SO2 oxidation in supercooled droplets in the presence of O2

Sulphur dioxide oxidation in supercooled monodisperse droplets at T4213 7C was studied in the presence of oxygen. The SO2 concentration was found to range from 0.08 to 7.1 ppmv and the contact time between gases and droplets was 210 s. The experimental results showed that sulphate concentration due to SO2 oxidation is independent of temperature, i.e. the increase of SO2 solubility in the liquid phase balances the rate constant decrease of the oxidation reaction. Following McKay’s kinetics (Atmos. Environ., 5 (1971) 7), we calculated the rate constant at T4213 7C and the activation energy. A comparison was made between experimental S(VI) oxidation concentrations due to oxygen and theoretical oxidation values due to O3, H2O2 and oxygen in the presence of catalyzers (Fe31, Mn21)

A combined observational and modeling approach to study modern dust transport from the Patagonia desert to East Antarctica

The understanding of present atmospheric transport processes from Southern Hemisphere (SH) landmasses to Antarctica can improve the interpretation of stratigraphic data in Antarctic ice cores. In addition, long range transport can deliver key nutrients normally not available to marine ecosystems in the Southern Ocean and may trigger or enhance primary productivity. However, there is a dearth of observational based studies of dust transport in the SH. <br><br> This work aims to improve current understanding of dust transport in the SH by showing a characterization of two dust events originating in the Patagonia desert (south end of South America). The approach is based on a combined and complementary use of satellite retrievals (detectors MISR, MODIS, GLAS, POLDER, OMI), transport model simulation (HYSPLIT) and surface observations near the sources and aerosol measurements in Antarctica (Neumayer and Concordia sites). <br><br> Satellite imagery and visibility observations confirm dust emission in a stretch of dry lakes along the coast of the Tierra del Fuego (TdF) island (~54° S) and from the shores of the Colihue Huapi lake in Central Patagonia (~46° S) in February 2005. Model simulations initialized by these observations reproduce the timing of an observed increase in dust concentration at the Concordia Station and some of the observed increases in atmospheric aerosol absorption (here used as a dust proxy) in the Neumayer station. The TdF sources were the largest contributors of dust at both sites. The transit times from TdF to the Neumayer and Concordia sites are 6–7 and 9–10 days respectively. Lidar observations and model outputs coincide in placing most of the dust cloud in the boundary layer and suggest significant deposition over the ocean immediately downwind. Boundary layer dust was detected as far as 1800 km from the source and ~800 km north of the South Georgia Island over the central sub-Antarctic Atlantic Ocean. Although the analysis suggests the presence of dust at ~1500 km SW of South Africa five days after, the limited capabilities of existing satellite platforms to differentiate between aerosol types do not permit a definitive conclusion. In addition, the model simulations show dust lifting to the free troposphere as it travels south but it could not be confirmed by the satellite observations due to cloudiness. <br><br> This work demonstrates that complementary information from existing transport models, satellite and surface data can yield a consistent picture of the dust transport from the Patagonia desert to Antarctica. It also illustrates the limitation of using any of these approaches individually to characterize the transport of dust in a heavily cloudy area

In situ atomic force microscopy in the study of electrogeneration of polybithiophene on Pt electrode

Electrochemical AFM technique has been used for the in situ study of the electrogeneration-deposition process of polybithiophene at varying the polymerisation conditions, such as supporting electrolyte, i.e., LiClO4 or tetrabutylammonium hexafluorophosphate, and polymerisation procedure, i.e., either potentiostatic or potentiodynamic method. In order to better follow the evolution of the morphology of the deposit, particularly during the early stages of the polymer film growth, a suitable home-made electrochemical cell has been used

Spatial distribution of biogenic sulphur compounds (MSA, nssSO4 2- ) in the northern Victoria Land-Dome C-Wilkes Land area, East Antarctica

AbstractDuring the 1992–2002 Antarctic expeditions, in the framework of the International Trans-Antarctic Expedition (ITASE) project, about 600 sites were sampled (superficial snow, snow pits and firn cores) along traverses in the northern Victoria Land–Dome C–Wilkes Land region. The sites were characterized by different geographical (distance from the sea, altitude) and climatological (annual mean accumulation rate, temperature) conditions and were affected by air masses from different marine sectors (Ross Sea, Pacific Ocean). Mean anion and cation contents were calculated at each site, in order to evaluate the spatial distribution of chemical impurities in snow. Here we discuss the distribution of non-sea-salt sulphate (nssSO42–) and of methanesulphonic acid (MSA) mainly originating from atmospheric oxidation of biogenic dimethyl sulphide; these compounds play a key role in climate control processes by acting as cloud condensation nuclei. The spatial distribution of nssSO42– and MSA is discussed as a function of distance from the sea, altitude and accumulation rate. Depositional fluxes of nssSO42– and MSA decrease as a function of distance from the sea, with a higher gradient in the first 200km step. There is an analogous trend with the site altitude, and the first 1600m step is relevant in determining the nssSO42– and MSA content in snow. The nssSO42–/MSA ratio depends on the distance from the sea and the biogenic source strength. At coastal sites, where biogenic inputs are dominant, this ratio is ~2. As biogenic input decreases (low MSA content) inland, the ratio increases, indicating the presence of alternative sources of nssSO42– (crustal, volcanic background) or advection of low-latitude air masses. By plotting total flux as a function of accumulation rate, dry depositional contributions were evaluated for nssSO42– and MSA in the Ross Sea and Pacific Ocean sectors. Non-sea-salt sulphate wet deposition prevails at sites where the accumulation rate (expressed as water equivalent) is higher than 70 kgm–2 a–1 (Ross Sea sector) or 370 kgm–2 a–1 (Pacific Ocean sector). MSA threshold values in these sectors are respectively 90 and 220 kgm–2 a–1

