Abstract:In an attempt to clarify the release of trace elements from the seasonal coastal sea ice, samples were periodically collected in a nearshore station inside the Gerlache Inlet (Terra Nova Bay, Western Ross Sea), during the summer 2000/01 and analysed for dissolved and particulate cadmium, copper, iron, manganese and lead, as well as salinity, suspended particulate matter, nutrients and phytoplankton pigments. In order to provide insight on the metal association with the particles included in the sea ice, the metal solid speciation was also investigated. Both vertical distributions within the ice cores and temporal variations at the seawater interface were studied, in an effort to fully characterize the system and correlation among the considered parameters. Concentrations and speciation patterns clearly indicate metal incorporation within the annual sea ice due to resuspension of sediments, followed by release of particulate metals during melting as a primary process affecting trace metal availability in the Antarctic coastal waters.

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In order to provide a new insight into the Antarctic snow chemistry, partitioning of major and trace elements between dissolved and particulate (i.e. insoluble particles, >0.45 μm) phases have been investigated in a number of coastal and inland snow samples, along with their total and acid-dissolvable (0.5% nitric acid) concentrations. Alkaline and alkaline-earth elements (Na, K, Ca, Mg, Sr) were mainly present in the dissolved phase, while Fe and Al were predominantly associated with the particulate matter, without any significant difference between inland and coastal samples. On the other hand, partitioning of trace elements depended on the sampling site position, showing a general decrease of the particulate fraction by moving from the coast to the plateau. Cd, Cu, Pb and Zn were for the most part in the dissolved phase, while Cr was mainly associated with the particulate fraction. Co, Mn and V were equally distributed between dissolved and particulate phases in the samples collected from the plateau and preferentially associated with the particulate in the coastal samples. The correlation between the elements and the inter-sample variability of their concentration significantly decreased for the plateau samples compared to the coastal ones, according to a change in the relative contribution of the metal sources and in good agreement with the estimated marine and crustal enrichment factors. In addition, samples from the plateau were characterised by higher enrichment factors of anthropogenic elements (Cd, Cr, Cu, Pb and Zn), compared to the coastal area. Finally, it was observed that the acid-dissolvable metal concentrations were generally lower than the total concentration values, showing that the acid treatment can dissolve only a given fraction of the metal associated with the particulate (<20% for iron and aluminium).

Abstract:In an attempt to improve the understanding of the natural variability and distribution of trace elements in Antarctic organisms, the concentrations of arsenic, cadmium, cobalt, chromium, copper, manganese, nickel, vanadium and zinc in representative benthic species from two pristine coastal environments were measured and compared with literature data for other uncontaminated coastal ecosystems. Correlations between the elements, differences between the species and between the sampling sites were examined by principal component analysis. Metal accumulation was particularly evident in the tissues of the sea star Odontaster validus, the bivalve mollusc Laternula elliptica and in the red alga Phyllophora antarctica. However, metal accumulation was not the same for all the analytes, but, rather, depended on the organism characteristics. In particular, the soft tissues of Odontaster validus were characterized by high concentrations of cadmium, zinc and copper, those of Phyllophora antarctica by high concentrations of manganese and nickel, and the tissues of Laternula elliptica by high concentrations of all measured elements, particularly in its digestive gland. The Antarctic data as well as those reported for other pristine coastal ecosystems showed remarkably high natural variability in metal content, which must be taken into account when interpreting results from biomonitoring programmes.

During the 2010-2011 austral summer, size-segregated aerosol samples were collected at a coastal Antarctic site (Terra Nova Bay, Victoria Land) and analysed for major and trace elements and lead isotopic composition, in order to provide a better understanding of the sources of metals and their transportation pathways towards Antarctica. Aerosol size fractionation was performed by a cascade impactor, able to collect aerosol particles of aerodynamic diameter 10-7.2, 7.2-3.0, 3.0-1.5, 1.5-0.95 and 0.95-0.49 mu m. It was found that Al, Co, Fe, Li, Mn, Rb, Y and V were mainly related to crustal inputs, whereas the marine contribution was significant for Li, Mg, Na and Rb. An additional anthropogenic source influencing the concentration of Cr, Cu, Mo and Pb was clearly demonstrated. The concentration of the elements associated to the crustal and marine inputs showed high values in the coarse mode (7.2-3.0 mu m), whereas the anthropogenic elements were also characterised by a high concentration in the finer (1.5-0.95 mu m) particles. The study of the temporal trends of the measured chemical markers along with the meteorological variables revealed that both the crustal and anthropogenic elements were related to the air masses carried by the katabatic wind from the inland, whereas the marine input appeared to be higher in January when the sea-ice extent was reduced. Finally, lead isotope ratios pointed out that the anthropogenic input was likely related to the polluted aerosols from South America and Australia, representing the predominant fraction (50-70%) of the lead measured in the samples

In this work, a new sensitive procedure for the determination of ultratrace elements in snow samples based on quadrupole ICP-MS has been developed. After filtration through a 0.5 microm PTFE membrane (for dissolved element determination) or acidification with 0.5% nitric acid (for acid dissolvable element determination), the analytes were preconcentrated by sample volume reduction and analysed by ICP-MS. Micro-samples were efficiently introduced into the plasma source at 20 microl min(-1) uptake rate by using a PFA micronebulizer coupled to an evaporation chamber of the torch integrated sample introduction system (TISIS). As a result, the amount of sample required was about one order of magnitude lower than that required with a conventional liquid sample introduction system. In order to improve the transport efficiency, the TISIS chamber was electrically-heated at 70 degrees C and a sheathing gas stream was used to protect the aerosol from the chamber walls. Under these conditions, negative solvent plasma effects were no more severe than for conventional systems, because the total solvent plasma load was 20 mg min(-1). The operating parameters were optimized to obtain maximum sensitivity, while limiting oxides and double charge ion formation. The polyatomic interferences were removed by applying the dynamic reaction cell (DRC) technique, using ammonia as the reaction gas. Under the optimized conditions, limits of detection ranged from 0.02 to 4.5 pg g(-1), allowing the determination of Cr, V, Fe, Mn, Pb, Zn, Cd, Co and Cu in Antarctic snow samples. Signal repeatability was lower than 10% which prevented the use of an internal standard. Precision of the procedure ranged from 2.0% to 5.6%. The accuracy of the method was verified by the analysis of both certified reference water and surface snow samples collected in coastal and inland areas of Antarctica. The DRC program used, the short wash out and signal stabilization times registered under these conditions led to a 10 h(-1) sample throughput.

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