Falcone, Edda Elisa

Trace metals and Rare Earth Element (REE) are amply discharged by submarine hydrothermal vents, sometimes leading to the formation of ore deposits of economic interest. We report on first data on the geochemical processes involving REE and trace metals, at the solid-liquid interface, in the hydrothermal area of Levante Bay at Vulcano Island (Aeolian Archipelago, Italy). Samples were collected from several submarine springs and seeps, a mud pool and one thermal well, and analyzed for Al, Si, Ti, V, Cr, Mn, Fe, Co, As, Rb, Sr, Cs, Ba, U and REE, besides major ions. Within the bay, hydrothermal fluids contaminate seawater and promote the leaching of metals from sediments through the dissolution of CO2 and H2S, while the particulate matter removes several elements from the water. The leaching of the bottom sediments and the contribution of steam-heated water produce an enrichment of some metals and REE in the Levante Bay with respect to the concentrations expected in the ambient seawater. An enrichment up to one order of magnitude is measured for Fe, Al, Ba, Cs and Rb, and up to two orders of magnitude for Mn in the submarine samples. Other transition metals (Ti, V, Co, Cr), U, As and Sr have concentrations similar or slightly lower than the ambient seawater. REE are in concentrations higher than in ambient seawater up to two orders of magnitude. Despite being significantly higher than uncontaminated seawater, the concentrations of some metals (namely Fe, Al, Ti, Cr, V, Co, U) and REE in most samples are lower than expected by the mixing between seawater and the steam-heated water, discharging from submarine springs. Indeed, equilibrium and reaction path modeling indicate the likely precipitation of Fe-oxyhydroxides, able to remove minor elements, such as Ti, Cr, Co, V and As, and REE. The last ones are significantly removed by newly-forming solid phases, due to the presence of a large amount of Fe released by the acidic fluids through the leaching of sediments. The low pH limits the formation of solution complexes of REE with carbonate ions (the main complexing agent for REE in seawater), whereas the sorption onto particles is still effective, even at close distance from the submarine springs and seeps. This study brings new insights on the geochemical processes occurring in submarine hydrothermal systems, in particular, those in subduction-related context.

The Zirconium and Hafnium concentrations in worldwide fumaroles fed by magmatic fluids reveal that the Zr/Hf ratio is inversely related to the temperature of emission. Lower Zr/Hf ratio values below the chondritic signature are found in fluids having the highest temperature while super-chondritic Zr/Hf ratio values are found in lower temperatures. Sub-chondritic values of the Zr/Hf ratio may be related to larger volatility of Hf-chloride gas species with respect to Zr-Cl gas species, while super-chondritic ratios may correspond to fluid-rock processes resulting from cooling of uprising magmatic fluids. We propose that subchondritic Zr/Hf ratio values in fumaroles associated with high temperature may be an appropriate marker of fast magmatic rising representing a new sensitive tool for volcanic risks strategies.

We report on original geochemical data, which combine the rainfall trace metal contents from three different areas of Mt. Etna, variably fumigated by the volcanic plume, and those from soils, collected over the whole volcano. Trace element contents in rainfall appear mostly related to acidic ash leaching, while only for the most volatile elements (Cu, Zn, Cd, Pb, As, Sb, Tl, Se). We analyzed separately the labile fraction of soil samples, considered the fraction bioavailable to plants and soil organisms living in. The complexing medium used to extract the bioavailable fraction simulates the growth environment of plant roots.The contents of trace elements in the bioavailable fraction from soil samples showed peculiar patterns, apparently unrelated to the plume fumigation. The transition metal contents in the bioavailable fraction account for less than 15 % of the pseudo-total fraction and the highest contents were measured in the less acidic soil samples and farthest from the summit craters. In particular, high Fe, Mn, Co, Ni, Pb, Zn, Cd contents were paralleled by high soil organic carbon concentrations, which increased in the samples collected downwind the summit vents. Concerning immobile elements, their abundance in the bioavailable fraction was related to the degree of alteration of soils. Two elements, Se and Tl, were enriched in soil samples collected at closer distance from the summit vents. Their origin is probably related to the plume deposition.The study highlighted that the accessibility of plants to potentially harmful trace elements present in the soil is not simply related to the exposure to pollutants, but also to their fate in the pedogenetic environment.

Preliminary interpretation of geological processes during field measurement campaigns require fast data analysis to adapt ongoing target strategies. It is the case of soil investigations where coupling geochemical and geophysical records favors a better understanding of subsurface processes. This task requires (i) statistical analysis to identify areas of interest during spatial surveys and (ii) signal processing to analyze temporal series. Here we present SoilExp, an open-source Python-based Graphical User Interface (GUI) that permits to process spatial and temporal surveys of soil gases (e.g. soil CO2 flux) combined with common physical parameters (e.g. self-potential, temperature) that are synchronously recorded on the field. SoilExp mixes innovative algorithms with the more common tools used for the analysis of both spatial surveys or temporal series. It offers the possibility to display distribution plots, maps, comparative plots, spectra and spectrograms, as well as data statistical analysis, in order to deal efficiently with datasets acquired on the field. Field measurements performed at Stromboli (Italy) supports that such software solution facilitates a quick visualization of the data output and is a powerful tool on the geochemical and geophysical analysis.

In this study, the REE distribution between volcanic fluids and related solids in fumaroles with temperatures ranging from approximately 100 to 421 °C was investigated in different geological scenarios. The treatment of geochemical REE data was carried out by calculating the REE enrichment factors (EFREE) relative to the volcanic host rocks in studied sites under the assumption that the REE transport takes place as silicate aerosol in volcanic fluids. Shale-normalised REE concentrations in these fluids have been assessed to investigate whether the REE transport as aqueous complexes in water-saturated volcanic gas is reasonable. The REE behaviour in alkaline condensates according to the above mentioned treatments of geochemical data is very similar, being characterised by positive Ce and Gd anomalies and significant W-type tetrad effects. These evidences suggest that the geochemical behaviour of REE in fumarolic fluids is firstly influenced by the sublimate deposition along the fumarolic conduit or around the vents rather than by the transport mechanism of these elements in volcanic fluids. The Gd enrichment relative to its neighbours Eu and Tb induces the growth of positive Gd anomalies recognised in condensates that in turn results in Gd fluxes from the studied fumarolic systems ranging from 0.01 to 0.92 kg y− 1. This indication represents a novelty in the well-known geochemical Gd behaviour, where recognised positive Gd anomalies have usually been attributed to anthropogenic contamination.