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An inductively coupled plasma sector field mass spectrometer (ICP-SFMS) was used to develop an analytical method for the fast determination of Na, Al, Sc, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Y, Mo, Cd, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Pb in Arctic size-segregated aerosol samples (PM 10 ), after microwave acidic digestion. The ICP-SFMS was coupled with a microflow nebulizer and a desolvation system for the sample introduction, which reduced the isobaric interferences due to oxides and the required volume of sample solutions, compared to the usual nebulization chamber methods. With its very low limit of detection, and taking into account the level of blanks, this method allowed the quantification of many metals in very low concentration. Particular attention was given to Rare Earth Elements (REEs - La to Lu). The efficiency in the extraction of REEs was proved to be acceptable, with recoveries over 83% obtained with a Certified Reference Material (AMiS 0356). The analytical method was then applied to particulate matter samples, collected at ground level in Ny Ålesund (Svalbard Islands, Norway), during spring and summer, from 2010 to 2015, with daily resolution and using a low-volume device. Thus, for the first time, a large atmospheric concentrations dataset of metals in Arctic particulate matter at high temporal resolution is presented. On the basis of differences in LREE/HREE ratio and Ce and Eu anomalies in spring and summer samples, basic information to distinguish local and long-range transported dust were achieved., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Background: Platinum-based drugs such as Cisplatin are commonly employed for cancer treatment. Despite an initial therapeutic response, Cisplatin treatment often results in the development of chemoresistance. To identify novel approaches to overcome Cisplatin resistance, we tested Cisplatin in combination with K + channel modulators on colorectal cancer (CRC) cells., Methods: The functional expression of Ca 2+ -activated (K Ca 3.1, also known as KCNN4) and voltage-dependent (K v 11.1, also known as KCNH2 or hERG1) K + channels was determined in two CRC cell lines (HCT-116 and HCT-8) by molecular and electrophysiological techniques. Cisplatin and several K + channel modulators were tested in vitro for their action on K + currents, cell vitality, apoptosis, cell cycle, proliferation, intracellular signalling and Platinum uptake. These effects were also analysed in a mouse model mimicking Cisplatin resistance., Results: Cisplatin-resistant CRC cells expressed higher levels of K Ca 3.1 and K v 11.1 channels, compared with Cisplatin-sensitive CRC cells. In resistant cells, K Ca 3.1 activators (SKA-31) and K v 11.1 inhibitors (E4031) had a synergistic action with Cisplatin in triggering apoptosis and inhibiting proliferation. The effect was maximal when K Ca 3.1 activation and K v 11.1 inhibition were combined. In fact, similar results were produced by Riluzole, which is able to both activate K Ca 3.1 and inhibit K v 11.1. Cisplatin uptake into resistant cells depended on K Ca 3.1 channel activity, as it was potentiated by K Ca 3.1 activators. K v 11.1 blockade led to increased K Ca 3.1 expression and thereby stimulated Cisplatin uptake. Finally, the combined administration of a K Ca 3.1 activator and a K v 11.1 inhibitor also overcame Cisplatin resistance in vivo., Conclusions: As Riluzole, an activator of K Ca 3.1 and inhibitor of K v 11.1 channels, is in clinical use, our results suggest that this compound may be useful in the clinic to improve Cisplatin efficacy and overcome Cisplatin resistance in CRC.

The causes of the recent increase in Antarctic sea ice extent, characterised by large regional contrasts and decadal variations, remain unclear. In the Ross Sea, where such a sea ice increase is reported, 50% of the sea ice is produced within wind-sustained latent-heat polynyas. Combining information from marine diatom records and sea salt sodium and water isotope ice core records, we here document contrasting patterns in sea ice variations between coastal and open sea areas in Western Ross Sea over the current interglacial period. Since about 3600 years before present, an increase in the efficiency of regional latent-heat polynyas resulted in more coastal sea ice, while sea ice extent decreased overall. These past changes coincide with remarkable optima or minima in the abundances of penguins, silverfish and seal remains, confirming the high sensitivity of marine ecosystems to environmental and especially coastal sea ice conditions.

