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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.

19 pages, 9 figures, 1 table, Aerosols are an integral part of the Arctic climate system due to their direct interaction with radiation and indirect interaction through cloud formation. Understanding aerosol size distributions and their dynamics is crucial for the ability to predict these climate relevant effects. When of favourable size and composition, both long-rangetransported-and locally formed particles-may serve as cloud condensation nuclei (CCN). Small changes of composition or size may have a large impact on the low CCN concentrations currently characteristic of the Arctic environment. We present a cluster analysis of particle size distributions (PSDs; size range 8-500 nm) simultaneously collected from three high Arctic sites during a 3-year period (2013-2015). Two sites are located in the Svalbard archipelago: Zeppelin research station (ZEP; 474 m above ground) and the nearby Gruvebadet Observatory (GRU; about 2 km distance from Zeppelin, 67 m above ground). The third site (Villum Research Station at Station Nord, VRS; 30 m above ground) is 600 km west-northwest of Zeppelin, at the tip of northeastern Greenland. The GRU site is included in an inter-site comparison for the first time. K-means cluster analysis provided eight specific aerosol categories, further combined into broad PSD classes with similar characteristics, namely pristine low concentrations (12 %-14 % occurrence), new particle formation (16 %-32 %), Aitken (21 %-35 %) and accumulation (20 %-50 %). Confined for longer time periods by consolidated pack sea ice regions, the Greenland site GRU shows PSDs with lower ultrafine-mode aerosol concentrations during summer but higher accumulation-mode aerosol concentrations during winter, relative to the Svalbard sites. By association with chemical composition and cloud condensation nuclei properties, further conclusions can be derived. Three distinct types of accumulation-mode aerosol are observed during winter months. These are associated with sea spray (largest detectable sizes, > 400 nm), Arctic haze (main mode at 150 nm) and aged accumulation-mode (main mode at 220 nm) aerosols. In contrast, locally produced particles, most likely of marine biogenic origin, exhibit size distributions dominated by the nucleation and Aitken mode during summer months. The obtained data and analysis point towards future studies, including apportioning the relative contribution of primary and secondary aerosol formation pro cesses and elucidating anthropogenic aerosol dynamics and transport and removal processes across the Greenland Sea. In order to address important research questions in the Arctic on scales beyond a singular station or measurement events, it is imperative to continue strengthening international scientific cooperation, This research has been supported by the Spanish Ministry of Economy through project BIO-NUC (CGL2013-49020-R), PI-ICE (CTM2017-89117-R) and the Ramon y Cajal fellowship (RYC-2012-11922). The research leading to these results has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement no. 654109, the Danish Council for Independent Research (project NUMEN, DFF-FTP-4005-00485B) and previously from the European Union Seventh Framework Programme (FP7/2007-2013) under grant agreement no. 262254. The work at Villum Research Station, Station Nord, was financially supported by the Danish Environmental Protection Agency via the MIKA/DANCEA funds for Environmental Support to the Arctic Region. The Villum Foundation funded the construction of Villum Research Station, Station Nord. CCN measurements are supported by a KOPRI program (PN19081), funded by a National Research Foundation of Korea grant (NRF-2016M1A5A1901769). The authors acknowledge financial support (to David C. S. Beddows) from the Natural Environment Research Council's funding of the National Centre for Atmospheric Science (NCAS) (grant number R8/H12/83/011)

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

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

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 (

The results of a preliminary investigation of the dust sources in the Arctic based on their geochemical properties by potential source contribution function (PSCF) analysis are presented in this paper. For this purpose, we considered one year of aerosol geochemical data from Ny-Ålesund, Svalbard, and a short list of chemical elements (i.e., Al, Fe, Mn, Ti, Cr, V, Ni, Cu, and Zn) variably related to the dust fraction. Based on PSCF analysis: (i) four different dust source areas (i.e., Eurasia, Greenland, Arctic-Alaska, and Iceland) were characterized by distinguishing geochemical ranges and seasonal occurrence, and (ii) a series of typical dust days from the distinct source areas were identified based on the corresponding back trajectory patterns. Icelandic dust samples revealed peculiar but very variable characteristics in relation to their geographical source regions marked by air mass back trajectories. The comparison between pure and mixed Icelandic dust samples (i.e., aerosols containing Icelandic dust along with natural and/or anthropogenic components) revealed the occurrence of different mixing situations. Comparison with Icelandic soils proved the existence of dilution effects related to the emission and the transport processes.

