Contaminants of emerging concern in water and sediment of the Venice Lagoon, Italy.

This study investigates for the first time the contamination of water and sediment of the Venice Lagoon by twenty Contaminants of Emerging Concern (CECs): three hormones, six pharmaceutical compounds (diclofenac and five antibiotics, three of which are macrolides), nine pesticides (methiocarb, oxadiazon, metaflumizone, triallate, and five neonicotinoids), one antioxidant (BHT), and one UV filter (EHMC). Water and sediment samples were collected in seven sites in four seasons, with the aim of investigating the occurrence, distribution, and possible emission sources of the selected CECs in the studied transitional environment. The most frequently detected contaminants in water were neonicotinoid insecticides (with a frequency of quantification of single contaminants ranging from 73% to 92%), and EHMC (detected in the 77% of samples), followed by BHT (42%), diclofenac (39%), and clarithromycin (35%). In sediment the highest quantification frequencies were those of BHT (54%), estrogens (ranging from 35% to 65%), and azithromycin (46%). Although this baseline study does not highlight seasonal or spatial trends, results suggested that two of the major emission sources of CECs in the Venice Lagoon could be tributary rivers from its drainage basin and treated wastewater, due to the limited removal rates of some CECs in WWTPs. These preliminary results call for further investigations to better map priority emission sources and improve the understanding of CECs environmental behavior, with the final aim of drawing up a site-specific Watch List of CECs for the Venice Lagoon and support the design of more comprehensive monitoring plans in the future.

Neonicotinoids and pharmaceuticals in hair of the Red fox (Vulpes vulpes) from the Cavallino-Treporti peninsula, Italy.

Neonicotinoids (NEOs) and active pharmaceuticals ingredients (API) are contaminants widely diffused worldwide, causing increasing concern for potential adverse effects on wildlife. However, research on these contaminants have focused on target and non-target invertebrates, while information on potential effects in terrestrial mammals is lacking. We performed preliminary non-invasive monitoring of NEOs and API in a suburban and agricultural area using hair of the Red fox. The Red fox is a widely diffused mesopredator in Europe, and its plasticity in feeding habits makes it an excellent indicator for assessing exposure to environmental contamination. We observed the presence of NEOs in many Red fox hair samples (n = 11), including imidacloprid (IMI), acetamiprid (ACE), and clothianidin (CLO). The highest quantified concentrations were 6.4 ng g-1 dry weight (dw), 6.7 ng g-1 dw, and 0.9 ng g-1 dw for IMI, ACE, and CLO, respectively. The targeted APIs included non-steroidal anti-inflammatory drugs (NSAIDs) and antidepressants. APIs were less frequently detected than NEOs, and the compounds with the highest prevalence were the NSAID ketoprofen (36%), the antidepressant sertraline (36%), and its active metabolite norsertraline (27%). The presence of human pharmaceuticals such as the NSAID ibuprofen and the antidepressants sertraline, fluoxetine, and their active metabolites norsertraline and norfluoxetine suggest environmental contamination due to untreated and partially treated wastewater discharged in surface waters and soils of the study area. The detection and quantification of ketoprofen and flunixin also suggest the possible use of contaminated manure on farmland. Findings indicate that hair may be used for monitoring environmental exposure to NEOs and provide evidence that hair is a good marker of exposure for antidepressants and certain NSAIDs, including ibuprofen, ketoprofen, and flunixin.

Characterization of free L- and D-amino acids in size-segregated background aerosols over the Ross Sea, Antarctica.

The study of airborne chemical markers is crucial for identifying sources of aerosols, and their atmospheric processes of transport and transformation. The investigation of free amino acids and their differentiation between the L- and D- enantiomers are even more important to understand their sources and atmospheric fate. Aerosol samples were collected with a high-volume sampler with cascade impactor at Mario Zucchelli Station (MZS) on the coast of the Ross Sea (Antarctica) for two summer campaigns (2018/19 and 2019/20). The total mean concentration of free amino acids in PM10 was 4 ± 2 pmol m-3 for both campaigns and most of free amino acids were distributed in fine particles. The coarse mode of airborne D-Alanine and dimethylsufoniopropionate in seawater showed a similar trend during both Antarctic campaigns. Thus, the study of D/L Ala ratio in fine, coarse and PM10 fractions indicated the microlayer as the local source. This paper demonstrated that free amino acids follow the trend of DMS and MSA release occurred in the Ross Sea, confirming their applicability as markers for phytoplankton bloom also in paleoclimatic studies.

