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This study investigated the elemental composition of PM10 collected in a polar environment (Ny-Alesund, Norwegian Arctic), to identify its sources and to understand the effects of short- and long-range transport processes. Natural (crustal and marine) and anthropogenic Arctic PM sources were identified, and specific emission sources were recognised by means of Principal Component Analysis and Hierarchical Cluster Analysis: airborne pollution deriving from ship fuels, local vehicle (non-exhaust) and continental emissions (e.g. incinerators or industries) were the main sources of anthropogenic elements. The results obtained so far from samples collected during four successive spring-summer sampling campaigns (2010–2013) show a remarkable seasonal trend for most of the investigated elements. For both geogenic and anthropogenic elements, concentrations are generally higher in March and April, when the ground is almost entirely covered by snow and ice, suggesting that long-range transport processes might be taking place. On the other hand, the concentrations of anthropogenic metals related to ship emissions (i.e. Co, Ni and V) peak in late spring and summer, when the marine traffic in the fjord is generally higher. For most of the analytes, the four campaigns were not significantly different; therefore, in the studied period, the composition of PM10 in Ny-Alesund did not vary remarkably. Finally, the behaviour of Rare Earth Elements was discussed in terms of parent material mineralogy.

A particulate matter (PM) source apportionment study was carried out in one of the most polluted districts of Tuscany (Italy), close to an old waste incinerator plant. Due to the high PM10 levels, an extensive field campaign was supported by the Regional Government to identify the main PM sources and quantify their contributions. PM10 daily samples were collected for one year and analysed by different techniques to obtain a complete chemical characterisation (elements, ions and carbon fractions). Hourly fine (2.5 μm) and coarse (2.5-10 μm) aerosol samples were collected by a Streaker sampler for a shorter period and hourly elemental concentrations were obtained by PIXE. Positive Matrix Factorization (PMF) analysis of daily and hourly data allowed the identification of 10 main sources: six anthropogenic (Biomass Burning, Traffic, Secondary Nitrates, Secondary Sulphates, Incinerator, Heavy Oil combustion), two natural (Saharan Dust and Fresh Sea Salt) and two mixed sources (Local Dust and Aged Sea Salt). Biomass burning turned out to be the main source of PM, accounting for 30% of the PM10 mass as annual average, followed by Traffic (18%) and Secondary Nitrates (14%). Emissions from the Incinerator turned out to be only 2% of PM10 mass on average. PM10 composition and source apportionment have been assessed in a polluted area near a waste incinerator, by PMF analysis on daily and hourly compositional data sets.

A long-term study of the chemical composition of Arctic aerosol has been carried out at the Gruvebadet Observatory located in Ny-Ålesund since 2010. The PM10 aerosol has been collected continuously every year on a daily/2-day basis, each covering at least the spring and summer months, and the ionic content was evaluated using simultaneously three IC-systems. In order to determine the contribution of different sources (sea spray, crustal, biogenic and anthropogenic) to the total sulphate budget, specific markers and characteristic marker-to-sulphate ratios were used (Na+, Ca2+ and methanesulphonate). The obtained data set was then compared with the one from the Zeppelin Observatory, also located in Ny-Ålesund. The anthropogenic fraction resulted to be the major component, reaching the highest value in March and April during the Haze period, followed by the sea salt, biogenic and crustal ones. The comparison between the two datasets confirms the seasonal trend of these fractions even though some differences in magnitude were observed, likely due to discrepancies in the timing and resolution of sampling campaigns. The temporal profile of the anthropogenic fraction, evaluated in both sites, showed no evident continuous trend from 2010 to 2019, although the 2017-19 period revealed higher concentration with respect to the previous years. Focusing on single months, two opposite trends in the sulphate budget along 10 years were observed for March against April and September. Whereas a decrease was observed in March, April and September showed an increase in the monthly mean concentration values. Finally, the correlation between the non-sea salt non-crustal sulphate fraction and ammonium was evaluated. An increase in the ammonia neutralizing effect, resulting in a decrease in aerosol acidity, was observed at GVB, from the 2010 to 2017, then stabilized. Conversely, a decrease in the concentration of ammonia was found in ZEP since 2015, leading to an increase of the nssSO42-/NH4+ ratio in the same period.