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.

The current inadequate understanding of ice nucleating particle (INP) sources in the Arctic region affects the uncertainty in global radiative budgets and in regional climate predictions. In this study, we present atmospheric INP concentrations by offline analyses on samples collected at ground level in Ny-Ålesund (Svalbard), in spring and summer 2018. The ice nucleation properties of the samples were characterized by means of two offline instruments: the Dynamic Filter Processing Chamber (DFPC), detecting condensation freezing INPs, and the West Texas Cryogenic Refrigerator Applied to Freezing Test system (WT-CRAFT), measuring INPs by immersion freezing. Both measurements agreed within an order of magnitude although with some notable offset. INP concentration measured by DFPC ranged 33–185 (median 88), 5–107 (50) and 3–66 (20) m−3, for T = −22, −18 and −15 °C, respectively, while at the same activation temperatures WT-CRAFT measured 3–199 (26), 1–34 (6) and 1–4 (2) m−3, with an offset apparently dependent on the INP activation temperature. This observation may indicate a different sensitivity of Arctic INPs to different ice nucleation modes, even though a contribution from measurement and/or sampling uncertainties cannot be ruled out. An increase in the coarse INP fraction was observed from spring to summer, particularly at the warmest temperature (up to ~ 70 % at −15 °C). This suggests a non-negligible contribution from local sources of biogenic aerosol particles. This conclusion is also supported by the INP temperature spectra, showing ice-forming activity at temperatures higher than −15 °C. Contrary to recent works (e.g., INP measurements from Ny-Ålesund in 2012), our results do not show a sharp spring-to-summer increase of the INP concentration, with distinct behaviors for particles active in different temperature ranges. This likely indicates that the inter-annual variability of conditions affecting the INP emission by local sources may be wider than previously considered and suggests a complex interplay between INP sources. This demonstrate the necessity of further data coverage. Analysis of INP concentrations, active site density, low-travelling back-trajectories (

An extensive field campaign was carried out in Florence (Tuscany) to investigate the PM2.5 composition and to identify its sources. The scientific objective of this study is providing a reliable source apportionment, which is mandatory for the application of effective mitigation actions. Particulate matter (PM) was collected for one year, simultaneously in a traffic site, in an urban background, and in a regional background site. While the use of two filter types (quartz and Teflon) allowed obtaining a comprehensive chemical characterization (elemental and organic carbon, ions, elements) by the application of different analytical techniques, the location of the three sampling sites allowed getting a better separation among local, urban, regional and transboundary sources. During shorter periods, the aerosol was also collected by means of a streaker sampler and PIXE (Particle Induced X-ray Emission) analysis of these samples allowed the assessment of hourly resolution elemental time trends. Positive matrix factorisation (PMF) identified seven main sources: traffic, biomass burning, secondary sulphate, secondary nitrates, urban dust, Saharan dust and marine aerosol. Traffic mass concentration contributions were found to be strong only at the traffic site (~8 &mu, g&middot, m&minus, 3, 33% of PM2.5). Biomass burning turned out to be an important PM2.5 source in Florence (~4 &mu, 3), with very similar weights in both city sites while at the regional background site its weight was negligible. Secondary sulphate is an important PM2.5 source on a regional scale, with comparable values in all three sites (~3.5 &mu, 3). On average, the contribution of the &ldquo, natural&rdquo, components (e.g., mineral dust and marine aerosols) to PM2.5 is moderate (~1 &mu, 3) except during Saharan dust intrusions where this contribution is higher (detected simultaneously in all three sites). High-time resolution data confirmed and reinforced these results.

