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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 aim of the presented study was to investigate the impact on the radiation budget of a biomass-burning plume, transported from Alaska to the High Arctic region of Ny-Ålesund, Svalbard, in early July 2015. Since the mean aerosol optical depth increased by the factor of 10 above the average summer background values, this large aerosol load event is considered particularly exceptional in the last 25 years. In situ data with hygroscopic growth equations, as well as remote sensing measurements as inputs to radiative transfer models, were used, in order to estimate biases associated with (i) hygroscopicity, (ii) variability of single-scattering albedo profiles, and (iii) plane-parallel closure of the modelled atmosphere. A chemical weather model with satellite-derived biomass-burning emissions was applied to interpret the transport and transformation pathways. The provided MODTRAN radiative transfer model (RTM) simulations for the smoke event (14:00 9 July–11:30 11 July) resulted in a mean aerosol direct radiative forcing at the levels of −78.9 and −47.0 W m−2 at the surface and at the top of the atmosphere, respectively, for the mean value of aerosol optical depth equal to 0.64 at 550 nm. This corresponded to the average clear-sky direct radiative forcing of −43.3 W m−2, estimated by radiometer and model simulations at the surface. Ultimately, uncertainty associated with the plane-parallel atmosphere approximation altered results by about 2 W m−2. Furthermore, model-derived aerosol direct radiative forcing efficiency reached on average −126 W m−2∕τ550 and −71 W m−2∕τ550 at the surface and at the top of the atmosphere, respectively. The heating rate, estimated at up to 1.8 K day−1 inside the biomass-burning plume, implied vertical mixing with turbulent kinetic energy of 0.3 m2 s−2.

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

The Toba eruption that occurred some 74 ka ago in Sumatra, Indonesia, is among the largest volcanic events on Earth over the last 2 million years. Tephra from this eruption has been spread over vast areas in Asia, where it constitutes a major time marker close to the Marine Isotope Stage 4/5 boundary. As yet, no tephra associated with Toba has been identified in Greenland or Antarctic ice cores. Based on new accurate dating of Toba tephra and on accurately dated European stalagmites, the Toba event is known to occur between the onsets of Greenland interstadials (GI) 19 and 20. Furthermore, the existing linking of Greenland and Antarctic ice cores by gas records and by the bipolar seesaw hypothesis suggests that the Antarctic counterpart is situated between Antarctic Isotope Maxima (AIM) 19 and 20. In this work we suggest a direct synchronization of Greenland (NGRIP) and Antarctic (EDML) ice cores at the Toba eruption based on matching of a pattern of bipolar volcanic spikes. Annual layer counting between volcanic spikes in both cores allows for a unique match. We first demonstrate this bipolar matching technique at the already synchronized Laschamp geomagnetic excursion (41 ka BP) before we apply it to the suggested Toba interval. The Toba synchronization pattern covers some 2000 yr in GI-20 and AIM-19/20 and includes nine acidity peaks that are recognized in both ice cores. The suggested bipolar Toba synchronization has decadal precision. It thus allows a determination of the exact phasing of inter-hemispheric climate in a time interval of poorly constrained ice core records, and it allows for a discussion of the climatic impact of the Toba eruption in a global perspective. The bipolar linking gives no support for a long-term global cooling caused by the Toba eruption as Antarctica experiences a major warming shortly after the event. Furthermore, our bipolar match provides a way to place palaeo-environmental records other than ice cores into a precise climatic context.

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.

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.

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.

