Dissolved major and trace elements in meteoric depositions on the flanks of Mt. Etna (Italy): the impact of volcanic activity on the environment

In the framework of the “Save the Etna World” research project, which investigates the impact of the volcanic activity on the surrounding environment, three bulk collectors were deployed on the flank of the Mt. Etna volcano to collect the meteoric depositions. The sampling sites were at distances between 5.5 and 13 km from the summit vents of the volcano on its eastern flank, that is the most exposed to the volcanic plume due to the high-altitude prevailing winds direction. The sites were selected in order to have a gradient of exposition with respect to the volcanic emissions, the most exposed being CIT, the intermediate ILI and the least NIC. Samples were collected monthly from July 2017 to July 2018 and analysed for major ions and for a large suite of trace elements. The influence of volcanic emissions is evidenced by the low pH of the collected depositions in the most exposed site, showing values mostly below 3.5 and never exceeding 5.72. The lowest values are related to high fluoride, chloride and sulfate concentrations in the collected water, deriving from the acid gases (HF, HCl and SO2) of the volcanic plume. The other two sites show pH values in range from 3.95 to 7.21. While the lowest values indicate a lower but significant volcanic influence, the highest values can be related to the dissolution of geogenic (mainly carbonate) particulate of local or regional (Saharan) origin. The latter process is evidenced by high concentrations of Ca and HCO3 in the samples with the highest pHs. Trace elements show almost all higher concentrations in the most exposed site. Highly volatile elements like Pb, Te and Tl, which are known to have strong enrichment factors in volcanic plumes with respect to the average upper crust composition, are found at CIT at concentrations always at least one order of magnitude higher than at NIC. Also lithophile elements like Si, Al, Ti and Fe are sometimes strongly enriched at CIT deriving from the interaction of the acid gases of the plume with the occasionally emitted volcanic ash. These new results confirm the importance of meteoric deposition as main carrier of volcanogenic elements to earth’s surface. “Etna World” is a fascinating natural laboratory, and the study of atmospheric depositions in this peculiar environment allows to understand better the general processes that influence the cycles of trace metals. Furthermore, the quantitative estimation of both emission and deposition of volcanogenic elements is a key factor for complementary studies on the geochemical mobility of trace elements and their distribution between atmosphere, soils, vegetation, and lastly, animals and humans in active volcanic areas

Maximum Independent Set: Self-Training through Dynamic Programming

This work presents a graph neural network (GNN) framework for solving the maximum independent set (MIS) problem, inspired by dynamic programming (DP). Specifically, given a graph, we propose a DP-like recursive algorithm based on GNNs that firstly constructs two smaller sub-graphs, predicts the one with the larger MIS, and then uses it in the next recursive call. To train our algorithm, we require annotated comparisons of different graphs concerning their MIS size. Annotating the comparisons with the output of our algorithm leads to a self-training process that results in more accurate self-annotation of the comparisons and vice versa. We provide numerical evidence showing the superiority of our method vs prior methods in multiple synthetic and real-world datasets.Comment: Accepted in NeurIPS 202

Impact of Etna’s volcanic emission on major ions and trace elements composition of the atmospheric deposition

