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Variability of aerosol properties over Eastern Europe observed from ground and satellites in the period from 2003 to 2011

The paper presents some results of the study on aerosol variability in the period from 2003 to 2011 over the Eastern Europe region, with latitude ranging from 40° N to 60° N and longitude from 20° E to 50° E. The analysis was based on the POLDER/PARASOL and POLDER-2/ADEOS satellites and AERONET (AErosol RObotic NETwork) ground-based sun photometer observations. The aerosol optical thickness (AOT) of the studied area is characterized by values (referenced to 870 nm wavelength) ranging from 0.05 to 0.2, except for in the period of July–August 2010 with strong forest and peat wildfires when the AOT typical values range from 0.3 to 0.5 according to both retrievals. The analysis of seasonal dynamics of aerosol loading has revealed two AOT high value peaks. The spring peak observed in April–May is the result of solitary transportation of Saharan dust in the atmosphere over Eastern Europe, infrequent agricultural fires, transportation of sea salt aerosols by southern winds to Ukraine and Moldova from the Black and Azov seas. The autumn peak in August–September is associated with forest and peat wildfires, considerable transportation of Saharan dust and the presence of soil dust aerosols due to harvesting activity. The maximum values of AOT are observed in May 2006 (0.1–0.15), April 2009 (0.07–0.15) and August 2010 (0.2–0.5). Furthermore, the study has identified a distinct pattern of anthropogenic aerosols over the industrial areas, especially in central Ukraine and eastern Belarus as well as Moscow region in Russia. The comparison of the AOT derived by standard algorithm POLDER/PARASOL with those recomputed from AERONET inversions for fine mode particles with radius < 0.3 μm was performed over several AERONET sites. The correlation coefficients for the POLDER/AERONET AOT retrieval comparisons are equal: 0.78 for Moscow site, 0.76 – Minsk, 0.86 – Belsk, 0.81 – Moldova (period 2005–2009), 0.93 – Kyiv and 0.63 for Sevastopol sites (2008–2009). The deviations are explained by the spatial inhomogeneity of the surface polarization that has a stronger effect on aerosol retrieval for clear atmospheric conditions with low aerosol loading when surface impact on satellite observations is more pronounced. In addition, the preliminary analysis of the detailed aerosol properties derived by a new generation PARASOL algorithm was evaluated. The comparison of AOT and single scattering albedo retrieved from the POLDER/PARASOL observations over Kyiv with the closest AERONET retrievals within 30 min of satellite overpass time and with a cloudless day shows acceptable agreement of the aerosol dynamics. The correspondence of those data is observed even for extreme AOT440 value 1.14, which was caused by the forest and peat fires in August 2010.
Atmospheric inversion of SO2 and primary aerosol emissions for the year 2010