Long-term effects of neonicotinoids on reproduction and offspring development in the copepod Acartia tonsa.

Neonicotinoids (NEOs) are neurotoxic pesticides acting as nicotinic acetylcholine receptor agonists. NEOs' efficacy against pest insects has favoured their spreading use in agriculture, but their proven effectiveness against non-target insects in terrestrial and aquatic ecosystems also raised concern over their environmental impact. Crustaceans were often studied for the impacts of NEOs due to their economic values and nervous' system similarity with insects. However, most studies on crustaceans focused on acute effects or exposure of early-life stages, while long-term effects were seldom explored. The present study aimed to assess the potential long-term effects of four commercially available NEOs on the reproduction and offspring of the calanoid copepod Acartia tonsa, a key species in the food webs of several coastal and estuarine environments. NEOs were confirmed as potent interferents of copepod reproduction. The first-generation compound acetamiprid significantly inhibited egg production and hatching ratio at 10 ng L-1, while larval survival and development were affected at 81 ng L-1. Similarly, the first-generation compound thiacloprid significantly inhibited the hatching ratio and larval development at 9 ng L-1, while it did not affect egg production and larval survival. Second-generation compounds were less toxic than acetamiprid and thiacloprid: clothianidin affected significantly only larval development of the offspring at 62 ng L-1, while thiamethoxam was not toxic at both the tested concentrations (8 ng L-1 and 84 ng L-1). These data evidenced that effects on copepods may occur at concentrations below the chronic aquatic life benchmarks reported by USEPA for acetamiprid (2100 ng L-1) and thiacloprid (970 ng L-1), suggesting that long-term effects of NEOs have been underestimated. A comparison with environmental concentrations evidenced that NEO-mediated effects on copepods are more liable in coastal areas receiving discharge from wastewater treatment plants or diffuse inputs from agricultural land during pesticide application periods.

Airborne polar pesticides in rural and mountain sites of North-Eastern Italy: An emerging air quality issue.

North-Eastern Italy and in particular Veneto Region, stands out as a major centre of agriculture and viticulture which has rapidly expanded in the last decade with high productivity indexes. In this context, assessing atmospheric pollution caused by crop spraying with pesticides in rural areas and their transport to high-altitude remote sites is crucial to provide a basis for understanding possible impacts on the environment and population health. We aim to improve existing methods with a highly sensitive technique by using high pressure anion exchange chromatography coupled to a triple quadrupole mass spectrometer. Thus, a total of fourteen polar pesticides were determined in aerosol samples collected from August to December 2021 at Roncade (Venetian plain) and Col Margherita Observatory (Dolomites). The observatory was chosen as the background site as it is representative of the surrounding alpine region. Some samples revealed a substantial amount of cyanuric acid mainly at Roncade (mean concentration of 10 ± 10 ng m-3), glyphosate and fosetyl-aluminium (0.1 ± 0.2 and 0.1 ± 0.1 ng m-3, respectively). Surprisingly, some pesticides have been also found at Col Margherita, a high mountain background site, with concentrations an order of magnitude lower than at Roncade. This is the first time that fourteen polar pesticides have been assessed in the aerosol phase of the Po' Valley and detected at a high-altitude remote site, and consequently this study provides the first data on their occurrences in Italian aerosols. It represents a basis for the assessment of risks for humans.

Inhibition of Larval Development of Marine Copepods Acartia tonsa by Neonicotinoids.

