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The Arctic atmosphere is warming rapidly and its relatively pristine environment is sensitive to the long-range transport of atmospheric pollutants. While carbon dioxide is the main cause for global warming, short-lived climate forcers (SLCFs) such as methane, ozone, and particles also play a role in Arctic climate on near-term time scales. Atmospheric modelling is critical for understanding the abundance and distribution of SLCFs throughout the Arctic atmosphere, and is used as a tool towards determining SLCF impacts on climate and health in the present and in future emissions scenarios. In this study, we evaluate 18 state-of-the-art atmospheric and Earth system models, assessing their representation of Arctic and Northern Hemisphere atmospheric SLCF distributions, considering a wide range of different chemical species (methane, tropospheric ozone and its precursors, black carbon, sulfate, organic aerosol, and particulate matter) and multiple observational datasets. Model simulations over four years (2008–2009 and 2014–2015) conducted for the 2021 Arctic Monitoring and Assessment Programme (AMAP) SLCF assessment report are thoroughly evaluated against satellite, ground, ship and aircraft-based observations. The results show a large range in model performance, with no one particular model or model type performing well for all regions and all SLCF species. The multi-model mean was able to represent the general features of SLCFs in the Arctic, though vertical mixing, long-range transport, deposition, and wildfire emissions remain highly uncertain processes. These need better representation within atmospheric models to improve their simulation of SLCFs in the Arctic environment.

In this work, we present chemical stratigraphies of two sampling lines collected within a 4 m depth snow pit dug in Dome C during the Antarctic summer Campaign 2017/2018, 12 years after the last reported snow pit. The first sampling line was analyzed for nine anionic and cationic species using Ion Chromatography (IC), the second sampling line was analyzed for seven major elements in an innovative way with Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) after sample pre-concentration, allowing the study of deposition processes of new markers especially related to crustal source. This coupled analysis, besides confirming previous studies, allowed us to investigate the depositions of the last decades at Dome C, enriching the number of the detected chemical markers, and yielding these two techniques complementary for the study of different markers in this kind of matrix. As a result of the dating, the snow layers analyzed covered the last 50 years of snow depositions. The assessment of the accumulation rate, estimated about 9 cm yr−1, was accomplished only for the period 1992–2016, as the eruption of 1992 constituted the only tie-point found in nssSO42− depth profile. Na, the reliable sea salt marker, together with Mg and Sr, mainly arose from marine sources, whereas Ca, Al and Fe originated from crustal inputs. Post-depositional processes occurred on Cl− as well as on NO3− and methanesulfonic acid (MSA), compared to the latter, Cl− had a more gradual decrease, reporting a threshold at 2.5 m for the post-depositional process completion. For NO3− and MSA, instead, the threshold was shallower, at about 1 m depth, with a loss of 87% for NO3− and of 50% for MSA.

Ten years of data of biogenic aerosol (methane sulfonic acid, MSA, and non-sea salt sulfate, nssSO42−) collected at Concordia Station in the East Antarctic plateau (75° 06′ S, 123° 20′ E) are interpreted as a function of the Southern Annular Mode (SAM), Chlorophyll-a concentration (Chl-a; a proxy for phytoplankton biomass), sea ice extent and area. It is possible to draw three different scenarios that link these parameters in early, middle, and late summer. In early summer, the biogenic aerosol is significantly correlated to sea ice retreats through the phytoplankton biomass increases. Chl-a shows a significant correlation with nssSO42− in the finest fraction (< 1 μm). In contrast, only Chl-a in West Pacific and Indian Ocean sectors correlates with MSA in the coarse fraction. The transport routes towards the inner Antarctic plateau and aerosol formation processes could explain the different correlation patterns of the two compounds both resulting from the DMS oxidation. In mid-summer, Chl-a concentrations are at the maximum and are not related to sea ice melting. Due to the complexity of transport processes of air masses towards the Antarctic plateau, the MSA concentrations are low and not related to Chl-a concentration. In late summer, MSA and nssSO42− present the highest concentrations in their submicrometric aerosol fraction, and both are significantly correlated with Chl-a but not with the sea ice. In early and mid-summer, the enhanced efficiency of transport processes from all the surrounding oceanic sectors with air masses traveling at low elevation can explain the highest concentrations of nssSO42− and especially MSA. Finally, considering the entire time series, MSA shows significant year-to-year variability. This variability is significantly correlated with SAM but with a different time lag in early (0-month lag) and late summer (4-months lag). This correlation likely occurs through the effect of the SAM on phytoplankton blooms.

