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Seasonal to interannual variations in the concentrations of sulfur aerosols (

Seasonal to interannual variations in the concentrations of sulfur aerosols (

Ice core dating is the first step for a correct interpretation of climatic and environmental changes. In this work, we release the dating of the uppermost 197 m of the 250 m deep GV7(B) ice core (drill site, 70∘41′ S, 158∘52′ E; 1950 m a.s.l. in Oates Land, East Antarctica) with a sub-annual resolution. Chemical records of NO3-, MSA (methanesulfonic acid), non-sea-salt SO42- (nssSO42-), sea-salt ions and water stable isotopes (δ18O) were studied as candidates for dating due to their seasonal pattern. Different procedures were tested but the nssSO42- record proved to be the most reliable on the short- and long-term scales, so it was chosen for annual layer counting along the whole ice core. The dating was constrained by using volcanic signatures from historically known events as tie points, thus providing an accurate age–depth relationship for the period 1179–2009 CE. The achievement of the complete age scale allowed us to calculate the annual mean accumulation rate throughout the analyzed 197 m of the core, yielding an annually resolved history of the snow accumulation on site in the last millennium. A small yet consistent rise in accumulation rate (Tr = 1.6, p<0.001) was found for the last 830 years starting around mid-18th century.

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

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

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.

The Biogenic Aerosol and Primary Production in the Ross Sea – BioAPRoS project, funded by funded by the Ministry for the Education, University and Scientific Research (MIUR) through the National Antarctic Research Programme (PNRA) aims to improve the understanding of the ocean-atmosphere interactions with particular attention to the interconnections between oceanic primary production and atmospheric gaseous and particulate compounds. These processes have a strong climatic relevance due to the aerosol interaction with solar radiation, its possible interaction with cloud formation and properties, in a region where other aerosol sources are very limited. To achieve the objectives of the project, measurements and sampling in the atmosphere (dimethylsulfide, in the gas phase, and methanesulfonic acid, sugars, amino acids and methoxyphenols in the aerosols) and in sea water (nutrients, chlorophyll, phytoplankton composition and physiological state, DMSP as a precursor of atmospheric DMS) were carried out simultaneously for the first time at the Italian "Mario Zucchelli" Station (MZS; 74.7°S, 164.1°E).We report here the data obtained in two Antarctic field campaigns carried out in summers of 2018-19 and 2019-20. The DMS atmospheric concentration was measured directly in situ by Gas Chromatography. It showed concentrations up to 921 pptv (the highest value obtained in both campaigns); the timing of maximum concentration was strongly related to the timing of sea ice melting in the surrounding oceanic areas. Within the project, the low-cost ACHAB (Antartic low-Cost Hydro Arduino Bio-optic profiler) probe has been developed for the acquisition of physical and bio-optical data along the water column, during the 2019-20 campaign. Furthermore, the Phyto-VFP (Phytoplankton Variable Fluorescence Production) bio-optical model was refined to be applied to the Southern Ocean for the estimation of primary production in Terranova Bay and Ross Sea at micro and mesoscale resolutions, respectively. Phyto-VFP was specifically set-up using as input chl a satellite data (merged products based on MODIS-A, MERIS, SeaWIFS, VIIRS-N for low resolution images and Sentinel-2 for high resolution ones) as well as the photosynthetic parameters obtained from a series of laboratory experiments conducted on polar species, enabling to take into account the effect of a nutrient limitation on their photosynthetic performance.The evolution of concentration of the atmospheric compounds arising from phytoplankton activity was investigated with respect to oceanic parameters (chlorophyll and primary productivity, in turn related to the phytoplankton taxonomic composition and physiological state), to the variations of solar and photosynthetically active radiation, and to the dynamics of sea ice in the Ross Sea.Understanding and quantifying the correlation between atmospheric compounds and oceanic primary productivity (affecting the oceanic and atmospheric CO2 budget) has a relevant importance in studies on global change because this interaction is influenced by, and in its turn influences, climatic variations.

We examined the relationships linking in-situ measurements of gas-phase methanesulfonic acid (MSA), sulfuric acid (SA), iodic acid (HIO3), Highly Oxidized Organic Molecules (HOM) and aerosol size-distributions with satellite-derived chlorophyll (Chl-a) and oceanic primary production (PP). Atmospheric data were collected at Ny-Ålesund site during spring-summer 2017 (30th March-4th August). We compared ocean color data from Barents Sea and Greenland Sea with concentrations of low-volatile vapours and new particle formation. The aim is to understand the main factors controlling the concentrations of atmospheric components in the Arctic in different ocean domains and seasons. Early phytoplanktonic bloom starting in April at the marginal ice zone caused Chl-a and PP in the Barents Sea to be higher than in the Greenland Sea during spring, whereas the pattern was opposite in summer. We found the correlation between ocean color data (Chl-a and PP) and MSA decreasing from spring to summer in Barents Sea and increasing in Greenland Sea. This establishes relationship between sea ice melting and phytoplanktonic bloom, which starts by sea ice melting. Similar pattern was observed for SA. Also HIO3 in both ocean domains correlated with Chl-a and PP during spring time. Greenland Sea was more active than Barents Sea. These results suggest that marine phytoplankton metabolism is an important source of MSA and SA, as expected, but also a source of HIO3 precursors (such as I2). HOMs had low correlation with ocean color parameters in comparison to other atmospheric vapours in this study both in spring and summer. The plausible explanation for low correlation is that the primary source of Volatile Organic Compounds (VOC) – precursors of HOM – is the soil of Svalbard archipelago rather than ocean. During spring, nucleation mode particles were found to correlate with Chl-a at Barents Sea and with PP at Greenland Sea. This means that biogenic productivity has a strong impact on new particle formation in spring although small particles are not related to biogenic parameters in summer.

