosphere's effectivity to serve as a protecting shield for the Earth, specifically against cosmic rays, is varying in time. Nonetheless, a debate is going on whether, amongst other drivers, the Sun or the cosmic rays are influencing the terrestrial climate, particularly on periods of hundred years and shorter. As the modelling of the transport of cosmic rays in the heliosphere has evolved from pure test particle simulations to far more consistent treatments, one can explain various correlations within the framework of physical models and one can make quantitative predictions regarding terrestrial indicators of interstellar-terrestrial relations. This level of understanding and modelling allows to identify a criterion with which one can discriminate between solar and cosmic ray forcing on a period of several decades. We define such a criterion and discuss related existing observations.

Description: Because of its ubiquitous release on land and well-characterized atmospheric loss, radon-222 has been very useful for deducing fluxes of greenhouse gases such as CO2, CH4, and N2O. It is shown here that the radon-tracer method, used in previous studies to calculate regional-scale greenhouse gas fluxes, returns a weighted-average flux (the flux field F weighted by the sensitivity of the measurements to that flux field, f) rather than an evenly-weighted spatial average flux. A synthetic data study using a Lagrangian particle dispersion model and modeled CO2 fluxes suggests that the discrepancy between the sensitivity-weighted average flux and evenly-weighted spatial average flux can be significant in the case of CO2, due to covariance between F and f for biospheric CO2 fluxes during the growing season and also for anthropogenic CO2 fluxes in general. A technique is presented to correct the radon-tracer derived fluxes to yield an estimate of evenly-weighted spatial average CO2 fluxes. A new method is also introduced for correcting the CO2 flux estimates for the effects of radon-222 radioactive decay in the radon-tracer method.

Description: The role of the retention coefficient (i.e. the fraction of a dissolved trace gas which is retained in hydrometeors during freezing) for the scavenging and redistribution of highly soluble trace gases by deep convective cloud systems is investigated using a modified version of the Weather Research and Forecasting (WRF) model. Results from cloud system resolving model runs (in which deep convection is initiated by small random perturbations in association with so-called "large scale forcings (LSF)") for a tropical oceanic (TOGA COARE) and a mid-latitude continental case (ARM) are compared to two runs in which bubbles are used to initiate deep convection (STERAO, ARM). In the LSF runs scavenging is found to almost entirely prevent a highly soluble tracer initially located in the lowest 1.5 km of the troposphere from reaching the upper troposphere, independent of the retention coefficient. The release of gases from freezing hydrometeors leads to mixing ratio increases in the upper troposphere comparable to those calculated for insoluble trace gases only in runs in which bubbles are used to initiate deep convection. This result indicates that previous cloud resolving model studies using bubbles to initiate deep convection may possibly have over-estimated the influence of the retention coefficient on the vertical transport of highly soluble tracers. The retention coefficient is, however, found to play an important role for the scavenging and redistribution of highly soluble trace gases with a (chemical) source in the free troposphere and also for trace gases for which even relatively inefficient transport may be important.

Description: This paper gives an overview of the MIPAS Level 1B (L1B) processor whose main objective is to calibrate atmospheric measurements radiometrically, spectrally and geo-located. It presents also the results of instrument characterization done during the first years in-flight. MIPAS has shown very good performance and stability.

Description: We present the adjoint of the global chemical transport model GEOS-Chem, focusing on the chemical and thermodynamic relationships between sulfate – ammonium – nitrate aerosols and their gas-phase precursors. The adjoint model is constructed from a combination of manually and automatically derived discrete adjoint algorithms and numerical solutions to continuous adjoint equations. Explicit inclusion of the processes that govern secondary formation of inorganic aerosol is shown to afford efficient calculation of model sensitivities such as the dependence of sulfate and nitrate aerosol concentrations on emissions of SOx, NOx, and NH3. The adjoint model is extensively validated by comparing adjoint to finite difference sensitivities, which are shown to agree within acceptable tolerances; most sets of comparisons have a nearly 1:1 correlation and R2〉0.9. We explore the robustness of these results, noting how insufficient observations or nonlinearities in the advection routine can degrade the adjoint model performance. The potential for inverse modeling using the adjoint of GEOS-Chem is assessed in a data assimilation framework through a series of tests using simulated observations, demonstrating the feasibility of exploiting gas- and aerosol-phase measurements for optimizing emission inventories of aerosol precursors.

Description: Principal component analysis provides a fast and robust method to reduce the data dimensionality of an aerosol size distribution data set. Here we describe a methodology for applying principal component analysis to aerosol size distribution measurements. We illustrate the method by applying it to data obtained during five field studies. Most variations in the sub-micrometer aerosol size distribution over periods of weeks can be described using 5 components. Using 6 to 8 components preserves virtually all the information in the original data. A key aspect of our approach is the introduction of a new method to weight the data; this preserves the orthogonality of the components while taking the measurement uncertainties into account. We also describe a new method for identifying the approximate number of aerosol components needed to represent the measurement quantitatively. Applying Varimax rotation to the resultant components decomposes a distribution into independent monomodal distributions. Normalizing the components provides physical meaning to the component scores. The method is relatively simply, computationally fast, and numerically robust. The resulting data simplification provides an efficient method of representing complex data sets and should greatly assist in the analysis of size distribution data.

Description: We have estimated impacts of alternative aviation routings on the radiative forcing. Changes in ozone and OH have been estimated in four Chemistry Transport Models (CTMs) participating in the TRADEOFF project. Radiative forcings due to ozone and methane have been calculated accordingly. In addition radiative forcing due to CO2 is estimated based on fuel consumption. Three alternative routing cases are investigated; one scenario assuming additional polar routes and two scenarios assuming aircraft cruising at higher (+2000 ft) and lower (−6000 ft) altitudes. Results from the base case in year 2000 are included as a reference. Taking first a steady state backward looking approach, adding the changes in the forcing from ozone, CO2 and CH4, the ranges of the models used in this work are −0.8 to −1.8 and 0.3 to 0.6 m Wm−2 in the lower (−6000 ft) and higher (+2000 ft) cruise levels, respectively. In relative terms, flying 6000ft lower reduces the forcing by 5–10% compared to the current flight pattern, whereas flying higher, while saving fuel and presumably flying time, increases the forcing by about 2–3%. Taking next a forward looking approach we have estimated the integrated forcing (m Wm−2 yr) over 20 and 100 years time horizons. The relative contributions from each of the three climate gases are somewhat different from the backward looking approach. The differences are moderate adopting 100 year time horizon, whereas under the 20 year horizon CO2 naturally becomes less important relatively. Thus the forcing agents impact climate differently on various time scales. Also, we have found significant differences between the models for ozone and methane. We conclude that we are not yet at a point where we can include non-CO2 effects of aviation in emission trading schemes. Nevertheless, the rerouting cases that have been studied here yield relatively small changes in the radiative forcing due to the radiatively active gases.

Description: The Tropospheric ORganic CHemistry experiment (TORCH) took place during the heatwave of summer 2003 at Writtle College, a site 2 miles west of Chelmsford in Essex and 25 miles north east of London. The experiment was one of the most highly instrumented to date. A combination of a large number of days of simultaneous, collocated measurements, a consequent wealth of model constraints and a highly detailed chemical mechanism, allowed the atmospheric chemistry of this site to be studied in detail. The concentrations of the hydroxyl radical, the hydroperoxy radical and the sum of peroxy radicals, were measured between 25 July and 31 August using laser-induced fluorescence at low pressure and the peroxy radical chemical amplifier techniques. The concentrations of the radical species were predicted using a zero-dimensional box model based on the Master Chemical Mechanism version 3.1, which was constrained with the observed concentrations of relatively long-lived species. The model included a detailed parameterisation to account for heterogeneous loss of hydroperoxy radicals onto aerosol particles. Quantile-quantile plots were used to assess the model performance in respect of the measured radical concentrations. On average, measured hydroxyl radical concentrations were over-predicted by 24%. Modelled and measured hydroperoxy radical concentrations agreed very well, with the model over-predicting on average by only 7%. The sum of peroxy radicals was under-predicted when compared with the respective measurements by 22%. OH initiation was dominated by the reactions of excited oxygen atoms with water, nitrous acid photolysis and the ozone reaction with alkene species. Photolysis of aldehyde species was the main initiation route for HO2 and RO2. Termination, under all conditions, primarily involved reactions with NOx for OH and heterogeneous chemistry on aerosol surfaces for HO2. The OH chain length varied between 2 and 8 cycles, the longer chain lengths occurring before and after the most polluted part of the campaign. Peak local ozone production of 17 ppb hr−1 occurred on 3 and 5 August, signifying the importance of local chemical processes to ozone production on these days. On the whole, agreement between model and measured radicals is good, giving confidence that our understanding of atmospheres influenced by nearby urban sources is adequate.

Description: New atmospheric particles with diameters of 3–10 nm and their subsequent growth to cloud condensation nucleus have been observed at various places in the European boundary layer. These events have been observed simultaneously within wide geographical areas (over 1000 km) in connection to specific weather systems, the cold air behind cyclones. Here we show that atmospheric aerosol formation (i.e. nucleation and initial growth) is favoured by the outbreak of cold Arctic air over northern Europe. Aerosol formation was about twice as common in Arctic air as in sub-Polar air, and even more so compared to other air masses. The most important general factor favouring aerosol formation in Arctic air and marine air was weaker competing condensational sink (CS) for the precursor gases (less pre-existing aerosols), while high CS prevented aerosol formation in heated sub-Polar air and mid-latitude air. High SO2 levels favoured nucleation in continental air and high UV-B radiation in sub-tropical air. The critical factor that determined if aerosol formation would start on a day with Arctic air was the UV-B radiation. The same applied to sub-Polar air and continental air, while increased SO2 concentration could trigger formation in heated sub-Polar and mid-latitude air, and reduced CS could cause formation in mid-latitude, marine or mixed/transient air. We speculate that strong emissions of volatile organic compounds from the Boreal forest and strong boundary layer dynamics may have caused aerosol formation in sub-Polar air masses and air in transition from a marine to a continental character. The monthly frequency of Arctic air masses and the probability for photo-chemically driven aerosol formation explains the observed annual cycle in monthly particle formation frequency as well as much of the inter annual variability. The same cyclones that transport cold, clean air from the Arctic to Europe will also transport warm polluted air in the other direction, which help cause the Arctic Haze phenomena. The cyclones have a key role for the atmospheric aerosol life cycle in mid to high latitudes. Due to the observed growth to the size of CCN in one to two days, there is a potential feed back from the effects on the CCN population and cloud albedo even within the same weather system, but also on the climatic time scale.

