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Concentrations of higher dicarboxylic acids C5–C13 in fresh snow samples collected at the High Alpine Research Station Jungfraujoch during CLACE 5 and 6

Samples of freshly fallen snow were collected at the high alpine research station Jungfraujoch (Switzerland) in February and March 2006 and 2007, during the Cloud and Aerosol Characterization Experiments (CLACE) 5 and 6. In this study a new technique has been developed and demonstrated for the measurement of organic acids in fresh snow. The melted snow samples were subjected to solid phase extraction and resulting solutions analysed for organic acids by HPLC-MS-TOF using negative electrospray ionization. A series of linear dicarboxylic acids from C5 to C13 and phthalic acid, were identified and quantified. In several samples the biogenic acid pinonic acid was also observed. In fresh snow the median concentration of the most abundant acid, adipic acid, was 0.69 μg L−1 in 2006 and 0.70 μg L−1 in 2007. Glutaric acid was the second most abundant dicarboxylic acid found with median values of 0.46 μg L−1 in 2006 and 0.61 μg L−1 in 2007, while the aromatic acid phthalic acid showed a median concentration of 0.34 μg L−1 in 2006 and 0.45 μg L−1 in 2007. The concentrations in the samples from various snowfall events varied significantly, and were found to be dependent on the back trajectory of the air mass arriving at Jungfraujoch. Air masses of marine origin showed the lowest concentrations of acids whereas the highest concentrations were measured when the air mass was strongly influenced by boundary layer air.
Update on emissions and environmental impacts from the international fleet of ships: the contribution from major ship types and ports

A reliable and up-to-date ship emission inventory is essential for atmospheric scientists quantifying the impact of shipping and for policy makers implementing regulations and incentives for emission reduction. The emission modelling in this study takes into account ship type and size dependent input data for 15 ship types and 7 size categories. Global port arrival and departure data for more than 32 000 merchant ships are used to establish operational profiles for the ship segments. The modelled total fuel consumption amounts to 217 Mt in 2004 of which 11 Mt is consumed in in-port operations. This is in agreement with international sales statistics. The modelled fuel consumption is applied to develop global emission inventories for CO2, NO2, SO2, CO, CH4, VOC (Volatile Organic Compounds), N2O, BC (Black Carbon) and OC (Organic Carbon). The global emissions from ships at sea and in ports are distributed geographically, applying extended geographical data sets covering about 2 million global ship observations and global port data for 32 000 ships. In addition to inventories for the world fleet, inventories are produced separately for the three dominating ship types, using ship type specific emission modelling and traffic distributions. A global Chemical Transport Model (CTM) was used to calculate the environmental impacts of the emissions. We find that ship emissions is a dominant contributor over much of the world oceans to surface concentrations of NO2 and SO2. The contribution is also large over some coastal zones. For surface ozone the contribution is high over the oceans but clearly also of importance over Western North America (contribution 15–25%) and Western Europe (5–15%). The contribution to tropospheric column ozone is up to 5–6%. The overall impact of ship emissions on global methane lifetime is large due to the high NOx emissions. With regard to acidification we find that ships contribute 11% to nitrate wet deposition and 4.5% to sulphur wet deposition globally. In certain coastal regions the contributions may be in the range 15–50%. In general we find that ship emissions have a large impact on acidic deposition and surface ozone in Western North America, Scandinavia, Western Europe, western North Africa and Malaysia/Indonesia. For most of these regions container traffic, the largest emitter by ship type, has the largest impact. This is the case especially for the Pacific and the related container trade routes between Asia and North America. However, the contributions from bulk ships and tank vessels are also significant in the above mentioned impact regions. Though the total ship impact at low latitudes is lower, the tank vessels have a quite large contribution at low latitudes and near the Gulf of Mexico and Middle East. The bulk ships are characterized by large impact in Oceania compared to other ship types. In Scandinavia and north-Western Europe, one of the major ship impact regions, the three largest ship types have rather small relative contributions. The impact in this region is probably dominated by smaller ships operating closer to the coast. For emissions in ports impacts on NO2 and SO2 seem to be of significance. For most ports the contribution to the two components is in the range 0.5–5%, for a few ports it exceeds 10%. The approach presented provides an improvement in characterizing fleet operational patterns, and thereby ship emissions and impacts. Furthermore, the study shows where emission reductions can be applied to most effectively minimize the impacts by different ship types.
Stratospheric ozone in the post-CFC era