Natural and anthropogenic emissions of primary aerosols and sulphur dioxide (SO2) are estimated for the year 2010 by assimilating daily total and fine mode aerosol optical depth (AOD) at 550 nm from the Moderate Resolution Imaging Spectroradiometer (MODIS) satellite instrument into a global aerosol model of intermediate complexity. The system adjusts monthly emission fluxes over a set of predefined regions tiling the globe. The resulting aerosol emissions improve the model performance, as measured from usual skill scores, both against the assimilated observations and a set of independent ground-based measurements. The estimated emission fluxes are 67 Tg S yr−1 for SO2, 12 Tg yr−1 for black carbon (BC), 87 Tg yr−1 for particulate organic matter (POM), 17 000 Tg yr−1 for sea salt (SS, estimated at 80 % relative humidity) and 1206 Tg yr−1 for desert dust (DD). They represent a difference of +53, +73, +72, +1 and −8%, respectively, with respect to the first guess (FG) values. Constant errors throughout the regions and the year were assigned to the a priori emissions. The analysis errors are reduced with respect to the a priori ones for all species and throughout the year, they vary between 3 and 18% for SO2, 1 and 130% for biomass burning, 21 and 90 % for fossil fuel, 1 and 200% for DD and 1 and 5% for SS. The maximum errors on the global-yearly scale for the estimated fluxes (considering temporal error dependence) are 3% for SO2, 14% for BC, 11% for POM, 14% for DD and 2% for SS. These values represent a decrease as compared to the global-yearly errors from the FG of 7% for SO2, 40% for BC, 55% for POM, 81% for DD and 300% for SS. The largest error reduction, both monthly and yearly, is observed for SS and the smallest one for SO2. The sensitivity and robustness of the inversion system to the choice of the first guess emission inventory is investigated by using different combinations of inventories for industrial, fossil fuel and biomass burning sources. The initial difference in the emissions between the various set-ups is reduced after the inversion. Furthermore, at the global scale, the inversion is sensitive to the choice of the BB (biomass burning) inventory and not so much to the industrial and fossil fuel inventory. At the regional scale, however, the choice of the industrial and fossil fuel inventory can make a difference. The estimated baseline emission fluxes for SO2, BC and POM are within the estimated uncertainties of the four experiments. The resulting emissions were compared against projected emissions for the year 2010 for SO2, BC and POM. The new estimate presents larger emissions than the projections for all three species, with larger differences for SO2 than POM and BC. These projected SO2 emissions are outside the uncertainties of the estimated emission inventories.
Immersion freezing of water and aqueous ammonium sulfate droplets initiated by humic-like substances as a function of water activity

Immersion freezing of water and aqueous (NH4)2SO4 droplets containing leonardite (LEO) and Pahokee peat (PP) serving as surrogates for humic-like substances (HULIS) has been investigated. Organic aerosol containing HULIS are ubiquitous in the atmosphere; however, their potential for ice cloud formation is uncertain. Immersion freezing has been studied for temperatures as low as 215 K and solution water activity, aw, from 0.85 to 1.0. The freezing temperatures of water and aqueous solution droplets containing LEO and PP are 5–15 K warmer than homogeneous ice nucleation temperatures. Heterogeneous freezing temperatures can be represented by a horizontal shift of the ice melting curve as a function of solution aw by Δaw = 0.2703 and 0.2466, respectively. Corresponding hetrogeneous ice nucleation rate coefficients, Jhet, are (9.6 ± 2.5)×104 and (5.4 ± 1.4)×104 cm−2 s−1 for LEO and PP containing droplets, respectively, and remain constant along freezing curves characterized by Δaw. Consequently predictions of freezing temperatures and kinetics can be made without knowledge of the solute type when relative humidity and ice nuclei (IN) surface areas are known. The acquired ice nucleation data are applied to evaluate different approaches to fit and reproduce experimentally derived frozen fractions. In addition, we apply a basic formulation of classical nucleation theory (α(T)-model) to calculate contact angles and frozen fractions. Contact angles calculated for each ice nucleus as a function of temperature, α(T)-model, reproduce exactly experimentally derived frozen fractions without involving free-fit parameters. However, assigning the IN a single contact angle for the entire population (single-α model) is not suited to represent the frozen fractions. Application of α-PDF, active sites, and deterministic model approaches to measured frozen fractions yield similar good representations. Furthermore, when using a single parameterization of α-PDF or active sites distribution to fit all individual aw immersion freezing data simultaneously, frozen fraction curves are not reproduced. This implies that these fitting formulations cannot be applied to immersion freezing of aqueous solutions, and suggests that derived fit parameters do not represent independent particle properties. Thus, from fitting frozen fractions only, the underlying ice nucleation mechanism and nature of the ice nucleating sites cannot be inferred. In contrast to using fitted functions obtained to represent experimental conditions only, we suggest to use experimentally derived Jhet as a function of temperature and aw that can be applied to conditions outside of those probed in laboratory. This is because Jhet(T) is independent of time and IN surface areas in contrast to the fit parameters obtained by representation of experimentally derived frozen fractions.
Vapor pressures of substituted polycarboxylic acids are much lower than previously reported