Atmospheric new particle formation (NPF) and growth significantly influences climate by supplying new seeds for cloud condensation and brightness. Currently, there is a lack of understanding of whether and how marine biota emissions affect aerosol-cloud-climate interactions in the Arctic. Here, the aerosol population was categorised via cluster analysis of aerosol size distributions taken at Mt Zeppelin (Svalbard) during a 11 year record. The daily temporal occurrence of NPF events likely caused by nucleation in the polar marine boundary layer was quantified annually as 18%, with a peak of 51% during summer months. Air mass trajectory analysis and atmospheric nitrogen and sulphur tracers link these frequent nucleation events to biogenic precursors released by open water and melting sea ice regions. The occurrence of such events across a full decade was anti-correlated with sea ice extent. New particles originating from open water and open pack ice increased the cloud condensation nuclei concentration background by at least ca. 20%, supporting a marine biosphere-climate link through sea ice melt and low altitude clouds that may have contributed to accelerate Arctic warming. Our results prompt a better representation of biogenic aerosol sources in Arctic climate models.

Antarctic sea ice has shown an increasing trend in recent decades, but with strong regional differences from one sector to another of the Southern Ocean. The Ross Sea and the Indian sectors have seen an increase in sea ice during the satellite era (1979 onwards). Here we present a record of ssNa + flux in the Talos Dome region during a 25-year period spanning from 1979 to 2003, showing that this marker could be used as a potential proxy for reconstructing the sea ice extent in the Ross Sea and Western Pacific Ocean at least for recent decades. After finding a positive relationship between the maxima in sea ice extent for a 25-year period, we used this relationship in the TALDICE record in order to reconstruct the sea ice conditions over the 20th century. Our tentative reconstruction highlighted a decline in the sea ice extent (SIE) starting in the 1950s and pointed out a higher variability of SIE starting from the 1960s and that the largest sea ice extents of the last century occurred during the 1990s., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