Description: It is important to obtain the year-to-year trend of stratospheric minor species in the context of global changes. An important example is the trend in global ozone depletion. The purpose of this paper is to report the accuracy and precision of measurements of stratospheric chemical species that are made at our Poker Flat site in Alaska (65° N, 147° W). Since 1999, minor atmospheric molecules have been observed using a Fourier-Transform solar-absorption infrared Spectrometer (FTS) at Poker Flat. Vertical profiles of the abundances of ozone, HNO3, HCl, and HF for the period from 2001 to 2003 were retrieved from the FTS spectra by using Rodgers' formulation of the Optimal Estimation Method (OEM). The accuracy and precision of the retrievals were estimated by formal error analysis. Errors for the total column were estimated to be 5.3%, 3.4%, 5.9%, and 5.3% for ozone, HNO3, HCl, and HF, respectively. The ozone vertical profiles were in good agreement with profiles derived from collocated ozonesonde measurements that were smoothed with averaging kernel functions that had been obtained with the retrieval procedure used in the analysis of spectra from the ground-based FTS (gb-FTS). The O3, HCl, and HF columns that were retrieved from the FTS measurements were consistent with Earth Probe/Total Ozone Mapping Spectrometer (TOMS) and HALogen Occultation Experiment (HALOE) data over Alaska within the error limits of all the respective datasets. This is the first report from the Poker Flat FTS observation site on a number of stratospheric gas profiles including a comprehensive error analysis.

Description: The volatility of sub-micrometer atmospheric aerosol particles was studied in a rural background environment in Finland using a combination of a heating tube and a scanning mobility particle sizer. The analysis focused on nano-particles formed from nucleation bursts which were subsequently observed during their growth in the diameter range between 5 and 60 nm. During the 6 days of new particle formation shown in detail, the concentrations of newly formed particles increased up to 10 000 cm−3. The number of nucleation mode particles measured after volatilization in the heating tube at 280°C was up to 90% of the total number under ambient conditions. Taking into account the absolute accuracy of the size distribution measurements, all ambient particles found in the rural atmosphere could have a non-volatile core after volatilization at 280°C. As the regional new particle formation events developed over time as a result of further vapor condensation, the newly formed particles grew at an average growth rate of 2.4±0.3 nm h−1. Importantly, the non-volatile cores of nucleation mode particles were also observed to grow over time, however, at a lower average growth rate of 0.6±0.3 nm h−1. One implication of the volatility analysis is that the newly formed particles, which have reached ambient diameters of 15 nm, are unlikely to consist of sulfuric acid, ammonium sulfate, and water alone. A relatively constant ratio between the growth rate of the ambient particles as well as their non-volatile cores indicates that non-volatile matter is formed only gradually in the growing particles. The non-volatile fraction of the particles showed some correlation with the ambient temperature. The composition and formation mechanism of this non-volatile material in nucleation mode particles are, to date, not known.

Description: The temperature dependence of secondary organic aerosol (SOA) formation from ozonolysis of β-pinene was studied in a flow reactor at 263–303 K and 1007 hPa. The observed SOA yields were of similar magnitude as predicted by a two-product model based on detailed gas phase chemistry (Jenkin, 2004), reaching maximum values of 0.22–0.39 at high particle mass concentrations. However, the measurement data exhibited significant deviations (up to 50%) from the predicted linear dependence on inverse temperature. When fitting the measurement data with a two-product model, we found that both the partitioning coefficients (Kom,i) and the stoichiometric yields (αi) of the low-volatile and semi-volatile species vary with temperature. The results indicate that not only the reaction product vapour pressures but also the relative contributions of different gas-phase or multiphase reaction channels are dependent on temperature. We suggest that the modelling of secondary organic aerosol formation in the atmosphere needs to take into account the effects of temperature on the pathways and kinetics of the involved chemical reactions as well as on the gas-particle partitioning of the reaction products.

Description: Absolute principal component analysis can be applied, with suitable modifications, to atmospheric aerosol size distribution measurements. This method quickly and conveniently reduces the dimensionality of a data set. The resulting representation of the data is much simpler, but preserves virtually all the information present in the original measurements. Here we demonstrate how to combine the simplified size distribution data with trace gas measurements and meteorological data to determine the origins of the measured particulate matter using absolute principal component analysis. We have applied the analysis to four different sets of field measurements that were conducted at three sites in southern Ontario. Several common factors were observed at all the sites; these were identified as photochemically produced secondary aerosol particles, regional pollutants (including accumulation mode aerosol particles), and trace gas variations associated with boundary layer dynamics. Each site also exhibited a factor associated specifically with that site: local industrial emissions in Hamilton (urban site), processed nucleation mode particles at Simcoe (polluted rural site), and transported fine particles at Egbert (downwind from Toronto).

Description: Boundary layer concenrations of several volatile organic compounds (VOC) were measured during two campaigns in springs of 2003 and 2006. Measurements were conducted over boreal forests near SMEAR II measurement station in Hyytiälä, Southern Finland. In 2003 the measuremens were performed using light aircraft and in 2006 using hot air ballon. Isoprene concentrarions were low, usually below detection limit. This is explained by low biogenic production due to cold weather. Monoterpenes were observed frequently. Average total monoterpene concentration in the boundary layer was 33 pptv. Many anthropogenic compounds e.g. benzene, xylene and toluene, were observed in high amounts. Ecosystem scale surface emissions were estimated using simple mixed box budget methodology. Total monoterpene fluxes varied up to 80 μg m−2 h−1, α-pinene contributing typically more than two thirds of that. Highest fluxes of anthropogenic compounds were those of p/m xylene.

Description: The performance of a new chemical ionization reaction time-of-flight mass spectrometer (CIR-TOF-MS) utilising the environment chamber SAPHIR (Simulation of Atmospheric Photochemistry In a large Reaction Chamber – Forschungzentrum Jülich, Germany) is described. The work took place as part of the ACCENT (Atmospheric Composition and Change the European NeTwork for excellence) supported oxygenated volatile organic compound (OVOC) measurement intercomparison during January 2005. The experiment entailed the measurement of 14 different atmospherically significant OVOCs at various mixing ratios in the approximate range 10.0–0.6 ppbV. The CIR-TOF-MS operated throughout the exercise with the hydronium ion (H3O+) as the primary chemical ionization (CI) reagent in order to facilitate proton transfer to the analyte OVOCs. The results show the CIR time-of-flight mass spectrometer is capable of detecting a wide range of atmospheric OVOCs down to sub-ppbV mixing ratios with high accuracy and precision. It is demonstrated that the technique has rapid multi-channel response at the required sensitivity, accuracy and precision for atmospheric OVOC measurements.

Description: A fire storm that occured on 28 May 2001 devastated the town of Chisholm, ~150 km north of Edmonton, Alberta, induced a violent fire-invigorated cumulonimbus cloud. This pyro-cumulonimbus (pyro-Cb) had overshooting tops of 2.5–3 km above the tropopause, and injected massive amounts of smoke into the lower stratosphere. Fortunately, this event occurred under good coverage of radar, rain gauge, lightning and satellite measurements, which allowed in-depth documentation of the event. The combination of heat and smoke created a cloud with extremely small drops, which ascended rapidly in violent updrafts. There appeared to be little freezing up to the homogeneous freezing isotherm level of –38°C. A cloud with such small and short-lived highly supercooled drops is incapable of producing precipitation except for few large graupel and hail, which produced the observed radar echoes and charged the cloud with positive lightning. The small cloud drops froze homogeneously to equally small ice particles, for which there is no mechanism to aggregate into precipitation particles that hence remain in the anvil. The small precipitation efficiency implies that only a small fraction of the smoke is scavenged, so that most of it is exhausted through the anvil to the upper troposphere and lower stratosphere. Comparisons with other cases suggest that a pyro-Cb does not have to be as violent as the Chisholm case to have strongly suppressed precipitation. However, this level of convective vigor is necessary to create the overshooting updraft that injects the smoke into the lower stratosphere.

Description: The results of a comparison exercise of radiative transfer models (RTM) of various international research groups for Multiple AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) viewing geometry are presented. In contrast to previous comparison exercises, box-air-mass-factors (box-AMFs) for various atmospheric height layers were modelled, which describe the sensitivity of the measurements as a function of altitude. In addition, radiances were calculated allowing the identification of potential errors, which might be overlooked if only AMFs are compared. Accurate modelling of radiances is also a prerequisite for the correct interpretation of satellite observations, for which the received radiance can strongly vary across the large ground pixels, and might be also important for the retrieval of aerosol properties as a future application of MAX-DOAS. The comparison exercises included different wavelengths and atmospheric scenarios (with and without aerosols). The results were systematically investigated with respect to their dependence on the telescope's elevation angle and the azimuth angle. For both dependencies, a strong and systematic influence of aerosol scattering was found indicating that from MAX-DOAS observations also information on atmospheric aerosols can be retrieved. During the various iterations of the exercises, the results from all models showed a substantial convergence, and the final data sets agreed for most cases within about 5%. Larger deviations were found for cases with low atmospheric optical depth, for which the photon path lengths along the line of sight of the instrument can become very large. The differences occurred between models including full spherical geometry and those using only plane parallel approximation indicating that the correct treatment of the Earth's sphericity becomes indispensable. The modelled box-AMFs constitute an universal data base for the calculation of arbitrary (total) AMFs by simple convolution with a given trace gas concentration profile. Together with the modelled radiances and the specified settings for the various exercises, they can serve as test cases for future RTM developments.