The partitioning of compounds between the aerosol and gas phase is a primary focus in the study of the formation and fate of secondary organic aerosol. We present measurements of the vapor pressure of 2-methylmalonic (isosuccinic) acid, 2-hydroxymalonic (tartronic) acid, 2-methylglutaric acid, 3-hydroxy-3-carboxy-glutaric (citric) acid and DL-2,3-dihydroxysuccinic (DL-tartaric) acid, which were obtained from the evaporation rate of supersaturated liquid particles levitated in an electrodynamic balance. Our measurements indicate that the pure component liquid vapor pressures at 298.15 K for tartronic, citric and tartaric acids are much lower than the same quantity that was derived from solid state measurements in the only other room temperature measurement of these materials (made by Booth et al., 2010). This strongly suggests that empirical correction terms in a recent vapor pressure estimation model to account for the inexplicably high vapor pressures of these and similar compounds should be revisited, and that due caution should be used when the estimated vapor pressures of these and similar compounds are used as inputs for other studies.
Particle hygroscopicity during atmospheric new particle formation events: implications for the chemical species contributing to particle growth

This study examines the hygroscopicity of newly formed particles (diameters range 25–45 nm) during two atmospheric new particle formation (NPF) events in the German mid-level mountains during the Hill Cap Cloud Thuringia 2010 (HCCT-2010) field experiment. At the end of the NPF event involving clear particle growth, we measured an unusually high soluble particle fraction of 58.5% at 45 nm particle size. The particle growth rate contributed through sulfuric acid condensation only accounts for around 6.5% of the observed growth rate. Estimations showed that sulfuric acid condensation explained, however, only around 10% of that soluble particle fraction. Therefore, the formation of additional water-soluble matter appears imperative to explain the missing soluble fraction. Although direct evidence is missing, we consider water-soluble organics as candidates for this mechanism. For the case with clear growth process, the particle growth rate was determined by two alternative methods based on tracking the mode diameter of the nucleation mode. The mean particle growth rate obtained from the inter-site data comparison using Lagrangian consideration is 3.8 (± 2.6) nm h−1. During the same period, the growth rate calculated based on one site data is 5.0 nm h−1 using log-normal distribution function method. In light of the fact that considerable uncertainties could be involved in both methods, we consider both estimated growth rates consistent.
Kinetic regimes and limiting cases of gas uptake and heterogeneous reactions in atmospheric aerosols and clouds: a general classification scheme

Heterogeneous reactions are important to atmospheric chemistry and are therefore an area of intense research. In multiphase systems such as aerosols and clouds, chemical reactions are usually strongly coupled to a complex sequence of mass transport processes and results are often not easy to interpret. Here we present a systematic classification scheme for gas uptake by aerosol or cloud particles which distinguishes two major regimes: a reaction-diffusion regime and a mass transfer regime. Each of these regimes includes four distinct limiting cases, characterised by a dominant reaction location (surface or bulk) and a single rate-limiting process: chemical reaction, bulk diffusion, gas-phase diffusion or mass accommodation. The conceptual framework enables efficient comparison of different studies and reaction systems, going beyond the scope of previous classification schemes by explicitly resolving interfacial transport processes and surface reactions limited by mass transfer from the gas phase. The use of kinetic multi-layer models instead of resistor model approaches increases the flexibility and enables a broader treatment of the subject, including cases which do not fit into the strict limiting cases typical of most resistor model formulations. The relative importance of different kinetic parameters such as diffusion, reaction rate and accommodation coefficients in this system is evaluated by a quantitative global sensitivity analysis. We outline the characteristic features of each limiting case and discuss the potential relevance of different regimes and limiting cases for various reaction systems. In particular, the classification scheme is applied to three different datasets for the benchmark system of oleic acid reacting with ozone in order to demonstrate utility and highlight potential issues. In light of these results, future directions of research needed to elucidate the multiphase chemical kinetics in this and other reaction systems are discussed.
Performance of the Line-By-Line Radiative Transfer Model (LBLRTM) for temperature, water vapor, and trace gas retrievals: recent updates evaluated with IASI case studies