An extended study on the oxidative potential (OP) of PM10 particles collected from December 2014 to October 2015 at a peninsular site of the Central Mediterranean basin has been performed. PM10 particles have been selected to better account for all different aged/fresh particle types. Two acellular assays, i.e., the dithiothreitol (DTT) and ascorbic acid (AA) methods, were used to measure the OP of PM10 particles chemically speciated by more than 40 species. DTT and AA assays provide close mean values of volume normalized OPV responses, with similar variability range, i.e., mean OPDTTV = 0.24 ± 0.12 nmolDTT min−1 m−3 and mean OPAAV = 0.29 ± 0.18 nmolAA min−1 m−3. Also mass normalized OPm responses are similar for both assays, with mean value close to 0.008 nmol min−1 μg−1. The measured OPDTTV and OPAAV are correlated with several inorganic species, namely ions and metals, and with organic/elemental carbon. The discrimination of the data according seasonality, i.e., Autumn-Winter (AW, October–March) and Spring-Summer (SS, April–September) days, shows a clear seasonal trend of correlation coefficients. In AW, OPDTTV is strongly correlated with nss-K+ and nss-Ca2+, in addition to Ba, Cd, Ce, Cr, Cu, Fe, and Mn (traffic-related metals) and with EC, OC, and POC associated with the traffic exhaust source and/or with the combustion including biomass-burning source. Otherwise, OPDTTV of SS samples is correlated only with NH4+, Cu, EC, OC, and POC. The OPAAV of AW samples is well correlated with Ba, Ce, Cr, Cu, Fe, Mn, nss-K+, EC, OC, and POC, which are related with traffic and/or combustion emissions. Conversely, in SS, OPAAV is mainly correlated with NH4+, nss-K+, nss-Mg2+, nss-Ca2+, nss-SO42−, Cu, Mn, P, Pb, and oxalate, that are species related to secondary aerosols and resuspended soil from vehicular traffic and/or transported Saharan dust. These findings point the importance of both organic components and transition metals to PM oxidative properties, and also suggest that synergistic/antagonistic interactions and cross-correlations between the PM redox-active components are likely responsible for the seasonal variation of the AA and DTT assay response. The inter-correlation among all analysed species has been investigated to explain contrasting results and the negative correlations between OP values and some chemical species.

This work focuses on the near-surface O3 variability over the eastern Antarctic Plateau. In particular, eight years (2006–2013) of continuous observations at the WMO/GAW contributing station “Concordia” (Dome C–DMC: 75°06′S, 123°20′E, 3280 m) are presented, in the framework of the Italian Antarctic Research Programme (PNRA). First, the characterization of seasonal and diurnal O3 variability at DMC is provided. Then, for the period of highest data coverage (2008–2013), we investigated the role of specific atmospheric processes in affecting near-surface summer O3 variability, when O3 enhancement events (OEEs) are systematically observed at DMC (average monthly frequency peaking up to 60% in December). As deduced by a statistical selection methodology, these OEEs are affected by a significant interannual variability, both in their average O3 values and in their frequency. To explain part of this variability, we analyzed OEEs as a function of specific atmospheric variables and processes: (i) total column of O3 (TCO) and UV-A irradiance, (ii) long-range transport of air masses over the Antarctic Plateau (by Lagrangian back-trajectory analysis – LAGRANTO), (iii) occurrence of “deep” stratospheric intrusion events (by using the Lagrangian tool STLEFLUX). The overall near-surface O3 variability at DMC is controlled by a day-to-day pattern, which strongly points towards a dominating influence of processes occurring at “synoptic” scales rather than “local” processes. Even if previous studies suggested an inverse relationship between OEEs and TCO, we found a slight tendency for the annual frequency of OEEs to be higher when TCO values are higher over DMC. The annual occurrence of OEEs at DMC seems related to the total time spent by air masses over the Antarctic plateau before their arrival to DMC, suggesting the accumulation of photochemically-produced O3 during the transport, rather than a more efficient local production. Moreover, the identification of recent (i.e., 4-day old) stratospheric intrusion events by STEFLUX suggested only a minor influence (up to 3% of the period, in November) of “deep” events on the variability of near-surface summer O3 at DMC. © 2018 The Authors

