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The chemical composition of rainwater depends on (i) the dissolution of gases and particulate matter emitted by different sources, (ii) the chemical and physical reactions occurring during local and regional scale transport, and (iii) removal processes. The source of major and trace elements dissolved in rainwater can be both natural (e.g. sea salts, volcanic emissions, geogenic dust, biogenic material) and anthropogenic (e.g. industrial plants, vehicular traffic, domestic heating, vessel traffic). A group of trace elements has been recently brought to attention, especially for their possible environmental impacts, the Technology-critical elements (TCEs): Ga, Ge, In, Te, Nb, Ta, Tl, the Platinum Group Elements and most of the rare-earth elements (REE). The current knowledge about the geochemical cycle of TCEs is still scarce and there are not many studies about the concentrations of them in the rainwater. Nevertheless, recent studies (e.g. Brugnone et al., 2020) evidenced a contribution from the volcanic activity for some of them (Te, Tl, and REE). The main aim of this research is to produce an unedited geochemical database on major and trace element concentrations and bulk depositions, in different areas of Sicily: a volcanic area (Mt Etna), two urban (Palermo and Catania), and two industrial areas (Milazzo and Priolo) and a rural monitoring site representative of the regional atmospheric background (Cesarò, Nebrodi Regional Park). The samples will be collected monthly, for almost two years, through a network of 15 bulk collectors, most of which were installed at atmospheric monitoring stations of the “Agenzia Regionale per la Protezione Ambientale - ARPA Sicilia”. Moreover, the isotopic ratios of H and O in the rainwater will be investigated, while an innovative feature of the research will be the determination of the isotopic ratios of isotopes not investigated in previous similar studies: 34S/32S, 11B/10B, 87Sr/86Sr. These isotopes have been studied in matrices such as groundwaters, river and marine waters, in which the above elements show higher concentrations than rainwater. Therefore, a new analytical methodology will be developed to measure these isotopic ratios in rainwater. The isotope fingerprint enables to distinguish the contribution of sea-salt from terrestrial and anthropogenic components, allowing to discriminate the different sources that contribute to the chemical and the isotopic composition of atmospheric bulk deposition in the Mediterranean basin.

Here we report on the first assessment of volatile fluxes from the hyperacid crater lake hosted within the summit crater of Copahue, a very active volcano on the Argentina-Chile border. Our observations were performed using a variety of in situ and remote sensing techniques during field campaigns in March 2013, when the crater hosted an active fumarole field, and in March 2014, when an acidic volcanic lake covered the fumarole field. In the latter campaign, we found that 566 to 1373 t d -1 of SO 2 were being emitted from the lake in a plume that appeared largely invisible. This, combined with our derived bulk plume composition, was converted into flux of other volcanic species (H 2 O ~ 10989 t d -1 , CO 2 ~ 638 t d -1 , HCl ~ 66 t d -1 , H 2 ~ 3.3 t d -1 , and HBr ~ 0.05 t d -1 ). These levels of degassing, comparable to those seen at many open-vent degassing arc volcanoes, were surprisingly high for a volcano hosting a crater lake. Copahue's unusual degassing regime was also confirmed by the chemical composition of the plume that, although issuing from a hot (65°C) lake, preserves a close-to-magmatic signature. EQ3/6 models of gas-water-rock interaction in the lake were able to match observed compositions and demonstrated that magmatic gases emitted to the atmosphere were virtually unaffected by scrubbing of soluble (S and Cl) species. Finally, the derived large H 2 O flux (10,988 t d -1 ) suggested a mechanism in which magmatic gas stripping drove enhanced lake water evaporation, a process likely common to many degassing volcanic lakes worldwide. Key Points First volatile flux record of crater lake gas emissions from Copahue volcano Magmatic gases breaching through the lake surface Magmatic gas stripping drive enhanced lake water evaporation Fil: Tamburello, G.. Università degli Studi di Palermo; Italia Fil: Caselli, Alberto Tomás. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Estudios Andinos "Don Pablo Groeber". Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Estudios Andinos "Don Pablo Groeber"; Argentina Fil: Tassi, F.. Università degli Studi di Firenze; Italia Fil: Vaselli, O.. Università degli Studi di Firenze; Italia Fil: Calabrese, S.. Università degli Studi di Palermo; Italia Fil: Rouwet, D.. Istituto Nazionale di Geofisica e Vulcanologia; Italia Fil: Capaccioni, B.. Universidad de Bologna; Italia Fil: Di Napoli, R.. Università degli Studi di Palermo; Italia Fil: Cardellini, C.. Università di Perugia; Italia Fil: Chiodini, G.. Istituto Nazionale di Geofisica e Vulcanologia; Italia Fil: Bitetto, M.. Università degli Studi di Palermo; Italia Fil: Brusca, L.. Istituto Nazionale Geofisica e Vulcanologia; Italia Fil: Bellomo, S.. Istituto Nazionale Geofisica e Vulcanologia; Italia Fil: Aiuppa, A.. Istituto Nazionale Geofisica e Vulcanologia; Italia