Different analytical techniques were used in this work to investigate the relationships between oxidative potential (OP) and metal, Br, P, S, and Se concentration in PM10 samples. Dithiothreitol and ascorbic acid acellular assays were used to determine the oxidative potential (OP) in PM10 samples. The particle-induced X-ray emission technique was used to estimate the mass concentration of specific chemical elements. PM10 samples were collected in Lecce, a coastal site of the Central Mediterranean away from large sources of local pollution. Both winter and spring samples were analyzed to study the seasonal dependence of the relationships between OP values and chemical element concentrations. The Redundancy Discriminant Analysis (RDA) was applied to (volume- and mass-normalized) OP values as response variables and metal, Br, P, S, and Se concentrations as explanatory variables. RDA triplots allowed to visualize the main relationships between PM10 OP values and corresponding chemical element concentrations. Spearman correlation coefficients were also used to investigate the relationships between OP values and metal, Br, P, S, and Se concentrations, besides comparing RDA outcomes. The integrated approach based on two different techniques allowed to better highlight the potentially harmful effects associated with specific metals and other chemical elements in PM10 samples.

This paper reports an exceptional biomass burning (BB) advection event from Alaska registered at Ny‐Alesund from 10 to 17 July 2015 with particular interest on the influence of the airborne particle characteristics on the optical properties of the aerosol during the event. To this purpose we considered two DEKATI 12‐stage aerosol samples spanning the entire advection and analyzed them by scanning electron microscopy techniques. Aerosol chemical data and microphysical properties were also evaluated in order to correlate any change of individual particle characteristics with the bulk properties of the aerosol. The results of individual particle analysis depict a complex event characterized by a first phase (P1) of massive input of BB carbonaceous particles (i.e., tar balls, popcorn refractory particles, and organic particles), and by a second phase (P2) dominated by inorganic salts. The peculiar feature of this BB event is the exceptionally large grain size of the subspherical organic particles at the beginning of the event with respect to the background. At these conditions a significant increase of the scattering efficiency may occur even for a small increase of the size parameter. Results of the simulation of the complex refractive indices (n‐ik) confirm this evaluation. Aerosol evolution during the event resulted from the combination of three distinct occurrences: (a) progressive rotation of air mass circulation toward non‐BB source areas, (b) development of a thick fog layer in the planetary boundary layer, and (c) sea salt spray direct advection of local/regional provenance.

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.

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.

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

A closure experiment was conducted over Svalbard by comparing Lidar measurements and optical aerosol properties calculated from aerosol vertical profiles measured using a tethered balloon. Arctic Haze was present together with Icelandic dust. Chemical analysis of filter samples, aerosol size distribution and a full set of meteorological parameters were determined at ground. Moreover, scanning electron microscopy coupled with energy-dispersive X-ray (SEM-EDS) data were at disposal showing the presence of several mineralogical phases (i.e., sheet silicates, gypsum, quartz, rutile, hematite). The closure experiment was set up by calculating the backscattering coefficients from tethered balloon data and comparing them with the corresponding lidar profiles. This was preformed in three subsequent steps aimed at determining the importance of a complete aerosol speciation: (i) a simple, columnar refractive index was obtained by the closest Aerosol Robotic Network (AERONET) station, (ii) the role of water-soluble components, elemental carbon and organic matter (EC/OM) was addressed, (iii) the dust composition was included. When considering the AERONET data, or only the ionic water-soluble components and the EC/OM fraction, results showed an underestimation of the backscattering lidar signal up to 76, 53 and 45% (355, 532 and 1064 nm). Instead, when the dust contribution was included, the underestimation disappeared and the vertically-averaged, backscattering coefficients (1.45±0.30, 0.69±0.15 and 0.34±0.08 Mm-1 sr-1, at 355, 532 and 1064 nm) were found in keeping with the lidar ones (1.60±0.22, 0.75±0.16 and 0.31±0.08 Mm-1 sr-1). Final results were characterized by low RMSE (0.36, 0.08 and 0.04 Mm-1 sr-1) and a high linear correlation (R2 of 0.992, 0.992 and 0.994) with slopes close to one (1.368, 0.931 and 0.977, respectively). This work highlighted the importance of all the aerosol components and of the synergy between single particle and bulk chemical analysis for the optical property characterization in the Arctic .