Background: Platinum-based drugs such as Cisplatin are commonly employed for cancer treatment. Despite an initial therapeutic response, Cisplatin treatment often results in the development of chemoresistance. To identify novel approaches to overcome Cisplatin resistance, we tested Cisplatin in combination with K+ channel modulators on colorectal cancer (CRC) cells. Methods: The functional expression of Ca2+-activated (KCa3.1, also known as KCNN4) and voltage-dependent (Kv11.1, also known as KCNH2 or hERG1) K+ channels was determined in two CRC cell lines (HCT-116 and HCT-8) by molecular and electrophysiological techniques. Cisplatin and several K+ channel modulators were tested in vitro for their action on K+ currents, cell vitality, apoptosis, cell cycle, proliferation, intracellular signalling and Platinum uptake. These effects were also analysed in a mouse model mimicking Cisplatin resistance. Results: Cisplatin-resistant CRC cells expressed higher levels of KCa3.1 and Kv11.1 channels, compared with Cisplatin-sensitive CRC cells. In resistant cells, KCa3.1 activators (SKA-31) and Kv11.1 inhibitors (E4031) had a synergistic action with Cisplatin in triggering apoptosis and inhibiting proliferation. The effect was maximal when KCa3.1 activation and Kv11.1 inhibition were combined. In fact, similar results were produced by Riluzole, which is able to both activate KCa3.1 and inhibit Kv11.1. Cisplatin uptake into resistant cells depended on KCa3.1 channel activity, as it was potentiated by KCa3.1 activators. Kv11.1 blockade led to increased KCa3.1 expression and thereby stimulated Cisplatin uptake. Finally, the combined administration of a KCa3.1 activator and a Kv11.1 inhibitor also overcame Cisplatin resistance in vivo. Conclusions: As Riluzole, an activator of KCa3.1 and inhibitor of Kv11.1 channels, is in clinical use, our results suggest that this compound may be useful in the clinic to improve Cisplatin efficacy and overcome Cisplatin resistance in CRC. Published version

The aim of the presented study was to investigate the impact on the radiation budget of biomass burning smoke plume transported from Alaska to high Arctic region (Ny-Alesund, Svalbard) in early July 2015. This high aerosol load event is considered exceptional in the last 25 years with mean aerosol optical depth increased by the factor of 10 in comparison to the average summer background values. We utilised in-situ data with hygroscopic growth equations as well as remote sensing measurements as inputs to radiative transfer models with an objective to estimate biases associated with (i) hygroscopicity, (ii) variability of ω profiles and (iii) plane-parallel closure of the modelled atmosphere. A chemical weather model with satellite-derived biomass burning emissions was used to interpret the transport and transformations pathways. Provided MODTRAN simulations resulted in the mean aerosol direct radiative forcing on the level of −78.9 W m−2 and −47.0 W m−2 at the surface and the top of the atmosphere respectively for the mean value of aerosol optical depth equal to 0.64 at 550 nm. It corresponded to the average clear-sky direct radiative forcing of −43.3 W m−2 estimated by radiometers and model simulations. Furthermore, model-derived aerosol direct radiative forcing efficiency reached on average −126 W m−2 / τ550 and −71 W m−2 / τ550 at the surface and at the top of the atmosphere. Estimated heating rate up to 1.8 K day−1 inside the BB plume implied vertical mixing with the turbulent kinetic energy of 0.3 m2 s−2. Ultimately, uncertainty connected with the plane-parallel atmosphere approximation altered results by about 2 W m−2.

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).

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, 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 not 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 to the permafrost dynamics at the ground and several accumulation windows were recognized coherently to the meteo-climatic conditions occurring at the study site.

