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International audience; We investigated the distribution of Zr, Hf, and rare earth elements (REE) as the sum of lanthanides plus Y in the hydrothermal system in the Lake Van area of south-eastern Turkey. This system is characterised by water with variable pH in alkaline conditions resulting from hydrothermal CO2 upraise and neoformation of calcite minerals in near equilibrium with the interacting waters. Zr, Hf, and REE determinations were carried out for aqueous phases and suspended solids in lake water and surrounding thermal springs. We found that dissolved Hf is partitioned relative to Zr during calcite formation and that such fractionation is a function of the Ca2+ activity in warm water. The observed Zrsingle bondHf fractionation is explained by coulombic interactions that occur between suspended solid particles and dissolved phases at the calcite-water interface. There, the surfaces of carbonate minerals demonstrated greater reactivity towards aqueous Hf-bearing species relative to Zr-complexes. This evidence involves a coulombic mechanism of reactivity at the calcite-water interface because Hf complexes are negatively charged while Zr compounds are uncharged. Thus, authigenic calcite can behave as a suitable host for dissolved metal ion species to adsorb on crystal surfaces to remediate waste waters from mine drainage.

Several shallow landslides occurred at La Fossa cone (Vulcano Island, Aeolian Archipelago, Italy) in the last 30 years, during both unrests and periods of quiet volcanic activity. The main event occurred in 1988, during a volcanic unrest, when a landslide collapsed into the sea from the NE flank of La Fossa cone, producing a small tsunami. Hydrothermal activity has been suggested as a potential trigger for landslide generation in this area. However, no specific investigations were carried out to test this hypothesis. With the aim of filling this gap, we studied the mineralogy and hydraulic conductivity of La Fossa cone deposits, the relationships between shallow hydrothermal circulation and rainfall dynamics and their role in triggering slope failures. We also measured rainfall rate, volumetric soil moisture content and soil suction at two automated stations installed in areas with and without active hydrothermal circulation. We found that hydrothermally altered low-conductivity materials show higher background water contents and lower soil suctions than pristine deposits, and their water content is modulated by impulsive increments following rainfalls. This behaviour is due to the combination of lower permeability and direct condensation of hydrothermal vapour. We conclude that shallow hydrothermal circulation produces conditions for slope failures following transients in soil moisture content caused by rainfall infiltration. These considerations allow to identify the areas immediately NW and SE of the 1988 landslide as the most prone to future mass movements.

Venere Lake, in the Pantelleria Island thermal system (Central Mediterranean Sea) consists of a mix of seawater and hydrothermal volcanic fluids containing high levels of dissolved SiO 2 . Close to the lake's thermal springs, siliceous stromatolites are deposed under high bacterial activity conditions whereas roughly interlaminated Ca-carbonates and microbial mats are widely scattered in the lake. The dissolved REE speciation in lake waters is dominated by [REE(CO 3 ) 2 ] − , [REE(CO 3 )] + and [REE(H 3 SiO 4 )] 2 + complexes. On the contrary the most abundant Zr and Hf species are hydroxyl- and fluoride-complexes. The behavior of REE Zr and Hf in the Venere lake waters is controlled by precipitation of amorphous silica, carbonates and bacterial activity. Chondrite-normalized REE patterns in stromatolites are characterized by positive La anomalies, superchondritic Y/Ho ratios and negative Eu anomalies. The Eu depletion is also found in microbial mats where is associated to a “chondritic” Y/Ho signature. Zr and Hf differently behave in dissolved phase and in newly-formed siliceous and carbonatic material: Hf reacts easily into amorphous silica surfaces whereas Zr is preferentially partitioned onto phosphate binding sites on microbial cell surfaces similar to the observed behavior of heavy REE (HREE). We suggest that the Zr-Hf relationship reflect the interface processes between mineral phases and bacterial membranes or compounds produced by bacterial activity.

Rare earth elements (REE) were investigated in siliceous stromatolites forming in the Specchio di Venere Lake on Pantelleria Island. Chondrite-normalised patterns show significant La enrichments and Eu depletions suggesting that fluids involved in stromatolite growth experienced strong rock-water interactions under hydrothermal conditions. At the same time, enrichments in heavy REE (HREE) with respect to intermediate REE (MREE) suggest that hydrothermal fluids interacted with microbial mats during deposition of the stromatolites. The above-mentioned features suggest that rock-water interactions and bacterial activity were simultaneously recorded in the REE patterns of stromatolites, and can be discriminated in terms of amplitudes of the La anomaly, and the HREE/MREE ratio.