A methodology to detect the weekly cycle impact of the particulate matter (PM), and PM sources on the near surface temperature and wind speed is discussed in the paper. Chemically-speciated PM10 and PM2.5 samples are analyzed to detect the weekly cycle of both the PM mass concentrations and the PM sources identified by the Positive Matrix Factorization technique. The average percent departure (APD) of the PM mass concentration from the mean value calculated for each day of the week shows that a positive (higher values during midweek) and a negative (higher values during weekend) weekly cycle characterizes the PM10 and PM2.5 mass concentrations in Autumn-Winter (AW, September–February) and Spring-Summer (SS, March–August), respectively. The westerly transport of pollution seems to have a role on the negative PM weekly cycle found in SS. The analysis of the six identified aerosol sources indicates that in SS the mixed anthropogenic and the reacted dust sources likely impact the PM10 negative weekly cycle and that the mixed anthropogenic source likely impacts the PM2.5 negative weekly cycle. The mixed anthropogenic and soil dust sources likely affect in AW the positive weekly cycle of the PM10 mass concentration. Both sources in addition to the reacted dust source seem to affect the PM2.5 mass concentration in AW. The APD analysis of the temperature (T) and wind speed (WS) at the surface from measurements co-located in space and time with the PM ones reveals that the WS and T values are characterized by a negative weekly cycle in AW. Conversely, in SS, the WS-APD value decreases on Sunday and the T-APD values increase in the second half of the week. These last results likely give evidence of the PM impact on the near-surface temperature and wind speed at the study site.

We use an ultrahigh-resolution 15-T Fourier transform ion cyclotron resonance mass spectrometer to elucidate the compositional changes in Arctic organic aerosols collected at Ny-angstrom lesund, Sv ...

In this work, we analysed aerosol measurements from lidar and PM10 samples around the European Arctic site of Ny-Ålesund during late winter–early spring 2019. Lidar observations above 700 m revealed time-independent values for the aerosol backscatter coefficient (ββ), colour ratio (CR), linear particle depolarisation ratio (δδ) and lidar ratio (LR) from January to April. In contrast to previous years, in 2019 the early springtime backscatter increase in the troposphere, linked to Arctic haze, was not observed. In situ nss-sulphate (nss-SO42−) concentration was measured both at a coastal (Gruvebadet) and a mountain (Zeppelin) station, a few kilometres apart. As we employed different measurement techniques at sites embedded in complex orography, we investigated their agreement. From the lidar perspective, the aerosol load (indicated by ββ) above 700 m changed by less than a factor of 3.5. On the contrary, the daily nss-SO42− concentration erratically changed by a factor of 25 (from 0.1 to 2.5 ng m−3) both at Gruvebadet and Zeppelin station, with the latter mostly lying above the boundary layer. Moreover, daily nss-SO42− concentration was remarkably variable (correlation about 0.7 between the sites), despite its long-range origin. However, on a seasonal average basis the in situ sites agreed very well. Therefore, it can be argued that nss-SO42− advection mainly takes place in the lowest free troposphere, while under complex orography it is mixed downwards by local boundary layer processes. Our study suggests that at Arctic sites with complex orography ground-based aerosol properties show higher temporal variability compared to the free troposphere. This implies that the comparison between remote sensing and in situ observations might be more reasonable on longer time scales, i.e., monthly and seasonal basis even for nearby sites.