Background: Platinum-based drugs such as Cisplatin are commonly employed for cancer treatment. Despite an initial therapeutic response, Cisplatin treatment often results in the development of chemoresistance. To identify novel approaches to overcome Cisplatin resistance, we tested Cisplatin in combination with K+ channel modulators on colorectal cancer (CRC) cells. Methods: The functional expression of Ca2+-activated (KCa3.1, also known as KCNN4) and voltage-dependent (Kv11.1, also known as KCNH2 or hERG1) K+ channels was determined in two CRC cell lines (HCT-116 and HCT-8) by molecular and electrophysiological techniques. Cisplatin and several K+ channel modulators were tested in vitro for their action on K+ currents, cell vitality, apoptosis, cell cycle, proliferation, intracellular signalling and Platinum uptake. These effects were also analysed in a mouse model mimicking Cisplatin resistance. Results: Cisplatin-resistant CRC cells expressed higher levels of KCa3.1 and Kv11.1 channels, compared with Cisplatin-sensitive CRC cells. In resistant cells, KCa3.1 activators (SKA-31) and Kv11.1 inhibitors (E4031) had a synergistic action with Cisplatin in triggering apoptosis and inhibiting proliferation. The effect was maximal when KCa3.1 activation and Kv11.1 inhibition were combined. In fact, similar results were produced by Riluzole, which is able to both activate KCa3.1 and inhibit Kv11.1. Cisplatin uptake into resistant cells depended on KCa3.1 channel activity, as it was potentiated by KCa3.1 activators. Kv11.1 blockade led to increased KCa3.1 expression and thereby stimulated Cisplatin uptake. Finally, the combined administration of a KCa3.1 activator and a Kv11.1 inhibitor also overcame Cisplatin resistance in vivo. Conclusions: As Riluzole, an activator of KCa3.1 and inhibitor of Kv11.1 channels, is in clinical use, our results suggest that this compound may be useful in the clinic to improve Cisplatin efficacy and overcome Cisplatin resistance in CRC.

Dall'Osto, Manuel ... et al.-- 10 pages, 6 figures, supporting information https://dx.doi.org/10.1038/s41598-017-03328-1, Atmospheric new particle formation (NPF) and growth significantly influences climate by supplying new seeds for cloud condensation and brightness. Currently, there is a lack of understanding of whether and how marine biota emissions affect aerosol-cloud-climate interactions in the Arctic. Here, the aerosol population was categorised via cluster analysis of aerosol size distributions taken at Mt Zeppelin (Svalbard) during a 11 year record. The daily temporal occurrence of NPF events likely caused by nucleation in the polar marine boundary layer was quantified annually as 18%, with a peak of 51% during summer months. Air mass trajectory analysis and atmospheric nitrogen and sulphur tracers link these frequent nucleation events to biogenic precursors released by open water and melting sea ice regions. The occurrence of such events across a full decade was anti-correlated with sea ice extent. New particles originating from open water and open pack ice increased the cloud condensation nuclei concentration background by at least ca. 20%, supporting a marine biosphere-climate link through sea ice melt and low altitude clouds that may have contributed to accelerate Arctic warming. Our results prompt a better representation of biogenic aerosol sources in Arctic climate models, The study was funded by the Spanish Ministry of Economy through projects BIO-NUC (CGL2013-49020-R), and by the EU though the FP7-PEOPLE-2013-IOF programme (Project number 624680, MANU – Marine Aerosol NUcleations) and the Ramon y Cajal fellowship (RYC-2012-11922). CCNC measurement was supported by KOPRI project PN16081.The National Centre for Atmospheric Science NCAS Birmingham group is funded by the UK Natural Environment Research Council

The connection between marine biogenic dimethyl sulfide (DMS) and the formation of aerosol particles in the Arctic atmosphere was evaluated by analyzing atmospheric DMS mixing ratios, aerosol particle size distributions and aerosol chemical composition data that were concurrently collected at Ny-Ålesund, Svalbard (78.5° N, 11.8° E) during April and May 2015. Measurements of aerosol sulfur (S) compounds showed distinct patterns during periods of Arctic haze (April) and phytoplankton blooms (May). Specifically, during the phytoplankton bloom period the contribution of DMS-derived SO42− to the total aerosol SO42− increased by 7-fold compared with that during the proceeding Arctic haze period, accounting for up to 70 % of fine SO42− particles (