In this work we present the isotopic, chemical and dust stratigraphies of two snow pits sampled in 2013/14 at GV7 (coastal East Antarctica: 70°41' S - 158°51' E, 1950 m a.s.l.). A large number of chemical species are measured aiming to study their potentiality as environmental changes markers. Seasonal cluster backward trajectories analysis was performed and compared with chemical marker stratigraphies. Sea spray aerosol is delivered to the sampling site together with snow precipitation especially in autumn-winter by air masses arising from Western Pacific Ocean sector. Dust show maximum concentration in spring when the air masses arising from Ross Sea sector mobilize mineral dust from ice-free areas of the Transantarctic mountains. The clear seasonal pattern of sulfur oxidized compounds allows the dating of the snow-pit and the calculation of the mean accumulation rate, which is 242 ± 71 mm w.e. for the period 2008-2013. Methanesulfonic acid and NO 3 - do not show any concentration decreasing trend as depth increases, also considering a 12 m firn core record. Therefore these two compounds are not affected by post-depositional processes at this site and can be considered reliable markers for past environmental changes reconstruction. The rBC snow-pit record shows the highest values in summer 2012 likely related to large biomass burning even occurred in Australia in this summer. The undisturbed accumulation rate for this site is demonstrated by the agreement between the chemical stratigraphies and the annual accumulation rate of the two snow-pits analysed in Italian and Korean laboratories., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Continuous all year-round samplings of atmospheric aerosol and surface snow at high (daily to 4-day) resolution were carried out at Dome C since 2004-05 to 2013 and nitrate records are here presented. Basing on a larger statistical data set than previous studies, results confirm that nitrate seasonal pattern is characterized by maxima during austral summer for both aerosol and surface snow, occurring in-phase with solar UV irradiance. This temporal pattern is likely due to a combination of nitrate sources and post-depositional processes whose intensity usually enhances during the summer. Moreover, it should be noted that a case study of the synoptic conditions, which took place during a major nitrate event, showed the occurrence of a stratosphere-troposphere exchange. The sampling of both matrices at the same time with high resolution allowed the detection of a an about one-month long recurring lag of summer maxima in snow with respect to aerosol. This result can be explained by deposition and post-deposition processes occurring at the atmosphere-snow interface, such as a net uptake of gaseous nitric acid and a replenishment of the uppermost surface layers driven by a larger temperature gradient in summer. This hypothesis was preliminarily tested by a comparison with surface layers temperature data in the 2012-13 period. The analysis of the relationship between the nitrate concentration in the gas phase and total nitrate obtained at Dome C (2012-13) showed the major role of gaseous HNO 3 to the total nitrate budget suggesting the need to further investigate the gas-to-particle conversion processes., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Five snow pits and five firn cores were sampled during the 2003-2004 Italian Antarctic Campaign at Talos Dome (East Antarctica), where a deep ice core (TALDICE, TALos Dome Ice CorE, 1650m depth) was drilled in 2005-2008 and analyzed for ionic content. Particular attention is spent in applying decontamination procedures to the firn cores, as core sections were stored for approximately 10years before analysis. By considering the snow pit samples to be unperturbed, the comparison with firn core samples from the same location shows that ammonium, nitrate and MSA are affected by storage post-depositional losses. All the other measured ions are confirmed to be irreversibly deposited in the snow layer. The removal of the most external layers (few centimeters) from the firn core sections is proved to be an effective decontamination procedure. High-resolution profiles of seasonal markers (nitrate, sulfate and MSA) allow a reliable stratigraphic dating and a seasonal characterization of the samples. The calculated mean accumulation-rate values range from 70 to 85mmw.e.year(-1), in the period 2003-1973 with small differences between two sectors: 70-74mmw.e.year(-1) in the NNE sector (spanning 2003-1996years) and 81-92mmw.e.year(-1) in the SSW sector (spanning 2003-1980years). This evidence is interpreted as a coupled effect of wind-driven redistribution processes in accumulation/ablation areas. Statistical treatment applied to the concentration values of the snow pits and firn cores samples collected in different points reveals a larger temporal variability than spatial one both in terms of concentration of chemical markers and annual accumulation. The low spatial variability of the accumulation rate and chemical composition measured in the five sites demonstrates that the TALDICE ice core paleo-environmental and paleo-climatic stratigraphies can be considered as reliably representative for the Talos Dome area., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Here we present the first direct comparison of cosmogenic (10)Be and chemical species in the period of 38-45.5 kyr BP spanning the Laschamp geomagnetic excursion from the EPICA-Dome C ice core. A principal component analysis (PCA) allowed to group different components as a function of the main sources, transport and deposition processes affecting the atmospheric aerosol at Dome C. Moreover, a wavelet analysis highlighted the high coherence and in-phase relationship between (10)Be and nitrate at this time. The evident preferential association of (10)Be with nitrate rather than with other chemical species was ascribed to the presence of a distinct source, here labelled as "cosmogenic". Both the PCA and wavelet analyses ruled out a significant role of calcium in driving the (10)Be and nitrate relationship, which is particularly relevant for a plateau site such as Dome C, especially in the glacial period during which the Laschamp excursion took place. The evidence that the nitrate record from the EDC ice core is able to capture the Laschamp event hints toward the possibility of using this marker for studying galactic cosmic ray flux variations and thus also major geomagnetic field excursions at pluri-centennial-millennial time scales, thus opening up new perspectives in paleoclimatic studies.

Recently, the increasing interest in the understanding of global climatic changes and on natural processes related to climate yielded the development and improvement of new analytical methods for the analysis of environmental samples. The determination of trace chemical species is a useful tool in paleoclimatology, and the techniques for the analysis of ice cores have evolved during the past few years from laborious measurements on discrete samples to continuous techniques allowing higher temporal resolution, higher sensitivity and, above all, higher throughput. Two fast ion chromatographic (FIC) methods are presented. The first method was able to measure Cl(-), NO3(-) and SO4(2-) in a melter-based continuous flow system separating the three analytes in just 1 min. The second method (called Ultra-FIC) was able to perform a single chromatographic analysis in just 30 s and the resulting sampling resolution was 1.0 cm with a typical melting rate of 4.0 cm min(-1). Both methods combine the accuracy, precision, and low detection limits of ion chromatography with the enhanced speed and high depth resolution of continuous melting systems. Both methods have been tested and validated with the analysis of several hundred meters of different ice cores. In particular, the Ultra-FIC method was used to reconstruct the high-resolution SO4(2-) profile of the last 10,000 years for the EDML ice core, allowing the counting of the annual layers, which represents a key point in dating these kind of natural archives.

