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Coupling aerosol surface and bulk chemistry with a kinetic double layer model (K2-SUB): oxidation of oleic acid by ozone

We present a kinetic double layer model coupling aerosol surface and bulk chemistry (K2-SUB) based on the PRA framework of gas-particle interactions (Pöschl-Rudich-Ammann, 2007). K2-SUB is applied to a popular model system of atmospheric heterogeneous chemistry: the interaction of ozone with oleic acid. We show that our modelling approach allows de-convoluting surface and bulk processes, which has been a controversial topic and remains an important challenge for the understanding and description of atmospheric aerosol transformation. In particular, we demonstrate how a detailed treatment of adsorption and reaction at the surface can be coupled to a description of bulk reaction and transport that is consistent with traditional resistor model formulations. From literature data we have derived a consistent set of kinetic parameters that characterise mass transport and chemical reaction of ozone at the surface and in the bulk of oleic acid droplets. Due to the wide range of rate coefficients reported from different experimental studies, the exact proportions between surface and bulk reaction rates remain uncertain. Nevertheless, the model results suggest an important role of chemical reaction in the bulk and an approximate upper limit of ~10−11 cm2 s−1 for the surface reaction rate coefficient. Sensitivity studies show that the surface accommodation coefficient of the gas-phase reactant has a strong non-linear influence on both surface and bulk chemical reactions. We suggest that K2-SUB may be used to design, interpret and analyse future experiments for better discrimination between surface and bulk processes in the oleic acid-ozone system as well as in other heterogeneous reaction systems of atmospheric relevance.
On the roles of circulation and aerosols in the decline of mist and dense fog in Europe over the last 30 years

Fog and mist are meteorological phenomena that have significant contributions to temperature variations. Understanding and predicting them is also crucial for transportation risk management. It has been shown that low visibility phenomena over Europe have been declining over the past three decades. The trends in mist and haze have been correlated to atmospheric aerosol trends. However, dense fog has not received yet such focus. The goal of this paper is to examine the roles of synoptic atmospheric circulation and aerosol content on the trends of dense fog. We show that sulphur emission trends are spatially correlated with visibility trends, with a maximum correlation when visibility is between 1 km and 10 km. We find that atmospheric dynamics overall contributes up to 40% of the variability of the frequency of fog occurrences. This contribution is spatially variable and highly depends on the topography and the season, with higher values in the winter. The observed long-term circulation changes do not contribute much to the trends in low visibility found in the data. This process is illustrated on three stations (De Bilt, Zürich Airport and Potsdam) for which a long-term visibility data and a thorough meteorological description are available. We conclude that to properly represent fog in future climate simulations, it is necessary to include realistic representations of aerosol emissions and chemistry, land surface properties and atmospheric dynamics.
Measurement and modelling of tropospheric reactive halogen species over the tropical Atlantic Ocean

Although tropospheric reactive halogen chemistry is well studied in coastal and polar environments, the presence of halogens over the open ocean environment has not been widely reported. The impacts of halogens on the tropical open ocean marine boundary layer (MBL), in particular, are not well characterised. This paper describes observations of iodine monoxide (IO) and bromine oxide (BrO) over eight months in the tropical open ocean MBL, on the north-eastern side of São Vicente (Cape Verde Islands, 16.85° N, 24.87° W). The highest BrO mixing ratio observed was 5.6±1 pmol mol−1, while the maximum observed IO mixing ratio was 3.1±0.4 pmol mol−1. The average values seen between 09:00–17:00 GMT were ~2.8 pmol mol−1 for BrO and ~1.5 pmol mol−1 for IO; these averages showed little variability over the entire campaign from November 2006 to June 2007. A 1-dimensional chemistry and transport model is used to study the evolution of iodine species and quantify the combined impact of iodine and bromine chemistry on the oxidising capacity of the MBL. It appears that the measured fluxes of iodocarbons are insufficient to account for the observed levels of IO, and that an additional I atom source is required, possibly caused by the deposition of O3 onto the ocean surface in the presence of solar radiation. Modelling results also show that the O3 depletion observed at Cape Verde cannot be explained in the absence of halogen chemistry, which contributes ~45% of the observed O3 depletion at the height of measurements (10 m) during summer. The model also predicts that halogens decrease the hydroperoxy radical (HO2) concentration by ~14% and increase the hydroxyl radical (OH) concentration by ~13% near the ocean surface. The oxidation of dimethyl sulphide (DMS) by BrO takes place at a comparable rate to oxidation by OH in this environment. Finally, the potential of iodine chemistry to form new particles is explored and conditions under which particle formation could be important in the remote MBL are discussed.
Detailed cloud resolving model simulations of the impacts of Saharan air layer dust on tropical deep convection – Part 1: Dust acts as ice nuclei