Description: Odin-SMR is a limb-sounder operating in the 500 region with the capability of performing measurements down to altitudes of about 10 with relatively low influence of ice clouds. Until now spectra from tropospheric tangent altitudes have been disregarded due to inadequate handling of scattering. A first method to extract upper tropospheric quantities has now been developed, yielding the humidity in two layers around 200 and 130 and information on cloud ice content above 200. The main concern for these retrievals is the calibration performance. A careful analysis indicates a systematic calibration error of about 1 K, but also a random component that differs between the two bands. The random calibration uncertainty results in retrieval errors of 10–60% depending on humidity and band. Presently this prohibits use of single retrievals, but averages can be presented with good accuracy. The fixed calibration error can largely be removed, leaving the spectroscopic uncertainties to dominate the humidity retrieval accuracy, estimated to be around 20%. First results are presented that are in agreement with seasonal structure obtained from other satellite measurements. An encouraging comparison between MOZAIC data and measurements for the 200 layer gives further confidence in the capability of Odin-SMR to measure humidity in the upper tropical troposphere.

Description: We present the first detailed microphysical simulations which are performed online within the framework of a global 3-D chemical transport model (CTM) with full chemistry. The model describes the formation and evolution of four types of polar stratospheric cloud (PSC) particles. Aerosol freezing and other relevant microphysical processes are treated in a full explicit way. Each particle type is described by a binned size distribution for the number density and chemical composition. This set-up allows for an accurate treatment of sedimentation and for detailed calculation of surface area densities and optical properties. Simulations are presented for the Antarctic winter of 2003 and comparisons are made to a diverse set of satellite observations (optical and chemical measurements of POAM III and MIPAS) to illustrate the capabilities of the model. This study shows that a combined resolution approach where microphysical processes are simulated in coarse-grained conditions gives good results for PSC formation and its large-scale effect on the chemical environment through processes such as denitrification, dehydration and ozone loss. It is also shown that the influence of microphysical parameters can be measured directly from these processes.

Description: We report in situ and remote observations proving occasional occurrence of solid particles in the tropical lowest stratosphere, far away from deep convective events. The particles were found during field campaigns in Southeast Brazil (49.03 W 22.36 S). They occur in the altitude range from 17.5 to 20.8 km, at temperatures up to at least 10 K above the expected frost point temperature. While stability of ice particles at these altitudes is unexpected from a theoretical point of view, it is argued that these observations are indications of tropospheric air masses penetrating into the stratosphere during convective overshoots. It is concluded that the intrusion of tropospheric air must have carried a large amount of water with it, which effectively hydrated the lowest stratosphere, and consequently suppressed sublimation. This conclusion is further supported by a separate water vapor mixing ratio profile obtained at the same observation site.

Description: More than three years of measurements of aerosol size-distribution and different gas and meteorological parameters made in Po Valley, Italy were analysed for this study to examine which of the meteorological and trace gas variables effect on the emergence of nucleation events. As the analysis method, we used discriminant analysis with non-parametric Epanechnikov kernel, included in non-parametric density estimation method. The best classification result in our data was reached with the combination of relative humidity, ozone concentration and a third degree polynomial of radiation. RH appeared to have a preventing effect on the new particle formation whereas the effects of O3 and radiation were more conductive. The concentration of SO2 and NO2 also appeared to have significant effect on the emergence of nucleation events but because of the great amount of missing observations, we had to exclude them from the final analysis.

Description: Aerosol spectral measurements by sunphotometers can be characterized by three independent pieces of information: 1) the optical thickness (AOT), a measure of the column aerosol concentration, 2) the optical thickness average spectral dependence, given by the Angstrom exponent (α), and 3) the spectral curvature of α (δα). We propose a simple graphical method to visually convert (α, δα) to the contribution of fine aerosol to the AOT and the size of the fine aerosols. This information can be used to track mixtures of pollution aerosol with dust, to distinguish aerosol growth from cloud contamination and to observe aerosol humidification. The graphical method is applied to the analysis of yearly records at 8 sites in 3 continents, characterized by different levels of pollution, biomass burning and mineral dust concentrations. Results depict the dominance of fine mode aerosols in driving the AOT at polluted sites. In stable meteorological conditions, we see an increase in the size of the fine aerosol as the pollution stagnates and increases in optical thickness. Coexistence of coarse and fine particles is evidenced at the polluted sites downwind of arid regions.

Description: The properties of atmospheric aerosol particles in Marseille and Athens were investigated. The studies were performed in Marseille, France during July 2002 and in Athens Greece during June 2003. The aerosol size distribution and the formation and growth rates of newly formed particles were characterized using Differential Mobility Particle Sizers. Hygroscopic properties were observed using a Hygroscopic Tandem Differential Mobility Analyzer setup. During both campaigns, the observations were performed at suburban, almost rural sites, and the sites can be considered to show general regional background behavior depending on the wind direction. At both sites there were clear pattern for both aerosol number concentration and hygroscopic properties. Nucleation mode number concentration increased during the morning hours indicating new particle formation, which was observed during more than 30% of the days. The observed formation rate was typically more than 1 cm−3 s−1, and the growth rate was between 1.2–9.9 nm h−1. Based on hygroscopicity measurements in Athens, the nucleation mode size increase was due to condensation of both water insoluble and water soluble material. However, during a period of less anthropogenic influence, the growth was to a larger extent due to water insoluble components. When urban pollution was more pronounced, growth due to condensation of water soluble material dominated.

Description: A statistical synthesis of marine aerosol measurements from experiments in four different oceans is used to evaluate a global aerosol microphysics model (GLOMAP). We compare the model against observed size resolved particle concentrations, probability distributions, and the temporal persistence of different size particles. We attempt to explain the observed size distributions in terms of sulfate and sea spray and quantify the possible contributions of anthropogenic sulfate and carbonaceous material to the number and mass distribution. The model predicts a bimodal size distribution that agrees well with observations as a grand average over all regions, but there are large regional differences. Notably, observed Aitken mode number concentrations are more than a factor 10 higher than in the model for the N Atlantic but a factor 7 lower than the model in the NW Pacific. We also find that modelled Aitken mode and accumulation mode geometric mean diameters are generally smaller in the model by 10–30%. Comparison with observed free tropospheric Aitken mode distributions suggests that the model underpredicts growth of these particles during descent to the MBL. Recent observations of a substantial organic component of free tropospheric aerosol could explain this discrepancy. We find that anthropogenic continental material makes a substantial contribution to N Atlantic marine boundary layer (MBL) aerosol, with typically 60–90% of sulfate across the particle size range coming from anthropogenic sources, even if we analyse air that has spent an average of 〉120 h away from land. However, anthropogenic primary black carbon and organic carbon particles do not explain the large discrepancies in Aitken mode number. Several explanations for the discrepancy are suggested. The lack of lower atmospheric particle formation in the model may explain low N Atlantic particle concentrations. However, the observed and modelled particle persistence at Cape Grim in the Southern Ocean, does not reveal a diurnal cycle consistent with a photochemically driven local particle source. We also show that a physically based cloud drop activation scheme is needed to explain the observed change in accumulation mode geometric mean diameter with particle number.

Description: In this study, we evaluate the ability of the BRAMS mesoscale model compared to ECMWF global analysis to simulate the observed vertical variations of water vapour in the tropical upper troposphere and lower stratosphere (UTLS). The observations are balloon-borne measurements of water vapour mixing ratio and temperature from micro-SDLA (Tunable Diode Laser Spectrometer) instrument. Data from two balloon flights performed during the 2004 HIBISCUS field campaign are used to compare with the mesoscale simulations and to ECMWF analysis. The mesoscale model performs significantly better than ECMWF analysis for water vapour in the upper troposphere and similarly or slightly worse for temperature. The improvement provided by the mesoscale model for water vapour comes mainly from (i) the enhanced vertical resolution in the UTLS (250 m for BRAMS and ~1 km for ECMWF model) and (ii) the more detailed microphysical parameterization providing ice supersaturations as in the observations. The ECMWF vertical resolution (~1 km) is too coarse to capture the observed fine scale vertical variations of water vapour in the UTLS. In near saturated or supersaturated layers, the mesoscale model relative humidity with respect to ice saturation is close to observations provided that the temperature profile is realistic. For temperature, ECMWF analysis gives good results partly thanks to data assimilation. The analysis of the mesoscale model results showed that in undersaturated layers, the water vapour profile depends mainly on the dynamics. In saturated/supersaturated layers, microphysical processes play an important role and have to be taken into account on top of the dynamical processes to understand the water vapour profiles. In the lower stratosphere, the ECMWF model and the BRAMS model give very similar water vapour profiles that are significantly dryer than micro-SDLA measurements. This similarity comes from the fact that BRAMS is initialised using ECMWF analysis and that no mesoscale process acts in the stratosphere leading to no modification of the BRAMS results with respect to ECMWF analysis.

Description: We present a simple method to perform degradation correction to Global Ozone Monitoring Experiment (GOME) reflectance spectra by comparing the average reflectance for 60° N–60° S with that at the beginning of GOME observations after removing the dependences on solar zenith angle and seasonal variation. The results indicate positive degradation of up to ~15–25% in the wavelength range 289–370 nm during 2000–2002; the degradation also exhibits significant dependence on wavelength and view zenith angle. These results are consistent with previous studies using radiative transfer models and ozone observations or climatology. The degradation causes retrieval biases of up to ~3% (10 DU, 1 DU=2.69×1016 molecules cm−2), 30% (10 DU), 10%, and 40% in total column ozone, tropospheric column ozone, stratospheric ozone and tropospheric ozone, respectively, from our GOME ozone profile retrieval algorithm. The application of this degradation correction generally improves the retrievals relative to Dobson and ozonesonde measurements during 2000–2003 and improves the retrieval consistency during 1996–2003.