New modeling of the Vostok ice flow line and implication for the glaciological chronology of the Vostok ice core

International audienceWe have used new spaceborne (elevation) and airborne (ice thickness) data to constrain a 2D1/2 model of snow accumulation and ice flow along the Ridge B‐Vostok station ice flow line (East Antarctica). We show that new evaluations of the ice flow line geometry (from the surface elevation), ice thickness (from low‐frequency radar data), and basal melting and sliding change significantly the chronology of the Vostok ice core. This new Vostok dating model reconciles orbital and glaciological timescales and is in good agreement with the Dome Fuji glaciological timescale. At the same time, the new model shows significantly older ages than the previous GT4 timescale for the last glacial part, being thus in better agreement with the GRIP and GISP2 chronologies

Sea-spray deposition in Antarctic coastal and plateau areas from ITASE traverses

AbstractSea-salt markers (Na+, Mg2+ and Cl–) were analyzed in recent snow collected at more than 600 sites located in coastal and central areas of East Antarctica (northern Victoria Land–Dome C–Wilkes Land), in order to understand the effect of site remoteness, transport efficiency and depositional and post-depositional processes on the spatial distribution of the primary marine aerosol. Firn-core, snow-pit and 1m integrated superficial snow samples were collected in the framework of the International Trans-Antarctic Scientific Expeditions (ITASE) project during recent Italian Antarctic Campaigns (1992–2002). The sampling sites were mainly distributed along coast–inland traverses (northern Victoria Land– Dome C) and an east–west transect following the 2100m contour line (Wilkes Land). At each site, the snow ionic composition was determined. Here, we discuss the distribution of sea-spray components (Na+, Mg2+ and Cl–) as a function of distance from the sea, altitude and accumulation rate, in order to discover the pulling-down rate, possible fractionating phenomena and alternative sources moving inland from coastal areas. Sea-spray depositional fluxes decrease as a function of distance from the sea and altitude. A two-order-of-magnitude decrease occurs in the first 200km from the sea, corresponding to about 2000ma.s.l. Correlations of Mg2+ and Cl– with Na+ and trends of Mg2+/Na+ and Cl–/Na+ ratios showed that chloride has other sources than sea spray (HCl) and is affected by post-depositional processes. Accumulation rate higher than 80 kgm–2 a–1 preserves the chloride record in the snow. Sea-spray atmospheric scavenging is dominated by wet deposition in coastal and inland sites

Aluminium and iron record for the last 28 kyr derived from the Antarctic EDC96 ice core using new CFA methods

AbstractSpectrofluorimetric and spectrophotometric continuous flow analysis (CFA) methods were developed and applied to the determination of aluminium and iron in EPICA Dome C (East Antarctica) ice-core samples (6–585m depth). The methods are able to measure the fraction of Al and Fe which can be detected once the sample is filtered on a 5.0 μm membrane and acidified to pH 2. Both the methods present high sensitivity (detection limit of 10 ng L–1 for Al and 50 ng L–1 for Fe) and reproducibility (5% at sub-ppb level). The Fe and Al profiles show sharp decreases in concentrations in the last glacial/interglacial transition, reflecting the decreasing dust aerosol load. The two elements show a different pattern during the Antarctic Cold Reversal (ACR) climatic change, with high iron concentrations (similar to the glacial period) and low but increasing Al content during the ACR minimum. In order to interpret the Al and Fe data obtained by CFA, a comparison with Al and Fe composition, as measured by inductively coupled plasma sector field mass spectrometry (ICP-SFMS), was performed for Holocene, ACR and glacial periods. The percentage of CFA-Al with respect to ICP-SFMS-Al in the three periods shows a lower variability than CFA-Fe (3% in the glacial period and 64% in the ACR). This pattern may be explained by the different dominant iron sources in the different climatic periods. During the Last Glacial Maximum, Fe is proposed to arise mainly from insoluble continental dust, while a variety of ocean-recycled Fe, mainly distributed in fine particles and as more soluble species, shows a higher contribution in the ACR and, to a lesser extent, in the Holocene