Observational studies suggest that the Saharan Air Layer (SAL), an elevated layer (850–500 hPa) of Saharan air and mineral dust, has strong impacts on the microphysical as well as dynamical properties of tropical deep convective cloud systems along its track. In this case study, numerical simulations using a two-dimensional Detailed Cloud Resolving Model (DCRM) were carried out to investigate the dust-cloud interactions in the tropical deep convection, focusing on the dust role as Ice Nuclei (IN). The simulations showed that mineral dust considerably enhanced heterogeneous nucleation and freezing at temperatures warmer than −40 °C, resulting in more ice hydrometeors number concentration and reduced precipitating size of ice particles. Because of the lower in the saturation over ice as well as more droplet freezing, total latent heating increased, and consequently the updraft velocity was stronger. On the other hand, the increased ice deposition consumed more water vapor at middle troposphere, which induces a competition for water vapor between heterogeneous and homogeneous freezing and nucleation. As a result, dust suppressed the homogeneous droplet freezing and nucleation due to the heterogeneous droplet freezing and the weakened transport of water vapor at lower stratosphere, respectively. These effects led to decreased number concentration of ice cloud particles in the upper troposphere, and consequently lowered the cloud top height during the stratus precipitating stage. Acting as IN, mineral dust also influenced precipitation in deep convection. It initiated earlier the collection because dust-related heterogeneous nucleation and freezing at middle troposphere occur earlier than homogeneous nucleation at higher altitudes. Nevertheless, the convective precipitation was suppressed by reduced collection of large graupel particles and insufficient fallout related to decreased sizes of precipitating ice hydrometeors. On the contrary, dust increased the precipitation in stratiform precipitation through deposition growth. Overall, the comprehensive effects of mineral dust suppressed the precipitation by up to 22%.
Organic aerosol components observed in Northern Hemispheric datasets from Aerosol Mass Spectrometry

In this study we compile and present results from the factor analysis of 43 Aerosol Mass Spectrometer (AMS) datasets (27 of the datasets are reanalyzed in this work). The components from all sites, when taken together, provide a holistic overview of Northern Hemisphere organic aerosol (OA) and its evolution in the atmosphere. At most sites, the OA can be separated into oxygenated OA (OOA), hydrocarbon-like OA (HOA), and sometimes other components such as biomass burning OA (BBOA). We focus on the OOA components in this work. In many analyses, the OOA can be further deconvolved into low-volatility OOA (LV-OOA) and semi-volatile OOA (SV-OOA). Differences in the mass spectra of these components are characterized in terms of the two main ions m/z 44 (CO2+) and m/z 43 (mostly C2H3O+), which are used to develop a new mass spectral diagnostic for following the aging of OA components in the atmosphere. The LV-OOA component spectra have higher f44 (ratio of m/z 44 to total signal in the component mass spectrum) and lower f43 (ratio of m/z 43 to total signal in the component mass spectrum) than SV-OOA. A wide range of f44 and O:C ratios are observed for both LV-OOA (0.17±0.04, 0.73±0.14) and SV-OOA (0.07±0.04, 0.35±0.14) components, reflecting the fact that there is a continuum of OOA properties in ambient aerosol. The OOA components (OOA, LV-OOA, and SV-OOA) from all sites cluster within a well-defined triangular region in the f44 vs. f43 space, which can be used as a standardized means for comparing and characterizing any OOA components (laboratory or ambient) observed with the AMS. Examination of the OOA components in this triangular space indicates that OOA component spectra become increasingly similar to each other and to fulvic acid and HULIS sample spectra as f44 (a surrogate for O:C and an indicator of photochemical aging) increases. This indicates that ambient OA converges towards highly aged LV-OOA with atmospheric oxidation. The common features of the transformation between SV-OOA and LV-OOA at multiple sites potentially enable a simplified description of the oxidation of OA in the atmosphere. Comparison of laboratory SOA data with ambient OOA indicates that laboratory SOA are more similar to SV-OOA and rarely become as oxidized as ambient LV-OOA, likely due to the higher loadings employed in the experiments and/or limited oxidant exposure in most chamber experiments.
How can aerosols affect the Asian summer monsoon? Assessment during three consecutive pre-monsoon seasons from CALIPSO satellite data

