Bromine, iodine and sodium along the EAIIST traverse: Bulk and surface snow latitudinal variability.

During the East Antarctic International Ice Sheet Traverse (Eaiist, december 2019), in an unexplored part of the East Antarctic Plateau, snow samples were collected to expand our knowledge of the latitudinal variability of iodine, bromine and sodium as well as their relation in connection with emission processes and photochemical activation in this unexplored area. A total of 32 surface (0-5 cm) and 32 bulk (average of 1 m depth) samples were taken and analysed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Our results show that there is no relevant latitudinal trend for bromine and sodium. For bromine they also show that it has no significant post-depositional mechanisms while its inland surface snow concentration is influenced by spring coastal bromine explosions. Iodine concentrations are several orders of magnitude lower than bromine and sodium and they show a decreasing trend in the surface samples concentration moving southward. This suggests that other processes affect its accumulation in surface snow, probably related to the radial reduction in the ozone layer moving towards central Antarctica. Even though all iodine, bromine and sodium present similar long-range transport from the dominant coastal Antarctic sources, the annual seasonal cycle of the ozone hole over Antarctica increases the amount of UV radiation (in the 280-320 nm range) reaching the surface, thereby affecting the surface snow photoactivation of iodine. A comparison between the bulk and surface samples supports the conclusion that iodine undergoes spring and summer snow recycling that increases its atmospheric lifetime, while it tends to accumulate during the winter months when photochemistry ceases.

Airborne bacteria structure and chemical composition relationships in winter and spring PM10 samples over southeastern Italy.

The Redundancy Discrimination Analysis (RDA) and Spearman correlation coefficients were used to investigate relationships between airborne bacteria at the phylum and genus level and chemical species in winter and spring PM10 samples over Southeastern Italy. The identification of main chemical species/pollution sources that were related to and likely affected the bacterial community structure was the main goal of this work. The 16S rRNA gene metabarcoding approach was used to characterize airborne bacteria. Seventeen phyla and seventy-nine genera contributing each by mean within-sample relative abundance percentage > 0.01% were identified in PM10 samples, which were chemically characterized for 33 species, including ions, metals, OC, and EC (organic and elemental carbon, respectively). Chemical species were associated with six different pollution sources. A shift from winter to spring in both bacterial community structure and chemical species mass concentrations/sources and the relationships between them was observed. RDA triplots pointed out significant correlations for all tested bacterial phyla (genera) with other phyla (genera) and/or with chemical species, in contrast to correlation coefficient results, which showed that few phyla (genera) were significantly correlated with chemical species. More specifically, in winter Bacillus and Chryseobacterium were the only genera significantly correlated with chemical species likely associated with particles from soil-dust and anthropogenic pollution source, respectively. In spring, Enterobacter and Sphingomonas were the only genera significantly correlated with chemical species likely associated with particles from the anthropogenic pollution and the marine and soil-dust sources, respectively. The results of this study also showed that the correlation coefficients were the best tool to obtain unequivocal identifications of the correlations of phyla (genera) with chemical species. The seasonal changes of the PM10 chemical composition, the microbial community structure, and their relationships suggested that the seasonal changes of atmospheric particles may have likely contributed to seasonal changes of bacterial community in the atmosphere.

Aerosol optical properties in the Arctic: The role of aerosol chemistry and dust composition in a closure experiment between Lidar and tethered balloon vertical profiles.

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 ±â€¯0.30, 0.69 ±â€¯0.15 and 0.34 ±â€¯0.08 Mm-1 sr-1, at 355, 532 and 1064 nm) were found in keeping with the lidar ones (1.60 ±â€¯0.22, 0.75 ±â€¯0.16 and 0.31 ±â€¯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.

Combined use of daily and hourly data sets for the source apportionment of particulate matter near a waste incinerator plant.

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.

Arctic sea ice melt leads to atmospheric new particle formation.

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.

Prominent features in isotopic, chemical and dust stratigraphies from coastal East Antarctic ice sheet (Eastern Wilkes Land).

In this work we present the isotopic, chemical and dust stratigraphies of two snow pits sampled in 2013/14 at 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 ± 71 mm w.e. for the period 2008-2013. Methanesulfonic acid and NO3- do not show any concentration decreasing trend as depth increases, also considering a 12 m 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.

Sea salt sodium record from Talos Dome (East Antarctica) as a potential proxy of the Antarctic past sea ice extent.

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.

Multi-year record of atmospheric and snow surface nitrate in the central Antarctic plateau.

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.

The Laschamp geomagnetic excursion featured in nitrate record from EPICA-Dome C ice core.

Here we present the first direct comparison of cosmogenic (10)Be 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 (10)Be and nitrate at this time. The evident preferential association of (10)Be 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 (10)Be 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.

Biomass burning contributions estimated by synergistic coupling of daily and hourly aerosol composition records.

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 diameter<10 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).

Ultra-sensitive Flow Injection Analysis (FIA) determination of calcium in ice cores at ppt level.

A Flow Injection Analysis (FIA) spectrofluorimetric method for calcium determination in ice cores was optimised in order to achieve better analytical performances which would make it suitable for reliable calcium measurements at ppt level. The method here optimised is based on the formation of a fluorescent compound between Ca and Quin-2 in buffered environment. A careful evaluation of operative parameters (reagent concentration, buffer composition and concentration, pH), influence of interfering species possibly present in real samples and potential favourable effect of surfactant addition was carried out. The obtained detection limit is around 15 ppt, which is one order of magnitude lower than the most sensitive Flow Analysis method for Ca determination currently available in literature and reproducibility is better than 4% for Ca concentrations of 0.2 ppb. The method was validated through measurements performed in parallel with Ion Chromatography on 200 samples from an alpine ice core (Lys Glacier) revealing an excellent fit between the two chemical series. Calcium stratigraphy in Lys ice core was discussed in terms of seasonal pattern and occurrence of Saharan dust events.