19 pages, 8 figures,1 table, 1 appendix.-- Data availability: The APS data can be accessed from https://doi.org/10.5281/zenodo.3961473 (Traversi et al., 2020). The absorption coefficient data are available upon request from Gilardoni et al. (2020). Data supporting this publication can be accessed upon request from the corresponding authors, Understanding aerosol–cloud–climate interactions in the Arctic is key to predicting the climate in this rapidly changing region. Whilst many studies have focused on submicrometer aerosol (diameter less than 1 µm), relatively little is known about the supermicrometer aerosol (diameter above 1 µm). Here, we present a cluster analysis of multiyear (2015–2019) aerodynamic volume size distributions, with diameter ranging from 0.5 to 20 µm, measured continuously at the Gruvebadet Observatory in the Svalbard archipelago. Together with aerosol chemical composition data from several online and offline measurements, we apportioned the occurrence of the coarse-mode aerosols during the study period (mainly from March to October) to anthropogenic (two sources, 27 %) and natural (three sources, 73 %) origins. Specifically, two clusters are related to Arctic haze with high levels of black carbon, sulfate and accumulation mode (0.1–1 µm) aerosol. The first cluster (9 %) is attributed to ammonium sulfate-rich Arctic haze particles, whereas the second one (18 %) is attributed to larger-mode aerosol mixed with sea salt. The three natural aerosol clusters were open-ocean sea spray aerosol (34 %), mineral dust (7 %) and an unidentified source of sea spray-related aerosol (32 %). The results suggest that sea-spray-related aerosol in polar regions may be more complex than previously thought due to short- and long-distance origins and mixtures with Arctic haze, biogenic and likely blowing snow aerosols. Studying supermicrometer natural aerosol in the Arctic is imperative for understanding the impacts of changing natural processes on Arctic aeroso, This research has been supported by the Natural Environment Research Council (grant no. NE/S00579X/1). We acknowledge support of the publication fee by the CSIC Open Access Publication Support Initiative through its Unit of Information Resources for Research (URICI), With the institutional support of the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000928-S)

Seasonal to interannual variations in the concentrations of sulfur aerosols (

11 pags., 4 figs., New particle formation in the Arctic atmosphere is an important source of aerosol particles. Understanding the processes of Arctic secondary aerosol formation is crucial due to their significant impact on cloud properties and therefore Arctic amplification. We observed the molecular formation of new particles from low-volatility vapors at two Arctic sites with differing surroundings. In Svalbard, sulfuric acid (SA) and methane sulfonic acid (MSA) contribute to the formation of secondary aerosol and to some extent to cloud condensation nuclei (CCN). This occurs via ion-induced nucleation of SA and NH and subsequent growth by mainly SA and MSA condensation during springtime and highly oxygenated organic molecules during summertime. By contrast, in an ice-covered region around Villum, we observed new particle formation driven by iodic acid but its concentration was insufficient to grow nucleated particles to CCN sizes. Our results provide new insight about sources and precursors of Arctic secondary aerosol particles., The authors acknowledge European Research Council (GASPARCON, Grant no. 714621 and COALA, Grant no. 638703), Academy of Finland (Project nos. 296628, 306853, 317380, 316114, and 320094), INTERACT, European Regional Development Fund (project MOBTT42), Austrian Science Fund (FWF, Project J3951-N36), the European Union's Horizon 2020 Research and Innovation Program (Grant no. 689443) via project iCUPE (Integrative and Comprehensive Understanding on Polar Environments) and Project ERC-2016- COG 726349 CLIMAHAL, National Research Foundation (NRF) of the Ministry of Science, ICT and Future Planning (NRF-2018R1A2A1A19019281), Knut-and-Alice-Wallenberg Foundation within the Arctic Climate Across Scales (Project No. \,2016.0024), the Swedish EPA's (Naturvårdsverket) Environmental monitoring program (Miljöövervakning), the Swedish Research Council FORMAS (Project "Interplay between water, clouds and Aerosols in the Arctic," \# 2016-01427), Climate Change Tower – Integrated Project of the National Research Council of Italy and the National Interest Project by the Italian Minister of Education, University and Research (PRIN2007 and PRIN2009). The authors thank Department of Earth System Sciences and Technologies for the Environment, Department of Earth Sciences and Technology of the Environment of CNR and the doctoral program in atmospheric sciences at the University of Helsinki for financial support. Aarhus University acknowledge financial support from Danish Ministry of Environment and food and Ministry of Climate, Energy and Utilities by means of DANCEA.

Oceanic dimethyl sulfide (DMS) emissions have been recognized as a biological regulator of climate by contributing to cloud formation. Despite decades of research, the climatic role of DMS remains ambiguous largely because of limited observational evidence for DMS-induced cloud condensation nuclei (CCN) enhancement. Here, we report concurrent measurement of DMS, physiochemical properties of aerosol particles, and CCN in the Arctic atmosphere during the phytoplankton bloom period of 2010. We encountered multiple episodes of new particle formation (NPF) and particle growth when DMS mixing ratios were both low and high. The growth of particles to sizes at which they can act as CCN accelerated in response to an increase in atmospheric DMS. Explicitly, the sequential increase in all relevant parameters (including the source rate of condensable vapor, the growth rate of particles, Aitken mode particles, hygroscopicity, and CCN) was pronounced at the DMS-derived NPF and particle growth events. This field study unequivocally demonstrates the previously unconfirmed roles of DMS in the growth of particles into climate-relevant size and eventual CCN activation.