Neonicotinoids (NEOs) are neurotoxic pesticides widely used in agriculture due to their high effectiveness against pest insects. Despite their widespread use, very little is known about their toxicity towards marine organisms, including sensitive and ecologically relevant taxa such as copepods. Thus, we investigated the toxicity of five widely used NEOs, including acetamiprid (ACE), clothianidin (CLO), imidacloprid (IMI), thiacloprid (THI), and thiamethoxam (TMX), to assess their ability to inhibit the larval development of the copepod Acartia tonsa. The more toxic NEOs were ACE (EC50 = 0.73 µg L-1), TMX (EC50 = 1.71 µg L-1) and CLO (EC50 = 1.90 µg L-1), while the less toxic compound was IMI (EC50 = 8.84 µg L-1). Early life-stage mortality was unaffected by NEOs at all of the tested concentrations. The calculated toxicity data indicated that significant effects due to ACE (EC20 = 0.12 µg L-1), THI (EC20 = 0.88 µg L-1) and TMX (EC20 = 0.18 µg L-1) are observed at concentrations lower than established chronic aquatic life benchmarks reported by USEPA for freshwater invertebrates. Nevertheless, since environmental concentrations of NEOs are generally lower than the threshold concentrations we calculated for A. tonsa, the effects may be currently of concern only in estuaries receiving wastewater discharges or experiencing intense runoff from agriculture.

Assessing the exposure to human and veterinary pharmaceuticals in waterbirds: The use of feathers for monitoring antidepressants and nonsteroidal anti-inflammatory drugs.

Exposure to active pharmaceutical ingredients (APIs) from both human and veterinary sources is an increasing threat to wildlife welfare and conservation. Notwithstanding, tracking the exposure to pharmaceuticals in non-target and sensitive vertebrates, including birds, is seldom performed and relies almost exclusively on analysing internal organs retrieved from carcasses or from experimentally exposed and sacrificed birds. Clearly, this excludes the possibility of performing large-scale monitoring. Analysing feathers collected from healthy birds may permit this, by detecting APIs in wild birds, including protected and declining species of waterbirds, without affecting their welfare. To this end, we set up a non-destructive method for analysing the presence of non-steroidal anti-inflammatory drugs (NSAIDs), selective serotonin reuptake inhibitors (SSRIs) and noradrenaline reuptake inhibitors (SNRIs) in the feathers of fledglings of both the Mediterranean gull (Ichtyaetus melanocephalus) and the Sandwich tern (Thalasseus sandvicensis). The presence of several NSAIDs and SSRIs above the method quantification limits have confirmed that feathers might be a suitable means of evaluating the exposure of birds to APIs. Moreover, the concentrations indicated that waterbirds are exposed to NSAIDs, such as diclofenac, ibuprofen and naproxen, and SSRIs, such as citalopram, desmethylcitalopram, fluvoxamine and sertraline, possibly due to their widespread use and incomplete removal in wastewater treatment plants (WWTPs). The active ingredient diclofenac raises a the primary concern for the ecosystem and the welfare of the waterbirds, due to its high prevalence (100% and 83.3% in Mediterranean gull and Sandwich tern, respectively), its concentrations detected in feathers (11.9 ng g-1 and 6.7 ng g-1 in Mediterranean gull and Sandwich tern, respectively), and its documented toxicity toward certain birds.

The ubiquity of neonicotinoid contamination: Residues in seabirds with different trophic habits.