The impact of aerosols above and around the Tibetan Plateau on the Asian Summer Monsoon during pre-monsoon seasons March-April-May 2007, 2008, and 2009 is investigated by means of remote sensing and radiative transfer modelling. Four source regions are found to be responsible for the high aerosol loading around the Tibetan Plateau: the Taklamakan Desert, the Ganges Plains, the Indus Plains, and the Arabian Sea. CALIPSO lidar satellite data, providing vertically resolved images of aerosols, shows aerosol concentrations to be highest in the lower 5 km of the atmosphere with only little amounts reaching the Tibetan Plateau altitude. Using a radiative transfer model we find that aerosol plumes reduce shortwave radiation throughout the Monsoon region in the seasonal average by between 20 and 30 W/m2. Peak shortwave heating in the lower troposphere reaches 0.2 K/day. In higher layers this shortwave heating is partly balanced by longwave cooling. Although high-albedo surfaces, such as deserts or the Tibetan Plateau, increase the shortwave heating by around 10%, the overall effect is strongest close to the aerosol sources. A strong elevated heating which could influence large-scale monsoonal circulations as suggested by previous studies is not found.
IASI-METOP and MIPAS-ENVISAT data fusion

The combination of data obtained with different sensors (data fusion) is a powerful technique that can provide target products of the best quality in terms of precision and accuracy, as well as spatial and temporal coverage and resolution. In this paper the results are presented of the data fusion of measurements of ozone vertical profile performed by two space-borne interferometers (IASI on METOP and MIPAS on ENVISAT) using the new measurement-space-solution method. With this method both the loss of information due to interpolation and the propagation of possible biases (caused by a priori information) are avoided. The data fusion products are characterized by means of retrieval errors, information gain, averaging kernels and number of degrees of freedom. The analysis is performed both on simulated and real measurements and the results demonstrate and quantify the improvement of data fusion products with respect to measurements of a~single instrument.
Observations of the 2008 Kasatochi volcanic SO2 plume by CARIBIC aircraft DOAS and the GOME-2 satellite

The 2008 Kasatochi volcanic eruption emitted ≈1.5–2.5 Tg SO2 into the upper troposphere and lower stratosphere. Parts of the main volcanic plume (gases and particles) reached central Europe a week after the eruption and were detected there by the CARIBIC (Civil Aircraft for Regular investigation of the Atmosphere based on an Instrument Container) flying observatory. The plume was also observed by the GOME-2 satellite instrument, only a few hours after the CARIBIC aircraft had crossed the plume, thus giving a unique opportunity to compare results. Trajectories and local wind speeds are investigated in detail using the GOME-2 and CARIBIC observations for better comparison of the results from these two observational systems. A comparison of the satellite spatial pattern with the local observations of the wind speed and the trajectory model TRAJKS showed a slight discrepancy, which has to be considered for satellite validation. Hence, it appears that detailed analyses of wind speeds are required. Emitted and secondary particles, partly measured and sampled by the CARIBIC in situ instruments, affected the DOAS SO2 measurements, of both CARIBIC and GOME-2. Overall GOME-2 and the CARIBIC SO2 measurements agree very well. The major uncertainties remain the actual wind speed needed to properly correct for the advection of the plume between the different overpass times and effects of aerosols on DOAS retrievals. The good agreement can be seen as validation for both GOME-2 and CARIBIC DOAS observations.
Particle number size distributions in urban air before and after volatilisation