While more and more studies are being conducted on carbonaceous fractions—organic carbon (OC) and elemental carbon (EC)—in urban areas, there are still too few studies about these species and their effects in polar areas due to their very low concentrations, further, studies in the literature report only data from intensive campaigns, limited in time. We present here for the first time EC–OC concentration long-time data records from the sea-level sampling site of Ny-Ålesund, in the High Arctic (5 years), and from Dome C, in the East Antarctic Plateau (1 year). Regarding the Arctic, the median (and the interquartile range (IQR)) mass concentrations for the years 2011–2015 are 352 (IQR 283–475) ng/m3 for OC and 4.8 (IQR: 4.6–17.4) ng/m3 for EC, which is responsible for only 3% of total carbon (TC). From both the concentration data sets and the variation of the average monthly concentrations, the influence of the Arctic haze on EC and OC concentrations is evident. Summer may be interesting owing to high concentration episodes mainly due to long-range transport (e.g., from wide wildfires in the Northern Hemisphere, as happened in 2015). The average ratio of EC/OC for the summer period is 0.05, ranging from 0.02 to 0.10, and indicates a clean environment with prevailing biogenic (or biomass burning) sources, as well as aged, highly oxidized aerosol from long-range transport. Contribution from ship emission is not evident, but this result may be due to the sampling time resolution. In Antarctica, a 1 year-around data set from December 2016 to February 2018 is shown, which does not present a clear seasonal trend. The OC median (and IQR) value is 78 (64–106) ng/m3, for EC, it is 0.9 (0.6–2.4) ng/m3, weighing for 3% on TC values. The EC/OC ratio mean value is 0.20, with a range of 0.06–0.35. Due to the low EC and OC concentrations in polar areas, correction for the blank is far more important than in campaigns carried out in other regions, largely affecting uncertainties in measured concentrations. Through the years, we have thus developed a new sampling strategy that is presented here for the first time: samplers were modified in order to collect a larger amount of particulates on a small surface, enhancing the capability of the analytical method since the thermo-optical analyzer is sensitive to carbonaceous aerosol areal density. Further, we have recently coupled such modified samplers with a sampling strategy that makes a more reliable blank correction of every single sample possible.

Near infrared (NIR)‐resonant gold nanoparticles (AuNPs) hold great promise in cancer diagnostics and treatment. However, translating the theranostic potential of AuNPs into clinical applications still remains a challenge due to the difficulty to improve the efficiency and specificity of tumor delivery in vivo as well as the clearance from liver and spleen to avoid off target toxicity. In this study, endothelial colony forming cells (ECFCs) are exploited as vehicles to deliver AuNPs to tumors. It is first demonstrated that ECFCs display a great capability to intake AuNPs without losing viability, and exert antitumor activity per se. Using a human melanoma xenograft mouse model, it is next demonstrated that AuNP‐loaded ECFCs retain their capacity to migrate to tumor sites in vivo 1 day after injection and stay in the tumor mass for more than 1 week. In addition, it is demonstrated that ECFC‐loaded AuNPs are efficiently cleared by the liver over time and do not elicit any sign of damage to healthy tissue., The findings herein firmly establish gold nanoparticle (AuNP)‐loaded endothelial colony forming cells (ECFCs) as excellent theranostic agents that can be tracked with simple imaging methods and display inherent antitumor properties. The study highlights their capacity to migrate to tumor sites in vivo 1 day after injection and remain in the tumor mass for more than 1 week.

Atmospheric fluxes of dissolved organic matter (DOM) were studied for the first time on the island of Lampedusa, a remote site in the central Mediterranean Sea (Med Sea), between 19 March 2015 and 1 April 2017. The main goals of this study were to quantify total atmospheric deposition of DOM in this area and to evaluate the impact of Saharan dust deposition on DOM dynamics in the surface waters of the Mediterranean Sea. Our data show high variability in DOM deposition rates without a clear seasonality and a dissolved organic carbon (DOC) input from the atmosphere of 120.7 mmol DOC m−2 yr−1. Over the entire time series, the average dissolved organic phosphorus (DOP) and dissolved organic nitrogen (DON) contributions to the total dissolved pools were 40 % and 26 %, respectively. The data on atmospheric elemental ratios also show that each deposition event is characterized by a specific elemental ratio, suggesting a high variability in DOM composition and the presence of multiple sources. This study indicates that the organic substances transported by Saharan dust on Lampedusa mainly come from a natural sea spray and that Saharan dust can be an important carrier of organic substances even though the load of DOC associated with dust is highly variable. Our estimates suggest that atmospheric input has a larger impact on the Med Sea than on the global ocean. Further, DOC fluxes from the atmosphere to the Med Sea can be up to 6 times larger than total river input. Longer time series combined with modeling would greatly improve our understanding of the response of DOM dynamics in the Med Sea to the change in aerosol deposition pattern due to the effect of climate change.