From January to December 2010, surface snow samples were collected with monthly resolution at the Concordia station (75°06'S, 123°20'E), on the Antarctic plateau, and analysed for major and trace elements in both dissolved and particulate (i.e. insoluble particles, >0.45 μm) phase. Additional surface snow samples were collected with daily resolution, for the determination of sea-salt sodium and not-sea-salt calcium, in order to support the discussion on the seasonal variations of trace elements. Concentrations of alkaline and alkaline-earth elements were higher in winter (April-October) than in summer (November-March) by a factor of 1.2-3.3, in agreement with the higher concentration of sea-salt atmospheric particles reaching the Antarctic plateau during the winter. Similarly, trace elements were generally higher in winter by a factor of 1.2-1.5, whereas Al and Fe did not show any significant seasonal trend. Partitioning between dissolved and particulate phases did not change with the sampling period, but it depended only on the element: alkaline and alkaline-earth elements, as well as Co, Cu, Mn, Pb and Zn were for the most part (>80%) in the dissolved phase, whereas Al and Fe were mainly associated with the particulate phase (>80%) and Cd, Cr, V were nearly equally distributed between the phases. Finally, the estimated marine and crustal enrichment factors indicated that Cd, Cr, Cu, Pb and Zn have a dominant anthropogenic origin, with a possible contribution from the Concordia station activities., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Biomass burning (BB) is a significant source of particulate matter (PM) in many parts of the world. Whereas numerous studies demonstrate the relevance of BB emissions in central and northern Europe, the quantification of this source has been assessed only in few cities in southern European countries. In this work, the application of Positive Matrix Factorisation (PMF) allowed a clear identification and quantification of an unexpected very high biomass burning contribution in Tuscany (central Italy), in the most polluted site of the PATOS project. In this urban background site, BB accounted for 37% of the mass of PM10 (particulate matter with aerodynamic diameter<10 μm) as annual average, and more than 50% during winter, being the main cause of all the PM10 limit exceedances. Due to the chemical complexity of BB emissions, an accurate assessment of this source contribution is not always easily achievable using just a single tracer. The present work takes advantage of the combination of a long-term daily data-set, characterized by an extended chemical speciation, with a short-term high time resolution (1-hour) and size-segregated data-set, obtained by PIXE analyses of streaker samples. The hourly time pattern of the BB source, characterised by a periodic behaviour with peaks starting at about 6 p.m. and lasting all the evening-night, and its strong seasonality, with higher values in the winter period, clearly confirmed the hypothesis of a domestic heating source (also excluding important contributions from wildfires and agricultural wastes burning)., (Copyright © 2014 Elsevier B.V. All rights reserved.)

This study was carried out to evaluate whether high-frequency ultrasounds, a commonly used aesthetic medicine treatment for skin rejuvenation, may enhance the penetration of the Mn-containing compound Mn(II)(Me2DO2A) (manganese(II) 4,10-dimethyl-1,4,7,10-tetraazacyclododecane-1,7-diacetate) biologically active as a superoxide anion scavenger, in the cutaneous layers of ex vivo human skin explants. Although its antioxidant properties are well known and the compound is basically not toxic in animal models, its trans-cutaneous permeation and its toxicological profile at a systemic level have not yet fully analyzed. Therefore, its possible penetration in the deep cutaneous layers was also evaluated. To this purpose, Mn(II)(Me2DO2A) was formulated as emulsion-gel, lipogel and hydrogel. These different formulations were also tested in combination with high-frequency ultrasounds (10-3500 Hz frequency modulation on a 5 MHz main frequency) used as physical permeation enhancers, delivered by a MedVisage™ device (General Project, Montespertoli, Italy) currently used for aesthetic medicine purposes. The permeation of the Mn-containing compound from the formulations was evaluated by inductively coupled plasma atomic emission spectrometry (ICP-AES) measurements of Mn in horizontal cryosections of the skin samples cut at different depths to separate the epidermis, papillary and reticular dermis, as well as by vertical Franz diffusion cells. The results show that the hydrogel formulation yielded the highest transepidermal delivery of Mn(II)(Me2DO2A) and that the application of ultrasounds (3 W, FM 100 Hz, 2×10 s) significantly enhanced its penetration into the epidermis and upper dermal layers. Of note, nearly undetectable amounts of Mn(II)(Me2DO2A) were detected in the reticular dermis and the Franz cell fluid. Although an in vivo confirmation of these results will be necessary, this method may allow to minimize undesired drug passage to the bloodstream and undesired delivery to non-target internal organs and avoiding its renal excretion and release into the environment., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Ice cores are widely used to reconstruct past changes of the climate system. For instance, the ice core record of numerous water-soluble and insoluble chemical species that are trapped in snow and ice offer the possibility to investigate past changes of various key compounds present in the atmosphere (i.e., aerosol, reactive gases). We developed a new method for the quantitative determination of fluoride in ice cores at sub-μg L(-1) levels by coupling a flow injection analysis technique with a fast ion chromatography separation based on the "heart cut" column switching technology. Sensitivity, linear range (up to 60 μg L(-1)), reproducibility, and detection limit (0.02 μg L(-1)) were evaluated for the new method. This method was successfully applied to the analysis of fluoride at trace levels in more than 450 recent snow samples collected during the 1998-1999 International Trans-Antarctica Scientific Expedition traverse in East Antarctica at sites located between 170 and 850 km from the coastline.