In this work we present the isotopic, chemical and dust stratigraphies of two snow pits sampled in 2013/14at GV7 (coastal East Antarctica: 70°41′ S - 158°51′ E, 1950 m a.s.l.). A large number of chemical species are measured aiming to study their potentiality as environmental changes markers. Seasonal cluster backward trajectories analysis was performed and compared with chemical marker stratigraphies. Sea spray aerosol is delivered to the sampling site together with snow precipitation especially in autumn-winter by air masses arising from Western Pacific Ocean sector. Dust show maximum concentration in spring when the air masses arising from Ross Sea sector mobilize mineral dust from ice-free areas of the Transantarctic mountains. The clear seasonal pattern of sulfur oxidized compounds allows the dating of the snow-pit and the calculation of the mean accumulation rate, which is 242±71mm w.e. for the period 2008–2013. Methanesulfonic acid and NO3− do not show any concentration decreasing trend as depth increases, also considering a 12m firn core record. Therefore these two compounds are not affected by post-depositional processes at this site and can be considered reliable markers for past environmental changes reconstruction. The rBC snow-pit record shows the highest values in summer 2012 likely related to large biomass burning even occurred in Australia in this summer. The undisturbed accumulation rate for this site is demonstrated by the agreement between the chemical stratigraphies and the annual accumulation rate of the two snow-pits analysed in Italian and Korean laboratories.

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

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

Particulate matter with aerodynamic diameters lower than 10 µm, (PM10) aerosol samples were collected during summer 2013 within the framework of the Chemistry and Aerosol Mediterranean Experiment (ChArMEx) at two sites located north (Capo Granitola) and south (Lampedusa Island), respectively, of the main Mediterranean shipping route in the Straight of Sicily. The PM10 samples were collected with 12 h time resolutions at both sites. Selected metals, main anions, cations and elemental and organic carbon were determined. The evolution of soluble V and Ni concentrations (typical markers of heavy fuel oil combustion) was related to meteorology and ship traffic intensity in the Straight of Sicily, using a high-resolution regional model for calculation of back trajectories. Elevated concentration of V and Ni at Capo Granitola and Lampedusa are found to correspond with air masses from the Straight of Sicily and coincidences between trajectories and positions of large ships; the vertical structure of the planetary boundary layer also appears to play a role, with high V values associated with strong inversions and a stable boundary layer. The V concentration was generally lower at Lampedusa than at Capo Granitola V, where it reached a peak value of 40 ng m−3. Concentrations of rare earth elements (REEs), La and Ce in particular, were used to identify possible contributions from refineries, whose emissions are also characterized by elevated V and Ni amounts; refinery emissions are expected to display high La ∕ Ce and La ∕ V ratios due to the use of La in the fluid catalytic converter systems. In general, low La ∕ Ce and La ∕ V ratios were observed in the PM samples. The combination of the analyses based on chemical markers, air mass trajectories and ship routes allows us to unambiguously identify the large role of the ship source in the Straight of Sicily. Based on the sampled aerosols, ratios of the main aerosol species arising from ship emission with respect to V were estimated with the aim of deriving a lower limit for the total ship contribution to PM10. The estimated minimum ship emission contributions to PM10 were 2.0 µg m−3 at Lampedusa and 3.0 µg m−3 at Capo Granitola, corresponding with 11 and 8.6 % of PM10, respectively.