Samples of efflorescences and encrustations of hydrothermal origin have been collected at three fumarolic areas in Greece. The three sites are Sousaki, Thiafi (Methana) and Kokkino Nero (Kos) and all belong to the South Aegean Active Volcanic Arc. Samples were analysed for their mineralogical (XRD and SEM-EDS) and chemical composition. Solutions obtained from both mineralization with HNO3 and leaching with distilled water, were analysed for major (ICP-OES), minor and trace metals (ICP-MS) and for sulfate contents (IC). Results show that their composition is mainly controlled by the petrological composition of the substrate (ultramafic rocks at Sousaki, felsic volcanic rocks at Methana and low-grade metamorphic rocks at Kos). The microenvironmental conditions (humidity, oxidizing or anoxic, exposed or sheltered from meteoric agents) as well as the rainfall regime of the area play also an important role. The presence of highly soluble sulfate minerals with elevated contents of many metals further underscores the significant influence of hydrothermal activity on elements’ mobility. The sometimes very high concentrations in toxic elements like Al, As, Co, Cr, Ni evidence also a potential environmental impact.

Nisyros Island (Greece) is an active volcano hosting a high-enthalpy geothermal system. During June 2013, an extensive survey on Hg concentrations in different matrices (fumarolic fluids, atmosphere, soils, and plants) was carried out at the Lakki Plain, an intracaldera area affected by widespread soil and fumarolic degassing. Concentrations of gaseous elemental mercury (GEM), together with H2S and CO2, were simultaneously measured in both the fumarolic emissions and the atmosphere around them. At the same time, 130 samples of top soils and 31 samples of plants (Cistus creticus and salvifolius and Erica arborea and manipuliflora) were collected for Hg analysis. Mercury concentrations in fumarolic gases ranged from 10,500 to 46,300 ng/m3, while Hg concentrations in the air ranged from high background values in the Lakki Plain caldera (10-36 ng/m3) up to 7100 ng/m3 in the fumarolic areas. Outside the caldera, the concentrations were relatively low (2-5 ng/m3). The positive correlation with both CO2 and H2S in air highlighted the importance of hydrothermal gases as carrier for GEM. On the other hand, soil Hg concentrations (0.023-13.7 μg/g) showed no significant correlations with CO2 and H2S in the soil gases, whereas it showed a positive correlation with total S content and an inverse one with the soil pH, evidencing the complexity of the processes involving Hg carried by hydrothermal gases while passing through the soil. Total Hg concentrations in plant leaves (0.010-0.112 μg/g) had no direct correlation with soil Hg, with Cistus leaves containing higher values of Hg with respect to Erica. Even though GEM concentrations in the air within the caldera are sometimes orders of magnitude above the global background, they should not be considered dangerous to human health. Values exceeding the WHO guideline value of 1000 ng/m3 are very rare (