Neonicotinoids are one of the most diffusely used classes of pesticides whose level of danger toward non-target invertebrate and vertebrate species has raised increasing concern in the last decades. Among vertebrates, birds are particularly susceptible to unintentional neonicotinoid poisoning since they can be exposed through different pathways, including ingestion of dressed seeds, sucking of contaminated pollen, ingestion of sprayed insects, predation on contaminated aquatic and terrestrial preys. In the present study, we investigated the possible exposure of seabirds by measuring the residues of five neonicotinoids (acetamiprid, clothianidin, imidacloprid, thiacloprid and thiamethoxam) in samples of pooled feathers collected from fledglings of the strictly piscivorous Sandwich tern (Thalasseus sandvicensis) and the mixotrophic species Mediterranean gull (Ichthyaetus melanocephalus). At least one neonicotinoid was quantified in all the Mediterranean gull samples (n = 11) and 89% of the analysed Sandwich tern samples (n = 36). The active principles with the highest quantification rates were imidacloprid (100% in Mediterranean gulls and 58% in Sandwich terns) and clothianidin (100% in Mediterranean gulls and 61% in Sandwich terns), while thiacloprid was the less frequently detected pesticide (<20% of samples in both species). Mean concentrations ± standard error for imidacloprid, clothianidin and thiamethoxam were 8.8 ± 1.4, 4.5 ± 0.19 and 0.16 ± 0.02 ng g-1 for the Mediterranean gull, and 5.8 ± 0.55, 0.60 ± 0.08 and 0.36 ± 0.03 ng g-1for the Sandwich tern, respectively. Our data evidenced the exposure of seabirds to neonicotinoids and the further need to investigate the extent of neonicotinoid contamination in non-agricultural ecosystems.

Assessing glyphosate in water, marine particulate matter, and sediments in the Lagoon of Venice.

Lagoon water, suspended particulate matter, and sediment samples from seven sites at Lagoon of Venice were collected from 2019 to 2021 in order to study the presence of the herbicide glyphosate (N-(phosphonomethyl)glycine), among the most widely used agricultural chemicals worldwide, but its occurrence in lagoon water environment has not been deeply investigated. The sites were selected considering a supposed diversity of inputs and of pollution levels. An analytical method based on ion chromatography coupled with tandem mass spectrometry was optimized and validated for lagoon water, marine particulate matter, and sediment samples. Maximum concentrations of glyphosate were 260 and 7 ng L-1 for lagoon water and suspended particulate matter, respectively, and 15 ng g-1 for sediment, with some spatial and temporal fluctuations. Our results demonstrate that glyphosate content in the Venice Lagoon mainly depends on external forcing from river inlets and agricultural lagoon activities.

Year-round measurements of size-segregated low molecular weight organic acids in Arctic aerosol.

Organic acids in aerosols Earth's atmosphere are ubiquitous and they have been extensively studied across urban, rural and polar environments. However, little is known about their properties, transport, source and seasonal variations in the Svalbard Archipelago. Here, we present the annual trend of organic acids in the aerosol collected at Ny-Ålesund and consider their size-distributions to infer their possible sources and relative contributions. A series of carboxylic acids were detected with a predominance of C2-oxalic acid. Pinic acid and cis-pinonic acid were studied in order to better understand the oxidative and gas-to-particle processes occurred in the Arctic atmosphere. Since the water-soluble organic fraction is mainly composed by organic acids and ions, we investigated how the seasonal variation leads to different atmospheric transport mechanisms, focusing on the chemical variations between the polar night and boreal summer. Using major ions, levoglucosan and MSA, the Positive Matrix Factorization (PMF) identified five different possible sources: a) sea spray; b) marine primary production; c) biomass burning; d) sea ice related process and e) secondary products.

Carbohydrate determination in honey samples by ion chromatography-mass spectrometry (HPAEC-MS).

Honey is a complex mixture of carbohydrates, in which the monosaccharides glucose and fructose are the most abundant compounds. Currently, more than 20 oligosaccharides have been identified in different varieties of honey normally at quite low concentration. A method was developed and validated using high-performance anion-exchange chromatography coupled to a mass spectrometry detector to investigate the composition of carbohydrates in honey samples. The method was tested for linearity range, trueness, instrumental and method detection and quantification limits, repeatability, and reproducibility. It was applied to determine seven monosaccharides, eight disaccharides, four trisaccharides, and one tetrasaccharide in various honey samples. The present work describes the composition of sugars in unifloral, multifloral, and some honeydew honey, which were produced and collected by beekeepers in the Trentino Alto-Adige region. Statistical techniques have been used to establish a relationship based on levels of carbohydrates among different Italian honey. The results emphasize that mono- and oligosaccharide profiles can be useful to discriminate different honeys according to their floral characteristics and inter-annual variability.

