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As an update to our previous use of the collection 4 Moderate Resolution Imaging Spectroradiometer (MODIS) over-ocean aerosol optical depth (AOD) data, we examined ten years of Terra and eight years of Aqua collection 5 data for its potential usage in aerosol assimilation. Uncertainties in the over-ocean MODIS AOD were studied as functions of observing conditions, such as surface characteristics, aerosol optical properties, and cloud artifacts. Empirical corrections and quality assurance procedures were developed and compared to collection 4 data. After applying these procedures, the Root-Mean-Square-Error (RMSE) in the MODIS Terra and Aqua AOD are reduced by 30% and 10–20%, respectively, with respect to AERONET data. Ten years of Terra and eight years of Aqua quality-assured level 3 MODIS over-ocean aerosol products were produced. The newly developed MODIS over-ocean aerosol products will be used in operational aerosol assimilation and aerosol climatology studies, as well as other research based on MODIS products.
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In situ measurements of aerosol optical properties were made in summer 2008 at the ALOMAR station facility (69°16 N, 16°00 E), located at a rural site in the North of the island of Andøya (Vesterålen archipelago), about 300 km north of the Arctic Circle. The extended three months campaign was part of the POLAR-CAT Project of the International Polar Year (IPY-2007-2008), and its goal was to characterize the aerosols of this sub-Arctic area which frequently transporte to the Arctic region. The ambient light-scattering coefficient, σ<sub>s</sub>(550 nm), at ALOMAR had a hourly mean value of 5.412 Mm<sup>−1</sup> (StD = 3.545 Mm<sup>−1</sup>) and the light-absorption coefficient, σ<sub>a</sub>(550 nm), had an hourly mean value of 0.400 Mm<sup>−1</sup> (StD = 0.273 Mm<sup>−1</sup>). The scattering/absorption Ångström exponents, α<sub>s,a</sub>, are used for detailed analysis of the variations of the spectral shape of σ<sub>s,a</sub>. The single scattering albedo, &omega<sub>0</sub>, ranges from 0.622 to 0.985 (mean = 0.913, StD = 0.052) and the relation of this property to the absorption/scattering coefficients and the Ångström exponents is presented. The relationships between all the parameters analyzed, mainly those related to the single scattering albedo, allow us to describe the local atmosphere as extremely clean.
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New developments in the turbulence parameterization in the general circulation model ECHAM5-HAM are presented. They consist mainly of an explicit entrainment closure at the top of stratocumulus-capped boundary layers and the addition of an explicit contribution of the radiative divergence in the buoyancy production term. The impact of the new implementations on a single column model study and on the global scale is presented here. The parameterization has a "smoothing" effect: the abnormally high values of turbulence kinetic energy are reduced, both in the single column and in the Californian stratocumulus region. A sensitivity study with prescribed droplet concentration shows a reduction in the sensitivity of liquid water path to increasing cloud aerosol optical depth. We also study the effect of the new implementation on a Pacific cross-section. The entrainment parameterization leads to an enhanced triggering of the convective activity.
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Eddy covariance (EC) is the preferable technique for flux measurements since it is the only direct flux determination method. It requires a continuum of high time resolution measurements (e.g. 5–20 Hz). For volatile organic compounds (VOC) soft ionization via proton transfer reaction has proven to be a quantitative method for real time mass spectrometry; here we use a proton transfer reaction time of flight mass spectrometer (PTR-TOF) for 10 Hz EC measurements of full mass spectra up to <i>m/z</i> 315. The mass resolution of the PTR-TOF enabled the identification of chemical formulas and separation of oxygenated and hydrocarbon species exhibiting the same nominal mass. We determined 481 ion mass peaks from ambient air concentration above a managed, temperate mountain grassland in Neustift, Stubai Valley, Austria. During harvesting we found significant fluxes of 18 compounds distributed over 43 ions, including protonated parent compounds, as well as their isotopes and fragments and VOC-H<sup>+</sup> – water clusters. The dominant BVOC fluxes were methanol, acetaldehyde, ethanol, hexenal and other C<sub>6</sub> leaf wound compounds, acetone, acetic acid, monoterpenes and sequiterpenes. <br><br> The smallest reliable fluxes we determined were less than 0.1 nmol m<sup>−2</sup> s<sup>−1</sup>, as in the case of sesquiterpene emissions from freshly cut grass. Terpenoids, including mono- and sesquiterpenes, were also deposited to the grassland before and after the harvesting. During cutting, total VOC emission fluxes up to 200 nmolC m<sup>−2</sup> s<sup>−1</sup> were measured. Methanol emissions accounted for half of the emissions of oxygenated VOCs and a third of the carbon of all measured VOC emissions during harvesting.