The bioavailability of trace elements in marine sediments from Kongsfjorden (Svalbard Islands, Norwegian Arctic) was assessed and discussed. Total concentrations of several elements were determined in two granulometric fractions and their bioavailability evaluated by both applying a sequential-selective extraction procedure and using a biomimetic approach based on proteolytic enzymes. Total concentration values and solid speciation patterns indicated overall that the anthropogenic impact of trace elements in the investigated area is negligible, although a minor enrichment with respect to crustal values was found for As, Cd, Cr, Ni, and V. Enrichment of trace elements in the <63-μm fraction compared to the coarser one was evident for As, Cd, Cr, and Ni. The evaluation of the bioavailable fractions showed that a large part of the total content of trace elements cannot enter the aquatic food chain and emphasised the risk of overestimating the environmental impact of heavy metals if the assessment is only based on total concentrations., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

In Milan (MI), the largest city in Northern Italy, the annually average PM2.5 concentration is above 25 μg m(-3), the value that the EU established as a target for 2010, and the upper limit from 2015 onwards (2008/30/CE). Over a three-year period (2006-2009) PM concentrations and chemical compositions were measured in an urban site (MI), a rural site (OB) and a remote site (ASC) in Northern Italy. Chemical characterization (EC/OC, inorganic ions, elements, C20-C32 n-alkanes, C2-C5 mono and dicarboxylic acids, levoglucosan and PAHs) was carried out on PM2.5 samples from the three sites, and PM10 from MI. Molecular markers were used in Chemical Mass Balance (CMB) modelling to estimate the contributions of primary sources to OC, and then PM mass from each source was reconstructed in MI, OB and ASC for different seasons. Estimates of the traffic (TR) source contribution to PM2.5 mass ranged from 4.1 (± 2.0) μg m(-3) during the summer, to 13.3 (± 6.7) μg m(-3) during the winter in MI. TR was the main primary source for PM2.5 concentrations in MI (17-24%). Its contribution was lower at the OB site (7-9%) and at the remote ASC site (3-4%). TR is a local source, while biomass burning (BB) is a diffuse regional source in Northern Italy: during fall and winter, BB was 25-30% and 27-31% of PM2.5 at MI and OB respectively. Other primary sources accounted for a small amount of the PM2.5, i.e. natural gas combustion (0-1%), plant debris (0-4%), road dust (RD=0-4%; but 15% at ASC during winter and 10% of PM10 at MI during summer) and sea salt (0-1%). Secondary inorganic+organic aerosol constituted the major part of the PM2.5 mass during spring and summer (50-65%) at the three sites., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Inductively coupled plasma quadrupole mass spectrometry (ICP-QMS), ICP sector field mass spectrometry (ICP-SFMS) and ICP atomic emission spectrometry (ICP-AES) were compared with regard to the direct determination of rare earth elements (REEs) in geological samples. In order to reduce the polyatomic interferences occurring in ICP-QMS, the use of a cooled spray chamber was optimized, obtaining a significant decrease of the oxide ions formation (about 50%) and a consequent mitigation of the interfering effects. Precision and accuracy of the method were demonstrated by the analyses of sediment and soil certified reference materials. ICP-SFMS working in high-resolution mode also provided accurate results, with similar precision to ICP-QMS (RSD%: 3-8%) and comparable or better limits of detection. Quantification limits of the procedures were 18-52 ng g(-1) and 10-780 ng g(-1) for sector field- and quadrupole-ICP-MS, respectively. Accurate and precise determination of most REEs was also achieved by ICP-AES using both pneumatic and ultrasonic nebulization, after a careful selection of the emission lines and compensation for non-spectral interferences by internal standardization. The three techniques were finally applied to glaciomarine sediment samples collected in Antarctica, providing comparable analytical data on REE abundance and depth pattern., (Copyright © 2010 Elsevier B.V. All rights reserved.)