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 AIRUSE-LIFE+ project aims at characterizing similarities and heterogeneities in particulate matter (PM) sources and contributions in urban areas from southern Europe. Once the main PMx sources are identified, AIRUSE aims at developing and testing the efficiency of specific and non-specific measures to improve urban air quality. This article reports the results of the source apportionment of PM and PM conducted at three urban background sites (Barcelona, Florence and Milan, BCN-UB, FI-UB and MLN-UB), one suburban background site (Athens, ATH-SUB) and one traffic site (Porto, POR-TR). After collecting 1047 PM and 1116 PM 24 h samples during 12 months (from January 2013 on) simultaneously at the five cities, these were analysed for the contents of OC, EC, anions, cations, major and trace elements and levoglucosan. The USEPA PMF5 receptor model was applied to these data sets in a harmonized way for each city. The sum of vehicle exhaust (VEX) and non-exhaust (NEX) contributes between 3.9 and 10.8 μ (16-32 %) to PM and 2.3 and 9.4 μ (15-36 %) to PM, although a fraction of secondary nitrate is also traffic-related but could not be estimated. Important contributions arise from secondary particles (nitrate, sulfate and organics) in PM (37-82 %) but also in PM (40-71 %), mostly at background sites, revealing the importance of abating gaseous precursors in designing air quality plans. Biomass burning (BB) contributions vary widely, from 14-24 % of PM in POR-TR, MLN-UB and FI-UB, 7 % in ATH-SUB, to < 2 % in BCN-UB. In PM, BB is the second most important source in MLN-UB (21 %) and in POR-TR (18 %), the third one in FI-UB (21 %) and ATH-SUB (11 %), but is again negligible (< 2 %) in BCN-UB. This large variability among cities is mostly due to the degree of penetration of biomass for residential heating. In Barcelona natural gas is very well supplied across the city and is used as fuel in 96 % of homes, while in other cities, PM levels increase on an annual basis by 1-9 μ due to biomass burning influence. Other significant sources are the following. - Local dust, 7-12 % of PM10 at SUB and UB sites and 19 % at the TR site, revealing a contribution from road dust resuspension. In PM2.5 percentages decrease to 2-7 % at SUB-UB sites and 15 % at the TR site. - Industry, mainly metallurgy, contributing 4-11 % of PM (5-12 % in PM), but only at BCN-UB, POR-TR and MLN-UB. No clear impact of industrial emissions was found in FI-UB and ATH-SUB. - Natural contributions from sea salt (13 % of PM10 in POR-TR, but only 2-7 % in the other cities) and Saharan dust (14 % in ATH-SUB, but less than 4 % in the other cities). During high pollution days, the largest sources (i.e. excluding secondary aerosol factors) of PM10 and PM2.5 are VEX + NEX in BCN-UB (27-22 %) and POR-TR (31-33 %), BB in FI-UB (30-33 %) and MLN-UB (35-26 %) and Saharan dust in ATH-SUB (52-45 %). During those days, there are also quite important industrial contributions in BCN-UB (17-18 %) and local dust in POR-TR (28-20 %)., Acknowledgements.This work was funded by the AIRUSE LIFE+(ENV/ES/584) EU project. Fulvio Amato is a beneficiary of theJuan de la Cierva postdoctoral grant (JCI-2012-13473) from theSpanish Ministry of Economy and Competitiveness. Danilo Custó-dio acknowledges the doctoral fellowship SFRH/BD/76283/2011from the Portuguese Science Foundation. Support is acknowledgedto Generalitat de Catalunya 2014 SGR33 and to AXA Research Fund

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.

Major explosive volcanic eruptions may significantly alter the global atmosphere for about 2&ndash, 3 years. During that period, volcanic products (mainly H2SO4) with high residence time, stored in the stratosphere or, for shorter times, in the troposphere are gradually deposited onto polar ice caps. Antarctic snow may thus record acidic signals providing a history of past volcanic events. The high resolution sulphate concentration profile along a 197 m long ice core drilled at GV7 (Northern Victoria land) was obtained by Ion Chromatography on around 3500 discrete samples. The relatively high accumulation rate (241 &plusmn, 13 mm we yr &minus, 1) and the 5-cm sampling resolution allowed a preliminary counted age scale. The obtained stratigraphy covers roughly the last millennium and 24 major volcanic eruptions were identified, dated, and tentatively ascribed to a source volcano. The deposition flux of volcanic sulphate was calculated for each signature and the results were compared with data from other Antarctic ice cores at regional and continental scale. Our results show that the regional variability is of the same order of magnitude as the continental one.

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

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.

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.

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

In this paper, results on the potential toxicity of ultrafine particles (UFPs d

Two common types of wood (beech and fir) were burned in commercial pellet (11.1 kW) and wood (8.2 kW) stoves following a combustion cycle simulating the behavior of a real-world user. Ultrafine particulate matter (UFP, dp

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

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.