This study aims to determine the mineral contribution to PM10 in the central Mediterranean Sea, based on 7 yr of daily PM10 samplings made on the island of Lampedusa (35.5° N, 12.6° E). The chemical composition of the PM10 samples was determined by ion chromatography for the main ions, and, on selected samples, by particle-induced X-ray emission (PIXE) for the total content of crustal markers. Aerosol optical depth measurements were carried out in parallel to the PM10 sampling. The average PM10 concentration at Lampedusa over the period June 2004–December 2010 is 31.5 μg m−3, with low interannual variability. The annual means are below the EU annual standard for PM10, but 9.9% of the total number of daily data exceeds the daily threshold value established by the European Commission for PM (50 μg m−3, European Community, EC/30/1999). The Saharan dust contribution to PM10 was derived by calculating the contribution of Al, Si, Fe, Ti, non-sea-salt (nss) Ca, nssNa, and nssK oxides in samples in which PIXE data were available. Cases in which crustal content exceeded the 75th percentile of the crustal oxide content distribution were identified as elevated dust events. Using this threshold, we obtained 175 events. Fifty-five elevated dust events (31.6%) displayed PM10 higher than 50 μg m−3, with dust contributing by 33% on average. The crustal contribution to PM10 has an annual average value of 5.42 μg m−3, and reaches a value as high as 67.9 μg m−3 (corresponding to 49% of PM10) during an intense Saharan dust event. The crustal content estimated from a single tracer, such as Al or Ca, is in good agreement with the one calculated as the sum of the metal oxides. Conversely, larger crustal contents are derived by applying the EU guidelines for demonstration and subtraction of exceedances in PM10 levels due to high background of natural aerosol. The crustal aerosol amount and contribution to PM10 showed a very small seasonal dependence; conversely, the dust columnar burden displays an evident annual cycle, with a strong summer maximum (monthly average aerosol optical depth at 500 nm up to 0.28 in June–August). We found that 71.3% of the dust events identified from optical properties over the atmospheric column display a high dust content at the ground level. Conversely, the remaining 28.7% of cases present a negligible or small impact on the surface aerosol composition due to the transport processes over the Mediterranean Sea, where dust frequently travels above the marine boundary layer, especially in summer. Based on backward trajectories, two regions, one in Algeria–Tunisia, and one in Libya, are identified as main source areas for intense dust episodes occurring mainly in autumn and winter. Data on the bulk composition of mineral aerosol arising from these two source areas are scarce; results on characteristic ratios between elements show somewhat higher values of Ca / Al and (Ca + Mg) / Fe (2.5 ± 1.0, and 4.7 ± 2.0, respectively) for Algeria–Tunisia than for Libyan origin (Ca / Al = 1.9 ± 0.7 and (Ca + Mg) / Fe = 3.3 ± 1.1).

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.

Organic (OC) and elemental carbon (EC), inorganic ions (Cl−, NO3−, SO42−, Na+, NH4+, K+, Ca2+), methanesulfonate (MSA−) and metals (Al, Fe, Pb, Mn, Ba, V) were monitored in PM1 and PM2.5 samples collected at a suburban site in south-eastern Italy, to contribute to the characterisation of fine particles in the Central Mediterranean. Mean mass concentrations are 13 µg/m3 and 22 µg/m3 in PM1 and PM2.5, respectively. OC, EC, SO42−, NH4+, NO3−, K+ and Ca2+ are predominant components and account for 54% and 56% of the PM1 and PM2.5 mass, respectively. OC, EC, SO42−, NH4+, K+ and Ca2+ concentrations lie in the range of the corresponding ones measured in PM1 and PM2.5 samples collected at suburban/urban Mediterranean sites. NO3− and trace element concentrations lie in the range of the corresponding ones measured in PM1 and PM2.5 samples collected at remote/background Mediterranean sites. The biogenic nss-SO42− accounts for ~5% and 4% of nss-SO42− in PM1 and PM2.5, respectively. The seasonal trend of the component...

In this paper we present results from a systematic study of vertical profiles of aerosol number size distribution and black carbon (BC) concentrations conducted in the Arctic, over Ny-Ålesund (Svalbard). The campaign lasted 2 years (2011–2012) and resulted in 200 vertical profiles measured during the spring and summer seasons. In addition, chemical analysis of filter samples, aerosol size distribution and a full set of meteorological parameters were determined at ground to put on a firmer grounds the analysis of the vertical profiles. The collected experimental data allowed a classification of the vertical profiles into different typologies which allowed to describe a seasonal phenomenology of vertical aerosol properties in the Arctic. During spring, four main types of profiles were found and their behaviour was related to the main aerosol and atmospheric dynamics occurring at the measuring site. Background conditions generated homogenous profiles. Transport events caused an increase of aerosol concentration with altitude. High Arctic haze pollution trapped below thermal inversions promoted a decrease of aerosol concentration with altitude. Finally, ground-based plumes of locally formed secondary aerosol determined profiles with decreasing aerosol concentration located at different altitude in function of size. During the summer season, the impact from shipping caused aerosol and BC pollution plumes constrained close to the ground, indicating that increasing shipping emissions in the Arctic could bring anthropogenic aerosol and BC in the summer Arctic affecting the climate.