Aerosols play an important role in the climatic system through their direct and indirect effects on radiation. Beside this, they are also part of the complex chain of chemical reactions taking place in the atmosphere. Indirect effects involve aerosols acting as cloud and ice condensation nuclei, brightening of clouds, modification of precipitation capabilities etc. After deposition, they also change reflectivity properties of bright surfaces, particularly important in polar regions. In the Artic few natural aerosol sources exist, except oceans for sea-salt and soil for dust, both of them increasing in magnitude due to global warming. Beside this, anthropogenic aerosols are easily transported to the Arctic by atmospheric transport from middle latitudes, in particular during winter and early spring, forming the so-called Artic Haze. In this contribution the processes causing the development of Arctic Haze and its characteristics are introduced. Following, a review of the physical and optical properties as well as chemical composition of Arctic aerosols are reviewed using data obtained from numerous monitoring stations in the Arctic.

The estimation of radon progeny in the Arctic region represents a scientific challenge due to the required low limit of detection in consideration of the limited radon emanation associated with permafrost dynamics. This preliminary study highlighted, for the first time above 70∘ N, the possibility to monitor radon progeny in the Arctic region with a higher time resolution. The composition of the radon progeny offered the opportunity to identify air masses dominated by long-range transport, in presence or absence of near-constant radon progeny instead of long- and short-lived progenies. Furthermore, the different ratio between radon and thoron progenies evidenced the contributions of local emissions and atmospheric stability. Two different emanation periods were defined in accordance with the permafrost dynamics at the ground and several accumulation windows were recognized coherently to the meteo-climatic conditions occurring at the study site.

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

Three different partners, ENEA, JAEA ed University of Tokyo, have been involved during 2014-2015 in the Round Robin experimentation for the assessment of the soundness of the analitycal procedure for the determination of the Nitrogen impurities contained inside a solid Lithium sample. Two different kinds of Lithium samples, differing by about an order of magnitude in Nitrogen concentration (∼230 wppm; ∼20-30 wppm), have been selected for this cross analysis. The agreement of the achieved results appears very good for what concerns the most concentrated Lithium and indicates each partner's procedure is appropriate and intrinsecally able to lead to meaningful values, characterized by a relative uncertainty of just few %. The smaller agreement in the case of the less concentrated Lithium anyway points out that particular attention must be paid to reduce as much as possible any source of external contamination and highlights the importance of the proper blank subtraction. © 2016 EURATOM-ENEA.

In article number 2001175, Paolo Armanetti and co‐workers demonstrate the tumor‐homing efficiency and antitumoral activity of Au nanoparticles‐loaded Endothelial Colony Forming Cells (ECFCs). The image represents a cell loaded with AuNPs which acts as a Trojan horse vehicle to smuggle nearinfrared (NIR) gold nanoparticles to the tumor site. Once in the tumor tissue, these cargo cells exposed to NIR light brighten the dark battlefield and neutralize the foes (cancer cells) with their inherent strength. [Image: see text]

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.

The Mediterranean basin is characterized by large concentrations of aerosols from both natural and anthropogenic sources. These aerosols affect tropospheric photochemistry by modulating the photolytic rates. Three simulations of the atmospheric composition at basin scale have been performed with the CHIMERE chemistry-transport model for the period from 6 June to 15 July 2013 covered by the ADRIMED campaign, a campaign of intense measurements in the western Mediterranean basin. One simulation takes into account the radiative effect of the aerosols on photochemistry, the second one does not, and the third one is designed to quantify the model sensitivity to a bias in the ozone column. These simulations are compared to satellite and ground-based measurements, with a particular focus on the area of Lampedusa. Values of the aerosol optical depth (AOD) are obtained from the MODIS instrument on the AQUA and TERRA satellites as well as from stations in the AERONET network and from the MFRSR sun photometer deployed at Lampedusa. Additional measurements from instruments deployed at Lampedusa either permanently or exceptionally are used for other variables: MFRSR sun photometer for AOD, diode array spectrometer for actinic fluxes, LIDAR for the aerosol backscatter, sequential sampler for speciation of aerosol and Brewer spectrophotometer for the total ozone column. It is shown that CHIMERE has a significant ability to reproduce observed peaks in the AOD, which in Lampedusa are mainly due to dust outbreaks during the ADRIMED period, and that taking into account the radiative effect of the aerosols in CHIMERE considerably improves the ability of the model to reproduce the observed day-to-day variations of the photolysis rate of ozone to O2 and O(1D), J(O1D), and that of NO2 to NO and O(3P), J(NO2). While in the case of J(O1D) other variation factors such as the stratospheric ozone column are very important in representing correctly the day-to-day variations, the day-to-day variations of J(NO2) are captured almost completely by the model when the optical effects of the aerosols are taken into account. Finally, it is shown that the inclusion of the direct radiative effect of the aerosols in the CHIMERE model leads to reduced J(O1D) and J(NO2) values over all the simulation domain, which range from a few percents over continental Europe and the north-east Atlantic Ocean to about 20 % close to and downwind from Saharan dust sources. The effect on the modelled ozone concentration is 2-fold: the effect of aerosols leads to reduced ozone concentrations over the Mediterranean Sea and continental Europe, close to the sources of NOx, but it also leads to increased ozone concentrations over remote areas such as the Sahara and the tropical Atlantic Ocean.