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Three recently-completed sets of simulations of multiple chemistry-climate models with greenhouse gases only, with all anthropogenic forcings, and with anthropogenic and natural forcings, allow the causes of observed stratospheric changes to be quantitatively assessed using detection and attribution techniques. The total column ozone response to halogenated ozone depleting substances and to natural forcings is detectable in observations, but the total column ozone response to greenhouse gas changes is not separately detectable. In the middle and upper stratosphere, simulated and observed SBUV/SAGE ozone changes are broadly consistent, and separate anthropogenic and natural responses are detectable in observations. The influence of ozone depleting substances and natural forcings can also be detected separately in observed lower stratospheric temperature, and the magnitudes of the simulated and observed responses to these forcings and to greenhouse gas changes are found to be consistent. In the mid and upper stratosphere the simulated natural and combined anthropogenic responses are detectable and consistent with observations, but the influences of greenhouse gases and ozone-depleting substances could not be separately detected in our analysis.
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The impact of two recent gas-phase chemical kinetic mechanisms (CB05 and RACM2) on the formation of secondary inorganic and organic aerosols is compared for simulations of PM<sub>2.5</sub> over Europe between 15 July and 15 August 2001. The host chemistry transport model is Polair3D of the Polyphemus air-quality platform. Particulate matter is modeled with a sectional aerosol model (SIREAM), which is coupled to the thermodynamic model ISORROPIA for inorganic species and to a module (MAEC) that treats both hydrophobic and hydrophilic species for secondary organic aerosol (SOA). Modifications are made to the gas-phase chemical mechanisms to handle the formation of SOA. In order to isolate the effect of the original chemical mechanisms on PM formation, the addition of reactions and chemical species needed for SOA formation was harmonized to the extent possible between the two gas-phase chemical mechanisms. Model performance is satisfactory with both mechanisms for speciated PM<sub>2.5</sub>. The monthly-mean difference of the concentration of PM<sub>2.5</sub> is less than 1 μg m<sup>−3</sup> (6%) over the entire domain. Secondary chemical components of PM<sub>2.5</sub> include sulfate, nitrate, ammonium and organic aerosols, and the chemical composition of PM<sub>2.5</sub> is not significantly different between the two mechanisms. Monthly-mean concentrations of inorganic aerosol are higher with RACM2 than with CB05 (+16% for sulfate, +11% for nitrate, and +10% for ammonium), whereas the concentrations of organic aerosols are slightly higher with CB05 than with RACM2 (+22% for anthropogenic SOA and +1% for biogenic SOA). Differences in the inorganic and organic aerosols result primarily from differences in oxidant concentrations (OH, O<sub>3</sub> and NO<sub>3</sub>). Nitrate formation tends to be HNO<sub>3</sub>-limited over land and differences in the concentrations of nitrate are due to differences in concentration of HNO<sub>3</sub>. Differences in aerosols formed from aromatic SVOC are due to different aromatic oxidation between CB05 and RACM2. The aromatic oxidation in CB05 leads to more cresol formation, which then leads to more SOA. Differences in the aromatic aerosols would be significantly reduced with the recent CB05-TU mechanism for toluene oxidation. Differences in the biogenic aerosols are due to different oxidant concentrations (monoterpenes) and different particulate organic mass concentrations affecting the gas-particle partitioning of SOA (isoprene). These results show that the formulation of a gas-phase chemical kinetic mechanism for ozone can have significant direct (e.g., cresol formation) and indirect (e.g., oxidant levels) effects on PM formation. Furthermore, the incorporation of SOA into an existing gas-phase chemical kinetic mechanism requires the addition of reactions and product species, which should be conducted carefully to preserve the original mechanism design and reflect current knowledge of SOA formation processes (e.g., NO<sub>x</sub> dependence of some SOA yields). The development of chemical kinetic mechanisms, which offer sufficient detail for both oxidant and SOA formation is recommended.