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 (PM10), 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 Alesund (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.

A prolonged and exceptionally intense air mass advection event transporting biomass burning aerosols generated in Alaska affected Ny-Ålesund in the mid of July 2015. This paper reports the morphochemical characteristics and mixing state of individual aerosol particles collected during the event. To this aim aerosol samples were collected on nucleopore polycarbonate membrane filters using a DEKATI 12-stage low volume impactor and analyzed by scanning electron microscopy (SEM) techniques. Results of SEM investigations depict a complex aerosol characterized by an external mixing between a main part of carbonaceous organic particles (tar balls and organic particles), lower ammonium sulfate and minor potassium chloride and mineral dust amounts. The carbonaceous particles are spherical to slightly elongated and the organic particles show an internal mixing of low density organics and/or ammonium sulfate upon denser nuclei. Most particles are in the accumulation mode size range although the size and the morphology of the chloride and the sulfate salts evidence the growth of these species both in the air and upon the sampling membranes. Individual particle analyses were complemented by aerosol size distribution (Aerodynamic Particle Sizer, Scanning Mobility Particle Sizer) and optical (Particle Soot Absorption Photometer, nephelometer) measurements at ground level in order to retrieve the optical and radiative properties of the aerosol in the atmosphere and to predict the fate and behaviour of particles upon deposition at ground level. Individual particle analyses were also compared with bulk chemical analyses on daily sampling filters and back-trajectory analyses of the air mass movement in order to enucleate distinct sources of the aerosol during the long range transport.

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 HNO3 to the total nitrate budget suggesting the need to further investigate the gas-to-particle conversion processes. © 2017 Elsevier Ltd

This paper presents the results of measurements of aerosol physical and chemical properties during iAREA2014 campaign that took place on Svalbard between 15th of Mar and 4th of May 2014. With respect to field area, the experiment consisted of two sites: NyeAlesund (78�550N, 11�560E) and Longyearbyen (78�130N, 15�330E) with further integration of Aerosol Robotic Network (AERONET) station in Hornsund (77�000N, 15�330E). The subject of this study is to investigate the inesitu, passive and active remote sensing observations as well as numerical simulations to describe the temporal variability of aerosol singleescattering properties during spring season on Spitsbergen. The retrieval of the data indicates several event days with enhanced singleescattering properties due to the existence of sulphate and additional seaesalt load in the atmosphere which is possibly caused by relatively high wind speed. Optical results were confirmed by numerical simulations made by the GEMeAQ model and by chemical observations that indicated up to 45% contribution of the seaesalt to a PM10 total aerosol mass concentration. An agreement between the in-situ optical and microphysical properties was found, namely: the positive correlation between aerosol scattering coefficient measured by the nephelometer and effective radius obtained from laser aerosol spectrometer as well as negative correlation between aerosol scattering coefficient and the Angstrom exponent indicated that slightly larger particles dominated during special events. The inesitu surface observations do not show any significant enhancement of the absorption coefficient as well as the black carbon concentration which might occur during spring. All of extensive singleescattering properties indicate a diurnal cycle in Longyearbyen, where 21:00e5:00 data stays at the background level, however increasing during the day by the factor of 3e4. It is considered to be highly connected with local emissions originating in combustion, traffic and harbour activities. On the other hand, no daily fluctuations in NyeAlesund are observed. Mean values in NyeAlesund are equal to 8.2, 0.8 Mm�1 and 103 ng/m3 for scattering, absorption coefficients and black carbon concentration; however in Longyearbyen (only data from 21:00e05:00 UTC) they reach 7.9, 0.6 Mm�1 as well as 83 ng/ m3 respectively. Overall, the spring 2014 was considerably clean and seaesalt was the major aerosol component