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.

We have reported on the synthesis and characterization of near-infrared- (NIR-) absorbing colloidal nanoparticles prepared by exploiting the one-step reaction of HAuCl4 and Na2S2O3, followed by their stabilization with chitosan. This reaction also produces a big amount of unwanted nanoparticles detuned with respect to the NIR spectral region. For this reason, it is usually assumed that the product has to be filtered and enriched to enhance its NIR absorption, and the possible exploitation of the simpler raw product has never been worthy to be considered. Aiming to investigate this missing aspect, we chose to avoid the purification steps and rather focused on the preparation of the unrefined colloid, identifying the synthesis conditions that maximize its NIR absorbance and, subsequently, testing it as an optothermal transducer by measuring its molar heating rate (MHR). As expected, we found that the performances of the raw colloid are indeed lower than those of its refined version, but only to a limited extent. Moreover, MHR is unexpectedly higher than that deducible for other classical NIR-absorbing nanoparticles, like Au nanorods or Au nanostars. Thus, the product of the simpler preparation protocol appears as a competitive trade-off solution between easy manufacturing and optothermal performances.

Particle Induced X-ray Emission (PIXE) analysis of aerosol samples allows simultaneous detection of several elements, including important tracers of many particulate matter sources. This capability, together with the possibility of analyzing a high number of samples in very short times, makes PIXE a very effective tool for source apportionment studies by receptor modeling. However, important aerosol components, like nitrates, OC and EC, cannot be assessed by PIXE: this limitation may strongly compromise the results of a source apportionment study if based on PIXE data alone. In this work, an experimental dataset characterised by an extended chemical speciation (elements, EC–OC, ions) is used to test the effect of reducing input species in the application of one of the most widely used receptor model, namely Positive Matrix Factorization (PMF). The main effect of using only PIXE data is that the secondary nitrate source is not identified and the contribution of biomass burning is overestimated, probably due to the similar seasonal pattern of these two sources.

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).

This paper presents the results of a comparative wavelet coherence analysis of a multimillennial nitrate record with a number of climatic and solar activity proxies. Distinguishing between these factors is important in the view of a possibility of nitrate deposited in a polar region to represent galactic cosmic ray flux and, consequently, solar activity. We used the data from the TALDICE drilling project (Talos Dome, Antarctica), which covers the age range 12,000–700 BP (years before present, i.e. before 1950) and includes records of nitrate as well as climatic proxies, such as Na+, Ca2+, MSA (methanesulphonic acid), δ18O, SO 4 2 − . The solar activity series is represented by reconstructions of the heliospheric modulation parameter from the 14C and 10Be data. We found (1) a confirmation of multimillennial relation between nitrate and galactic cosmic ray flux; (2) no clear signature of long-term variations of nitrate transport from lower latitudes. We suggest that variations in the nitrate record in the time scale of hundreds–thousands years are most likely caused by local production, deposition and post-deposition processes.

In this paper a new method for the removal of gypsum degradation layers from carbonatic matrices in cultural heritage conservation, using aqueous Highly Viscous Polymeric Dispersions (HVPDs) based on partially hydrolyzed poly(vinyl acetate) and borax, embedded with chelators, is presented. Due to their interesting viscoelasticity, these systems guarantee a good adhesion to the treated surface and easiness of removal in one step, minimizing the residues. Thus, they can potentially overcome the “residue question” limit associated to traditional methodologies that use thickened solutions of chelators. Here the rheological properties of HVPDs containing different amounts of selected chelating agents are explored and their efficacy in the extraction of gypsum is verified through cleaning tests onto artificially sulfated travertine tiles. The homogeneous removal of gypsum across the surface was checked non-invasively via Fourier Transform Infrared Spectroscopy (FTIR) 2D Imaging. An analytical protocol for the pre-treatment and the analysis of HVPD samples by means of Ion Cromatography (IC) and Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) was set up and the approximate amount of calcium sulfate removed was determined.