Mt. Etna, on the eastern coast of Sicily (Italy), is one of the most active volcanoes on the planet and it is widely recognized as a big source of volcanic gases (e.g., CO2 and SO2), halogens, and a lot of trace elements, to the atmosphere in the Mediterranean region. Especially during eruptive periods, Etna’s emissions can be dispersed over long distances and cover wide areas. A group of trace elements has been recently brought to attention for their possible environmental and human health impacts, the Technology-critical elements. The current knowledge about their geochemical cycles is still scarce, nevertheless, recent studies (Brugnone et al., 2020) evidenced a contribution from the volcanic activity for some of them (Te, Tl, and REE). In 2021, in the framework of the research project “Pianeta Dinamico”, by INGV, a network of 10 bulk collectors was implemented to collect, monthly, atmospheric deposition samples. Four of these collectors are located on the flanks of Mt. Etna, other two are in the urban area of Catania and three are in the industrial area of Priolo, all most of the time downwind of the main craters. The last one, close to Cesarò (Nebrodi Regional Park), represents the regional background. The research aims to produce a database on major ions and trace element compositions of the bulk deposition and here we report the values of the main physical-chemical parameters and the deposition fluxes of major ions and trace elements from the first year of research. The pH ranged from 3.1 to 7.7, with a mean value of 5.6, in samples from the Etna area, while it ranged between 5.2 and 7.6, with a mean value of 6.4, in samples from the other study areas. The EC showed values ranging from 5 to 1032 μS cm-1, with a mean value of 65 μS cm-1. The most abundant ions were Cl- and SO42- for anions, Na+ and Ca+ for cations, whose mean deposition fluxes, considering all sampling sites, were 16.6, 6.8, 8.4, and 6.0 mg m-2 d, respectively. The highest deposition fluxes of volcanic refractory elements, such as Al, Fe, and Ti, were measured in the Etna’s sites, with mean values of 948, 464, and 34.3 μg m-2 d-1, respectively, higher than those detected in the other sampling sites, further away from the volcanic source (26.2, 12.4, 0.5 μg m-2 d-1, respectively). The same trend was also observed for volatile elements of prevailing volcanic origin, such as Tl (0.49 μg m-2 d-1), Te (0.07 μg m-2 d-1), As (0.95 μg m-2 d-1), Se (1.92 μg m-2 d-1), and Cd (0.39 μg m-2 d-1). Our preliminary results show that, close to a volcanic area, volcanic emissions must be considered among the major contributors of ions and trace elements to the atmosphere. Their deposition may significantly impact the pedosphere, hydrosphere, and biosphere and directly or indirectly human health

Plume composition and volatile flux of Nyamulagira volcano, Democratic Republic of Congo, during birth and evolution of the lava lake, 2014–2015

Very little is known about the volatile element makeup of the gaseous emissions of Nyamulagira volcano. This paper tries to fill this gap by reporting the first gas composition measurements of Nyamulagira’s volcanic plume since the onset of its lava lake activity at the end of 2014. Two field surveys were carried out on 1 November 2014, and 13–15 October 2015. We applied a broad toolbox of volcanic gas composition measurement techniques in order to geochemically characterize Nyamulagira’s plume. Nyamulagira is a significant emitter of SO2, and our measurements confirm this, as we recorded SO2 emissions of up to ~ 14 kt/d during the studied period. In contrast to neighbouring Nyiragongo volcano, however, Nyamulagira exhibits relatively low CO2/SO2 molar ratios ( 92%of total gas emissions). Strong variations in the volatile composition, in particular for the CO2/SO2 ratio, were measured between 2014 and 2015, which appear to reflect the simultaneous variations in volcanic activity.We also determined the molar ratios for Cl/S, F/S and Br/S in the plume gas, finding values of 0.13 and 0.17, 0.06 and 0.11, and 2.3·10−4 and 1·10−4, in 2014 and 2015, respectively. A total gas emission flux of 48 kt/ d was estimated for 2014. The I/S ratio in 2015 was found to be 3.6·10−6. In addition, we were able to distinguish between hydrogen halides and non-hydrogen halides in the volcanic plume. Considerable amounts of bromine (18–35% of total bromine) and iodine (8–18%of total iodine) were found in compounds other than hydrogen halides. However, only a negligible fraction of chlorine was found as compounds other than hydrogen chloride.Published905V. Dinamica dei processi eruttivi e post-eruttiviJCR Journa

Degassing and Cycling of Mercury at Nisyros Volcano (Greece)

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 Lakki Plain, an intra-caldera area affected by widespread soil and fumarolic degassing. Concentrations of gaseous elemental mercury (GEM), 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 respect to Erica. Even though GEM concentrations in 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 (<0.1%) and only found very close to the main fumarolic vents, where the access to tourists is prohibited.PublishedID 47835146A. Geochimica per l'ambiente e geologia medicaJCR Journa