This study examines the relationships linking methanesulfonic acid (MSA, arising from the atmospheric oxidation of the biogenic dimethylsulfide, DMS) in atmospheric aerosol, satellite-derived chlorophyll a (Chl-a), and oceanic primary production (PP), also as a function of sea ice melting (SIM) and extension of the ice free area in the marginal ice zone (IF-MIZ) in the Arctic. MSA was determined in PM10 samples collected over the period 2010-2012 at two Arctic sites, Ny Ålesund (78.9°N, 11.9°E), Svalbard islands, and Thule Air Base (76.5°N, 68.8°W), Greenland. PP is calculated by means of a bio-optical, physiologically based, semi-analytical model in the potential source areas located in the surrounding oceanic regions (Barents and Greenland Seas for Ny Ålesund, and Baffin Bay for Thule). Chl-a peaks in May in the Barents sea and in the Baffin Bay, and has maxima in June in the Greenland sea; PP follows the same seasonal pattern of Chl-a, although the differences in absolute values of PP in the three seas during the blooms are less marked than for Chl-a. MSA shows a better correlation with PP than with Chl-a, besides, the source intensity (expressed by PP) is able to explain more than 30% of the MSA variability at the two sites; the other factors explaining the MSA variability are taxonomic differences in the phytoplanktonic assemblages, and transport processes from the DMS source areas to the sampling sites. The taxonomic differences are also evident from the slopes of the correlation plots between MSA and PP: similar slopes (in the range 34.2-36.2 ng m-3of MSA/(gC m-2 d-1)) are found for the correlation between MSA at Ny Ålesund and PP in Barents Sea, and between MSA at Thule and PP in the Baffin Bay; conversely, the slope of the correlation between MSA at Ny Ålesund and PP in the Greenland Sea in summer is smaller (16.7 ng m-3of MSA/(gC m-2 d-1)). This is due to the fact that DMS emission from the Barents Sea and Baffin Bay is mainly related to the MIZ diatoms, which are prolific DMS producers, whereas in the Greenland Sea the DMS peak is related to an offshore pelagic bloom where low-DMS producer species are present. The sea ice dynamic plays a key role in determining MSA concentration in the Arctic, and a good correlation between MSA and SIM (slope = 39 ng m-3 of MSA/106 km2 SIM) and between MSA and IF-MIZ (slope = 56 ng m-3 of MSA/106 km2 IF-MIZ) is found for the cases attributable to bloomings of diatoms in the MIZ. Such relationships are calculated by combining the data sets from the two sites and suggest that PP is related to sea ice melting and to the extension of marginal sea ice areas, and that these factors are the main drivers for MSA concentrations at the considered Arctic sites. © 2016 The Authors.

Ship traffic, population, infrastructure development, and mining activities are expected to increase in the Arctic due to its rising temperatures. This is expected to produce a major impact on aerosol composition. Metals contained in atmospheric particles are powerful markers and can be extremely helpful to gain insights on the different aerosol sources. This work aims at studying the sources of metals in the Arctic aerosol sampled at the Thule High Arctic Atmospheric Observatory (THAAO; Greenland, 76.5°N 68.8°W). Due to the particular composition of Greenlandic soils and to properties of other sources, it was possible to find several signatures of natural and anthropogenic aerosols transported from local and long-range regions. Arctic haze (AH) at Thule builds up on long-range transported aerosol mainly from Canada and Nord America. From a chemical standpoint, this aerosol is characterized by a high concentration of sulfate, Pb, As and Cd and by a La/Ce ratio larger than 1. The Ti/Al and Fe/Al ratios in the AH aerosol are lower (Ti/Al = 0.04 w/w; Fe/Al = 0.79 w/w) than for local aerosol (Ti/Al = 0.07 w/w; Fe/Al = 0.89 w/w). Conversely, aerosol arising from coastal areas of South-West Greenland is characterized by a high concentration of V, Ni, and Cr. These metals, generally considered anthropogenic, arise here mainly from natural crustal sources. In some summer samples, however, the V/Ni ratio becomes larger than 3. In particular, cases displaying this characteristic ratio, as also shown by backward trajectories, are associated with sporadic transport to Thule of ship aerosol from ships passing through Baffin Bay and arriving to Thule during summer. Although further measurements are necessary to confirm the discussed results, the analysis carried out in this work on a large number of metals sampled in coastal Greenland aerosol is unprecedented.