In this work multi wavelength Raman lidar data from Ny-Ålesund, Spitsbergen have been analysed for the spring 2014 Arctic haze season, as part of the iAREA campaign. Typical values and probability distributions for aerosol backscatter, extinction and depolarisation, the lidar ratio and the color ratio for 4 different altitude intervals within the troposphere are given. These quantities and their dependencies are analysed and the frequency of altitude-dependent observed aerosol events are given. A comparison with ground-based size distribution and chemical composition is performed. Hence the aim of this paper is to provide typical and statistically meaningful properties of Arctic aerosol, which may be used in climate models or to constrain the radiative forcing. We have found that the 2014 season was only moderately polluted with Arctic haze and that sea salt and sulphate were the most dominant aerosol species. Moreover the drying of an aerosol layer after cloud disintegration has been observed. Hardly any clear temporal evolution over the 4 week data set on Arctic haze is obvious with the exception of the extinction coefficient and the lidar ratio, which significantly decreased below 2 km altitude by end April. In altitudes between 2 and 5 km the haze season lasted longer and the aerosol properties were generally more homogeneous than closer to the surface. Above 5 km only few particles were found. The variability of the lidar ratio is discussed. It was found that knowledge of the aerosol’s size and shape does not determine the lidar ratio. Contrary to shape and lidar ratio, there is a clear correlation between size and backscatter: larger particles show a higher backscatter coefficient.

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).

Atmospheric particulate matter (PM10) was collected at Ny-Alesund (Svalbard Islands, Norwegian Arctic) during spring and summer from 2010 to 2014 and analysed for lead content, enrichment factor and isotopic composition (208Pb/206Pb and 207Pb/206Pb). It was found that atmospheric lead was mainly of anthropogenic origin and neither its mean concentration, nor its isotopic composition was subjected to significant inter-annual differences (p-value > 0.1). Seasonal differences in both lead content and isotopic compositions occurred (p-value 0.3), showing a prolonged influence of Eurasian sources also in summer. The results obtained by the Pb isotopic composition were corroborated by a back-trajectory cluster analysis of air-masses reaching the sampling site.

Aerosol samplings were performed both at ground level and at different heights upon the Ny-Alesund polar station in June–July 2012 using a tethered balloon equipped with a sampling pump and meteorological sensors. The samples were analyzed by ion chromatography and scanning electron microscopy to characterize the sources and the evolution of the aerosol particles in the planetary boundary layer. The results show the main contribution of long-range over local/regional transported particles and sediments in the aerosols in the period of interest. Among the long-range sources, a main contribution was represented by Siberian local soils and regional wildfires which provided typical particles (metal oxides, calcareous grains), and ion species (nss-K+, nss-SO4 2−) to the aerosols. Among the local sources, a main contribution was represented by fly ash emitted by the cruise ships frequently landing around Ny-Alesund during summer. Another aspect which results from aerosol particle characterization is the clear stratification of the planetary boundary layer upon Ny-Alesund. This typical feature, which has been already documented in spring on the same site (Moroni et al. 2015), is quite effective also in summertime despite the higher potential of local dust production and the lower atmospheric stability characterizing this period.

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.