Fine particulate matter (PM1 and PM2.5) was collected in Milan over the summer (August-September) and winter (January-March) seasons of 2007/2008. Particles were analyzed for their chemical composition (inorganic ions, elements and PAHs) and the effects produced on the human lung carcinoma epithelial cell line A549. In vitro tests were performed to assess cell viability with MTT assay, cytokine release (IL-6 and IL-8) with ELISA, and DNA damage with COMET assay. Results were investigated by bivariate analysis and multivariate data analysis (Principal Component Analysis, PCA) to investigate the relationship between PM chemical composition and the biological effects produced by cell exposure to 12 microg cm(-2). The different seasonal chemical composition of PM showed to influence some biological properties. Summer PM samples had a high mass contribution of SO(4)(=) (13+/-2%) and were enriched in some elements, like Al, As, Cr, Cu, and Zn, compared to winter PM samples. Cell viability reduction was two times higher for summer PM samples in comparison with winter ones (27+/-5% and 14+/-5%, respectively), and the highest correlation coefficients between cell viability reduction and single chemical components were with As (R(2)=0.57) and SO(4)(=) (R(2)=0.47). PM1 affected cell viability reduction and induced IL-8 release, and these events were interrelated (R(2)=0.95), and apparently connected with the same chemical compounds. PM2.5 fraction, which was enriched in Ca(++) and Mg(++) (from soil dust), and Al, Fe, Zn, Ba Mn, produced cell viability reduction and DNA damage (R(2)=0.73)., (Copyright (c) 2010 Elsevier Ltd. All rights reserved.)

An example of an integrated approach to assess air pollution threats to cultural heritage in a semi-confined environment is presented in this work, where the monitoring campaign carried out at the Michelozzo's Courtyard (in Palazzo Vecchio, Florence, Italy) is used as a case study. A wide research project was carried out, with the main aim of obtaining the first quantitative data on air quality and microclimate conditions inside the Courtyard, and, if possible, identifying the main causes of degradation and suggesting appropriate conservation strategies. The investigation adopted a holistic approach involving thermographic measurements on the wall paintings, microclimatic analysis, gaseous pollutant monitoring, atmospheric particles characterisation and dry deposition compositional analysis. Attention was focused on the wall painting depicting the city of Hall because of its anomalous and critical conservation conditions, which are visible at a glance, due to the contrast between a wide darker zone around the central subject of the painting and external lighter areas.

A detailed ionic component record was performed on EPICA Dome C ice core (East Antarctica) to a depth of 3190 m using Ion Chromatography and Fast Ion Chromatography (FIC). At depths greater than 2800 m, the sulfate profile shows intense, sharp spikes which are not expected due to the smoothing of sulfate peaks by diffusion processes. Moreover, these spikes show an "anomalous" chemical composition (e.g., unusually low acidity, high Mg(2+) concentration and high Mg(2+)/Ca(2+) ratio). These peaks and the surrounding layers also exhibit good Mg(2+) vs SO(4)(2-) and Cl(-) vs Na(+) correlations through both glacial and interglacial periods. Furthermore, the high-resolution analysis of two horizontally contiguous ice sections showed that some fraction of the impurities are characterized by a heterogeneous distribution. Altogether, these results suggest the occurrence of long-term postdepositional processes involving a rearrangement of impurities via migration in the vein network, characterized by sulfuric acidity and leading to the formation of soluble particles of magnesium sulfate salts, along with ionic association of ions in the liquid films along boundaries. This evidence should be taken into consideration when inferring information on for rapid climatic and environmental changes from ice core chemical records at great depths. At Dome C, the depth threshold was found to be 2800 m.