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Knudsen Effusion Mass Spectrometry (KEMS) has been used to measure for the first time the solid state vapour pressures of a series of aliphatic cyclic dicarboxylic acids with increasing ring size. Additionally the atmospherically important compounds; <i>cis</i>-pinonic acid and levoglucosan were also measured. Differential Scanning Calorimetry (DSC) was used to measure melting points, enthalpies and entropies of fusion, which were used to determine sub-cooled liquid vapour pressures for the compounds. The sub-cooled liquid vapour pressure of straight chain, branched and cyclic dicarboxylic acids was compared to a selection of estimation methods.
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The VAMOS<sup>1</sup> Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx) was an international field program designed to make observations of poorly understood but critical components of the coupled climate system of the southeast Pacific. This region is characterized by strong coastal upwelling, the coolest SSTs in the tropical belt, and is home to the largest subtropical stratocumulus deck on Earth. The field intensive phase of VOCALS-REx took place during October and November 2008 and constitutes a critical part of a broader CLIVAR program (VOCALS) designed to develop and promote scientific activities leading to improved understanding, model simulations, and predictions of the southeastern Pacific (SEP) coupled ocean-atmosphere-land system, on diurnal to interannual timescales. The other major components of VOCALS are a modeling program with a model hierarchy ranging from the local to global scales, and a suite of extended observations from regular research cruises, instrumented moorings, and satellites. The two central themes of VOCALS-REx focus upon (a) links between aerosols, clouds and precipitation and their impacts on marine stratocumulus radiative properties, and (b) physical and chemical couplings between the upper ocean and the lower atmosphere, including the role that mesoscale ocean eddies play. A set of hypotheses designed to be tested with the combined field, monitoring and modeling work in VOCALS is presented here. A further goal of VOCALS-REx is to provide datasets for the evaluation and improvement of large-scale numerical models. VOCALS-REx involved five research aircraft, two ships and two surface sites in northern Chile. We describe the instrument payloads and key mission strategies for these platforms and give a summary of the missions conducted. <br><br> <sup>1</sup> Variability of the American Monsoon Systems, an international CLIVAR program.
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Ozone, along with other air pollutants, has been measured for two years from a monitoring station placed on a cruise ship that follows a regular track in the Western Mediterranean between April and October. Conditions favouring high ozone levels have been studied by analysis of weather maps and back trajectories. This analysis was focused on a transect over the open sea in the South Western Mediterranean between Tunis and Palma de Mallorca. High ozone levels were found in situations with an anticyclonic circulation over the Western Mediterranean when subsidence brings air masses down from altitudes between 1000 and 3500 m a.s.l. Analysis of composite meteorological maps suggests a relevant contribution of breeze circulation to subsidence during events with high surface ozone concentrations; this points to an important contribution from local ozone formation. A detailed back trajectory analysis of the origin of air masses with high ozone concentrations was carried out for two "hot spots" for ozone pollution, in the Gulf of Genoa and between Naples and Palermo, respectively. The main cause of high ozone levels in the Gulf of Genoa was found to be outflow from the Po Valley and the Genoa area while such episodes along the Naples-Palermo transect were most often associated with trajectories from the Rome or Naples areas. Analysis of the relationship between measured concentrations of Black Carbon and ozone allowed to evaluate the degree of photochemical "ageing" of the air masses encountered along the route of the cruise ship.
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Chlorine dioxide, OClO, column amounts retrieved from measurements of the SCIAMACHY satellite instrument are presented and validated by comparison with simultaneous ground-based DOAS observations. In addition, the measurements are compared to model calculations taking into account the photochemical change along the light path. <br><br> Although OClO does not participate directly in the destruction of ozone, its accurate measurement as well as modelling is crucial to understand the highly perturbed chlorine chemistry in the polar vortices. SCIAMACHY OClO slant columns retrieved during spring 2005 have been quantitatively validated by comparison with slant columns retrieved from measurements made in Ny-Ålesund (79° N, 12° E) and Summit (73° N, 38° W) as well qualitatively for Bremen (53° N, 9° E). Fair to good agreement is found depending on location as well as time of year. <br><br> OClO slant column densities modelled with a set of stacked box models and considering the light path through the atmosphere are also included in this comparison. The model predictions differ significantly from the measured quantities. OClO amounts are underestimated for conditions of strong chlorine activation and at large solar zenith angles. Sensitivity studies for several parameters in the stacked box model have been performed and it is inferred that using the chemistry known to date, the observed OClO cannot be adequately reproduced within the range of uncertainties given for the various model parameters.