The object of this study was to investigate the different modal behavior of ultrafine aerosol particles collected at the Gruvebadet observatory located in Ny-lesund (Svalbard Islands, 78A degrees 55'N, 11A degrees 56'E). Aerosol particle size distribution was measured in the size range from 10 to 470 nm typically from the beginning of spring to the beginning of fall during four (non-consecutive) years (2010, 2011, 2013 and 2014). The median concentration for the whole period taken into account was 214 particles cm(-3), oscillating between the median maximum in July with a concentration of 257 particles cm(-3) and a median minimum in April with 197 particles cm(-3). The median total number concentration did not present a well-defined seasonal behavior, as shown by contrast looking at the sub/modal number concentration, where distinct trends appeared in the predominant accumulation concentration recorded during April/May and the preponderant concentration of Aitken particles during the summer months. Lastly, the short side-by-side spring 2013 campaign performed at the Zeppelin observatory with a differential mobility particle sizer was characterized by an aerosol concentration mean steady difference between the two instruments of around 14 %, thereby supporting the reliability of the device located at Gruvebadet.

Size-segregated (PM10) aerosol samples have been systematically collected at Ny-Alesund (Svalbard Islands, Norwegian Arctic) during the spring and summer 2010 and analysed for elemental composition (major and trace elements, rare earth elements) and stable lead isotope ratios (206Pb/207Pb, 208Pb/207Pb). The analysis of the obtained dataset provided valuable information on the sources and long-range transport processes of atmospheric particulate and associated contaminants reaching the Arctic. In particular, a seasonal pattern was evident for Ba, Cd, Mn, Mo, Pb (p value ≤0.05), showing a higher input of elements related to anthropogenic emissions in spring compared to summer. Pb isotope ratios clearly showed that the geographic source of the anthropogenic input is subjected to a seasonal shift with an increased contribution of air masses coming from the north Eurasia during spring, and air masses coming from North America during summer. This finding was further corroborated by back-trajectory analysis. Finally, the analysis of the rare earth elements revealed an uniform pattern, without significant differences between the two seasons.

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.

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.

Sea-salt aerosol (SSA) is the dominant contributor to cloud condensation nuclei over ocean areas, where wind speed is significant. Thereby, SSA could affect cloud formation and play an important role in the Earth weather and climate. Rainfall could produce large impact on SSA concentration due to wet removal processes. An analysis of changes in sea-salt aerosol concentration after rainfall is essential for a deeper understanding of the process of SSA loading in the boundary layer. The current experimental study focused on analyzing time variations of SSA mass concentration after rainfall, on the basis of long-term daily SSA measurements during the three-year period 2006–2008, at the tiny Mediterranean island of Lampedusa (Central Mediterranean). To study the effect of rainfall on SSA time variations, we used the superposed epoch method. We applied this approach to differing rainfall events related to different months and atmospheric/sea conditions. Integrated processing was applied to SSA concentration anomalies, in order to filter out random variability. Observational evidence of SSA mass concentration oscillations after rainfall with a maximum on the 2nd day and a minimum on the 4th day was obtained. The knowledge of SSA variations after rainfall is important for validating rainout parameterization in existing sea-salt aerosol and climate models.

The age scale synchronisation between the Talos Dome and the EPICA Dome C ice cores was carried on through the identification of several common volcanic signatures. This paper describes the rigorous method, using the signature of volcanic sulphate, which was employed for the last 42 kyr of the record. Using this tight stratigraphic link, we transferred the EDC age scale to the Talos Dome ice core, producing a new age scale for the last 12 kyr. We estimated the discrepancies between the modelled TALDICE-1 age scale and the new scale during the studied period, by evaluating the ratio R of the apparent duration of temporal intervals between pairs of isochrones. Except for a very few cases, R ranges between 0.8 and 1.2, corresponding to an uncertainty of up to 20% in the estimate of the time duration in at least one of the two ice cores. At this stage our approach does not allow us to unequivocally identify which of the models is affected by errors, but, taking into account only the historically known volcanic events, we found that discrepancies up to 200 yr appear in the last two millennia in the TALDICE-1 model, while our new age scale shows a much better agreement with the volcanic absolute horizons. Thus, we propose for the Talos Dome ice core a new age scale (covering the whole Holocene) obtained by a direct transfer, via our stratigraphic link, from the EDC modelled age scale by Lemieux-Dudon et al. (2010).