Description: The authors introduce the radiative transfer model CLOUD for reflection, transmission, and absorption characteristics of terrestrial clouds and discuss the accuracy of the approximations used within the model. A Fortran implementation of CLOUD is available for download. This model is fast, accurate, and capable of calculating multiple raditiative transfer characteristics of cloudy media including the spherical and plane albedo, reflection and transmission functions, absorptance as well as global and diffuse transmittance. The approximations are based on the asymptotic solutions of the radiative transfer equations. While the analytic part of the solutions is treated in the code in an approximate way, the correspondent reflection function (RF) of a semi-infinite water cloud R∞ is calculated using numerical solutions of the radiative transfer equations in the assumption of Deirmendjian's cloud C1 model. In the case of ice clouds, the fractal ice crystal model is used. The resulting values of R∞ with respect to the viewing geometry are stored in a look-up table (LUT).

Description: The Lagrangian transport model COMET has been developed to evaluate emission estimates based on atmospheric concentration observations. This paper describes the model and its application in modelling the methane concentrations at the European stations Cabauw and Macehead. The COMET model captures in most cases both synoptic and diurnal variations of the concentrations as a function of time and in absolute size quite well. The explained variability by COMET of the mixed layer concentration for Cabauw varies from 50% to 84%; for all hourly observations in 2002 the explained variability is 71% with a RMSE of 112 ppb. The explained variability for Macehead is 48%. The most important model parameters were tested for their influence on model performance, but in general the model is not very sensitive to variations within acceptable limits. For a regionally and locally polluted continental site the COMET model shows only a small bias and a moderate random error, and therefore is considered to capture the influence of the sources on the concentration variations quite well. It is therefore concluded that inverse methods and more specifically the COMET model is suitable to be applied in deriving independent estimates of greenhouse gas emissions using Source-Receptor relationships.

Description: A light aircraft was equipped with a bank of Condensation Particle Counters (CPCs) (50% cut from 3–5.4–9.6 nm) and a nano-Scanning Mobility Particle Sizer (nSMPS) and deployed along the west coast of Ireland, in the vicinity of Mace Head. The objective of the exercise was to provide high resolution micro-physical measurements of the coastal nucleation mode in order to map the spatial extent of new particle production regions and to evaluate the evolution, and associated growth rates of the coastal nucleation-mode aerosol plume. Results indicate that coastal new particle production is occurring over most areas along the land-sea interface with peak concentrations at the coastal plume-head in excess of 106 cm−3. Pseudo-Lagrangian studies of the coastal plume evolution illustrated significant growth of new particles to sizes in excess of 8 nm approximately 10 km downwind of the source region. Close to the plume head (

Description: MonteCarlo simulations have been performed to evaluate the importance of multiple scattering effects in co- and cross-polar radar returns for 94GHz radars in Cloudsat and airborne configurations. Thousands of vertically structured profiles derived from some different cloud resolving models are used as a test-bed. Mie theory is used to derive the single scattering properties of the atmospheric hydrometeors. Multiple scattering effects in the cross polar channel (reflectivity enhancement) are particularly elusive, especially in airborne configuration. They can be quite consistent in satellite configurations, like Cloudsat, especially in regions of high attenuation and in the presence of highly forward scattering layers associated with snow and graupel particles. When the cross polar returns are analysed, high LDR values appear both in space and in airborne configurations. The LDR signatures are footprints of multiple scattering effects since they cannot be explained by single scattering computations, even including non-spherical particles. We see these signatures confirmed by some experimental data collected during the Wakasa Bay experiment. Multiple scattering effects can be important for Clousat applications like rainfall and snowfall retrievals since single scattering based algorithms will be otherwise burdened by positive biases.

Description: Contrary to tropospheric CO2 whose oxygen isotopic composition follows a standard mass dependent relationship, i.e. δ17O~0.5 δ18O, stratospheric CO2 is preferentially enriched in 17O, leading to a strikingly different relation with δ17O~1.7δ18O. The isotope anomaly is likely inherited from O3 via photolytically produced O(1D) that undergoes isotope exchange with CO2 and the anomaly may well serve as a tracer of stratospheric chemistry if details of the exchange mechanism are understood. We have studied the photochemical isotope equilibrium in UV-irradiated O2-CO2 and O3-CO2 mixtures to quantify the transfer of the anomaly from O3 to CO2 at room temperature. By following the time evolution of the oxygen isotopic compositions of CO2 and O2 under varying initial isotopic compositions of both, O2/O3 and CO2, the isotope equilibria between the two reservoirs were determined. A very strong dependence of the isotope equilibrium on the O2/CO2-ratio was established. Equilibrium enrichments of 17O and 18O in CO2 relative to O2 diminish with increasing CO2 content, and this reduction in the equilibrium enrichments does not follow a standard mass dependent relation. When molecular oxygen exceeds the amount of CO2 by a factor of about 20, 17O and 18O in equilibrated CO2 are enriched by (142±4) and (146±4), respectively, at room temperature and at a pressure of 225 hPa, independent of the initial isotopic compositions of CO2 and O2 or O3. From these findings we derive a simple and general relation between the starting isotopic compositions and amounts of O2 and CO2 and the observed slope in a three oxygen isotope diagram. Predictions from this relation are compared with published laboratory and atmospheric data.

Description: Night-time chemistry in the Marine Boundary Layer has been modelled using a number of observationally constrained zero-dimensional box-models. The models were based upon the Master Chemical Mechanism (MCM) and the measurements were taken during the North Atlantic Marine Boundary Layer Experiment (NAMBLEX) campaign at Mace Head, Ireland in July–September 2002. The model could reproduce, within the combined uncertainties, the measured concentration of HO2 (within 30–40%) during the night 31 August–1 September and of HO2+RO2 (within 15–30%) during several nights of the campaign. The model always overestimated the NO3 measurements made by Differential Optical Absorption Spectroscopy (DOAS) by up to an order of magnitude or more, but agreed with the NO3 Cavity Ring-Down Spectroscopy (CRDS) measurements to within 30–50%. The most likely explanation of the discrepancy between the two instruments and the model is reaction of the nitrate radical with inhomogeneously distributed NO, which was measured at concentrations of up to 10 ppt, even though this is not enough to fully explain the difference between the DOAS measurements and the model. A rate of production and destruction analysis showed that radicals were generated during the night mainly by the reaction of ozone with light alkenes. The cycling between HO2/RO2 and OH was maintained during the night by the low concentrations of NO and the overall radical concentration was limited by slow loss of peroxy radicals to form peroxides. A strong peak in [NO2] during the night 31 August–1 September allowed an insight into the radical fluxes and the connections between the HOx and the NO3 cycles.

Description: In this study, we investigate the aerosol optical properties, namely aerosol optical thickness (AOT), Angström parameter (α440–870 and size distribution parameters over the Eastern Mediterranean Basin, using spectral measurements from the recently established FORTH (Foundation for Research and Technology-Hellas) AERONET station in Crete, for the two-year period 2003–2004. The location of the FORTH-AERONET station offers a unique opportunity to monitor aerosols from different sources. The AOT is maximum during spring, because of the high dust load transported mainly from African deserts, and minimum in winter. There are secondary maxima in AOT at 870 and 1020 nm in October, attributed to dust transport events occurring in autumn. Large values of AOT at 340 and 500 nm persisting during summer are associated with transport of fine aerosols of urban/industrial and biomass burning origin. The dust events are characterised by a drastic increase in AOT at all wavelengths accompanied by a drastic decrease in Angström parameter to values below 0.3. The mean annual values of AOT340, AOT500, AOT870 and α440–870, are equal to 0.34±0.14, 0.21±0.11, 0.11±0.09 and 1.17±0.53 respectively. The scatterplots of Angström parameter versus aerosol optical thickness indicate a great variety of aerosol types over the study region including dust, urban-industrial/biomass burning, maritime, as well as mixed aerosol types. This is supported by back-trajectory analyses, and agrees with the measurements of experimental campaigns that took place in Crete during summer. The aerosol volume-size distributions are bimodal over all seasons, with a fine and a coarse mode having effective mean radius of 0.13 μm and 2.12 μm, respectively, and columnar volume concentrations of about 0.038 and 0.061 μm3/μm2. There is a general dominance of coarse to fine mode in terms of aerosol volume, in agreement with other maritime locations persisting through the year except for summer. Our analysis shows that the highest values of AOT are related to wind directions from the east, southeast and south, as well as from northwest. Northwestern winds are associated with maximum fine aerosol loads from industrial areas, while eastern, southeastern and southern winds are related to maximum coarse aerosol loads, namely sea salt and desert dust.

Description: Atmosphere and Ocean General Circulation Model (AOGCM) experiments for the Intergovernmental Panel on Climate Change Fourth Assessment Report are analyzed using both 20th and 21st century model output to better understand model variability and assess the importance of various forcing mechanisms on stratospheric trends. While models represent the climatology of the stratosphere reasonably well in comparison with NCEP reanalysis, there are biases and large variability among models. In general, AOGCMs are cooler than NCEP throughout the stratosphere, with the largest differences in the tropics. Around half the AOGCMs have a top level beneath ~2 hPa and show a significant cold bias in their upper levels (~10 hPa) compared to NCEP, suggesting that these models may have compromised simulations near 10 hPa due to a low model top or insufficient stratospheric levels. In the lower stratosphere (50 hPa), the temperature variability associated with large volcanic eruptions is either absent (in about half of the models) or the warming is overestimated in the models that do include volcanic aerosols. There is general agreement on the vertical structure of temperature trends over the last few decades, differences between models are explained by the inclusion of different forcing mechanisms, such as stratospheric ozone depletion and volcanic aerosols. However, even when human and natural forcing agents are included in the simulations, significant differences remain between observations and model trends, particularly in the upper tropical troposphere (200 hPa–100 hPa), where, since 1979, models show a warming trend and the observations a cooling trend.

Description: Radiosonde temperature profiles from Belgrano (78° S) and other Antarctic stations have been compared with European Centre for Medium-Range Weather Forecasts (ECMWF) data during the winter of 2003. Results show a bias in the operational model which is height and temperature dependent, being too cold at layers peaking at 80 and 25–30 hPa, and hence resulting in an overestimation of the predicted potential PSC areas. Here we show the results of the comparison by considering the possibility of a bias in the sondes at extremely low temperatures and discuss the potential implications that this bias might have on the ozone depletion computed by Climate Transport Model based on ECMWF temperature fields.