Hyperalkaline mineral springs related to active continental serpentinization are a theme of growing interest since they may contain significant amounts of abiotic gas and have important implications for energy resource exploration, subsurface microbiology and astrobiology. We report the discovery of a new hyperalkaline (pH∼12) spring issuing in the Agioi Anargyroi monastery at Ermioni (Greece), connected to serpentinization of peridotites of the Argolis ophiolite. Two water samples have been collected from separated springs and analysed for the chemical composition of major, minor and trace elements, and isotopic composition (2H and 18O) of water by IC, ICP-OES, ICP-MS and IRMS, and for the chemical (H2, O2, N2, CH4, CO2 and C2H6) and isotopic (He, δ2H-CH4 and δ13C-CH4) composition of dissolved gases. The Iliokastron Mélange Unit, comprising abundant serpentinized harzburgite, represent the aquifer feeding the hyperalkaline springs. The isotopic composition of water indicates a recent meteoric recharge probably through the close by and stratigraphically higher limestones of the Faniskos Unit. The Ca-OH water composition resulted to be similar to other hyperalkaline waters of Greece and worldwide. Although the concentrations of dissolved H2 are very low (tens of nmol/L) compared to other gases collected in similar manifestations, the concentrations of CH4 are considerable (38–314 μmol/L) and display isotopic compositions indicating a substantial if not exclusive abiogenic origin. Methane oxidation is also hypothesized in one of the two springs. © 2017 Elsevier Ltd

The large amount of trace elements emitted from volcanoes has a strong impact on the close surrounding areas. Nyiragongo Volcano (Democratic Republic of Congo) belongs to the Virunga volcanic chain and is one of the most active volcanoes in Africa. It is characterized by the presence of an active and permanent lava lake with a persistent degassing activity. During a field trip in October-November 2014, we investigated the impact of the volcanogenic deposition in the surrounding of the crater by using different sampling techniques. Rain-gauges were used to collect atmospheric bulk deposition. Active and passive biomonitoring techniques (moss-bags and leaves of endemic plants – Senecio spp. and Amarantus viridis) were applied in order to investigate the dispersion of volcanic gas and particle emissions. We collected daily rainfall events at various sites: seven samples at the crater rim (on the western and southern side, 3470 m a.s.l.), one sample at the village Kibati (south-eastern flank, 1955 m a.s.l.) located at the up-wind base of the volcano (representing the local background), and four samples in the city of Goma (southern flank of the volcano, 1500 m a.s.l.). In order to implement our dataset, several samples of rainwater, amaranth leaves, soils and atmospheric depositions (by moss-bags and filters exposition) were sampled after the field trip by the researchers of the Goma Volcano Observatory (GVO). Since, the prevalent wind direction was blowing the plume in westerly or southwesterly direction, we exposed the raingauges in the villages of Bulengo, Rusayo and Kingi in the southwestern side respect to the volcano, and Kibumba in the southesthern as a background site, at increasing distance from the rim. In the same sites, leaves of Amarantus viridis, which is one of the principal vegetables eaten by the local population, were collected. Rainwater, moss bags and plant samples were analyzed for major and trace elements by IC, ICP-OES and ICP-MS. The large amount of emitted volcanic gases and particles includes sulfur, halogens and trace elements, that strongly affect rainwater chemistry and have a widespread impact on the surrounding vegetation of the volcano. Indeed, rainwater samples collected at the rim of the crater have low pH values (_ 3), high concentration of F- and Cl- (up to 12.0 and 12.8 mg/l, respectively) and dissolved toxic elements (such as Al, As, Cd, Cu, Fe and Pb), whereas samples from the city of Goma have pH values above 5 and the same elements show orders of magnitude lower concentrations. The biomonitoring results highlight that bioaccumulation of trace elements is extremely high in the proximity of the crater rim and decreases with the distance from the active craters. The data will be compared to earlier measurements taken in December 2011 and the impact of a slightly decreasing gas emission on the vegetation will be discussed.

