The study of aerosol composition and air–snow exchange processes is relevant to the reconstruction of past atmosphere composition from ice cores. For this purpose, aerosol samples, superficial snow layers and firn samples from snow pits were collected at Dome Concordia station, East Antarctica, during the 2000/01 summer field season. The aerosol was collected in a ‘coarse’ and a ‘fine’ fraction, roughly separated from each other by a stacked filter system (5.0 and 0.4 μm). Atomic Force Microscopy (AFM) direct measurements on the fine fraction showed that 72% of surface size distribution ranges from 1.0 x 105 to 1.2 x 106 nm2. Assuming a spherical model, the volume size distribution of particles smaller than 5.0 μm shows a mode in the radius range 0.2–0.6 μm. Ion chromatographic (IC) measurements of selected chemical components allowed calculation of the ionic balance of the two size fractions. The fine fraction is dominant, representing 86% of the total ionic budget, and it is characterized by high content of sulphate and acidity. Principal component analysis (PCA) identified sea-spray and biogenic aerosol sources and showed some particulars of the transport and depositional processes of some chemical components (Ca2+, MSA, nssSO42–). Comparative analysis of aerosol, surface hoar and superficial snow showed differences in chemical composition: nitrate and chloride exhibit very high concentrations in the uppermost snow layers and in the surface hoar, and low values in the aerosol. This evidence demonstrates that nitrate and chloride are mainly in gas phase at Dome C and they can be caught on the snow and hoar surface through dry deposition and adsorption processes.

During the 2002-2003 austral summer field season, aerosol samples were collected at a coastal (Terra Nova Bay--Northern Victoria Land) and an inland site (Dome C--East Antarctic Plateau). The sampling was carried out by stacked filter units made up of two filters at different porosity (5.0 and 0.4 microm at Terra Nova Bay and 3.0 and 0.4 microm at Dome C), able to roughly separate a coarse from a fine fraction. At Dome C, a further investigation on aerosol size distribution was performed by an inertial impactor able to collect aerosol particles on 8 size classes (from 10 to 0.4 microm). Atomic Force Microscopy was applied to the filter collecting the finer fraction in both sites in order to assess the real cut-off value of the filter sandwich apparatus and to reconstruct the volume size distribution. At the employed flow conditions, the real cut-off value was revealed to be about one third with respect to the filter nominal porosity in both stations. The size distribution plots showed a bimodal distribution with a mode centered around 0.22 microm in both the sites and a second broader mode which is centered between 0.3 microm and 1.2 microm diameter at Terra Nova Bay and shifted toward higher values (centred around 1.0 microm diameter) at Dome C. Each filter was analysed for the main and trace ionic components allowing evaluation of the contributions of primary and secondary aerosol sources at the two sites as a function of the particle size class. The coastal site is mainly affected by primary and secondary marine inputs: the sea spray contribution (Na+, Mg2+, Cl- and ssSO4(2-)) is dominant (77% w/w) in the coarse fraction whereas the biogenic source (methanesulfonate and nssSO4(2-)) prevails (67.5% w/w) in the fine fraction. In this fraction a significant contribution (15.5% w/w) is provided by ammonium likely to be related to surrounding penguin colonies. Dome C atmosphere is characterised by fine particles arising from secondary sources and long-range transport processes. The main component in the fine and coarse fractions at Dome C is sulfate whose nssSO4(2-) represents the 99.5% and the 92.3%(w/w) in fine and coarse fraction, respectively. The observed agreement between nssSO4(2-) and methanesulfonate temporal profiles in the fine fraction demonstrates that biogenic emissions dominate the inland background aerosol. Results from the sampling by the 8-stage impactor at Dome C are presented here: chloride and nitrate are mainly deposited on the 10-2.1 microm stages while the highest sulfate concentration was found in the submicrometric fraction which turned out to be the most acidic. Such a distribution is able to prevent nitrate and chloride re-emission as gaseous HCl and HNO3 in the 10-2.1 microm stages, arising from the exchange reaction between chloride and nitrate salts and sulfuric acid. Moreover, the concentration peak observed for nitrate in coarser fractions is probably related also to the formation of hygroscopic NH4NO3 particles and nitrate adsorption on sea salt particles.

International audienceSea-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 1 m 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 2100 m 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 200 km from the sea, corresponding to about 2000 ma.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 kg m−2a−1 preserves the chloride record in the snow. Seaspray atmospheric scavenging is dominated by wet deposition in coastal and inland sites

Spectrofluorimetric 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.