Aerosol particle number size distributions (size range 0.003–10 μm) in the urban atmosphere of Augsburg (Germany) were examined with respect to the governing anthropogenic sources and meteorological factors. The two-year average particle number concentration between November 2004 and November 2006 was 12 200 cm−3, i.e. similar to previous observations in other European cities. A seasonal analysis yielded twice the total particle number concentrations in winter as compared to summer as consequence of more frequent inversion situations and enhanced particulate emissions. The diurnal variations of particle number were shaped by a remarkable maximum in the morning during the peak traffic hours. After a mid-day decrease along with the onset of vertical mixing, an evening concentration maximum could frequently be observed, suggesting a re-stratification of the urban atmosphere. Overall, the mixed layer height turned out to be the most influential meteorological parameter on the particle size distribution. Its influence was even greater than that of the geographical origin of the prevailing synoptic-scale air mass. Size distributions below 0.8 μm were also measured downstream of a thermodenuder (temperature: 300 °C), allowing to retrieve the volume concentration of non-volatile compounds. The balance of particle number upstream and downstream of the thermodenuder suggests that practically all particles >12 nm contain a non-volatile core while additional nucleation of particles smaller than 6 nm could be observed after the thermodenuder as an interfering artifact of the method. The good correlation between the non-volatile volume concentration and an independent measurement of the aerosol absorption coefficient (R2=0.9) suggests a close correspondence of the refractory and light-absorbing particle fractions. Using the "summation method", an average diameter ratio of particles before and after volatilisation could be determined as a function of particle size. The results indicated that particles >60 nm contain a significantly higher fraction of non-volatile compounds, most likely black carbon, than particles <60 nm. The results are relevant for future health-related studies in that they explore the size distribution and time-dependent behaviour of the refractory component of the urban aerosol over an extended time period.
Trends in long-term gaseous mercury observations in the Arctic and effects of temperature and other atmospheric conditions

Gaseous elemental mercury (GEM) measurements at Alert, Canada, from 1995 to 2007 were analyzed for statistical time trends and for correlations with meteorological and climate data. A significant decreasing trend in annual GEM concentration is reported at Alert, with an estimated slope of −0.0086 ng m−3 yr−1 (−0.6% yr−1) over this 13-year period. It is shown that there has been a shift in the month of minimum mean GEM concentration from May to April due to a change in the timing of springtime atmospheric mercury depletion events (AMDEs). These AMDEs are found to decrease with increasing local temperature within each month, both at Alert and at Amderma, Russia. These results support the temperature dependence suggested by previous experimental results and theoretical kinetic calculations on both bromine generation and mercury oxidation and highlight the potential for changes in Arctic mercury chemistry with climate. A correlation between total monthly AMDEs at Alert and the Polar/Eurasian Teleconnection Index was observed only in March, perhaps due to higher GEM inputs in early spring in those years with a weak polar vortex. A correlation of AMDEs at Alert with wind direction supports the origin of mercury depletion events over the Arctic Ocean, in agreement with a previous trajectory study of ozone depletion events. Interannual variability in total monthly depletion event frequency at Alert does not appear to correlate significantly with total or first-year northern hemispheric sea ice area or with other major teleconnection patterns. Nor do AMDEs at either Alert or Amderma correlate with local wind speed, as might be expected if depletion events are sustained by stable, low-turbulence atmospheric conditions. The data presented here – both the change in timing of depletion events and their relationship with temperature – can be used as additional constraints to improve the ability of models to predict the cycling and deposition of mercury in the Arctic.