Hydrogen sulfide (H2S) is a gas pollutant discharged in air from a large number of natural and anthropogenic sources. Its peculiar rotten-egg smell, causing odor nuisance to neighboring communities, is detectable at concentrations between 0.7 and 42 μg/m3 (Schiffman & Williams, 2005). High H2S concentrations could cause eye irritation, damage to the upper respiratory apparatus and loss of smell. The effects of long-term low level (< 2,800 μg/m3) exposures to H2S are still matter of debate (Bates et al., 2013). Hence, the development of techniques for accurate measurements of H2S in air at a wide range of concentrations is a primary issue in environmental monitoring. Two different approaches are currently used: 1) passive samplers and 2) real-time measurements. The latter are generally expensive and require a power supply. On the contrary, passive samplers are low cost and can be deployed in the field with minimal maintenance. Therefore, passive samplers offer an appealing alternative to real-time measurements, especially for regional-scale monitoring. However, the reliability of passive samplers in outdoor applications strongly depends on several environmental factors, such as temperature, humidity and wind speed (Delgado-Saborit & Esteve-Cano, 2006). In this study a comparison between H2S measurements using diffusive radial-type passive samplers (Radiello) and a real-time gas analyzer (Thermo Scientific Model 450i) based on pulsed fluorescence, is presented. The measurements were carried out in areas affected by both anthropogenic and natural sources using both techniques. The results show substantial differences. The passive samplers systematically produce higher H2S concentrations than those of the active analyzer. The relative error was up to > 1,000% for concentrations < 7 μg/m3 and exposure duration ≥ 2 hours. H2S measurements by Radiello were affected by meteo parameters (wind, rain, humidity, temperature). The efficiency of this method was demonstrated to be also strongly dependent on H2S concentrations. In addition, passive samplers give an average concentration value for the exposure period, but are not able to detect short-term H2S increments. These results show that the use of passive samplers for environmental monitoring should thus be limited to preliminary largescale semi-quantitative assessment. A reliable study on the dispersion dynamics of contaminants in air cannot exclude the acquisition of high-frequency data through active analyzers.

A new eruption started at Stromboli on 6 August 2014, which had been preceded by 2 months of increased Strombolian activity and several lava overflows from the craters. The eruption was characterized by a lava effusion in Sciara del Fuoco from a fracture at 650 m above sea level that lasted until 13-17 November. Here we present the first geochemical observations of this eruption, based on the soil CO2 flux in the summit area and on 3He/4He ratios in the thermal waters near Stromboli village. We infer that this eruption was triggered by the gradual replenishment of the feeding system by a CO2- and 3He-rich magma at the end of 2013 and after June 2014, suggested by the increase in 3He/4He ratio before eruption, which reached its highest value since 2007. We thus infer that this eruption was unusual, and we finally speculate on the evolutionary scenario of posteruption.

In the winter 2013, mercury concentrations in air from the mine-polluted area of Mt. Amiata (1738 m a.s.l.), in southern Tuscany (Central Italy), were measured by active moss biomonitoring. This area is part of the geologic anomaly of Hg in the Mediterranean basin, which contains about 65 % of the world’s cinnabar (HgS). Mt. Amiata covers some 400 km2 and is drained by several rivers. Esploitation activity at Abbadia S. Salvatore, in the SE sector of the mountain, sprang up during the 19th century as one of the largest mercury mining and smelting plants in Europe, after those of Almaden Spain. In this area, Sphagnum moss bags were exposed for about two months, from October to December 2013. At each site (10 sites), one covered and one uncovered moss bag were deployed. Concentrations of mercury in air were also investigated in the same sites with a portable spectrophotometer (Lumex RA-915M). After exposure, mosses were oven-dried, grinded and each sample was divided in two aliquots: one was analyzed for mercury by using a Hydra C cold vapor atomic absorption analyzer (INGV-Palermo), following 7473 US EPA method; the second was microwave digested in acid solution (HNO3 + H2O2). Extraction solutions were analyzed by ICP-MS for total concentrations of a large suite of trace elements, including potentially toxic elements e.g. As, Cd, Cr, Cu, Mo, Sb, Se, V. Mercury air concentrations measured with the Lumex showed extremely high values in the mine district of Abbadia, with median values ranging from 2,000 to 4,000 ng/m3 and maximum values up to 20,000 ng/m3, in contrast with the lower values (median values from 20 to 200 ng/m3) measured in the distal sites few kilometres from the mine-district area. In agreement with these results, in the vicinity of the district uncovered bags were in the range of 10,000 – 100,000 ng/g of Hg, whereas in the distal sites they were in the range of 1,000 – 10,000 ng/g. The moss-blank (unexposed moss) was ~100 ng/g. Covered moss bags were not significantly enriched in Hg with respect to the concentrations recovered from the moss-blank, suggesting that the mercury trapped in the mosses was mainly in particulate form. The particles carried from the winds were probably associated with soils re-mobilization, as also confirmed by the associated enrichments of some lithophile elements (Li and lanthanides) and anthropogenic element (As, Cr, Cd, Fe, Se, V). These preliminary results confirm the intense contamination of the study area not only for mercury but also for other potentially toxic elements.