Dissolved organic matter in the deep TALDICE ice core: A nano-UPLC-nano-ESI-HRMS method.

Trace organic compounds in deep ice cores supply important paleoclimatic information. Untargeted analyses of dissolved organic matter provide an overview of molecular species in ice samples however, sample volumes usually required for these analyses are generally not available from deep ice cores. Here, we developed an analytical method using a nano-UPLC-nano-ESI-HRMS to detect major molecular species in ice cores. Samples (4 µL) from the TALos Dome Ice CorE (TALDICE), allowed investigating molecular species across a range of depths including during glacial and interglacial periods. We detected 317 chemical species that were tentatively assigned to fatty acids, hydroxy fatty acids and their degradation products (oxo-fatty acids and dicarboxylic acids), as well as oxidation byproducts of isoprene and monoterpenes. These compounds indicate that the main sources of the organic fraction are microbes as well as primary and secondary aerosols. Interglacial samples encompass a wide range of species including compounds from the oxidation of isoprene and monoterpenes as well as unsaturated fatty acids, while the glacial samples contained less diverse species. This difference may be due to decreased temperatures during the glacial period inhibiting terrestrial vegetation growth and increasing the sea ice extent, thereby weakening the emission sources.

Interannual variability of sugars in Arctic aerosol: Biomass burning and biogenic inputs.

The concentrations and particle-size distribution of sugars in Arctic aerosol samples were studied to investigate their potential sources and transport. Sugars are constituents of the water-soluble organic compounds (WSOC) fraction in aerosol particles where some saccharides are used as tracers of Primary Biological Aerosol Particles (PBAPs). Monosaccharides (arabinose, fructose, galactose, glucose, mannose, ribose, xylose), disaccharides (sucrose, lactose, maltose, lactulose), alcohol-sugars (erythritol, mannitol, ribitol, sorbitol, xylitol, maltitol, galactitol) and anhydrosugars (levoglucosan, mannosan and galactosan) were quantified in aerosol samples collected during three different sampling campaigns (spring and summer 2013, spring 2014 and 2015). The mean total concentrations of sugars were 0.4 ± 0.3, 0.6 ± 0.5 and 0.5 ± 0.6 ng m-3 for 2013, 2014 and 2015 spring campaigns, while the mean concentration increased to 3 ± 3 ng m-3 in the summer of 2013. This work identified a reproducibility in the sugars trend during spring, while the summer data in 2013 allowed to us to demonstrate strong local inputs when the ground was free of snow and ice. Furthermore, the study aims to show that the two specific ratios of sorbitol & galactiol to arabinose were diagnostic for the type of biomass that was burnt. This study demonstrates that not only is long-range atmospheric transport significant. But depending on seasonality, local inputs can also play an important role in the chemical composition of sugars in Arctic aerosol.

Free and combined L- and D-amino acids in Arctic aerosol.

Aerosol samples were collected with a high-volume cascade impactor with a 10 day sampling frequency at the Gruvebadet observatory, close to Ny-Ålesund (Svalbard Islands). A total of 42 filters were analyzed for free and combined amino acids, as they are key components of bio-aerosol. This article provides the first investigation of free and combined L- and d-amino acids in Arctic atmospheric particulate matter. The main aim of this study was to determine how these compounds are distributed in size-segregated aerosols after short-range and long-range atmospheric transport and understand the possible sources of amino acids. The total load of free amino acids ranged from 2.0 to 10.8 pmol m-3, while combined amino acids ranged from 5.5 to 18.0 pmol m-3. At these levels amino compounds could play a role in the chemistry of cloud condensation nuclei and fine particles, for example by influencing their buffering capacity and basicity. Free and combined amino acids were mainly found in the fine aerosol fraction (<0.49 µm) and their concentrations could be affect by several sources, the most important of which were biological primary production and biomass burning.

Characterization of the water soluble fraction in ultrafine, fine, and coarse atmospheric aerosol.

