O. Largiuni

SPATIAL AND TEMPORAL DISTRIBUTION OF ENVIRONMENTAL MARKERS FROM COASTAL TO PLATEAU AREAS IN ANTARCTICA BY FIRN CORE CHEMICAL ANALYSIS

The chemical analysis of shallow firn cores sampled in coastal and plateau areas in Northern Victoria Land and along a transect from Talos Dome to Dome C (East Antarctica, Pacific Ocean sector) allowed a global view of spatial and temporal changes in chemical composition of snow depositions over the last 100 years. Variations in concentration of primary (sea spray) and secondary (biogenic emission, atmospheric inputs) source markers were observed and discussed as a function of distance from the sea and altitude. In the stations characterized by relatively high snow accumulation rates, the sub-sampling resolution was sufficient to obtain a stratigraphic dating by using the periodical variations of seasonal markers. In these stations, a subdivision in “summer” and “winter” samples was carried out in order to study the seasonal changes of the contributions of the measured compounds to the snow composition as elevation and distance from the sea increase. Some evidence of post-depositional effects which are able to change the original deposition of chloride and nitrate, was observed at stations with low accumulation rates. The reliability of the depth/concentration profile of these substances for reconstructing past deposition was also discussed.

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.

Spectrophotometric determination of silicate in rain and aerosols by flow analysis

Abstract A flow analysis (FA) procedure for the measurement of soluble silicon with respect to the total Si concentration is described. After solubilization in H2O, in alkaline solutions or in concentrated HF, silicon is determined by the molybdenum blue spectrophotometric method. The effects of Si complexation by F− are considered as are the decomplexing capacities of H3BO3 or Al3+. The proposed method is applied to samples of rain and of aerosols on filters, collected in Florence. For both kind of samples, the water soluble silicon content is about 1% and practically independent of the total silicon content.

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.

Concentration of peroxides and formaldehyde in air and rain and gas-rain partitioning

Rain and air of Florence have been collected in a continuous way andanalysed by flow analysis spectrofluorimetric methods for formaldehydeand hydrogen peroxide. Diurnal and seasonal variations were observed;the mean/maximum concentrations of all data (as μ gm−3) are 3.3/23.4 for HCHO and 0.4/4.93 forH2O2. The effect of external sources and ofphotochemical reactions produces periods of positive and negativecorrelations for these compounds. The mean/maximum rain concentration ofall data are 98/443 μ g l−1 for HCHO and 84/685 μg l−1 for H2O2. Concentrationratios rain/air and discrepancies to Henrys Law equilibrium arediscussed.

Aluminium and iron record for the last 29kyrs derived from the EDC96 ice core using new CFA methods

Abstract 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.

Sensitivity Enhancement of the Formaldehyde Fluorimetric Determination by the use of a Surfactant

A sensitive method for the formaldehyde determination in aqueous samples by Flow Injection Analysis has been developed. Formaldehyde reacts with acetylacetone, acetic acid and ammonium acetate to form diacetyldihydrolutidine, detectable by its fluorescence; the effects of various surfactants upon this spectrofluorimetric method have been assessed. Fluorescence enhancements from 15-70% were observed in comparison with that without surfactant. The developed method has a detection limit of 55 ng/l and a precision of 2.5% at 1 µg/l level. The calibration graph is linear in over the range 0.1-3000 µ/l. The sensitivity, speed, ease of use and small volume of sample make this method ideal for formaldehyde determination in precipitation samples with concentration from very low to very high by continuous or semicontinuous analysis.

Preliminary study of HCHO spatial and temporal distribution from Coastal to Plateau areas in Antarctica

Formaldehyde concentrations were determined in over 1800 snow samples (snowpit, firn cores and superficial snow) from Antarctica by a sensitive spectrofluorimetric Flow Injection Analysis method. The method performances (detection limit: 55 ng/L; reproducibility: 2.5% at 1 µg/L level; linear range: 0.1–3000 µg/L) allowed a reliable determination of formaldehyde content in all the collected samples. The range of determined concentrations was 0–70 µg/L with a mean concentration of 7.7 µg/L and a median concentration of 5.8 µg/L. The formaldehyde background level was estimated at a few micrograms per liter in coastal and plateau areas of Northern Victoria Land. In some stations the background values are modulated by HCHO deposition events recurring over relatively large time periods.