The aim of the present work was to investigate the likely toxicological impact of atmospheric PM10 particles by comparing different effect-based methodologies, namely the Vibrio fischeri bioluminescence inhibition bioassay to evaluate ecotoxicity, the SOS Chromotest assay to estimate genotoxicity, and the Dithiothreitol (DTT) and Ascorbic Acid (AA) acellular assays to assess oxidative potential. The chemical composition was characterized for about 30 species, to assess the potential health impact of specific chemical components. Atmospheric particles were collected from spring to summer at a coastal site of the Central Mediterranean, away from large sources of local pollution. The Toxicity Unit (TU) index, used to assess the ecotoxicity, showed that 33% of the samples were toxic. The Induction Factor (IF), generally used to assess particle's genotoxicity, varied from 0.3 to 1.5 that represents the threshold value for genotoxicity. The oxidative potential (OP) determined by the DTT and AA assay varied within the 4.9–34.5 and 4.8–140.6 nmol min−1 range, respectively. DTT-OP and TU values were significantly correlated with OC, EC, and nss-K+, likely because the DTT and Vibrio fischeri responses were mainly associated with species from combustion sources. The IF factor was significantly correlated with some metals (Al, Ba, La, P, Sr, and Ti) likely from traffic sources and did not show any significant correlation with TU and OP values. Overall, paper's results proved the episodic occurrence of ecotoxicity and genotoxicity levels in PM10 particles sampled directly from their natural environment and away from strong pollution sources, highlighting the role mainly of carbonaceous compounds and heavy metals. The impact of spurious correlations between DTT- and AA-OPV and chemical species concentration has also been addressed.

Montale is a small town in Tuscany characterised by high PM10 levels. Close to the town there is a waste incinerator plant. There are many concerns in the population and in the press about the causes of the high levels of pollution in this area. Daily PM10 samples were collected for 1 year by the FAI Hydra Dual sampler and analysed by different techniques in order to obtain a complete chemical speciation (elements by PIXE and ICP-MS, ions by Ion Chromatography, elemental and organic carbon by a thermo-optical instrument); hourly fine ( Positive Matrix Factorization identified and quantified the major aerosol sources. Biomass burning turned out to be the most important source with an average percentage contribution to PM10 of 27% of and even higher percentages during the winter period when there are the highest PM10 concentrations. The contribution of the incinerator source has been estimated as about 6% of PM10.

Amongst Ion Beam Analysis (IBA) techniques applied to the study of atmospheric aerosol samples, Elastic Backscattering Spectrometry (EBS) and Particle Elastic Scattering Analysis (PESA) with MeV energy proton beams allows obtaining quantitative information about the concentration of C and other low-Z atoms like H, N and O in the sample. With these nuclear techniques a direct measurement of elemental carbon (EC) and organic carbon (EC) is not possible. Nevertheless, the detection of all the aforemetioned light elements may help to infer some information on the aerosol chemical composition. The H concentration obtained by PESA may be used as a proxy of OC; then, EC can be obtained as the difference between total carbon measured simultaneously by EBS and OC as estimated by PESA. The feasibility of the quantification of EC and OC following this approach in particulate matter samples collected on Teflon filters, where this information cannot be obtained by standard thermo-optical analyses, will be discussed. Moreover, thanks to the simultaneous measurements of H, C, N and O in the aerosol samples, the organic component of the aerosols (particulate organic matter, POM) can be directly calculated and thus the validity of the POM/OC conversion factors found in the literature can be tested.

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 diameter10 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).