Southern Ocean sea-ice extent, productivity and iron flux over the past eight glacial cycles.

Sea ice and dust flux increased greatly in the Southern Ocean during the last glacial period. Palaeorecords provide contradictory evidence about marine productivity in this region, but beyond one glacial cycle, data were sparse. Here we present continuous chemical proxy data spanning the last eight glacial cycles (740,000 years) from the Dome C Antarctic ice core. These data constrain winter sea-ice extent in the Indian Ocean, Southern Ocean biogenic productivity and Patagonian climatic conditions. We found that maximum sea-ice extent is closely tied to Antarctic temperature on multi-millennial timescales, but less so on shorter timescales. Biological dimethylsulphide emissions south of the polar front seem to have changed little with climate, suggesting that sulphur compounds were not active in climate regulation. We observe large glacial-interglacial contrasts in iron deposition, which we infer reflects strongly changing Patagonian conditions. During glacial terminations, changes in Patagonia apparently preceded sea-ice reduction, indicating that multiple mechanisms may be responsible for different phases of CO2 increase during glacial terminations. We observe no changes in internal climatic feedbacks that could have caused the change in amplitude of Antarctic temperature variations observed 440,000 years ago.

Chemical composition and physical features of summer aerosol at Terra Nova Bay and Dome C, Antarctica.

During the 2002-2003 austral summer field season, aerosol samples were collected at a coastal (Terra Nova Bay--Northern Victoria Land) and an inland site (Dome C--East Antarctic Plateau). The sampling was carried out by stacked filter units made up of two filters at different porosity (5.0 and 0.4 microm at Terra Nova Bay and 3.0 and 0.4 microm at Dome C), able to roughly separate a coarse from a fine fraction. At Dome C, a further investigation on aerosol size distribution was performed by an inertial impactor able to collect aerosol particles on 8 size classes (from 10 to 0.4 microm). Atomic Force Microscopy was applied to the filter collecting the finer fraction in both sites in order to assess the real cut-off value of the filter sandwich apparatus and to reconstruct the volume size distribution. At the employed flow conditions, the real cut-off value was revealed to be about one third with respect to the filter nominal porosity in both stations. The size distribution plots showed a bimodal distribution with a mode centered around 0.22 microm in both the sites and a second broader mode which is centered between 0.3 microm and 1.2 microm diameter at Terra Nova Bay and shifted toward higher values (centred around 1.0 microm diameter) at Dome C. Each filter was analysed for the main and trace ionic components allowing evaluation of the contributions of primary and secondary aerosol sources at the two sites as a function of the particle size class. The coastal site is mainly affected by primary and secondary marine inputs: the sea spray contribution (Na+, Mg2+, Cl- and ssSO4(2-)) is dominant (77% w/w) in the coarse fraction whereas the biogenic source (methanesulfonate and nssSO4(2-)) prevails (67.5% w/w) in the fine fraction. In this fraction a significant contribution (15.5% w/w) is provided by ammonium likely to be related to surrounding penguin colonies. Dome C atmosphere is characterised by fine particles arising from secondary sources and long-range transport processes. The main component in the fine and coarse fractions at Dome C is sulfate whose nssSO4(2-) represents the 99.5% and the 92.3%(w/w) in fine and coarse fraction, respectively. The observed agreement between nssSO4(2-) and methanesulfonate temporal profiles in the fine fraction demonstrates that biogenic emissions dominate the inland background aerosol. Results from the sampling by the 8-stage impactor at Dome C are presented here: chloride and nitrate are mainly deposited on the 10-2.1 microm stages while the highest sulfate concentration was found in the submicrometric fraction which turned out to be the most acidic. Such a distribution is able to prevent nitrate and chloride re-emission as gaseous HCl and HNO3 in the 10-2.1 microm stages, arising from the exchange reaction between chloride and nitrate salts and sulfuric acid. Moreover, the concentration peak observed for nitrate in coarser fractions is probably related also to the formation of hygroscopic NH4NO3 particles and nitrate adsorption on sea salt particles.

Formaldehyde determination in seawater. Preliminary application to coastal samples at Terra Nova Bay (Antarctica).

A sensitive spectrofluorimetric-FIA (flow injection analysis) method for formaldehyde (HCHO) determination was improved with the aim of analysing seawater samples. The fluorescence emission versus HCHO concentration shows a linear pattern from sub microg L(-1) to about 1000 microg L(-1). The reproducibility at 15 ppb level is about 2%. Interferences from other aldehydes were checked; only glyoxal shows a significative interference, but only when its concentration is about 6000 times higher than that of formaldehyde. Superficial (microlayer, just sub-pack or sea-ice free sea surface) and deep (along the water column, sub-pack or in sea-ice free areas) seawater samples were collected near the coast at Terra Nova Bay (Ross Sea, Antarctica) during the 1998/1999 and 2001/2002 Italian Antarctic Expedition. We report here the preliminary results of the spectrofluorimetric-FIA determination of the HCHO content. The mean seawater superficial formaldehyde concentration was 15 microg L(-1); the concentration along the water column ranged between 4.5 to over 40 microg L(-1)(20 microg L(-1) mean concentration), usually with a maximum value for the 30 m depth, corresponding to a fluorescence maximum. The sampling was repeated 7 times in the austral summer in order to evaluate seasonal changes in the formaldehyde concentration/seawater depth profiles. The results show changes in the formaldehyde concentration at different depths.