Vertical and latitudinal changes in the stratospheric ozone in the post-chlorofluorocarbon (CFC) era are investigated using simulations of the recent past and the 21st century with a coupled chemistry-climate model. Model results reveal that, in the 2060s when the stratospheric halogen loading is projected to return to its 1980 values, the extratropical column ozone is significantly higher than that in 1975–1984, but the tropical column ozone does not recover to 1980 values. Upper and lower stratospheric ozone changes in the post-CFC era have very different patterns. Above 15 hPa ozone increases almost latitudinally uniformly by 6 Dobson Unit (DU), whereas below 15 hPa ozone decreases in the tropics by 8 DU and increases in the extratropics by up to 16 DU. The upper stratospheric ozone increase is a photochemical response to greenhouse gas induced strong cooling, and the lower stratospheric ozone changes are consistent with enhanced mean advective transport due to a stronger Brewer-Dobson circulation. The model results suggest that the strengthening of the Brewer-Dobson circulation plays a crucial role in ozone recovery and ozone distributions in the post-CFC era.
Validation of an experimental setup to study atmospheric heterogeneous ozonolysis of semi-volatile organic compounds

There is currently a need for reliable experimental procedures to follow the heterogeneous processing simulating the atmospheric conditions. This work offers an alternative experimental device to study the behaviour of semi-volatile organic compounds (SVOC) that presumably exhibit extremely slow reactivity (e.g. pesticides) towards the atmospheric oxidants such as ozone and OH. Naphthalene was chosen as a test compound since it was widely studied in the past and hence represents a good reference. Prior to ozone exposure, the gaseous naphthalene was adsorbed via gas-solid equilibrium on silica and XAD-4 particles. Then, the heterogeneous reaction of ozone with adsorbed naphthalene was investigated in specially designed flow tube reactors. After the reaction, the remaining naphthalene (adsorbed on particles surface) was extracted, filtered and analyzed by Gas Chromatography-Flame Ionization Detector (GC-FID). Thus, the kinetics results were obtained following the consumption of naphthalene. Using this procedure, the rate constants of heterogeneous ozonolysis of naphthalene (kO3 silica=2.26 (±0.09)×10−17 cm3 molec−1 s−1 and kO3 XAD-4=4.29 (±1.06)×10−19 cm3 molec−1 s−1) were determined for silica and XAD-4 particles, at 25°C and relative humidity <0.7%. The results show that the nature of the particles significantly affects the kinetics and that heterogeneous ozonolysis of naphthalene is faster than its homogeneous ozonolysis in the gas phase.
Statistical properties of cloud lifecycles in cloud-resolving models

A new technique is described for the analysis of cloud-resolving model simulations, which allows one to investigate the statistics of the lifecycles of cumulus clouds. Clouds are tracked from timestep to timestep within the model run. This allows for a very simple method of tracking, but one which is both comprehensive and robust. An approach for handling cloud splits and mergers is described which allows clouds with simple and complicated time histories to be compared within a single framework. This is found to be important for the analysis of an idealized simulation of radiative-convective equilibrium, in which the moist, buoyant updrafts (i.e., the convective cores) were tracked. Around half of all such cores were subject to splits and mergers during their lifecycles. For cores without any such events, the average lifetime is 30 min, but events can lengthen the typical lifetime considerably.
Atmospheric tracers during the 2003–2004 stratospheric warming event and impact of ozone intrusions in the troposphere