Modern data assimilation algorithms depend on accurate infrared spectroscopy in order to make use of the information related to temperature, water vapor (H2O), and other trace gases provided by satellite observations. Reducing the uncertainties in our knowledge of spectroscopic line parameters and continuum absorption is thus important to improve the application of satellite data to weather forecasting. Here we present the results of a rigorous validation of spectroscopic updates to an advanced radiative transfer model, the Line-By-Line Radiative Transfer Model (LBLRTM), against a global dataset of 120 near-nadir, over-ocean, nighttime spectra from the Infrared Atmospheric Sounding Interferometer (IASI). We compare calculations from the latest version of LBLRTM (v12.1) to those from a previous version (v9.4+) to determine the impact of spectroscopic updates to the model on spectral residuals as well as retrieved temperature and H2O profiles. We show that the spectroscopy in the CO2 ν2 and ν3 bands is significantly improved in LBLRTM v12.1 relative to v9.4+, and that these spectroscopic updates lead to mean changes of ~0.5 K in the retrieved vertical temperature profiles between the surface and 10 hPa, with the sign of the change and the variability among cases depending on altitude. We also find that temperature retrievals using each of these two CO2 bands are remarkably consistent in LBLRTM v12.1, potentially allowing these bands to be used to retrieve atmospheric temperature simultaneously. The updated H2O spectroscopy in LBLRTM v12.1 substantially improves the a posteriori residuals in the P-branch of the H2O ν2 band, while the improvements in the R-branch are more modest. The H2O amounts retrieved with LBLRTM v12.1 are on average 14% lower between 100 and 200 hPa, 42% higher near 562 hPa, and 31% higher near the surface compared to the amounts retrieved with v9.4+ due to a combination of the different retrieved temperature profiles and the updated H2O spectroscopy. We also find that the use of a fixed ratio of HDO to H2O in LBLRTM may be responsible for a significant fraction of the remaining bias in the P-branch relative to the R-branch of the H2O ν2 band. There were no changes to O3 spectroscopy between the two model versions, and so both versions give positive a posteriori residuals of ~ 0.3 K in the R-branch of the O3 ν3 band. While the updates to the H2O self-continuum employed by LBLRTM v12.1 have clearly improved the match with observations near the CO2 ν3 band head, we find that these updates have significantly degraded the match with observations in the fundamental band of CO. Finally, significant systematic a posteriori residuals remain in the ν4 band of CH4, but the magnitude of the positive bias in the retrieved mixing ratios is reduced in LBLRTM v12.1, suggesting that the updated spectroscopy could improve retrievals of CH4 from satellite observations.
Aerosol effects on the cloud-field properties of tropical convective clouds

Aerosol effects on condensed water and precipitation in a tropical cloud system driven by deep convective clouds are investigated for two-dimensional simulations of 2-day duration. Although an assumed 10-fold increase in aerosol concentration results in a similar temporal evolution of mean precipitation and a small (9%) difference in cumulative precipitation between the high- and low-aerosol cases, the characteristics of the convection are much more sensitive to aerosol. The convective mass flux, and temporal evolution and frequency distribution of the condensed water path WP (sum of liquid- and ice-water paths) differ significantly between unperturbed and aerosol-perturbed simulations. There are concomitant differences in the relative importance of individual microphysical processes and the frequency distribution of the precipitation rate (P). With increasing aerosol (i) the convective mass flux increases, leading to increases in condensation, cloud liquid, and accretion of cloud liquid by precipitation; (ii) autoconversion of cloud water to rain water decreases; (iii) the WP spatial distribution becomes more homogeneous; and (iv) there is an increase in the frequencies of high and low WP and P, and a decrease in these frequencies at the mid-range of WP and P. Thus, while aerosol perturbations have a small influence on total precipitation amount, for the case considered, they do have substantial influence on the spatiotemporal distribution of convection and precipitation.
Scorched Earth: how will changes in the strength of the vegetation sink to ozone deposition affect human health and ecosystems?