Marine phytoplankton production (PP) represents an influential force on the carbon cycle and the climatic processes on a global scale, being responsible for up to 40% of the biological fixation of atmospheric CO2. Understanding and predicting the effects of climate change on marine phytoplankton is crucial within the analysis of climate change scenarios as it affects the ecological responses of the higher trophic levels. In this context, the development of predictive models for the estimation of PP provides useful scientific responses to address the issues of sustainability in a climatically changing world. The need to estimate PP more accurately allows to face the impacts of global change on highly vulnerable areas such as such as regional seas and polar regions. In this work we present the Phyto-VFP (Variable Fluorescence Phytoplankton Production), a new bio-optical model which enables to compute PP by integrating the effects of the photo-acclimation processes of phytoplankton with the dynamic conditions of the water column. To parametrise the photo-physiological behavour of phytoplankton cells a series of laboratory experiments based on in vivo variable fluorescence measures were conducted on culture species selected according to the ecological features of the investigated areas. The performance of Phyto-VFP was evaluated with concurrent estimates of radiocarbon (14C) uptakes and the results obtained with the use of the Morel bio-optical model, under different dynamic and optical conditions, during two oceanographic cruises in the Mediterranean Sea. Here we present the results of the model validation as well as the application of Phyto-VFP model to different highly vulnerable regions to climate change.

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 at the Island of Lampedusa, a remote site in the Central Mediterranean Sea (Med Sea), close to the Sahara desert, between 19 March 2015 and 1 April 2017. The main goals of this work are: to quantify total atmospheric deposition of DOM in this area and to evaluate the impact of 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 allow to estimate 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 phosphorous (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 at Lampedusa site mainly have natural origin, especially from sea spray and that Saharan dust can be an important carrier of organic substances, even if the load of DOC associated with dust is highly variable. Our estimates suggest that atmospheric input has an impact to the Med Sea larger than to the global ocean and that DOC fluxes from the atmosphere to the Med Sea can be up to 6-fold larger than river input. Longer time series, combined with a modelling effort, are therefore mandatory in order to investigate the response of DOM dynamics in the Med Sea to the change in aerosol deposition pattern due to the effect of climate change.

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

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

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

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 .

In this paper, we have applied an extensive back-trajectory calculation to describe a complex atmospheric circulation pattern in the Central Mediterranean, registered in late spring 2013, which led to successive advections of biomass burning and Saharan dust aerosols over Italy. We based our study on chemical results obtained at the two background Italian sites of Monte Martano and Lampedusa. The two sites feature different local aerosol sources and are geographically distant. In order to distinguish the contribution of long-range sources associated with the advection event, we set up a potential source contribution function analysis of the chemical composition of PM10 sampled at both sites. The main goal was to individuate the variability of the aerosol composition associated with the long-range transport and to trace back the source areas. We discussed the case of study in the context of the unusual synoptic meteorological conditions during the observational period. The wide geographical scale covered in this study allowed us to explore the extent to which an aerosol intrusion from Eastern Europe may impact on the Central Mediterranean. Also, we pointed out how a sudden shift of the synoptic meteorological conditions can induce, in a few days, a complete change in the chemistry of airborne dust, due to a contribution from Sahara, which was more significant in Central Italy with respect to lower latitudes.

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.