We use the stratospheric/tropospheric chemical transport model MOZART-3 to study the distribution and transport of stratospheric O3 during the remarkable stratospheric sudden warming event observed in January 2004 in the northern polar region. A comparison between observations by the MIPAS instrument on board the ENVISAT spacecraft and model simulations shows that the evolution of the polar vortex and of planetary waves during the warming event plays an important role in controlling the spatial distribution of stratospheric ozone and the downward ozone flux in the lower stratosphere and upper troposphere (UTLS) region. Compared to the situation during the winter of 2002–2003, lower ozone concentrations were transported from the polar region to mid-latitudes, leading to exceptional large areas of low ozone concentrations outside the polar vortex and "low-ozone pockets" in the middle stratosphere. The unusually long-lasting stratospheric westward winds (easterlies) during the 2003–2004 event greatly restricted the upward propagation of planetary waves, causing the weak transport of ozone-rich air originated from low latitudes to the middle polar stratosphere (30 km). The restricted wave activities led to a reduced extratropical downward ozone flux from the lower stratosphere to the lowermost stratosphere (or from the "overworld" into the "middleworld"), especially over East Asia. Consequently, during wintertime (15 December~15 February), the total downward ozone transport on 100 hPa surface by the descending branches of Brewer-Dobson circulation over this region was about 10% lower during the 2003–2004 event. Meanwhile, the extratropical total cross-tropopause ozone flux (CTOF) was also reduced by ~25%. Compared to the cold 1999–2000 winter, the vertical CTOF in high latitudes (60°~90° N) increased more than 10 times during the two warming winters, while the vertical CTOF in mid-latitudes (30°~60° N) decreased by 20~40%. Moreover, during the two warming winters, the meridional CTOF caused by the isentropic transport associating with the enhanced wave activity also increased and played an important role in the total extratropical CTOF budget.
Thermodynamic characterization of Mexico City aerosol during MILAGRO 2006

Fast measurements of aerosol and gas-phase constituents coupled with the ISORROPIA-II thermodynamic equilibrium model are used to study the partitioning of semivolatile inorganic species and phase state of Mexico City aerosol sampled at the T1 site during the MILAGRO 2006 campaign. Overall, predicted semivolatile partitioning agrees well with measurements. PM2.5 is insensitive to changes in ammonia but is to acidic semivolatile species. For particle sizes up to 1μm diameter, semi-volatile partitioning requires 15–30 min to equilibrate; longer time is typically required during the night and early morning hours. Aerosol and gas-phase speciation always exhibits substantial temporal variability, so that aerosol composition measurements (bulk or size-resolved) obtained over large integration periods are not reflective of its true state. When the aerosol sulfate-to-nitrate molar ratio is less than unity, predictions improve substantially if the aerosol is assumed to follow the deliquescent phase diagram. Treating crustal species as "equivalent sodium" (rather than explicitly) in the thermodynamic equilibrium calculations introduces important biases in predicted aerosol water uptake, nitrate and ammonium; neglecting crustals further increases errors dramatically. This suggests that explicitly considering crustals in the thermodynamic calculations is required to accurately predict the partitioning and phase state of aerosols.
Reactions of isoprene and sulphoxy radical-anions – a possible source of atmospheric organosulphites and organosulphates