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.

During the summers of 2011 and 2012, two scientific cruises were carried out over the Arctic Ocean aiming at the determination of the aerosol chemical composition in this pristine environment. First, mass spectrometry was applied to study the concentration and gas/particle partitioning of polycyclic aromatic hydrocarbons (PAHs) and n-alkanes. Experimental and modelled data of phase partitioning were compared: results demonstrated an equilibrium between gas and particle phase for PAHs, while n-alkanes showed a particle-oriented partitioning, due to the local marine origin of them, confirmed by the extremely low value of their carbon preference index. Moreover, the inorganic and organic ions (carboxylic acids and amines) concentrations, together with those of elemental carbon (EC) and organic matter (OM), were analyzed: 63% of aerosol was composed of ionic compounds (&gt, 90% from sea-salt) and the OM content was very high (30.5%, close to 29.0% of Cl&minus, ) in agreement with n-alkanes&rsquo, marine signature. Furthermore, the amines&rsquo, (dimethylamine, trimethylamine, diethylamine) concentrations were 3.98 &plusmn, 1.21, 1.70 &plusmn, 0.82, and 1.06 &plusmn, 0.56 p.p.t.v., respectively, fully in keeping with concentration values used in the CLOUD (Cosmics Leaving OUtdoor Droplet)-chamber experiments to simulate the ambient nucleation rate in a H2SO4-DMA-H2O system, showing the amines&rsquo, importance in polar regions to promote new particle formation. Finally, high resolution mass spectrometry was applied to determine trace elements, including Rare Earth Elements (REEs), highlighting the dominant natural versus anthropic inputs for trace metals (e.g., Fe, Mn, Ti vs. As, Cd, Ni) and possible signatures of such anthropic activity.

During the 2013 Arctic campaign, direct measurements and size-segregated samplings of atmospheric aerosol were carried out from March to September at the Gruvebadet observatory in Ny-lesund (78A degrees 56'N, 11A degrees 56'E; Svalbard Islands). Continuous size distribution measurements (104 size classes) were performed both in the nano- (TSI-SMPS system) and micro-metric (TSI-APS device) range with a resolution of 10 min. Aerosol sampling was carried out on daily basis (PM10 fraction, 00:01-23:59 UTC) and with a 4-day resolution (four-stage cascade impactor). A back-trajectory analysis was performed for specific events to understand transport processes and possible source areas of aerosol reaching Ny-lesund. Aerosol samples were analyzed for ion composition (inorganic cations and anions, selected organic anions) by a three-chromatograph system after extraction in ultra-sonic bath. Special attention was spent in identifying and interpreting the seasonal pattern of natural and anthropic chemical markers. Sea spray aerosol was evenly distributed along all the sampling period with maxima related to wind speed. Its size distribution peaks in 1.0-2.5 or 2.5-10 A mu m, depending on the transport conditions and distance from source areas. Anthropic sulfate dominates the spring aerosol load (Arctic Haze), both in acidic form (H2SO4) and in partially or totally neutralized ammonium salts. Biogenic contributions, marked by methanesulfonic acid, are relatively relevant in late spring-early summer and are distributed in the finest aerosol fraction (< 1.0 A mu m).

Daily PM10 aerosol samples were collected at the Gruvebadet observatory, Ny-Ålesund (Svalbard Islands), during the spring-summer 2014 Italian Arctic Campaign. A total of 136 samples were analysed for ion (inorganic anions and cations, selected organic anions) composition aiming to evaluate the seasonal pattern of sulfate, as a key component of the Arctic haze. Ionic balances indicated a strong sulfate seasonality with mean spring concentration about 1.5 times higher than that measured in summer. The spring and summer aerosol was almost neutral, indicating that ammonia was the major neutralizing agent for atmospheric acidic species. The linear regression between sulfate from potential acidic sources (non-sea salt sulfate and non-crustal sulfate) and ammonium indicated that the mean sulfate/ammonium ratio was intermediate between semi-(NH4HSO4) and complete ((NH4)2SO4) neutralization. Using sea-salt sodium as sea-spray marker, non-sea-salt calcium as crustal marker and methanesulfonic acid as biogenic marker, a detailed source apportionment for sulfate was carried out. The anthropogenic input (calculated as the differences between total sulfate and the sum of sea-salt, crustal and biogenic contributes) was found to be the most relevant contribution to the sulfate budget in the Ny-Ålesund aerosol in summer and, especially, in spring. In this last season, crustal, sea-salt, biogenic and anthropogenic sources accounted for 3.3, 12.0, 11.5 and 74.8 %, respectively.