Water soluble organic carbon significantly contributes to aerosol's carbon mass and its chemical composition is poorly characterized due to the huge number of species. In this study, we determined 94 water-soluble compounds: inorganic ions (Cl-, Br-, I-, NO3-, SO42-,K+, Mg+, Na+, NH4+, Ca2+), organic acids (methanesulfonic acid and C2-C7 carboxylic acids), monosaccharides, alcohol-sugars, levoglucosan and its isomers, sucrose, phenolic compounds, free l- and d-amino acids and photo-oxidation products of α-pinene (cis-pinonic acid and pinic acid). The sampling was conducted using a micro-orifice uniform deposit impactor (MOUDI) at the urban area of Mestre-Venice from March to May 2016. The main aim of this work is to identify the source of each detected compound, evaluating its particle size distribution. Clear differences in size distributions were observed for each class of analyzed compounds. The positive matrix factorization (PMF) model was used to identify six factors related to different sources: a) primary biogenic aerosol particles with particle size > 10 µm; b) secondary sulfate contribution; c) biomass burning; d) primary biogenic aerosol particles distributed between 10 and 1 µm; e) an aged sea salt input and f) SOA pinene. Each factor was also characterized by different composition in waters soluble compounds and different particles size distribution.

Free phenolic compounds in waters of the Ross Sea.

The presence of free phenolic compounds (PC) in Antarctic sea water has been investigated to explain their source and particle size distribution in the atmospheric aerosols, as determined in our previous research. The sea water samples were filtered to distinguish the PC concentrations in the particulate and dissolved fractions. Two sample preparation procedures were developed to quantify nine PC in both fractions. The highest concentrations were found in the dissolved fraction of Ross Sea water, with vanillin, vanillic acid, acetovanillone and p-coumaric acid being the most abundant PC. Dissolved PC were mainly found in the upper part of water column. This facilitated the sea water-air exchange by bubble busting processes. In the aerosol, they were mainly found in the fine fraction, where these compounds have a higher degree of oxidation than PC detected in seawater, suggesting that they were newly emitted and they have been not yet oxidized. These results supported our previous hypothesis that PC were locally emitted into the atmosphere from the Ross Sea. Three different possible sources of PC are hypothesized for Antarctic sea waters: 1) from the intrusion of Modified Circumpolar Deep Water that may transport oceanic lignin; 2) from phytoplankton biomass that may be a source of PC in Antarctic waters since diatoms produce exudates that contain vanillic acid, p-coumaric acid and syringic acid; 3) from the melting of glaciers and sea ice: glaciers contain lignin that can be degraded, while in the sea ice there are diatoms that may release PC. Statistical analysis and the low value of vanillic acid/vanillin ratio indicated that the most plausible source for PC in the dissolved fraction was the senescence of phytoplankton. As a contrast, particulate PC with higher vanillic acid/vanillin ratios were ascribed to degraded lignin or the sorption of diagenically oxidized material on particles.

Free amino acids in the Arctic snow and ice core samples: Potential markers for paleoclimatic studies.

The role of oceanic primary production on climate variability has long been debated. Defining changes in past oceanic primary production can help understanding of the important role that marine algae have in climate variability. In ice core research methanesulfonic acid is the chemical marker commonly used for assessing changes in past primary production. However, other organic compounds such as amino acids, can be produced and emitted into the atmosphere during a phytoplankton bloom. These species can be transported and deposited onto the ice cap in polar regions. Here we investigate the correlation between the concentration of chlorophyll-a, marker of marine primary production, and amino acids present in an ice core. For the first time, free l- and d-amino acids in Arctic snow and firn samples were determined by a sensitive and selective analytical method based on liquid chromatography coupled with tandem mass spectrometry. The new method for the determination of free amino acids concentrations was applied to firn core samples collected on April 2015 from the summit of the Holtedahlfonna glacier, Svalbard (N 79'08.424, E 13'23.639, 1120m a.s.l.). The main results of this work are summarized as follows: (1) glycine, alanine and proline, were detected and quantified in the firn core samples; (2) their concentration profiles, compared with that of the stable isotope δ18O ratio, show a seasonal cycling with the highest concentrations during the spring and summer time; (3) back-trajectories and Greenland Sea chlorophyll-a concentrations obtained by satellite measurements were compared with the amino acids profile obtained from ice core samples, this provided further insights into the present results. This study suggests that the amino acid concentrations in the ice samples collected from the Holtedahlfonna glaciers could reflect changes in oceanic phytoplankton abundance.