We have performed leaching experiments on the fine (< 2 mm) particulate sampled in seven active and quiescent volcanic systems in the Mediterranean area. We reacted the particulate both in pure water and in a synthetic gastric solution. The amount of As, Mn, Pb, Ba, U and Ni leached by pure water exceeded the MAC limits for drinking water in all the materials under investigation. We defined a tolerable ash intake index (TAI) to evaluate the impact of ash ingestion, and we find that 0.2 g and 12 g of ingested fine ash from Vesuvius and Vulcano are enough to exceed the safety limits for Pb and As. Six grams of fine ashes from Stromboli are sufficient to overstep the safety limits for As. Based on our mineralogical characterisation of the particulate, we expect that the submillimetric ash fraction, with a higher surface/volume ratio, releases a greater relative amount of trace metals, which are concentrated in the thin surface layer produced by the reaction of the pristine volcanic particles with coexisting volcanic gases. This means that our measurements represent lower bounds to the actual amount of metal released in aqueous solutions by the volcanic ashes from the locations under investigation. Our results place the first constraints on the mobilisation of toxic elements from volcanic ash, which are necessary to assess the associated potential health risk of volcanic areas. © 2017 Elsevier B.V.

It seems that the time of the employment contract as the standard legal device of employment is over and that a variety of employment relationships have emerged. Many forms raise questions and uncertainties about social protection. One of these forms are false or quasi self-employed workers. In the case of FNV KIEM the European Court of Justice (ECJ) ruled on this. In this contribution we assess to what extent the ruling of the ECJ has contributed to clarifying some of the qualification issues involved with these type of workers. Thereto, we describe how the case was raised in the Netherlands; we elaborate on the arguments raised in the subsequent national court decisions and the ECJ; we reflect on the notion of (false) self-employed from the perspective of the notion of undertaking/entrepreneur and that of employee in order to determine what the ECJ considers to be decisive requirements for each category; and we reflect on the meaning of the ruling of the ECJ in the FNV KIEM case for the Netherlands.

A comprehensive hydrogeochemical study of the cold and thermal groundwaters of the presently quiescent volcanic system at Methana was undertaken that involved collecting 71 natural water samples. Methana is a peninsula in Peloponnesus, Greece whose arid climate and hydrological situation is similar to that of the nearby small islands of the Aegean Sea. Similarly, the chemical and isotopic compositions of its water are dominated by the mixing of seawater with meteoric water both through direct intrusion and meteoric recharge. However, the simple mixing trends at Methana are modified by water–rock interaction processes, enhanced by the dissolution of endogenous CO2, which lead to strong enrichments in alkalinity, Ca, Ba, Fe and Mn. The thermal waters show very high salinity that is sometimes close to that of seawater [total dissolved solids (TDS) = 8.5–40 g/l]. Although the cold groundwaters sometimes also show elevated TDS values (up to 6.3 g/l), their overall quality is acceptable due to the trace metal and nitrate contents mostly being below acceptable limits. While the saltiest groundwaters are not acceptable for human consumption, they are used for irrigation without exerting toxic effects on plants, which is probably due to the high permeability of the soils not supporting salt accumulation and salinity-resistant crops being cultivated. © 2017 Elsevier B.V.