Determination of rare earth element and trace metals of geochemical interest in fumarolic gas. Validation of a ICP-MS method and statistical data evaluation through chemometric treatment

The variations of the chemical composition in volcanic gases emissions provide important information about the state of activity and evolutionary tendencies of the observed natural system. The purpose of this research is the validation of an analytical method for the quantification of the lanthanides and trace metals of geochemistry interest, in a complex matrix like fumarolic condensates collected on NaOH or in NH3 4M solution. The low concentrations of the searched species (ng/l) required the development of a preconcentration methodology on chelating resins followed by ICP-MS analysis, that has been tested on synthetic matrices, and subsequently, on sample withdrawn from the fumarolic gas of Volcano island. Problems concerning the recoveries of the analytes and the parameters of method validation are then discusses.PublishedCentro Congressi Hilton Palace Sorrento, Italy2.4. TTC - Laboratori di geochimica dei fluidiope

Monticchio Lakes

The crater lakes are a natural hazard for the population living near them because they can generate liminic explosions, like as the disaster of Nyos lake (Cameroon 1986), in which 1476 people and thousands of animals died. Crater lakes are able to store magmatic and hydrothermal gases and solubilising them into the water. An overpressure of the dissolved gases can generate a limnic eruption. Italy is characterised by an intense volcanic and seismic activity. Evidences of this past volcanism are the numerous crater lakes in Lazio and Campania. The most famous are Bolsena lakes, Vico, Bracciano, Monticchio lakes, Mezzano, Martignano, Albano, Nemi, Averno. The Monticchio lakes (Piccolo Lake (LPM) and the Grande Lake (LGM)) have formed in two maars localized in the Mt Vulture (Basilicata), a Quaternary, not active volcano, characterized by anomalous high flows of CO2 emitted by soils. They are separated by an isthmus of about 200 m. The two lakes have different morphological characteristics: LPM has an area of 160.000 m2, a steep floor and a maximum depth of 38 m. The LGM has an area of 380.000 m2, and the maximum depth of 36 m in its northern part. The two lakes solubilise high level of gases. The high CO2 tenors and the high values of He3/He4 isotope ratios are ascribable to a deep magmatic degassing. In this study we investigate the physicalchemical parameters (electrical conductivity, temperature, Eh and pH) and the chemical composition of major and traces elements along two bathymetric profiles. Monticchio Lakes were sampled in June 2018. The samples, taken in different depth, are 20 in total: ten from LMP and ten from LMG. The physicalchemical parameters were measured at different depth by a multiparametric probe. The major and trace elements are analyzed in the laboratory of INGV (Istituto Nazionale di Geofisica e Vulcanologia) in Palermo. The physicalchemical parameters show the different layers in Monticchio Lakes. In both lakes the range of temperature is 5.6 °C and 20 °C. Lakes show different range of pH being between 6.5 and 8.6 in LMP and between 6 and 7.6 in LMG. The range of Eh is between 152 and 258 mV and between 144 mV and 141 mV. in LMG and LMP respectively, being the negative values in depth due to anoxia phenomenon. The two lakes have a similar thermocline layer, around 6m. In summer, the both lakes are mostly layer because the sun energy warming the surface layer of lake. This phenomenon makes the hot layer upper the cold layer. In LMG, the range of electrical conductivity varies little with depth (411 526 microS/cm). Instead, in LMP, the range of electrical conductivity is greater ranging from 339 to 1456 microS/cm. For this reason, the halocline is different in both lakes, In LMP, the salt concentration increases with the depth. LMP and LMG waters in LangelierLudwing classificative plot have both bicarbonate earthalkaline compositions. On the contrary, traces elements (Li, Be, B, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Mo, Cd, Sn, Sb, Te, Cs, Ba, Pb, Bi and U) have different characteristics. In LMP, B, V, Mn, Zn, Sr, Cr, Fe and Mn show higher concentrations respect the other trace elements. Instead in LMG, the more concentrated trace elements are Li, Ti, Cs, Rb, Ba, Fe and Mn. In Both lakes’ Fe and Mn increase with the depth