Description: First results of a multiannual integration with the new global aerosol model system ECHAM4/MADE are presented. This model system enables explicit simulations of the particle number concentration and size-distribution, which is a fundamental innovation compared to previous global model studies considering aerosol mass cycles only. The data calculated by the model provide detailed insights into the properties of the global submicrometer aerosol regarding global burden, chemical composition, atmospheric lifetime, particle number concentration and aerosol size-distribution. The model takes into account sulfate (SO4), nitrate (NO3), ammonium (NH4), black carbon (BC), organic matter (OM), mineral dust, sea salt and aerosol water. The simulated climatological annual mean global atmospheric burdens (lifetime) of the dominant submicrometer aerosol components are 2.25 Tg (4.5 d) for SO4, 0.46 Tg (4.5 d) for NH4, 0.26 Tg (5.6 d) for BC, and 1.77 Tg (6.5 d) for OM. The contributions of individual processes such as emission, nucleation, condensation or dry and wet deposition to the global sources and sinks of a specific aerosol component and particle number concentration are quantified. Based on this analysis, the significance of aerosol dynamical processes (nucleation, condensation, coagulation) is evaluated by comparison to the importance of other processes relevant for the submicrometer aerosol on the global scale. The results reveal that aerosol dynamics are essential for the simulation of the particle number concentration and important but not vital for the simulation of particle mass concentration. Hence aerosol dynamics should be taken into account in simulations of atmospheric processes showing a significant dependence on aerosol particle number concentration.

Description: Consecutive reactions of adducts, resulting from OH radicals and aromatics, with the tropospheric scavenger molecules O2, NO and NO2 have been studied for benzene, toluene, m- and p-xylene, hexamethylbenzene, phenol, m-cresol and aniline by observing decays of OH at temperatures where the thermal back-decomposition to OH is faster than 3 s−1, typically between 300 and 340 K. The experimental technique was resonance fluorescence with flash photolysis of water as source of OH. Biexponential decays were observed in the presence of either O2 or NO, and triexponential decays were obtained in the presence of NO2. The kinetic analysis was performed by fitting the relevant rate constants of the reaction mechanism to whole sets of decays obtained at various concentrations of aromatic and scavenger. In the case of hexamethylbenzene, the biexponential decays suggest the existence of the ipso-adduct, and the slightly higher necessary temperatures show that it is even more stable. In addition, smog chamber experiments at O2 concentrations from atmospheric composition down to well below 100 ppm have been carried out for benzene, toluene and p-xylene. The drop of the effective rate constant of removal by OH occurs at reasonable O2 levels, given the FP/RF results. Comparison of the adduct reactivities shows for all aromatics of this study that the reaction with O2 predominates over that with NO2 under all tropospheric conditions, and that a reaction with NO may only occur after the reaction with O2.

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

Description: A wide array of volatile organic compound (VOC) measurements was conducted in the Valley of Mexico during the MCMA-2002 and 2003 field campaigns. Study sites included locations in the urban core, in a heavily industrial area and at boundary sites in rural landscapes. In addition, a novel mobile-laboratory-based conditional sampling method was used to collect samples dominated by fresh on-road vehicle exhaust to identify those VOCs whose ambient concentrations were primarily due to vehicle emissions. Five distinct analytical techniques were used: whole air canister samples with Gas Chromatography/Flame Ionization Detection (GC-FID), on-line chemical ionization using a Proton Transfer Reaction Mass Spectrometer (PTR-MS), continuous real-time detection of olefins using a Fast Olefin Sensor (FOS), and long path measurements using UV Differential Optical Absorption Spectrometers (DOAS). The simultaneous use of these techniques provided a wide range of individual VOC measurements with different spatial and temporal scales. The VOC data were analyzed to understand concentration and spatial distributions, diurnal patterns, origin and reactivity in the atmosphere of Mexico City. The VOC burden (in ppbC) was dominated by alkanes (60%), followed by aromatics (15%) and olefins (5%). The remaining 20% was a mix of alkynes, halogenated hydrocarbons, oxygenated species (esters, ethers, etc.) and other unidentified VOCs. However, in terms of ozone production, olefins were the most relevant hydrocarbons. Elevated levels of toxic hydrocarbons, such as 1,3-butadiene, benzene, toluene and xylenes were also observed. Results from these various analytical techniques showed that vehicle exhaust is the main source of VOCs in Mexico City and that diurnal patterns depend on vehicular traffic. Finally, examination of the VOC data in terms of lumped modeling VOC classes and its comparison to the VOC lumped emissions reported in other photochemical air quality modeling studies suggests that some, but not all, VOC classes are underestimated in the emissions inventory by factors of 1.1 to 3.

Description: We have noted sporadic instances of strong isolated reflections of medium frequency (MF) radar waves from the mesosphere from as low as 50 km altitude and have devised a set of criteria for isolating these apparently anomalous echoes from those normally occurring from progressive partial reflections in the D-region. The object of this study is therefore to map the occurrences of such echoes facilitating comparisons with other observations. For example, the similarity and simultaneity of the echo structure for the 20 January 2005 with VHF radar results presented by Lübken et al. (2006) are particularly striking. In presenting a number of such echo events since 2001 selected from the MF radar dataset (which spans 1997 to present), we find that virtually all echo occurrences coincide with enhanced solar proton fluxes suggesting that substantial ionisation of the mesosphere is a necessary condition. Strong partial reflections of the radio wave in the lower mesosphere combined with seasonally varying total absorption higher up, thus giving false impressions of lower mesospheric layers preferentially in winter, constitute a scenario consistent with our observations.

Description: Airborne measurements, obtained during the Asian Aerosol Characterisation Experiment (ACE-Asia), of SO2 and condensation nuclei (CN) concentrations were made in the local environment of a cumulus cloud band. Conserved quantities, wet equivalent potential temperature θq, and total water content Q, were used to identify the sources of air detrained on the downwind side of the cumulus band. It was found that ~65% of the detrained air originated from below cloud base and the remainder was air that had been entrained from the free troposphere upwind of the cloud and subsequently been detrained. Calculation of the sources of the detrained air parcels enabled a prediction of the concentration of SO2 and CN, assuming that SO2 and CN experienced no processing within cloud. A comparison of the predicted concentration of SO2 and CN was made with those observed. The concentration of SO2 observed was less than predicted and the amount of SO2 scavenged within cloud was calculated. The CN concentration observed was also less than predicted and, moreover, inclusion of the loss of CN to cloud droplets due to Brownian scavenging resulted in an enhanced decrease of the number concentration of CN predicted. Clear air regions around the cloud exhibited no indication of being a major source of new particles. It was concluded that new particles were formed within cloud.

Description: We present results from the first assimilation of carbon monoxide (CO) observations from the Tropospheric Emission Spectrometer (TES) into a global three-dimensional (3-D) chemistry and transport model (CTM). A sequential sub-optimal Kalman filter assimilation scheme (Khattatov et al., 2000) was applied to assimilate TES CO profiles during November 2004 into the GEOS-Chem global 3-D CTM. The assimilation results were compared with MOPITT and MOZAIC observations. The assimilation significantly improves model simulation of CO in the middle to upper troposphere, where the MOPITT versus model bias was reduced by up to two-thirds. Assimilation results show higher levels of CO in the southern tropics, consistent with MOPITT observations. We find good agreement between the TES assimilated model estimates of CO and in situ measurements from the MOZAIC program, which shows a negative bias of up to 10 ppbv in middle and upper tropospheric TES CO. The results demonstrate how assimilation can be used for non-coincident validation of TES CO profile retrievals.

Description: Aerosol number distribution measurements are reported at San Pietro Capofiume (SPC) station (44°39' N, 11°37' E) for the time period 2002–2005. The station is located in Po Valley, the largest industrial, trading and agricultural area in Italy with a high population density. New particle formation was studied based on observations of the particle size distribution, meteorological and gas phase parameters. The nucleation events were classified according to the event clarity based on the particle number concentrations, and the particle formation and growth rates. Out of a total of 769 operational days from 2002 to 2005 clear events were detected on 36% of the days whilst 33% are clearly non-event days. The event frequency was high during spring and summer months with maximum values in May and July, whereas lower frequency was observed in winter and autumn months. The average particle formation and growth rates were estimated as ~6 cm−3 s−1 and ~7 nm h−1, respectively. Such high growth and formation rates are typical for polluted areas. Temperature, wind speed, solar radiation, SO2 and O3 concentrations were on average higher on nucleation days than on non-event days, whereas relative and absolute humidity and NO2 concentration were lower; however, seasonal differences were observed. Backtrajectory analysis suggests that during majority of nucleation event days, the air masses originate from northern to eastern directions. We also study previously developed nucleation event correlations with environmental variables and show that they predict Po Valley nucleation events with variable success.

Description: In this study, we measured (to our knowledge, for the first time) the mobility distributions of cluster and intermediate ions with an ion spectrometer near a waterfall. We observed that the concentration of negative 1.5–10 nm ions was one-hundred fold compared to a reference point 100 m away from the waterfall. Also the concentration of positive intermediate ions was found to be higher by a factor of ten compared to the reference point. The increased concentration of negative intermediate ions is assumed to be due to the so-called waterfall effect. In the waterfall effect, autoionization causes free charges inside water droplets. These charges fluctuate and cause surface protrusions which produce free ions when a droplet collides with an obstacle. Differences between the polarities are supposed to be caused by the different interaction volumes of positive and negative ions and the formation of magical clusters in water. In addition to the waterfall effect, we assume that some of the ions of both polarities are formed in droplet breakup due to uneven distribution of charges inside the droplet.