Understanding aerosol size distributions is crucial to our ability to predict aerosol number concentrations. When of favourable size and composition, both long range transported particles as well as locally formed ones may serve as Cloud Condensation Nuclei (CCN); small changes may have a large impact on the low CCN concentrations currently characteristic of the Arctic environment. Here, we present a cluster analysis of particle size distributions (PSD, size range 8–500 nm) simultaneously collected from three high Arctic sites across Europe during a three year period (2013–2015). Two sites are located in the Svalbard archipelago: Zeppelin research station (474 m above ground), and the nearby Gruvebadet Observatory (about 2 km distance from Zepplelin, 67 m above ground). The third site (Villum Research Station – Station Nord, 30 m above ground) is 600 km to the west-northwest of Zeppelin, at the tip of north-eastern Greenland. An inter-site comparison exercise is carried out for the first time including the Gruvebadet site. K-means analysis provided eight specific aerosol categories, further combined into broad PSD with similar characteristics, namely: pristine low concentrations (12–14 %), 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 shows PSD 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, associated with sea spray (largest detectable sizes), Arctic haze (main mode at 150 nm) and aged accumulation mode (main mode at 220 nm) aerosols. In contrast, locally produced and most likely of marine biogenic origin particles exhibit size distributions dominated by the nucleation and Atiken mode aerosol during summer months. The obtained data and analysis set now the stage for future studies; including apportioning the relative contribution of primary and secondary aerosol formation processes to the aerosol size distribution in high Arctic, and elucidating anthropogenic aerosol dynamics, transport and removal processes across the Greenland sea. In a region of enormous importance for future climate on Earth, it is imperative to continue strengthening international scientific cooperation, in order to address important research questions on scales beyond singular station or measurement events.

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 Mediterranean Basin atmosphere is influenced by both strong natural and anthropogenic aerosol emissions, and is also subject to important climatic forcings. Several programs have addressed the study of the Mediterranean basin; nevertheless important pieces of information are still missing. In this framework, PM10 samples were collected on a daily basis on the island of Lampedusa (35.5° N, 12.6° E, 45 m a.s.l.), which is far from continental pollution sources (the nearest coast, in Tunisia, is more than 100 km away). After mass gravimetric measurements, different portions of the samples were analyzed to determine the ionic content by Ion Chromatography (IC), the soluble metals by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES), and the total (soluble + insoluble) elemental composition by Particle Induced X-ray Emission (PIXE). Data from years 2007 and 2008 are used in this study. The Positive Matrix Factorization (PMF) model was applied to the 2 year long data set of PM10 mass concentration and chemical composition to assess the aerosol sources affecting the Central Mediterranean basin. Seven sources were resolved: sea-salt, mineral dust, biogenic emissions, primary particulate ship emissions, secondary sulphate, secondary nitrate, and combustion emissions. Source contributions to the total PM10 mass were estimated to be about 40 % for sea-salt, around 25 % for mineral dust, 10 % each for secondary nitrate and secondary sulphate, and 5 % each for primary particulate ship emissions, biogenic emissions, and combustion emissions. Large variations in absolute and relative contributions are found and appear to depend on the season and on transport episodes. In addition, the secondary sulphate due to ship emissions was estimated, and found to contribute by about one third to the total sulphate mass. Results for the sea-salt and mineral dust sources were compared with estimates of the same contributions obtained from independent approaches, leading to an estimate of the water content bound to the sea salt in the marine source.

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

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

Biomass burning (BB) is a significant source of particulate matter (PM) in many parts of the world. Whereas numerous studies demonstrate the relevance of BB emissions in central and northern Europe, the quantification of this source has been assessed only in few cities in southern European countries. In this work, the application of Positive Matrix Factorisation (PMF) allowed a clear identification and quantification of an unexpected very high biomass burning contribution in Tuscany (central Italy), in the most polluted site of the PATOS project. In this urban background site, BB accounted for 37% of the mass of PM10 (particulate matter with aerodynamic diameter10 μm) as annual average, and more than 50% during winter, being the main cause of all the PM10 limit exceedances. Due to the chemical complexity of BB emissions, an accurate assessment of this source contribution is not always easily achievable using just a single tracer. The present work takes advantage of the combination of a long-term daily data-set, characterized by an extended chemical speciation, with a short-term high time resolution (1-hour) and size-segregated data-set, obtained by PIXE analyses of streaker samples. The hourly time pattern of the BB source, characterised by a periodic behaviour with peaks starting at about 6 p.m. and lasting all the evening-night, and its strong seasonality, with higher values in the winter period, clearly confirmed the hypothesis of a domestic heating source (also excluding important contributions from wildfires and agricultural wastes burning).

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

Solar radiation plays an important role in several terrestrial, atmospheric and biogeochemical processes, and in climate. This study focusses on the verification of a method for the determination of PAR, the Photosynthetically Active Radiation. The method is based on the use of measurements made with Multifilter Rotating Shadowband Radiometers (MFRSR). The MFRSR measures global and diffuse components of the solar irradiance in six narrowband and one broadband channel; four of the MFRSR bands fall within the spectral range of PAR. This study is based on measurements made at the Station for Climate Observations, on the island of Lampedusa, in the central Mediterranean. MFRSR measurements at Lampedusa are continuously calibrated on-site by using the Langley plot method. The MFRSR signals in the four bands within the PAR spectral interval are linearly combined to infer the corresponding PAR. The method is verified by comparing PAR determinations in days with very different aerosol and cloud conditions. A very good agreement between measured and estimated PAR is found in all conditions, confirming that the method has the capability to accurately retrieve PAR irradiances. The variability of the PAR diffuse component appears also well described. © 2017 Author(s).

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.