Knowledge of the long-term variability of solar activity is of both astrophysical and geoscientific interest. Reconstructions of solar activity over multiple millennia are traditionally based on cosmogenic isotopes 14C or 10Be measured in natural terrestrial archives, but the two isotopes exhibit significant differences on millennial time scales, so that our knowledge of solar activity at this time scale remains somewhat uncertain. Here we present a new potential proxy of solar activity on the centennial-millennial time scale, based on a chemical tracer, viz. nitrate content in an ice core drilled at Talos Dome (Antarctica). We argue that this location is optimal for preserving the solar signal in the nitrate content during the Holocene. By using the firn core from the same location we show that the 11-year and Gleissberg cycles are present with the variability of 10 - 25 % in nitrate content in the pre-industrial epoch. This is consistent with the results of independent efforts of modeling HNO 3 and NO y in Antarctic near surface air. However, meteorological noise on the interannual scale makes it impossible to resolve individual solar cycles. Based on different processes of formation and transport compared to cosmogenic isotopes, it provides new, independent insight into long-term solar activity and helps resolve the uncertainties related to cosmogenic isotopes as diagnostics of solar activity. © 2012 Springer Science+Business Media B.V.

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.

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.

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.

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.

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.

article i nfo Article history: An integrated system, based on Inductively Coupled Plasma-Sector Field Mass Spectrometry (ICP-SFMS) and Inductively Coupled Plasma-Atomic Emission Spectrophotometry (ICP-AES) techniques, was optimised for the geochemical characterisation of soils and marine sediments. Sample mineralization was carried out with HF, HNO3 and HClO4. Operative blanks were at least two orders of magnitude lower than the lowest concentration measured in real samples. For ICP-SFMS, the detection power of the method in high resolution mode was sufficientforanaccuratequantificationofmetals,yetavoidingREEs'(RareEarthElements)isobaricinterferences. Once tested the accuracy on six certified materials, the methods were applied to the analysis of 39 major and trace metals on the top 90 m of sediments from the ANDRILL AND-1B core, covering the last million years. Stratigraphies of REEs and of normalised markers from this core clearly highlight a discontinuity at about 660,000 years before present. This pattern is well shown by the results of a PMF (Positive Matrix Factorization) statistical analysis, revealing two different sources for the sedimentary material, whose relative contribution changed around that time. Such a result is consistent with previous studies and confirms the net change in the provenance of glacial fluxes in the McMurdo region (Ross Ice Shelf, Antarctica) in the last million years.

Size-segregated particle samples were collected in the Arctic (Ny-Ålesund, Svalbard) in April 2011 both at ground level and in the free atmosphere exploiting a tethered balloon equipped also with an optical particle counter (OPC) and meteorological sensors. Individual particle properties were investigated by scanning electron microscopy coupled with energy dispersive microanalysis (SEM-EDS). Results of the SEM-EDS were integrated with particle size and optical measurements of the aerosols properties at ground level and along the vertical profiles. Detailed analysis of two case studies reveals significant differences in composition despite the similar structure (layering) and the comparable texture (grain size distribution) of particles in the air column. Differences in the mineral chemistry of samples point at both local (plutonic/metamorphic complexes in Svalbard) and remote (basic/ultrabasic magmatic complexes in Greenland and/or Iceland) geological source regions for dust. Differences in the particle size and shape are put into relationship with the mechanism of particle formation, that is, primary (well sorted, small) or secondary (idiomorphic, fine to coarse grained) origin for chloride and sulfate crystals and transport/settling for soil (silicate, carbonate and metal oxide) particles. The influence of size, shape, and mixing state of particles on ice nucleation and radiative properties is also discussed.

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.

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.

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.

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-μ gL −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 μ gL −1 ), reproducibility, and detection limit (0.02 μ gL −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.