In remote marine areas, biogenic productivity and atmospheric particulate are coupled through dimethylsulfide (DMS) emission by phytoplankton. Once in the atmosphere, the gaseous DMS is oxidized to produce H2SO4 and methanesulfonic acid (MSA), both species can affect the formation of cloud condensation nuclei. This study analyses eight years of biogenic aerosol evolution and variability at two Arctic sites: Thule (76.5&deg, N, 68.8&deg, W) and Ny &Aring, lesund (78.9&deg, N, 11.9&deg, E). Sea ice plays a key role in determining the MSA concentration in polar regions. At the beginning of the melting season, in April, up to June, the biogenic aerosol concentration appears inversely correlated with sea ice extent and area, and positively correlated with the extent of the ice-free area in the marginal ice zone (IF-MIZ). The upper ocean stratification induced by sea ice melting might have a role in these correlations, since the springtime formation of this surface layer regulates the accumulation of phytoplankton and nutrients, allowing the DMS to escape from the sea to the atmosphere. The multiyear analysis reveals a progressive decrease in MSA concentration in May at Thule and an increase in July August at Ny &Aring, lesund. Therefore, while the MSA seasonal evolution is mainly related with the sea ice retreat in April, May, and June, the IF-MIZ extent appears as the main factor affecting the longer-term behavior of MSA.

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.

This work is part of the TOBICUP (TOxicity of BIomass Combustion generated Ultrafine Particles) project which aimed at providing the composition of ultrafine particles (UFPs, i.e. particles with aerodynamic diameter, dae, lower than 100nm) emitted by wood combustion and elucidating the related toxicity. Results here reported are from two ambient monitoring campaigns carried out at an alpine town in Northern Italy, where wood burning is largely diffused for domestic heating in winter. Wintertime and summertime UFP samples were analyzed to assess their chemical composition (i.e. elements, ions, total carbon, anhydrosugars, and polycyclic aromatic hydrocarbons) and biological activity. The induction of the pro-inflammatory cytokine interleukin-8 (IL-8) by UFPs was investigated in two human cells lines (A549 and THP-1) and in human peripheral blood leukocytes. In addition, UFP-induced oxidative stress and genotoxicity were investigated in A549 cells. Ambient UFP-related effects were compared to those induced by traffic-emitted particles (DEP) taken from the NIES reference material "vehicle exhaust particulates". Ambient air UFPs induced a dose-related IL-8 release in both A549 and THP-1 cells; the effect was more relevant on summer samples and in general THP-1 cells were more sensitive than A549 cells. On a weight basis our data did not support a higher biological activity of ambient UFPs compared to DEP. The production of IL-8 in the whole blood assay indicated that UFPs reached systemic circulation and activated blood leukocytes. Comet assay and γ-H2AX evaluation showed a significant DNA damage especially in winter UFPs samples compared to control samples. Our study showed that ambient UFPs can evoke a pulmonary inflammatory response by inducing a dose-related IL-8 production and DNA damage, with different responses to UFP samples collected in the summer and winter periods.

This study aimed to collect, characterize ultrafine particles (UFP) generated from the combustion of wood pellets and logs (softwood and hardwood) and to evaluate their pro-inflammatory effects in THP-1 and A549 cells. Both cell lines responded to UFP producing interleukin-8 (IL-8), with wood log UFP being more active compared to pellet UFP. With the exception of higher effect observed with beech wood log UFP in THP-1, the ability of soft or hard woods to induce IL-8 release was similar. In addition, on weight mass, IL-8 release was similar or lower compared to diesel exhaust particles (DEP), arguing against higher biological activity of smaller size particles. UFP-induced IL-8 could be reduced by SB203580, indicating a role of p38MAPK activation in IL-8 production. The higher activity of beech wood log UFP in THP-1 was not due to higher uptake or endotoxin contamination. Qualitatively different protein adsorption profiles were observed, with less proteins bound to beech UFP compared to conifer UFP or DEP, which may provide higher intracellular availability of bioactive components, i.e. levoglucosan and galactosan, toward which THP-1 were more responsive compared to A549 cells. These results contribute to our understanding of particles emitted by domestic appliances and their biological effects.

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 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).

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.

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.

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.

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.

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.

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