Description: MIPAS, on ENVISAT, has made high quality observations of ozone, methane and water vapour. Gridded fields, at 4 hourly intervals and approximately 2 degree resolution, have been calculated for all of 2003 using data assimilation with isentropic advection as a constraint. The gridded fields are validated against independent measurements (from 7 other instruments in the case of ozone, 3 for water vapour and one for methane). For ozone the results are in agreement with previously published results. For water vapour the bias relative to HALOE is below 10% between 20 and 48 km, and the standard error is below 12% in this range. Departures from SAGE II and POAM III are substantially larger. The methane analysis has a bias of less than 5% relative to HALOE between 23 and 40 km, with a standard error less than 10% in this height range. The water vapour field clearly reflects the upward motion in the lower tropical stratosphere, while both water vapour and methane show the signature of advection higher up. In the polar regions the descent in the vortex is clearly visible, with strong descent in autumn giving way to weaker descent through the winter. Descent rates of around 100 m/day are found during the formation of the polar vortices, slowing to around 30 m/day during the winter. Ascent of around 20 m/day in the tropics is revealed by the water vapour and total observed hydrogen fields (4 times the methane plus twice the water vapour concentration). The total observed hydrogen is depleted where air is advected down from the upper mesosphere.

Description: In global models of the atmosphere convection is parameterised, since the typical scale of this process is smaller than the model resolution. Here we address some of the uncertainties arising from the selection of different algorithms to simulate this process. Four different parameterisations for atmospheric convection, all used in state-of-the-art models, are implemented in the model system ECHAM5/MESSy for a consistent inter-comparison and evaluation against observations. Relatively large differences are found in the simulated precipitation patterns, whereas simulated water vapour columns distributions are quite similar and close to observations. The effects on the hydrological cycle and on the simulated meteorological conditions are discussed.

Description: The representation of the quasi-biennial oscillation (QBO) is investigated in the ERA-40 reanalysis. In the lower stratosphere, where there is a good number of observations, the representation of the QBO is equally well throughout the record. However, strong differences between the first and the second half of the zonal wind data set are found in the upper stratosphere, with a typical offset of −10 m/s in the equatorial zonal wind in the earlier part versus the later part of the ERA-40 data set. The strength of the QBO is also affected. Possible explanations are discussed. The identified change of the assimilated wind profiles over time in ERA-40 requires a careful use of equatorial upper stratospheric winds from the reanalysis for validation purposes.

Description: The INDian Ocean EXperiment (INDOEX) was an international, multi-platform field campaign to measure long-range transport of air masses from South and South-East-(SE) Asia towards the Indian Ocean. During the dry monsoon season between January and March 1999, local measurements were carried out from ground based platforms and were compared with satellite based data. The objective of this study was to characterise stratospheric and tropospheric trace gas amounts in the equatorial region, and to investigate the impact of air pollution at this remote site. For the characterisation of the chemical composition of the outflow from the S-SE-Asian region, we performed ground based dual-axis-DOAS (Differential Optical Absorption Spectroscopy) measurements at the KCO (Kaashidhoo Climate Observatory) in the Maldives (5.0° N, 73.5° E). The ground based dual-axis-DOAS measurements were conducted using two different observation modes (off-axis and zenith-sky). This technique allows the separation of the tropospheric and stratospheric columns for different trace gases like O3 and NO2. These dual-axis DOAS data were compared with O3-sonde measurements performed at KCO and satellite based GOME (Global Ozone Measuring Experiment) data during the intensive measuring phase of the INDOEX campaign in February and March 1999. From GOME observations, tropospheric and stratospheric columns for O3 and NO2 were retrieved. In addition, the analysis of the O3-sonde measurements allowed the determination of the tropospheric O3 amount. The comparison shows that the results of all three measurement systems agree within their error limits. During the INDOEX campaign, background conditions were observed most of the time, but in a single case an increase of tropospheric NO2 during a short pollution event was observed and the impact on the vertical columns was calculated. In the GOME measurements, evidence was found for large tropospheric contributions to the BrO budget, probably located in the free troposphere and present throughout the year. The latter has been investigated by the comparison of satellite pixels influenced by high and low cloud conditions based on GOME data which allows the determination of the detection limit of tropospheric BrO columns.

Description: In this study we present the seasonal variability of ozone production efficiencies (EN), defined as the net number of ozone molecules produced per molecule of nitrogen oxides (nitrogen oxide (NO) + nitrogen dioxide (NO2)=NOx) oxidized to NOz (total reactive nitrogen (NOy)-NOx) for a seven-year period (1998–2004) at the Swiss high-alpine research station Jungfraujoch (JFJ), 3580 m a.s.l. This dataset is a unique long-term data series of nitrogen levels in the free troposphere over Central Europe and hence it offers an excellent opportunity to perform such an analysis and provide further evidence to the photochemical origin of the ozone spring maximum at locations of the northern hemisphere distant from nearby pollution sources. Experimentally derived daily EN values have been selected for 571 days out of the 2557 days from 1998 to 2004, from which an average ozone production efficiency of 18.8±1.3 molecules of O3 produced per molecule of NOx oxidized was calculated. This value indicates the great potential and importance of photochemical ozone production in the free troposphere. The monthly means of experimentally derived daily EN values show a seasonal variation with lower values from May to August, which can be probably attributed to more efficient vertical transport of polluted air masses from the atmospheric boundary layer up to JFJ. In agreement, theoretically derived monthly EN values show similar seasonal variation. The ratio NOy/CO, a parameter to assess the aging process that has occurred in an air parcel, was used as a criterion to disaggregate the 571 selected days between undisturbed and disturbed free tropospheric (FT). The monthly means of experimentally derived EN values for the undisturbed FT conditions show a distinct seasonal cycle with higher values in the cold season from November to April. The EN values for undisturbed FT conditions are particularly higher than the respective monthly EN values for disturbed FT conditions from February to October. It should be noted that the monthly EN values of March (EN=35.8) and April (EN=34.9) are among the highest values throughout the year for undisturbed FT conditions at JFJ. These results highlight the key and possibly the dominant role for photochemistry in the observed build-up of tropospheric ozone in the winter-spring transition period.

Description: We have used the Modis satellite data and two global aerosol models to investigate relationships between aerosol optical depth (AOD) and cloud parameters that may be affected by the aerosol concentration. The relationships that are studied are mainly between AOD on the one hand and cloud cover, cloud liquid water path, and water vapour on the other. Additionally, cloud droplet effective radius, cloud optical depth, cloud top pressure and aerosol Ångström exponent, have been analysed in a few cases. In the Modis data we found as in earlier studies an enhancement in the cloud cover with increasing AOD. We find it likely that most of the strong increase in cloud cover with AOD, at least for AOD0.2 can be explained by larger water uptake close to clouds since relative humidity is higher in regions with higher cloud cover. The efficiency of the hygroscopic growth depends on aerosol type, hygroscopic nature of the aerosol, the relative humidity, and to some extent the cloud screening. By analysing the Ångström exponent we find that the hygroscopic growth of the aerosol is not likely to be a main contributor to the cloud cover increase with AOD. Since the largest increase in cloud cover with AOD is for low AOD (~0.2) and thus also for low cloud cover, cloud contamination is not likely to play a large role. However, interpretation of the complex relationships between AOD and cloud parameters should be made with great care and further work is clearly needed.

Description: The compact relationship between stratospheric temperatures (as well as ozone) and tropospheric generated planetary wave activity have been widely discussed. Higher wave activity leads to a strengthening of the Brewer-Dobson (BD) circulation, which results in warmer/colder temperatures in the polar/tropical stratosphere. The influence of this wave activity on stratospheric water vapor (WV) is not yet well explored primarily due to lack of high quality long term data sets. Using WV data from HALOE and SAGE II, an anti-correlation between planetary wave driving (here expressed by the mid-latitude eddy heat flux at 50 hPa added from both hemispheres) and tropical lower stratospheric (TLS) WV has been found. This appears to be the most direct manifestation of the inter-annual variability of the known relationship between ascending motion in the tropical stratosphere (due to rising branch of the BD circulation) and the amount of the WV entering into the stratosphere from the tropical tropopause layer. A decrease in planetary wave activity in the mid-nineties is probably responsible for the increasing trends in stratospheric WV until late 1990s. After 2000 a sudden decrease in lower stratospheric WV has been reported and was observed by different satellite instruments such as HALOE, SAGE II and POAM III indicating that the lower stratosphere has become drier since then. This is consistent with a sudden rise in the combined mid-latitude eddy heat flux with nearly equal contribution from both hemispheres. The low water vapor and enhanced strength of the Brewer-Dobson circulation has persisted until now. It is estimated that the strengthening of the BD circulation after 2000 contributed to a 0.7 K cooling in the TLS.

Description: In this technical note we present the exact form of the Zeldovich factor for heterogeneous nucleation on spherical pre-existing particles. We study the error caused by planar pre-existing surface approximations, which have been used in our earlier heterogeneous nucleation model and elsewhere in the literature. We also test the significance of widely used approximations for cluster surface area and circumference. We conclude that the approximations do not affect the predicted onset saturation. Especially for small pre-existing particles the nucleation rates calculated with the exact and approximative models differ significantly.

Description: The probability density on a height-meridional plane of negative refractive index squared f(nk2

Description: The sensitivity of the middle atmospheric temperature and circulation to the treatment of mean-flow forcing due to breaking gravity waves at the sub-grid scale was investigated using the University of Illinois at Urbana-Champaign 40-layer General Circulation Model (GCM). The gravity-wave forcing was represented either by Rayleigh friction or by a detailed parameterization scheme with different sets of parameters. The modeled middle atmospheric temperature and circulation exhibit large sensitivity to the parameterized sub-grid gravity-wave forcing. A large warm bias of up to 50°C was found in the model's summer upper mesosphere and lower thermosphere. This warm bias was caused by the inability of the GCM to simulate the reversal of the zonal winds from easterly to westerly crossing the mesopause in the summer hemisphere. Attempts were made to slow down the easterly winds near the mesopause and to reduce the warm bias. The GCM was able to realistically simulate the semi-annual oscillation in the upper stratosphere and lower mesosphere with observational constraints on certain parameter values, but failed to simulate the quasi-biennial oscillation in any of the experiments. Budget analysis indicates that in the middle atmosphere the forces that act to maintain a steady zonal-mean zonal wind are primarily those associated with the meridional transport circulation and breaking gravity waves. Contributions from the interaction of the model-resolved eddies with the mean flow are secondary.