article i nfo Wereportontheexistenceandnature of Holocene solar andclimaticvariationson centennialto millennial time- scales. We introduce a new solar activity proxy, based on nitrate (NO3 − ) concentration from the Talos Dome ice core, East Antarctica. We also use a new algorithm for computing multiple-cross wavelet spectra in time-fre- quency space that is generalized for multiple time series (beyond two). Our results provide a new interpretive framework for relating Holocene solaractivity variations on centennial to millennial timescales to co-varying cli- mate proxies drawn from a widespread area around the globe. Climatic proxies used represent variation in the North Atlantic Ocean, Western Pacific Warm Pool, Southern Ocean and the East Asian monsoon regions. Our wavelet analysis identifies fundamental solar modes at 2300-yr (Hallstattzeit), 1000-yr (Eddy), and 500-yr (unnamed) periodicities, leaves open the possibility that the 1500-1800-yr cycle may either be fundamental or derived, and identifies intermediary derived cycles at 700-yr and 300-yr that may mark rectified responses of the Atlantic thermohaline circulation to external solar modulation and pacing. Dating uncertainties suggest that the 1500-yr and 1800-yr cycles described in the literature may represent either the same or two separate cycles, but in either case, and irrespective too of whether it is a fundamental or derived mode in the sense of Dima and Lohmann (2009), the 1500-1800-yr periodicity is widely represented in a large number of paleoclimate proxy records. It is obviously premature to reject possible links between changing solar activity at these multiple scales and the variations that are commonly observed in paleoclimatic records.

The chemical characterization of size-segregated samples is helpful to study the aerosol effects on both human health and environment. The sampling with multi-stage cascade impactors (e.g., Small Deposit area Impactor, SDI) produces inhomogeneous samples, with a multi-spot geometry and a non-negligible particle stratification. At LABEC (Laboratory of nuclear techniques for the Environment and the Cultural Heritage), an external beam line is fully dedicated to PIXE–PIGE analysis of aerosol samples. PIGE is routinely used as a sidekick of PIXE to correct the underestimation of PIXE in quantifying the concentration of the lightest detectable elements, like Na or Al, due to X-ray absorption inside the individual aerosol particles. In this work PIGE has been used to study proper attenuation correction factors for SDI samples: relevant attenuation effects have been observed also for stages collecting smaller particles, and consequent implications on the retrieved aerosol modal structure have been evidenced.

PIXE and ICP-AES techniques are largely used in atmospheric aerosol studies. Since PIXE is able to provide the total elemental concentrations, while ICP-AES results depend on the extraction conditions, parallel PIXE and ICP-AES measurements of Fe, Al, Cu, Pb, Mn, Cr, Ni, V, As on PM10 and PM2.5 samples were compared. Two extraction procedures were applied to samples from 5 sites at different anthropization level in Italy: a “weak” extraction (HNO 3 at pH = 1.5) and a “strong” extraction (micro-wave oven in HNO 3 and H 2 O 2 – following EU rules). The amount of the metal extracted in the different conditions resulted to be strongly dependent on the sampling site, on the main sources of the particle (crustal or anthropic) containing the metal and on the sampled size class.

From November 2004 to December 2007, size-segregated aerosol samples were collected all-year-round at Dome C (East Antarctica) by using PM10 and PM2.5 samplers, and multi-stage impactors. The data set obtained from the chemical analysis provided the longest and the most time-resolved record of sea spray aerosol (sea salt Na+) in inner Antarctica. Sea spray showed a sharp seasonal pattern. The highest values measured in winter (Apr–Nov) were about ten times larger than in summer (Dec–Mar). For the first time, a size-distribution seasonal pattern was also shown: in winter, sea spray particles are mainly sub-micrometric, while their summer size-mode is around 1–2 μm. Meteorological analysis on a synoptic scale allowed the definition of atmospheric conditions leading sea spray to Dome C. An extreme-value approach along with specific environmental based criteria was taken to yield stronger fingerprints linking atmospheric circulation (means and anomalies) to extreme sea spray events. Air mass back-trajectory analyses for some high sea spray events allowed the identification of two major air mass pathways, reflecting different size distributions: micrometric fractions for transport from the closer Indian-Pacific sector, and sub-micrometric particles for longer trajectories over the Antarctic Plateau. The seasonal pattern of the SO 4 2 − /Na+ ratio enabled the identification of few events depleted in sulphate, with respect to the seawater composition. By using methanesulphonic acid (MSA) profile to evaluate the biogenic SO 4 2 − contribution, a more reliable sea salt sulphate was calculated. In this way, few events (mainly in April and in September) were identified originating probably from the “frost flower” source. A comparison with daily-collected superficial snow samples revealed that there is a temporal shift between aerosol and snow sea spray trends. This feature could imply a more complex deposition processes of sea spray, involving significant contribution of wet and diamond dust deposition, but further work has to be carried out to rule out the effect of wind re-distribution and to have more statistic significance.