Transformation of isoprene coupled with auto-oxidation of SIV in aqueous solutions was studied experimentally and by chemical-kinetic modelling over a broad range of solution acidities (pH=3–9) to complement the research on aqueous-phase and heterogeneous transformation of isoprene reported recently by many laboratories. Isoprene significantly slowed down the auto-oxidation in acidic and basic solutions, and accelerated it slightly in neutral solutions. Simultaneously, production of sulphate ions and formation of solution acidity were significantly reduced. Formation of sulphite and sulphate derivatives of isoprene - sulphurous acid mono-(2-methyl-4-oxo-but-2-enyl) ester (m/z=163), sulphurous acid mono-(4-hydroxy-2-methyl-but-2-enyl) ester (m/z=165), sulphuric acid mono-(2-methyl-4-oxo-but-2-enyl) ester (m/z=179), sulphuric acid mono-(4-hydroxy-2-methyl-but-2-enyl) ester (m/z=181), and possible structural isomers of these species – was indicated by electrospray ionisation mass spectrometric analysis of post-reaction mixtures. The experimental results were explained by changes in a subtle quantitative balance of three superimposed processes whose rates depended in different manner on the acidity of reacting solutions – the scavenging of sulphoxy radical-anions by isoprene, the formation of sulphoxy radical-anions during further reactions of isoprene radicals, and the auto-oxidation of SIV itself. A chemical mechanism based on this idea was explored numerically to show good agreement with experimental data. In basic and neutral solutions, the model overestimated the consumption of isoprene, probably because reactions of primary sulphite and sulphate derivatives of isoprene with sulphoxy radical-anions were not included. Interaction of isoprene with sulphur(IV) species and oxygen can possibly result in formation of new organosulphate and organosulphite components of atmospheric aerosols and waters, and influence the distribution of reactive sulphur and oxygen species in isoprene-emitting organisms exposed to SIV pollutants.
n-Aldehydes (C6–C10) in snow samples collected at the high alpine research station Jungfraujoch during CLACE 5

Samples of freshly fallen snow were collected at the high alpine research station Jungfraujoch, Switzerland, during the Cloud and Aerosol Characterization Experiments (CLACE) 5 in February and March 2006. Sampling was carried out on the Sphinx platform. Headspace-solid-phase-dynamic extraction (HS-SPDE) combined with gas chromatography/mass spectrometry (GC/MS) was used to quantify C6–C10 n-aldehydes in the snow samples. The most abundant n-aldehyde was n-hexanal (median concentration 1.324 μg L−1) followed by n-nonanal, n-decanal, n-octanal and n-heptanal (median concentrations 1.239, 0.863, 0.460, and 0.304 μg L−1, respectively). A wide range of concentrations was found among individual snow samples, even for samples taken at the same time. Higher median concentrations of all n-aldehydes were observed when air masses reached Jungfraujoch from the north-northwest in comparison to air masses arriving from the southeast-southwest. Results suggest that the n-aldehydes detected most likely are of direct and indirect biogenic origin, and that they entered the snow through the particle phase.
All weather IASI single field-of-view retrievals: case study – validation with JAIVEx data

Atmospheric thermodynamic parameters, such as atmospheric temperature and moisture profiles, cloud optical/microphysical properties, and surface properties are basic meteorological variables for weather forecasting. In addition, they are critical parameters in tropospheric chemistry studies. A physical, geophysical parameter retrieval scheme dealing with cloudy and cloud-free radiances observed with satellite ultraspectral infrared sounders has been developed to determine simultaneously surface, atmospheric thermodynamic, and cloud microphysical parameters. A one-dimensional variational (1-D Var.) multivariable inverse solution of the radiative transfer equation is used to iteratively improve a background state defined by eigenvector regression. This algorithm has been applied to data from the Infrared Atmospheric Sounding Interferometer (IASI) on the EUMETSAT Metop-A satellite. The IASI retrieved parameters presented herein are from radiance data gathered during the Joint Airborne IASI Validation Experiment (JAIVEx). JAIVEx provided intensive aircraft observations obtained from airborne Fourier Transform Spectrometer (FTS) systems, such as the NPOESS Airborne Sounder Testbed – Interferometer (NAST-I), in-situ measurements, and dedicated dropsonde and radiosonde measurements for the validation of the IASI products. Here, IASI atmospheric profile retrievals are compared with those obtained from dedicated dropsondes, radiosondes, and the airborne FTS system. The IASI examples presented here demonstrate the ability to retrieve fine-scale horizontal features with high vertical resolution from satellite ultraspectral sounder radiance spectra.