Two cyclic polyamine-polycarboxylate ligands, 1,4,7,10-tetraazacyclododecane-1,7-diacetic acid (H(2)L3) and 4,10-dimethyl-1,4,7,10-tetraazacyclododecane-1,7-diacetic acid (H(2)L4), and two noncyclic scaffolds, N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid (H(3)L1) and ethylene-bisglycol-tetracetic acid (H(4)L2), form stable complexes with Mn(II) in aqueous solutions. Cyclic voltammograms show that the complexes with the most hydrophobic ligands, [MnL2](2-) and [MnL4], are oxidized at higher potential than [MnL1](-) and [MnL3]. The pharmacological properties of these molecules were evaluated as superoxide ion scavengers and anti-inflammatory compounds. Among the four complexes, [MnL4] was the most bioactive, being effective in the nanomolar/micromolar range. It abates the levels of key markers of oxidative injury on cultured cells and ameliorates the outcome parameters in animal models of acute and chronic inflammation. [MnL4] toxicity was very low on both cell cultures in vitro and mice in vivo. Hence, we propose [MnL4] as a novel stable oxygen radical scavenging molecule, active at low doses and with a low toxicity.

To improve quantitative interpretation of ice core aeolian dust records, a systematic methodological comparison was made. This involved methods for water-insoluble particle counting (Coulter counter and laser-sensing particle detector), soluble ion analysis (ion chromatography and continuous flow analysis), elemental analysis (inductively coupled plasma mass spectroscopy at pH 1 and after full acid digestion), and water-insoluble elemental analysis (proton induced X-ray emission). Antarctic ice core samples covering the last deglaciation from the EPICA Dome C (EDC) and the EPICA Dronning Maud Land (EDML) cores were used. All methods correlate very well among each other, but the ratios of glacial age to Holocene concentrations, which are typically a factor approximately 100, differ between the methods by up to a factor of 2 with insoluble particles showing the largest variability. The recovery of ICP-MS measurements depends on the digestion method and is differentfor different elements and during different climatic periods. EDC and EDML samples have similar dust composition, which suggests a common dust source or a common mixture of sources for the two sites. The analyzed samples further reveal a change of dust composition during the last deglaciation.

A method was developed for the quantitative determination of cations and anions in Antarctic ice cores at microgL(-1) and sub-microgL(-1) levels by ion chromatography (IC), after ultra-clean decontamination procedures. Strict manipulation and decontamination procedures were used in sub-sampling, in order to minimise sample contamination. Na+, NH4+, K+, Mg2+ and Ca2+ were determined by 12-min isocratic elution (H2SO4 eluent). Contemporaneously, in a parallel device, F-, MSA (methanesulfonic acid), Cl-, NO3- and SO4(2-) were analysed in a single 12-min run with multiple-step elution using Na2CO3/NaHCO3 as eluent. Melted ice samples were pumped from their still-closed containers (polystyrene accuvettes with polyethylene caps), shared between the two ion chromatographic systems, online filtered (0.45 microm Teflon membrane) and pre-concentrated (anions and cations pre-concentration columns) using a flow analysis system, thus avoiding uptake of contaminants from the laboratory atmosphere. Sensitivity, linear range, reproducibility and detection limit were evaluated for each chemical species. Anion or cation detection limits ranged from 0.01 to 0.15 microgL(-1) by using a relatively small sample volume (1.5 mL). Such values are significantly lower than those reported in literature for almost all the components. These methods were successfully applied to the analysis of cations and anions at trace levels in the Dome C ice core. The composition of the atmospheric aerosol for the last 850 kyr was reconstructed by high-resolution continuous chemical stratigraphies. Concentration trends in the last nine glacial-interglacial climatic cycles were shown and briefly discussed.