This study investigates the effect of ozone (O3) deposition on ground level O3 concentrations and subsequent human health and ecosystem risk under hot summer "heat wave" type meteorological events. Under such conditions, extended drought can effectively "turn off" the O3 vegetation sink leading to a substantial increase in ground level O3 concentrations. Two models that have been used for human health (the CMAQ chemical transport model) and ecosystem (the DO3SE O3 deposition model) risk assessment are combined to provide a powerful policy tool capable of novel integrated assessments of O3 risk using methods endorsed by the UNECE Convention on Long-Range Transboundary Air Pollution. This study investigates 2006, a particularly hot and dry year during which a heat wave occurred over the summer across much of the UK and Europe. To understand the influence of variable O3 dry deposition three different simulations were investigated during June and July: (i) actual conditions in 2006, (ii) conditions that assume a perfect vegetation sink for O3 deposition and (iii) conditions that assume an extended drought period that reduces the vegetation sink to a minimum. The risks of O3 to human health, assessed by estimating the number of days during which running 8 h mean O3 concentrations exceeded 100 μg m−3, show that on average across the UK, there is a difference of 16 days exceedance of the threshold between the perfect sink and drought conditions. These average results hide local variation with exceedances between these two scenarios reaching as high as 20 days in the East Midlands and eastern UK. Estimates of acute exposure effects show that O3 removed from the atmosphere through dry deposition during the June and July period would have been responsible for approximately 460 premature deaths. Conversely, reduced O3 dry deposition will decrease the amount of O3 taken up by vegetation and, according to flux-based assessments of vegetation damage, will lead to a reduction in the impact of O3 on vegetation across the UK. The new CMAQ-DO3SE model was evaluated by comparing observation vs. modelled estimates of various health related metrics with data from both urban and rural sites across the UK; although these comparisons showed reasonable agreement there were some biases in the model predictions with attributable deaths at urban sites being over predicted by a small margin, the converse was true for rural sites. The study emphasises the importance of accurate estimates of O3 deposition both for human health and ecosystem risk assessments. Extended periods of drought and heat wave type conditions are likely to occur with more frequency in coming decades, therefore understanding the importance of these effects will be crucial to inform the development of appropriate national and international policy to mitigate against the worst consequences of this air pollutant.
Diffusion of volatile organics through porous snow: impact of surface adsorption and grain boundaries

Release of trace gases from surface snow on earth drives atmospheric chemistry, especially in the polar regions. The gas-phase diffusion of methanol and of acetone through the interstitial air of snow was investigated in a well-controlled laboratory study in the temperature range of 223 to 263 K. The aim of this study was to evaluate how the structure of the snowpack, the interaction of the trace gases with the snow surface, and the grain boundaries influence the diffusion on timescales up to 1 h. The diffusive loss of these two volatile organics into packed snow samples was measured using a chemical ionization mass spectrometer. The structure of the snow was analysed by means of X-ray-computed micro-tomography. The observed diffusion profiles could be well described based on gas-phase diffusion and the known structure of the snow sample at temperatures &geq; 253 K. At colder temperatures, surface interactions start to dominate the diffusive transport. Parameterizing these interactions in terms of adsorption to the solid ice surface, i.e. using temperature-dependent air–ice partitioning coefficients, better described the observed diffusion profiles than the use of air–liquid partitioning coefficients. No changes in the diffusive fluxes were observed by increasing the number of grain boundaries in the snow sample by a factor of 7, indicating that for these volatile organic trace gases, uptake into grain boundaries does not play a role on the timescale of diffusion through porous surface snow. For this, a snow sample with an artificially high amount of ice grains was produced and the grain boundary surface measured using thin sections. In conclusion, we have shown that the diffusivity can be predicted when the structure of the snowpack and the partitioning of the trace gas to solid ice is known.