A year-round study, which was conducted from November 2004 to November 2007, of atmospheric oxidised sulphur compounds (methanesulphonic acid (MSA) and sulphate) was carried out in the east Antarctic Plateau at Dome C (75° 06′ S, 123° 20′ E, 3220 m a.s.l. and 1100 km away from the nearest coast). The two sulphur-derived species exhibit a seasonal cycle characterised by maxima in the summer from November to March. Size-segregated sampling performed with Andersen 8-stage impactors revealed that SO 4 2− and MSA have different size distributions in early summer (November) in comparison with mid-late summer (February). In November, the size distribution exhibited two distinct modes, the accumulation (0.4–0.7 μm) and the micrometric mode (1.1–2.1 μm), which is in contrast to February when only the accumulation mode was observed. The two modes exhibited different speciation; in the finest mode, sulphate and methanesulphonate were present primarily in the acidic form, whereas they were present primarily as sodium or ammonium salts in the micrometric mode. The different size distributions and speciation patterns in the two months are related to different transport pathways from oceanic areas to the central Antarctic Plateau. In the early summer months, air masses came primarily from the Indian Ocean and lingered for a long time over the Antarctic continent. The transport of sulphur compounds is related to sea spray aerosols and the resulting condensation of H 2 SO 4 and MSA over sea salt particles to form sodium salts. In contrast, a rapid transport of H 2 SO 4 and MSA formed above the boundary layer over oceanic areas leads to higher concentrations of the acidic species in the fine fraction of aerosols reaching Dome C in February relative to other summer months.

Methylene Blue Active Substances (MBAS) and Linear Alkylbenzene Sulphonates (LAS) concentrations, together with organic carbon and ions were measured in atmospheric coastal aerosols in the NW Mediterranean Basin. Previous studies have suggested that the presence of surfactants in coastal aerosols may result in vegetation damage without specifically detecting or quantifying these surfactants. Coastal aerosols were collected at a remote site (Porquerolles Island-Var, France) and at a more anthropised site (San Rossore National Park-Tuscany, Italy). The chemical data were interpreted according to a comprehensive local meteorological analysis aiming to decipher the airborne source and transport processes of these classes of compounds. The LAS concentration (anthropogenic surfactants) was measured in the samples using LC-MS/MS, a specific analytical method. The values were compared with the MBAS concentration, determined by a non-specific analytical method. At Porquerolles, the MBAS concentration (103 ± 93 ng m −3 ) in the summer samples was significantly higher than in the winter samples. In contrast, LAS concentrations were rarely greater than in the blank filters. At San Rossore, the mean annual MBAS concentration (887 ± 473 ng m −3 in PM10) contributed about 10% to the total atmospheric particulate organic matter. LAS mean concentration in these same aerosol samples was 11.5 ± 10.5 ng m −3 . A similar MBAS (529 ± 454 ng m −3 ) – LAS (7.1 ± 4.1 ng m −3 LAS) ratio of ∼75 was measured in the fine (PM2.5) aerosol fraction. No linear correlation was found between MBAS and LAS concentrations. At San Rossore site the variation of LAS concentrations was studied on a daily basis over a year. The LAS concentrations in the coarse fraction (PM10–2.5) were higher during strong sea storm conditions, characterized by strong air flow coming from the sea sector. These events, occurring with more intensity in winter, promoted the formation of primary marine aerosols containing LAS from the sea surface microlayer. In contrast to LAS, MBAS concentrations in the coarse fraction peaked in summer. Therefore, different sources are suggested for the two classes of compounds. In summer, increased MBAS concentration could be an indicator of phytoplanktonic blows enriching the sea surface microlayer with biogenic surfactants. In winter, some spikes in MBAS concentrations in the coarse fraction could be related to LAS concentrations and sea storm events. Moreover, in the fine fraction MBAS have a large concentration maxima in winter, corresponding to air masses coming from polluted continental areas. It is concluded that MBAS concentration in the fine or the coarse fraction is not an appropriate surrogate measurement of LAS concentration in aerosols because of the significant contribution from other sources to the MBAS concentration.