Results of an interlaboratory comparison of analytical methods for quantification of anhydrosugars and biosugars in atmospheric aerosol.

An interlaboratory comparison was performed to evaluate the analytical methods for quantification of anhydrosugars - levoglucosan, mannosan, galactosan - and biosugars - arabitol, glucose and mannitol - in atmospheric aerosol. The performance of 10 laboratories in Italy currently involved in such analyses was investigated on twenty-six PM (particulate matter) ambient filters, three synthetic PM filters and three aqueous standard solutions. An acceptable interlaboratory variability was found, determined as the mean relative standard deviation (RSD%) of the results from the participating laboratories, with the mean RSD% values ranging from 25% to 46% and decreasing with increasing sugar concentration. The investigated methods show good accuracy, evaluated as the percentage error (ε%) related to mean values, since method biases ranged within ±20% for most of the analytes measured in the different laboratories. The detailed investigation (ANOVA analysis at p < 0.05) of the contribution of each laboratory to the total variability and the measurement accuracy shows that comparable results are generated by the different methods, despite the great diversity in terms of extraction conditions, chromatographic separation - more recent LC (liquid chromatography) and EC (exchange chromatography) methods compared to more widespread GC (gas chromatography) - and detection systems, namely PAD (pulsed amperometric detection) or mass spectrometry.

Aerosol and snow transfer processes: An investigation on the behavior of water-soluble organic compounds and ionic species.

The concentrations of water-soluble compounds (ions, carboxylic acids, amino acids, sugars, phenolic compounds) in aerosol and snow have been determined at the coastal Italian base "Mario Zucchelli" (Antarctica) during the 2014-2015 austral summer. The main aim of this research was to investigate the air-snow transfer processes of a number of classes of chemical compounds and investigate their potential as tracers for specific sources. The composition and particle size distribution of Antarctic aerosol was measured, and water-soluble compounds accounted for 66% of the PM10 total mass concentration. The major ions Na+, Mg2+, Cl- and SO42- made up 99% of the total water soluble compound concentration indicating that sea spray input was the main source of aerosol. These ionic species were found mainly in the coarse fraction of the aerosol resulting in enhanced deposition, as reflected by the snow composition. Biogenic sources were identified using chemical markers such as carboxylic acids, amino acids, sugars and phenolic compounds. This study describes the first characterization of amino acids and sugar concentrations in surface snow. High concentrations of amino acids were found after a snowfall event, their presence is probably due to the degradation of biological material scavenged during the snow event. Alcohol sugars increased in concentration after the snow event, suggesting a deposition of primary biological particles, such as airborne fungal spores.

Particle size distribution of inorganic and organic ions in coastal and inland Antarctic aerosol.

The concentration and particle-size distribution of ionic species in Antarctic aerosol samples were determined to investigate their potential sources, chemical evolution, and transport. We analyzed aerosol samples collected at two different Antarctic sites: a coastal site near Victoria Land close to the Italian Research Base "Mario Zucchelli", and another site located on the Antarctic plateau, close to Italian-French Concordia Research Station. We investigated anionic compounds using ion-chromatography coupled to mass spectrometry, and cationic species through capillary ion chromatography with conductometry. Aerosol collected close to the coast was mainly characterized by sea salt species such as Na+, Mg2+, and SO42-. These species represented a percentage of 88% of the total sum of all detected ionic species in the aerosol samples from the coastal site. These species were mainly distributed in the coarse fraction, confirming the presence of primary aerosol near the ocean source. Aerosol collected over the Antarctic plateau was characterized by high acidity, with nss-SO42-, NO3-, and methanesulfonic acid as the most abundant species. These species were mainly distributed in the <0.49 µm fraction, and they had a behavior of a typical secondary aerosol, where several chemical and physical processes occurred.