Explosive eruptions and volcanic passive degassing inject large quantities of gas and particles into the atmosphere that are ultimately deposited at the Earth’s surface through wet or dry deposition processes, affecting the atmosphere, the hydrosphere and the biosphere. Mount Etna (Italy) is one of the most prodigious and persistent sources of gases and particles to the troposphere. Volcanic emissions were studied at Etna volcano by using moss-bags technique. Mosses (Sphagnum species) were exposed around the volcano at different distances from the active vents to evaluate the impact of its emissions into the atmosphere and in the local surrounding. The results confirmed the huge amount of silicates, sulfates and halides compounds emitted into the atmosphere from Mount Etna. X-ray microanalysis showed that chemical composition of the particles is mostly defined by silicate (from pure silica to metal-rich silicate composition) and sulfate/halide compounds. The contents of major and trace elements in the Sphagnum moss-bags significantly increased after their exposure to volcanic emissions, confirming mosses as efficient accumulators. Metals uptake rate rapidly decreases with the distance from the volcanic emission vents. The elements that showed the greatest accumulation after exposition were S, Na, Fe, Al, Cu, V, As, Cd, Li, Se, Sc, Th, Bi and Tl. This study confirmed the marked environmental impact of volcanic emissions in the eastern sector of Etna, leading to an intense “geochemical anomaly” of volatile major and trace elements due to the fumigation by the volcanic plume, in agreement with passive biomonitoring studies reported by previous authors. Finally, moss-bags techniques provide a cheap and efficient method to investigate quantitatively in space and time the environmental impact of volcanogenic atmospheric deposition.

The studied area is a 130 km long fast spreading graben in Central Greece. Its complex geodynamical setting includes both the presence of a subduction slab at depth responsible for the recent (Quaternary) volcanic activity in the area and the western termination of a tectonic lineament of regional importance (the North-Anatolian fault). A high geothermal gradient is made evident by the presence of many thermal springs with temperatures from 19 to 82 C, that discharge along the normal faults bordering the graben. In the period 2004e2012, 58 gas and 69 water samples were collected and their chemical and isotopic analysis revealed a wide range of compositions. Two main groups of thermal waters can be distinguished on the basis of their chemical composition. The first, represented by dilute waters (E.C.

Biomonitoring techniques have been widely used in environmental studies to monitor anthropogenic pollutant. Recently such techniques have been applied also to ascertain the impact of contaminants naturally released by volcanic activity. In the present study a biomonitoring surveys has been performed in many different active volcanic systems: Mt. Etna and Vulcano (Italy), Nisyros (Greece), Nyiragongo (DRC), Masaya (Nicaragua), Gorely (Kamchatka, Russia). We sampled leaves of different species Betulla aethnensis, Pinus nigra, Populus tremula, Senecio aethnensis and Rumex aethnensis on Etna, Cistus creticus and salvifolius on Vulcano and Nisyros, Senecio ssp. on Nyiragongo, a Fern on Masaya and Salix arctica at Gorely. All samples were analyzed by ICP-MS and ICP-OES for 49 elements after acid digestion with a microwave oven (HNO3 + H2O2). Major constituents in leaves are K, Ca, Mg, Na, Si, Al and Fe ranging from about 10 3 to 105 ppm. Manganesium, Sr, Rb, Ba, Zn, B, Cu show also relatively high concentrations (100-103 ppm) while the remaining elements (As, Bi, Cd, Ce, Co, Cr, Cs, Ga, Li, Mo, Ni, Pb, Sb, Sc, Se, Th, Tl, U, V, Y and lanthanide series) display much lower values (10-4-101 ppm). Nearly all investigated elements show their highest concentrations in the samples collected closest to the main degassing vents (open craters, fumarolic fields). Increased concentrations are also found in the samples collected in the downwind direction where volcanic emissions are prevailingly dispersed. Leaves collected along radial transects from the active vents, highlight that the levels of metals decrease from one to two orders of magnitude with increasing distance from the source. The decrease is stronger for volatile elements, which are highly enriched in volcanic emissions, (As, Bi, Cd, Cs, Pb, Sb, Tl) than for more refractory elements (Al, Ba, Sc, Si, Sr, Th, U). The different species of plants show significant differences in the bioaccumulation processes for most of the analyzed elements, in particular lanthanides, which are systematically enriched in Rumex leaves. Needles of pine (non-deciduous tree) represent a good tool for biomonitoring investigation because they are important tracers of accumulation with time. The high concentrations of many toxic elements in the leaves allow us to consider some of these plants as highly tolerant species to the volcanic emissions, and suitable for biomonitoring researches further confirming their strong potential in tracing the impact and geographic distribution of these natural contaminants.