Operational regional sea-salt aerosol forecasts have been produced on a daily basis since February 2006 over the open sea in the Mediterranean, where sea-salt aerosol concentrations and their impact on the Mediterranean weather and climate could be significant under strong winds. In order to evaluate the model performance, the numerical simulations of sea-salt aerosol (SSA) were compared with sea-salt ground-based measurements taken at the tiny Mediterranean island of Lampedusa, Italy. Considerable effort was made in order to collect and analyze SSA measurements on a daily basis, during the two-year period from 2007 to 2008. In Lampedusa, the conditions of SSA measurements are considered similar to those in the open sea, given the small dimensions of the island. As estimated for all 380 days used in the analysis, model-vs.-measurement comparisons at Lampedusa show a relatively high correlation of 0.7 between model data and measurements; a rather low mean bias of −0.5 μg/m 3 ; and a mean normalized bias less than 20%. Therefore, the model was capable of producing reasonable SSA concentrations and their day-to-day variations over the open sea.

This paper compares chemical stratigraphies from snowpits collected at Dome C (East Antarctica) in order to assess site variability in terms of spatial distribution of chemical markers, annual accumulation rate and chemical species persistence in the snow layers. Since Dome C was chosen for deep drilling down to the bedrock in the framework of EPICA (European Project for Ice Coring in Antarctica), to provide 800 kyr of climatic and environmental records, evaluating site variability is fundamental for a reliable interpretation of the deep ice core stratigraphies. For this purpose, 4 snowpits were dug at Dome C (1997/98, 1998/99, 2000/01 and 2005/06 Antarctic Campaigns) and analysed for cations, inorganic anions and methane sulphonate by ion chromatography. Unlike the first three snowpits, the most recent one was analysed directly in situ, allowing to observe that no chemical contamination or loss due to sample storage and transport to Europe occurs for such a sampling. Accumulation rate variability was revealed to be around 4% in a common time range (1992–1964) for all snowpits. Intra-snowpit chemical variability was definitely higher than inter-snowpit variability, indicating that the variations observed in the chemical stratigraphies from Dome C can be reliably related to effective changes in source and transport mechanisms of the investigated markers more than to site variability. Post-depositional phenomena affecting chloride, nitrate and methane sulphonate were studied, revealing a logarithmic decay as a function of depth for Cl − and MSA and an exponential one for NO 3 − . The relative losses were quantified in the 75–80% range for Cl − , 66–83% for MSA and 89–94% for NO 3 − and were found to stop around 320, 320 and 60–80 cm depth, respectively.

A method was developed for the quantitative determination of cations and anions in Antarctic ice cores at μg L −1 and sub-μg L −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 + , NH 4 + , K + , Mg 2+ and Ca 2+ were determined by 12-min isocratic elution (H 2 SO 4 eluent). Contemporaneously, in a parallel device, F − , MSA (methanesulfonic acid), Cl − , NO 3 − and SO 4 2− were analysed in a single 12-min run with multiple-step elution using Na 2 CO 3 /NaHCO 3 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 μm 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 μg L −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.

Electrohydrodimerization (EHD) of fumarodinitrile (R) from dilute aqueous solutions of the strong surfactant Triton X-100 takes place both on liquid gallium and on mercury, via a rate-determining homogeneous radical–radical coupling step. However, the potential range over which EHD takes place is much narrower on gallium than on mercury. This behaviour is due to the fact that adsorbed water molecules act as proton donors towards the radical anion R − , giving rise to the neutral radical RH , which is immediately reduced to the saturated monomer RH 2 . Therefore, EHD requires the complete displacement of water molecules from the adsorbed state by Triton X-100; this is more difficult on the hydrophilic gallium than on the hydrophobic mercury. This also explains why, even though fumarodinitrile is much more strongly adsorbed on gallium than on mercury, no appreciable radical–radical coupling takes place in the adsorbed state on gallium. Acrylonitrile is reduced to the saturated monomer on gallium under the same experimental conditions in which it undergoes EHD on mercury. This is also due to the high hydrophilicity of gallium.