Description: Data obtained in Hong Kong during the Hong Kong and the Pearl River Delta (PRD) Pilot Air Monitoring Study in autumn 2002 are analyzed to unravel the relationship between ground-level ozone (O3), pollution precursors, and cross-border transport. Ten ozone episodes, during which the hourly O3 concentration exceeded 100 ppbv in 9 cases and 90 ppbv in one case, are subject to detailed analysis, including one case with hourly O3 of 203 ppbv, which is the highest concentration on record to date in Hong Kong. Combined with high-resolution back trajectories, dCO/dNOy is used to define whether O3 is locally or regionally produced. Five out of the ten Hong Kong O3-episodes studied show a ''pollution signature'' that is indicative of impact from Guangdong Province. Examination of speciated volatile organic compounds (VOCs) shows that the reactivity of VOCs is dominated by anthropogenic VOCs, of which the reactive aromatics dominate, in particular xylenes and toluene. Calculations using a photochemical box model indicate that between 50–100% of the O3 increase observed in Hong Kong during the O3 episodes can be explained by photochemical generation within the Hong Kong area, provided that nitrous acid (HONO) is present at the concentrations derived from this study. An Observation-Based Model (OBM) is used to calculate the sensitivity of the O3 production to changes in the concentrations of the precursor compounds. Generally the production of O3 throughout much of the Hong Kong area is limited by VOCs, while high nitric oxide (NO) concentrations suppress O3 concentration.

Description: We used a spectral radiative transfer model to compute the direct radiative effect (DRE) of natural plus anthropogenic aerosols in the solar near-infrared (IR), between 0.85–10 µm, namely, their effect on the outgoing near-IR radiation at the top of atmosphere (TOA, ΔFTOA), on the atmospheric absorption of near-IR radiation (ΔFatmab) and on the surface downward and absorbed near-IR radiation (ΔFsurf, and ΔFsurfnet, respectively). The computations were performed on a global scale (over land and ocean) under all-sky conditions, using spectral aerosol optical properties taken from the Global Aerosol Data Set (GADS) supplemented by realistic data for the rest of surface and atmospheric parameters. The computed aerosol DRE, averaged over the 12-year period 1984–1995 for January and July, shows that aerosols produce a planetary cooling by increasing the scattered near-IR radiation back to space (by up to 6 Wm−2), they warm the atmosphere (by up to 7 Wm−2) and cool the surface (by up to 12 Wm−2). However, they can also slightly warm the Earth-atmosphere system or cool the atmosphere (by less than 1 Wm−2) over limited areas. The magnitude of the near-IR aerosol DRE is smaller than that of the combined ultraviolet (UV) and visible DRE, but it is still energetically important, since it contributes to the total shortwave (SW) DRE by 22–31%. On a global mean basis, the DREs ΔFTOA, ΔFatmab, ΔFsurf, and ΔFsurfnet are equal to about 0.48, 0.37, −1.03 and −0.85 Wm−2, i.e. their magnitude is similar to that of climate forcing associated with increasing concentrations of greenhouse gases. The aerosol induced near-IR surface cooling combined with the atmospheric warming, affects the thermal dynamics of the Earth-atmosphere system, by increasing the atmospheric stability, decreasing thus cloud formation, and precipitation, especially over desertification threatened regions such as the Mediterranean basin. This, together with the fact that the sign of near-IR aerosol DRE is sometimes opposite to that of UV-visible DRE, demonstrates the importance of performing detailed spectral computations to provide estimates of the climatic role of aerosols for the Earth-atmosphere system.

Description: The combined effect of turbulent transport and radioactive decay on the distribution of 222Rn and its progeny in convective atmospheric boundary layers (CBL) is investigated. Large eddy simulation is used to simulate their dispersion in steady state CBL and in unsteady conditions represented by the growth of a CBL within a pre-existing reservoir layer. The exact decomposition of the concentration and flux budget equations under steady state conditions allowed us to determine which processes are responsible for the vertical distribution of 222Rn and its progeny. Their mean concentrations are directly correlated with their half-life, e.g. 222Rn and 210Pb are the most abundant whereas 218Po show the lowest concentrations. 222Rn flux decreases linearly with height and its flux budget is similar to the one of inert emitted scalar, i.e., a balance between on the one hand the gradient and the buoyancy production terms, and on the other hand the pressure and dissipation at smaller scales which tends to destroy the fluxes. While 222Rn exhibits the typical bottom-up behavior, the maximum flux location of the daughters is moving upwards while their rank in the 222Rn progeny is increasing leading to a typical top-down behavior for 210Pb. We also found that 222Rn short-lived daughters, e.g. 218Po and 214Pb, have relevant radioactive decaying contributions acting as flux sources leading to deviations from the linear flux shape. In addition, while analyzing the vertical distribution of the radioactive decay contributions to the concentrations, e.g. the decaying zone, we found a discrepancy in height of 222Rn daughters' radioactive transformations. Under unsteady conditions, the same behaviors reported under steady state conditions are found: deviation of the fluxes from the linear shape for 218Po, enhanced discrepancy in height of the radioactive transformation contributions for all the daughters. In addition, 222Rn and its progeny concentrations collapse due to the rapid growth of the CBL. The analysis emphasizes the crucial role of turbulent transport in the behavior of 222Rn morning concentrations, in particular the ventilation at the top of the boundary layer that leads to the dilution of 222Rn by mixing with radon low concentration air.

Description: Throughout the year 2001, size-segregated aerosol samples were collected continuously for 10 to 15 days at the French Antarctic Station Dumont d'Urville (DDU) (66°40' S, l40°01' E, 40 m above mean sea level). The nitrogen and oxygen isotopic ratios of particulate nitrate at DDU exhibit seasonal variations that are among the most extreme observed for nitrate on Earth. Associated with a late winter increase in the concentration of particulate nitrate, δ18O and Δ17O reach as high as 111.5 versus VSMOW and 41.1, respectively. These are best explained as a signal of stratospheric input, with halogen radicals extracting 17O- and 18O-rich terminal oxygen from ozone and incorporating it into the nitrogen oxides, even if we are unable to reproduce this high Δ17O value with the current knowledge of isotopic anomaly transfers during chemical reactions. This failure calls for the evaluation of polar ozone isotopic composition. During the late springtime peak in particulate nitrate, its δ15N falls to −46.9 versus atmospheric N2, suggesting that this peak results from snow re-emission, which has been shown previously to enrich in δ15N the retained nitrate fraction in continental Antarctic sites.

Description: Trace elements concentrations were determined in shallow snow samples from 21 sites in the Italian Eastern Alps in order to identify the sources of the contaminants present in the tropospheric winter boundary layer. The collection of superficial snow layers was carried out weekly at altitudes between 1000 and 3000 m next to meteorological stations, far away from villages, roads and ski slopes. Ultra clean procedures were adopted in order to avoid contamination of the snow during the different experimental phases. Trace elements (Ag, Ba, Bi, Cd, Co, Cr, Cu, Fe, Mo, Mn, Pb, Sb, Ti, U, V and Zn) were determined by Inductively Coupled Plasma Sector Field Mass Spectrometer (ICP-SFMS). Ancillary parameters such as major ions (SO42−, NO3−, Ca2+;, Mg2+, K

Description: There exists today no established satellite technique for measuring the amount of ice in thicker clouds. Sub-mm radiometry is a promising technique for the task, and a retrieval scheme for the first such instrument in space, Odin-SMR, is presented. Several advantages of sub-mm observations are confirmed, such as low influence of particle shape and orientation, and a high dynamic range of the retrievals. In the case of Odin-SMR, cloud ice amounts above ~12.5 km can be determined. The presented retrieval scheme gives a detection threshold of ~4 g/m2 without saturation even for thickest observed clouds. The main retrieval uncertainty is the assumed particle size distribution. Initial results are found to be consistent with similar Aura MLS retrievals. It is then shown that important differences compared to atmospheric models exist. This first retrieval algorithm is limited to lowermost Odin-SMR tangent altitudes, and further development should improve the detection threshold and the vertical resolution.

Description: Within the framework of the Network for Detection of Atmospheric Composition Change (NDACC), regular ground-based Fourier transform infrared (FTIR) measurements of many species are performed at several locations. Inversion schemes provide vertical profile information and characterization of the retrieved products which are therefore relevant for contributing to the validation of MIPAS profiles in the stratosphere and upper troposphere. We have focused on the species HNO3 and N2O at 5 NDACC-sites distributed in both hemispheres, i.e., Jungfraujoch (46.5° N) and Kiruna (68° N) for the northern hemisphere, and Wollongong (34° S), Lauder (45° S) and Arrival Heights (78° S) for the southern hemisphere. These ground-based data have been compared with MIPAS offline profiles (v4.61) for the year 2003, collocated within 1000 km around the stations, in the lower to middle stratosphere. To get around the spatial collocation problem, comparisons have also been made between the same ground-based FTIR data and the corresponding profiles resulting from the stratospheric 4D-VAR data assimilation system BASCOE. This paper discusses the results of the comparisons and the usefullness of using BASCOE profiles as proxies for MIPAS data. It shows good agreement between MIPAS and FTIR N2O partial columns: the biases are below 5% for all the stations and the standard deviations are below 7% for the three mid-latitude stations, and below 10% for the high latitude ones. The comparisons with BASCOE partial columns give standard deviations below 4% for the mid-latitude stations to less than 8% for the high-latitude ones. After making some corrections to take into account the known bias due to the use of different spectroscopic parameters, the comparisons of HNO3 partial columns show biases below 3% and standard deviations below 15% for all the stations except Arrival Heights (bias of 6%, standard deviation of 21%). The results for this species, which has a larger spatial variability, highlight the necessity of defining appropriate collocation criteria and of accounting for the spread of the observed airmasses. BASCOE appears to have more deficiencies in producing proxies of MIPAS HNO3 profiles compared to N2O, but the obtained standard deviation of less than 10% between BASCOE and FTIR is reasonable. Similar results on profiles comparisons are also shown in the paper, in addition to partial column ones.

