S. Benassai

Atmosphere–snow interaction by a comparison between aerosol and uppermost snow-layers composition at Dome C, East Antarctica

Abstract 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, nssSO4 2–). 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.

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

Abstract Sea-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.

Chemical and isotopic snow variability in East Antarctica along the 2001/02 ITASE traverse

Abstract As part of the International Trans-Antarctic Scientific Expedition (ITASE) project, a traverse was carried out from November 2001 to January 2002 through Terre Adélie, George V Land, Oates Land and northern Victoria Land, for a total length of about 1875 km. The research goal is to determine the latitudinal and longitudinal variability of physical, chemical and isotopic parameters along three transects: one west–east transect (WE), following the 2150m contour line (about 400 km inland of the Adélie, George V and Oates coasts), and two north–south transects (inland Terre Adélie and Oates Coast–Talos Dome–Victoria Land). The intersection between the WE and Oates Coast–Victoria Land transects is in the Talos Dome area. Along the traverse, eight 2 m deep snow pits were dug and sampled with a 2.5 cm depth resolution. For spatial variability, 1 m deep integrated samples were collected every 5 km (363 sampling sites). In the snow-pit stratigraphy, pronounced annual cycles, with summer maxima, were observed for nssSO4 2–, MSA, NO3 – and H2O2. The seasonality of these chemical trace species was used in combination with stable-isotope stratigraphy to derive reliable and temporally representative snow-accumulation rates. The study of chemical, isotopic and accumulation-rate variability allowed the identification of a distribution pattern which is controlled not only by altitude and distance from the sea, but also by the complex circulation of air masses in the study area. In particular, although the Talos Dome area is almost equidistant from the Southern Ocean and the Ross Sea, local atmospheric circulation is such that the area is strongly affected only by the Ross Sea. Moreover, we observed a decrease in concentration of aerosol components in the central portion of the WE transect and in the southern portion of the Talos Dome transect; this decrease was linked to the higher stability of atmospheric pressure due to the channelling of katabatic winds.

Sensitivity of chemical species to climatic changes in the last 45 kyr as revealed by high-resolution Dome C (East Antarctica) ice-core analysis

Abstract To assess the cause/effect relationship between climatic and environmental changes, we report high-resolution chemical profiles of the Dome C ice core (788m, 45 kyr), drilled in the framework of the European Project for Ice Coring in Antarctica (EPICA). Snow-concentration and depositional-flux changes during the last deglaciation were compared with climatic changes, derived by δD profile. Concentration and temperature profiles showed an anticorrelation, driven by changes in source intensity and transport efficiency of the atmospheric aerosol and by snow accumulation-rate variations. The flux calculation allowed correction for accumulation rate. While sulphate and ammonium fluxes are quite constant, Na+, Mg2+ and Ca2+ underwent the greatest changes, showing fluxes respectively about two, three and six times lower in the Holocene than in the Last Glacial Maximum. Chloride, nitrate and methanesulphonic acid (MSA) also exhibited large changes, but their persistence depends on depositional and post-depositional effects. The comparison between concentrations and δD profiles revealed leads and lags between chemical and temperature trends: Ca2+ and nitrate preceded by about 300 years the δD increase at the deglaciation onset, while MSA showed a 400 year delay. Generally, all components reached low Holocene values in the first deglaciation step (18.0–14.0 kyr BP), but Na+, Mg2+ and nitrate show changes during the Antarctic Cold Reversal (14.0– 12.5 kyr BP).

Chemical characterization of the last 250 years of snow deposition at Talos Dome (East Antarctica)

High-resolution chemical records of main and trace ionic components of snow precipitation over the last 250 years were obtained by analysing the first 36 m of a firn core drilled at Talos Dome, a dome located in the ice divide between northern Victoria Land and Oates Land (East Antarctica Pacific Ocean/Ross Sea sector). The concentration/depth profiles of some relevant chemical parameters are discussed on the basis of a previous stratigraphic dating, set up following the seasonal signatures of non-sea-salt (nss) sulphate deposition and synchronised by using tritium and volcanic temporally known horizons. Particular attention is paid to the study of the temporal trends of the sea spray components (Na+, Cl−, Mg2+) and S and N cycle compounds ( ) to understand the main sources, transport mechanisms and depositional processes of these compounds at the deposition site. Good correlations between the sea spray markers show that the primary marine contribution is relevant, though Talos Dome is located at a relatively high altitude (2316 m a.s.l.) and far from the coast line (about 250 km). The study of the snow chemical composition and of the recent (for the last few centuries) atmosphere/snow relationship at Talos Dome is important as a preliminary survey at this station, which will probably be chosen for a deep ice coring project.

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

Abstract During 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 (nssSO4 2–) 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 nssSO4 2– and MSA is discussed as a function of distance from the sea, altitude and accumulation rate. Depositional fluxes of nssSO4 2– 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 nssSO4 2– and MSA content in snow. The nssSO4 2–/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 nssSO4 2– (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 nssSO4 2– 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.