A Flow Injection Analysis (FIA) spectrofluorimetric method for calcium determination in ice cores was optimised in order to achieve better analytical performances which would make it suitable for reliable calcium measurements at ppt level. The method here optimised is based on the formation of a fluorescent compound between Ca and Quin-2 in buffered environment. A careful evaluation of operative parameters (reagent concentration, buffer composition and concentration, pH), influence of interfering species possibly present in real samples and potential favourable effect of surfactant addition was carried out. The obtained detection limit is around 15 ppt, which is one order of magnitude lower than the most sensitive Flow Analysis method for Ca determination currently available in literature and reproducibility is better than 4% for Ca concentrations of 0.2 ppb. The method was validated through measurements performed in parallel with Ion Chromatography on 200 samples from an alpine ice core (Lys Glacier) revealing an excellent fit between the two chemical series. Calcium stratigraphy in Lys ice core was discussed in terms of seasonal pattern and occurrence of Saharan dust events.

Sea ice and dust flux increased greatly in the Southern Ocean during the last glacial period. Palaeorecords provide contradictory evidence about marine productivity in this region, but beyond one glacial cycle, data were sparse. Here we present continuous chemical proxy data spanning the last eight glacial cycles (740,000 years) from the Dome C Antarctic ice core. These data constrain winter sea-ice extent in the Indian Ocean, Southern Ocean biogenic productivity and Patagonian climatic conditions. We found that maximum sea-ice extent is closely tied to Antarctic temperature on multi-millennial timescales, but less so on shorter timescales. Biological dimethylsulphide emissions south of the polar front seem to have changed little with climate, suggesting that sulphur compounds were not active in climate regulation. We observe large glacial-interglacial contrasts in iron deposition, which we infer reflects strongly changing Patagonian conditions. During glacial terminations, changes in Patagonia apparently preceded sea-ice reduction, indicating that multiple mechanisms may be responsible for different phases of CO2 increase during glacial terminations. We observe no changes in internal climatic feedbacks that could have caused the change in amplitude of Antarctic temperature variations observed 440,000 years ago.

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.

A sensitive spectrofluorimetric-FIA (flow injection analysis) method for formaldehyde (HCHO) determination was improved with the aim of analysing seawater samples. The fluorescence emission versus HCHO concentration shows a linear pattern from sub microg L(-1) to about 1000 microg L(-1). The reproducibility at 15 ppb level is about 2%. Interferences from other aldehydes were checked; only glyoxal shows a significative interference, but only when its concentration is about 6000 times higher than that of formaldehyde. Superficial (microlayer, just sub-pack or sea-ice free sea surface) and deep (along the water column, sub-pack or in sea-ice free areas) seawater samples were collected near the coast at Terra Nova Bay (Ross Sea, Antarctica) during the 1998/1999 and 2001/2002 Italian Antarctic Expedition. We report here the preliminary results of the spectrofluorimetric-FIA determination of the HCHO content. The mean seawater superficial formaldehyde concentration was 15 microg L(-1); the concentration along the water column ranged between 4.5 to over 40 microg L(-1)(20 microg L(-1) mean concentration), usually with a maximum value for the 30 m depth, corresponding to a fluorescence maximum. The sampling was repeated 7 times in the austral summer in order to evaluate seasonal changes in the formaldehyde concentration/seawater depth profiles. The results show changes in the formaldehyde concentration at different depths.

The Antarctic Vostok ice core provided compelling evidence of the nature of climate, and of climate feedbacks, over the past 420,000 years. Marine records suggest that the amplitude of climate variability was smaller before that time, but such records are often poorly resolved. Moreover, it is not possible to infer the abundance of greenhouse gases in the atmosphere from marine records. Here we report the recovery of a deep ice core from Dome C, Antarctica, that provides a climate record for the past 740,000 years. For the four most recent glacial cycles, the data agree well with the record from Vostok. The earlier period, between 740,000 and 430,000 years ago, was characterized by less pronounced warmth in interglacial periods in Antarctica, but a higher proportion of each cycle was spent in the warm mode. The transition from glacial to interglacial conditions about 430,000 years ago (Termination V) resembles the transition into the present interglacial period in terms of the magnitude of change in temperatures and greenhouse gases, but there are significant differences in the patterns of change. The interglacial stage following Termination V was exceptionally long--28,000 years compared to, for example, the 12,000 years recorded so far in the present interglacial period. Given the similarities between this earlier warm period and today, our results may imply that without human intervention, a climate similar to the present one would extend well into the future.