Description: In recent years evidence has emerged that the amount of isoprene emitted from a leaf is affected by the CO2 growth environment. Many – though not all – laboratory experiments indicate that emissions increase significantly at below-ambient CO2 concentrations and decrease when concentrations are raised to above ambient levels. A small number of process-based leaf isoprene emission models can reproduce this CO2-stimulation and -inhibition. These models are briefly reviewed, and their performance in standard conditions compared with each other and to an empirical algorithm. One of the models was judged particularly useful to be incorporated into a dynamic vegetation model framework, LPJ-GUESS, aiming to develop a tool that allows the interactive effects of climate and increasing CO2 concentration on vegetation distribution, productivity, and leaf and ecosystem isoprene emissions to be explored. The coupled vegetation dynamics-isoprene model is described and used here in a mode particularly suited for the ecosystem scale, but it can be employed at the global level as well. Annual and/or daily isoprene emissions simulated by the model were evaluated against flux measurements (or model estimates that had previously been evaluated with flux data) from a wide range of environments, and agreement between modelled and simulated values was generally good. By using a dynamic vegetation model, effects of canopy composition, disturbance history, or trends in CO2 concentration can be assessed. We show here for five model test sites that the suggested CO2-inhibition of leaf-isoprene metabolism can be large enough to offset increases in emissions due to CO2-stimulation of vegetation productivity and leaf area growth. When effects of climate change are considered atop the effects of atmospheric composition the interactions between the relevant processes will become even more complex. The CO2-isoprene inhibition may have the potential to significantly dampen the expected steep increase of ecosystem isoprene emission in a future warmer atmosphere with higher CO2 levels; this effect raises important questions for projections of future atmospheric chemistry and its connection to the terrestrial vegetation and carbon cycle.

Description: Because concentrations of fine particulate matter (PM) and ozone in Beijing often exceed healthful levels, China is to taking steps to improve Beijing's air quality for the 2008 Olympic Games. In this paper the Models-3 Community Multiscale Air Quality (CMAQ) Modeling System was used to investigate a heavy air pollution episode in Beijing during 3–7 April 2005. The modeling domain covered from East Asia with four nested grids with 81 to 3 km horizontal resolution focusing on urban Beijing. This was coupled with a regional emissions inventory with a 10 km resolution and a local 1km Beijing emissions database. The trend of predicted concentrations of various pollutants agreed reasonably well with the observations and captured the main features of this heavy pollution episode. The simulated column concentration distribution of PM was correlated reasonably with the MODIS remote sensing products. Control runs with and without Beijing emissions were conducted to quantify the contributions of non-Beijing sources (NBS) to the Beijing local air pollution. The contributions of NBS to each species differed spatially and temporally with the order of PM25〉PM10〉SO2〉SOIL for this episode. The percentage contribution of NBS to fine particle (PM2.5) in Beijing was averaged about 40%, up to 80% at the northwest of urban Beijing and only 10–20% at southwest. The spatial distribution of NBS contributions for PM10 was similar to that for PM2.5, with a slightly less average percentage of about 30%. The NBS contributions for SO2 and SOIL (diameter between 2.5 μm and 10 μm) were only 10–20% and 5–10%. In addition, the pollutant transport flux was calculated and compared at different levels to investigate transport pathway and magnitude. It was found that the NBS contribution correlated with the transport flux, contributing 70% of PM10 concentration in Beijing at the time of transport flux peak during a strong episode with a transport path from southwest to northeast.

Description: The new submodel AIRSEA for the Modular Earth Submodel System (MESSy) is presented. It calculates the exchange of chemical species between the ocean and the atmosphere with a focus on organic compounds. The submodel can be easily extended to a large number of tracers, including highly soluble ones. It is demonstrated that application of explicitly calculated air-sea exchanges with AIRSEA can induce substantial changes in the simulated tracer distributions in the troposphere in comparison to a model version in which this process is neglected. For example, the simulations of acetone, constrained with measured oceanic concentrations, shows relative changes in the atmospheric surface layer mixing ratios over the Atlantic Ocean up to 300%.

Description: Among the major factors controlling ozone loss in the polar winter is the kinetics of the ClO dimer catalytic cycle. The most important issues are the thermal equilibrium between ClO and Cl2O2, the rate of Cl2O2 formation, and the Cl2O2 photolysis rate. All these issues have been addressed in a large number of laboratory, field and theoretical studies, but large discrepancies between individual results exist and a self-consistent set of parameters compatible with field observations of ClO and Cl2O2 has not been identified. Here, we use thermodynamic calculations and unimolecular rate theory to constrain the ClO/Cl2O2 equilibrium constant and the rate constants for Cl2O2 formation and dissociation. This information is used together with available atmospheric data to examine Cl2O2 photolysis rates based on different Cl2O2 absorption cross sections. Good overall consistency is achieved using a ClO/Cl2O2 equilibrium constant recently suggested by Plenge et al. (2005), the Cl2O2 recombination rate constant reported by Nickolaisen et al. (1994) and Cl2O2 photolysis rates based on averaged absorption cross sections that are roughly intermediate between the JPL 2002 assessment and a laboratory study by Burkholder et al. (1990).

Description: During a field campaign at the Meteorological Observatory Hohenpeissenberg (MOHp) in July 2004, VOCs were measured using GCxGC-FID. Comparison to routinely made GC-MS measurements showed good agreement for a variety of anthropogenic and biogenic ambient VOCs ranging in concentration from below the detection limit (0.1 pmol mol−1) to 180 pmol mol−1. Pronounced diurnal cycles were found for both the biogenic and anthropogenic compounds, driven for the most part by the daily rise and fall of the boundary layer over the station. For the reactive compounds (lifetimes

Description: An episodic simulation is conducted to characterize ozone (O3) photochemical production and investigate its sensitivity to emission changes of ozone precursors in the Mexico City Metropolitan Area (MCMA) using the Comprehensive Air Quality Model with extensions (CAMx). High Ox (O3+NO2) photochemical production rates of 10–80 ppb/h are predicted due to the high reactivity of volatile organic compounds (VOCs) in which alkanes, alkenes, and aromatics exert comparable contributions. The predicted ozone production efficiency is between 4–10 O3 molecules per NOx molecule oxidized, and increases with VOC-to-NO2 reactivity ratio. Process apportionment analyses indicate significant outflow of pollutants such as O3 and peroxyacetyl nitrate (PAN) from the urban area to the surrounding regional environment. PAN is not in chemical-thermal equilibrium during the photochemically active periods. Sensitivity studies of O3 production suggest that O3 formation in the MCMA urban region with less chemical aging (NOz/NOy

Description: A new method for the satellite remote sensing of different types of vegetation and ocean colour is presented. In contrast to existing algorithms, our method analyses weak narrow-band reflectance structures (i.e. "fingerprint" structures) of vegetation in the red spectral range. It is based on differential optical absorption spectroscopy (DOAS), which is usually applied for the analysis of atmospheric trace gas absorptions. Since the spectra of atmospheric absorption and vegetation reflectance are simultaneously included in the analysis, the effects of atmospheric scattering and absorption are automatically corrected. The inclusion of the vegetation spectra also significantly improves the results of the trace gas retrieval. The global maps of the fitting coefficients for the vegetation spectra (indicating the fraction of the observed ground scene covered by vegetation) illustrate the seasonal cycle of different vegetation types. In addition to the vegetation distribution on land, they also show patterns of biological activity in the oceans. Our results indicate that improved sets of vegetation spectra might lead to more accurate and more specific identification of vegetation type in the future.

Description: This study investigates intraseasonal oscillations (ISOs) of upper tropospheric water vapor (UTWV) in the Asian monsoon region in boreal summer by using data with high spatial and temporal resolution from the AIRS instrument. There are robust intraseasonal cycles with periods of 30–60 days and 10–20 days in the UTWV field over both South Asia and East Asia. The 30–60-day oscillation accounts for more than 60 percent of the total variance. For the 30–60-day mode, the source and propagating signature of the UTWV disturbances are distinct in two monsoon sub-systems. Two patterns in the 30–60 day oscillation are seen: a South Asian pattern that originates on the western side of the Arabian Sea and moves eastward, and an East Asian pattern that develops over West Pacific and moves westward. The 10–20-day mode exhibits a uniform westward propagating signature from West Pacific to the Arabian Sea. The Asian summer monsoon region is identified as a main source for UTWV, so another special interest in this study is the relationship between monsoon activity and the 30–60-day oscillation of UTWV. The data show that the upper troposphere is moistened following intense monsoon convection with lags about 5–10 days. An examination of the low level circulation reveals that wet and dry periods in UTWV are closely related to active and break (inactive) periods in monsoon convection, suggesting that the Asian summer monsoon plays an important role in the intraseasonal variations of UTWV. Similar variability is seen in water vapor from European Center for Medium-Range Weather Forecasts (ECMWF) analyses.

Description: An airborne instrument that measures altitude temperature profiles is ideally suited for the task of characterizing statistical properties of the vertical displacement of isentrope surfaces. Prior measurements of temperature fluctuations during level flight could not be used to infer isentrope altitude variations because lapse rate information was missing. The Microwave Temperature Profiler instrument, which includes lapse rate measurements at flight level as a part of temperature profiles, has been used on hundreds of flights to produce altitude versus ground track cross-sections of potential temperature. These cross-sections show isentrope altitude variations with a horizontal resolution of ~3 km for a 〉6 km altitude region. An airborne isentrope-altitude cross-section (IAC) can be compared with a counterpart IAC generated from synoptic scale data, based on radiosondes and satellite instruments, in order to assess differences between the altitudes of isentrope surfaces sampled at mesoscale versus synoptic scale. It has been found that the synoptic scale isentropes fail to capture a significant component of vertical displacement of isentrope surfaces, especially in the vicinity of jet streams. Under the assumptions that air parcels flow along isentrope surfaces, and change temperature adiabatically while undergoing altitude displacements, it is possible to compute mesoscale temperature fluctuations that are not present in synoptic scale back trajectory parcel temperature histories. It has been found that the magnitude of the mesoscale component of temperature fluctuations varies with altitude, season, latitude and underlying topography. A model for these dependences is presented, which shows, for example, that mesoscale temperature fluctuations increase with altitude in a systematic way, are greatest over mountainous terrain, and are greater at polar latitudes during winter.