© 2014 R. Traversi et al. Here we present the first multi-year record of nitrate in the atmospheric aerosol (2005-2008) and surface snow (2006-08) from central Antarctica. PM10 and size-segregated aerosol, together with superficial snow, have been collected all year-round at high resolution (daily for all the snow samples and for most of aerosol samples) at Dome C since the 2004/05 field season and analysed for main and trace ionic markers. The suitability of the sampling location in terms of possible contamination from the base is shown in detail. In spite of the relevance of nitrate in Antarctic atmosphere, both for better understanding the chemistry of N cycle in the plateau boundary layer and for improving the interpretation of long-term nitrate records from deep ice core records, nitrate sources in Antarctica are not well constrained yet, neither in extent nor in timing. A recurring seasonal pattern was pointed out in both aerosol and snow records, showing summer maxima and winter minima, although aerosol maxima lead the snow ones of 1-2 months, possibly due to a higher acidity in the atmosphere in mid-summer, favouring the repartition of nitrate as nitric acid and thus its uptake by the surface snow layers. On the basis of a meteorological analysis of one major nitrate event, of data related to PSC I extent and of irradiance values, we propose that the high nitrate summer levels in aerosol and snow are likely due to a synergy of enhanced source of nitrate and/or its precursors (such as the stratospheric inputs), higher solar irradiance and higher oxidation rates in this season. Moreover, we show here a further evidence of the substantial contribution of HNO3/NOx re-emission from the snowpack, already shown in previous works, and which can explain a significant fraction of atmospheric nitrate, maintaining the same seasonal pattern in the snow. As concerning snow specifically, the presented data suggest that nitrate is likely to be controlled mainly by atmospheric processes, not on the daily timescale but rather on the seasonal one., This research was performed in the framework of the Air-Glacs1181 'Station Concordia' project, which was funded by the MIUR through the Italian 'Programma Nazionale di Ricerche in Antartide' (PNRA) and in the framework of 'PRIDE' (2009/A2.21) and 'DECA-POL' (2010/A3.05) PNRA projects. The field operations benefited from the support of the French-Italian Concordia Station. This paper is a contribution to the HOLOCLIP project, which is funded by the European Science Foundation. This is HOLOCLIP publication no. 25. Meteorological data and information were obtained from IPEV/PNRA Project >Routine Meteorological Observation at Station Concordia - www.climantartide.it. Moreover, the authors appreciate the support of the AMRC, SSEC, UW-Madison for the data set, NSF grant numbers ANT-0944018 and ANT-1245663. B. Funke was supported by the Spanish MCINN under grant AYA2011-23552 and EC FEDER funds. We are grateful to the anonymous reviewers whose comments markedly improved the final manuscript.

Measurements of aerosol chemical composition made on the island of Lampedusa, south of the Sicily channel, during years 2004–2008, are used to identify the influence of heavy fuel oil (HFO) combustion emissions on aerosol particles in the Central Mediterranean. Aerosol samples influenced by HFO are characterized by elevated Ni and V soluble fraction (about 80% for aerosol from HFO combustion, versus about 40% for crustal particles), high V and Ni to Si ratios, and values of Vsol>6 ng m−3. Evidence of HFO combustion influence is found in 17% of the daily samples. Back trajectories analysis on the selected events show that air masses prevalently come from the Sicily channel region, where an intense ship traffic occurs. This behavior suggests that single fixed sources like refineries are not the main responsible for the elevated V and Ni events, which are probably mainly due to ships emissions. Vsol, Nisol, and non-sea salt SO42− (nssSO42−) show a marked seasonal behaviour, with an evident summer maximum. Such a pattern can be explained by several processes: (i) increased photochemical activity in summer, leading to a faster production of secondary aerosols, mainly nssSO42−, from the oxidation of SO2 (ii) stronger marine boundary layer (MBL) stability in summer, leading to higher concentration of emitted compounds in the lowest atmospheric layers. A very intense event in spring 2008 was studied in detail, also using size segregated chemical measurements. These data show that elements arising from heavy oil combustion (V, Ni, Al, Fe) are distributed in the sub-micrometric fraction of the aerosol, and the metals are present as free metals, carbonates, oxides hydrates or labile complex with organic ligands, so that they are dissolved in mild condition (HNO3, pH1.5). Data suggest a characteristic nssSO42−/V ratio in the range 200–400 for HFO combustion aerosols in summer at Lampedusa. By using the value of 200 a lower limit for the HFO contribution to total sulphates is estimated. HFO combustion emissions account, as a summer average, at least for 1.2 μg m−3, representing about 30% of the total nssSO42−, 3.9% of PM10, 8% of PM2.5, and 11% of PM1. Within the used dataset, sulphate from HFO combustion emissions reached the peak value of 6.1 μg m−3 on 26 June 2008, when it contributed by 47% to nssSO42−, and by 15% to PM10.

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. © 2007 Elsevier B.V. All rights reserved.

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.

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

Formaldehyde content within the first 16 m of Lys Glacier firn core (Monte Rosa massif, Italy) was determined by a sensitive spectrofluorimetric method in flow injection analysis. The formaldehyde concentration range of all analysed samples was 3.8–24.8 μg l −1 , with 11.1 μg l −1 mean concentration and 10.7 μg l −1 median concentration. These values were found to be in agreement with other measurements carried out in high- and mid-latitude glaciers. Due to the exceptionally high annual snow accumulation rate at Lys Glacier sampling site (3.79 m w.e.), most formaldehyde is preserved, at least for the earlier metres of deposition. The general agreement between the formaldehyde profile and other parameters typically used as seasonal markers suggested a similar seasonal behaviour for formaldehyde in high snow accumulation alpine sites.