Determination of rare earth element and trace metals of geochemical interest in fumarolic gas. Validation of a ICP-MS method and statistical data evaluation through chemometric treatment

The variations of the chemical composition in volcanic gases emissions provide important information about the state of activity and evolutionary tendencies of the observed natural system. The purpose of this research is the validation of an analytical method for the quantification of the lanthanides and trace metals of geochemistry interest, in a complex matrix like fumarolic condensates collected on NaOH or in NH3 4M solution. The low concentrations of the searched species (ng/l) required the development of a preconcentration methodology on chelating resins followed by ICP-MS analysis, that has been tested on synthetic matrices, and subsequently, on sample withdrawn from the fumarolic gas of Volcano island. Problems concerning the recoveries of the analytes and the parameters of method validation are then discusses

Geochemical characterization of trace elements in thermomineral waters of Greece

Trace elements have a fundamental role in natural and anthropogenic systems. In waters, they present a great variability of concentrations that mostly depends on the degree of gaswaterrock interactions and geochemical conditions such as pH, temperature, redox and/or exchange reactions, etc. Even though, they are present in very low contents in hostrocks, elevated concentrations in ground or surface waters may have a hazardous impact on human and animal health and thus, it is important to both quantify and try to understand their behaviour in natural systems. Here we present the results of about 300 cold and thermal mineral waters collected along the entire Hellenic territory. Physicochemical parameters (temperature, pH, electrical conductivity and Eh) were measured in situ, whilst samples were analysed by Ionic Chromatography (IC) and Inductively Coupled Plasma Mass Spectrometry (ICPMS) for their major and trace elements’ content. The great variability in hydrogeological settings justifies the wide range of temperatures (6.5 98° C) and pH (1.96 11.98). Total Dissolved Solids (TDS) values also covered a wide range, from 0.06 to 43 g/L. Based on the combination of pH, T and TDS, samples were subdivided into 5 classes: i) thermal waters; ii) thermal waters affected by sea water contamination; iii) cold CO2rich waters; iv) hyperalkaline waters; and v) acidic waters. The great variability in chemical composition of the sampled waters is reflected in the large range of trace element contents (four to five orders of magnitude). Thermal waters affected by seawater contamination show the strongest enrichments in Li (up to 17,600 μg/L), B (up to 38,200 μg/L), Sr (up to 80,000 μg/L) and Rb (up to 9230 μg/L), mostly deriving from waterrock interaction. Cold CO2rich waters display elevated concentrations of Mn (up to 3970 μg/L), Ni (up to 111 μg/L) and Fe (up to 218,000 μg/L), whilst at the water outflow an extensive precipitation of iron oxihydroxides is observed. Hyperalkaline waters are generally strongly depleted in trace elements due to the precipitation of secondary minerals, however they are enriched in Al (up to 421 μg/L). Aluminium becomes soluble at extreme pH conditions and therefore also acidic waters present enhanced concentrations (up to 100,000 μg/L). Acidic waters show also enrichments in Fe (up to 58,400 μg/L), Mn (up to 15,600 μg/L) and Ni (up to 101 μg/L). In some cases, the maximum contaminant levels (MCLs) fixed by the Directive 98/83/EC for drinking water (and subsequent updates), are strongly exceeded in the under investigation waters. Such elevated concentrations of harmful elements may create hazards to human health either via direct consumption of cold mineral waters or through mixing of highly mineralized waters even in small proportions with shallow groundwater. For instance, As (MCL 10 μg/L) in the sampled waters reaches concentrations up to 1820 μg/L that derive from high temperature waterrock interaction within the hydrothermal circuit

Mobility of REE from a hyperacid brine to secondary minerals precipitated in a volcanic hydrothermal system: Kawah Ijen crater lake (Java, Indonesia)

info:eu-repo/semantics/publishe