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Methylglyoxal (MGO) and glyoxal (GO) are toxic reactive carbonyl species generated as by-products of glycolysis. The pre-emption pathway for detoxification of these products, the glyoxalase (GLX) system, involves two consecutive reactions catalyzed by GLXI and GLXII. In Arabidopsis thaliana, the GLX system is encoded by three homologs of GLXI and three homologs of GLXII, from which several predicted GLXI and GLXII isoforms can be derived through alternative splicing. We identified the physiologically relevant splice forms using sequencing data and demonstrated that the resulting isoforms have different subcellular localizations. All three GLXI homologs are functional in vivo, as they complemented a yeast GLXI loss-of-function mutant. Efficient MGO and GO detoxification can be controlled by a switch in metal cofactor usage. MGO formation is closely connected to the flux through glycolysis and through the Calvin Benson cycle; accordingly, expression analysis indicated that GLXI is transcriptionally regulated by endogenous sugar levels. Analyses of Arabidopsis loss-of-function lines revealed that the elimination of toxic reactive carbonyl species during germination and seedling establishment depends on the activity of the cytosolic GLXI;3 isoform. The Arabidopsis GLX system involves the cytosol, chloroplasts, and mitochondria, which harbor individual components that might be used at specific developmental stages and respond differentially to cellular sugar status.

The Arabidopsis genome annotation include 11 glyoxalase I (GLXI) genes, all encoding for protein members of the vicinal oxygen chelate (VOC) superfamily. The biochemical properties and physiological importance of three Arabidopsis GLXI proteins in the detoxification of reactive carbonyl species has been recently described. Analyses of phylogenetic relationships and conserved GLXI binding sites indicate that the other eight GLXI genes (GLXI-like) do not encode for proteins with GLXI activity. In this perspective article we analyse the structural features of GLXI and GLXI-like proteins, and explore splice forms and transcript abundance under abiotic stress conditions. Finally, we discuss future directions of research on this topic with respect to the substrate identification of GLXI and GLXI-like proteins and the need of reliable quantitative measurements of reactive carbonyl species in plant tissues.

We have analyzed the carbon isotopic composition of CO 2 , methane, ethane, propane and n-butane, the hydrogen isotopic composition of methane as well as total concentrations of gas constituents contained in the Mediterranean volcanic–hydrothermal discharges of Nisyros (Greece), Vesuvio, La Solfatara, Ischia and Pantelleria (all Italy) to determine the origin of the hydrocarbons. Isotopic criteria conventionally used for hydrocarbon classification suggest thermogenic origins, except for Pantelleria, for which an abiogenic origin is indicated. These findings would imply that thermogenic sources can provide methane/(ethane + propane) concentration ratios as high as those usually observed for microbial hydrocarbons. However, additional consideration of gas concentration data challenges the suitability of conventional criteria for the classification of hydrocarbons emanating from hydrothermal environments. Methane seems to be in close equilibrium with co-occurring CO 2 , whereas its higher chain homologues are not. Therefore, it cannot be excluded that methane on the one hand and ethane, propane and n-butane on the other hand have distinct origins. The carbon isotopic composition of methane might be controlled by the carbon isotopic composition of co-occurring inorganic CO 2 and by hydrothermal temperatures whereas the carbon isotopic composition of the higher n-alkanes could correspond to the maturity of organic matter and/or to the residence time of the gasses in the source system.

Greece belongs to the most geodynamically active regions of the world and as such, it has to be considered an area of intense geogenic degassing. In terms of carbon, the territory is characterized by the high hydrothermal and volcanic activity of the South Aegean Active Volcanic Arc (SAAVA), and by widespread geological seeps of buried carbon dioxide and methane. In the present work, we investigate the island of Gyali located in the volcanic system Kos-Gyali-Nisyros. Nine gas samples have been collected on the island of Gyali in areas found both on land, in a small lake (∼2000 m2) along its beach, and in the sea close to the shore at shallow depths (

Geothermal areas of Greece are located in regions affected by recent volcanism and in continental basins characterised by elevated heat flow. Many of them are found along the coast, and thus, water is often saline due to marine intrusion. In the current study, we present about 300 unpublished and literature data from thermal and cold mineral waters collected along Greece. Samples were analysed for major ions, Li, SiO2 and isotopes in water. Measured temperatures range from 6.5 to 98 °C, pH from 1.96 to 11.98, while Total Dissolved Solutes (TDS) from 0.22 to 51 g/L. Waters were subdivided into four main groups: (1) thermal; (2) cold; (3) acidic (pH 11). On statistical basis, thermal waters were subdivided into subgroups according to both their temperature [warm ( 75 °C)] and TDS [low salinity ( 30 g/L)]. Cold waters were subdivided based on their pCO2 [low ( 0.85 atm)]. δ18O–H2O ranges from − 12.7 to + 2.7‰ versus SMOW, while δ2H–H2O from − 91 to + 12‰ versus SMOW being generally comprised between the Global Meteoric Water Line and the East Mediterranean Meteoric Water Line. Positive δ18O shifts with respect to the former are mostly related to mixing with seawater, while only for a few samples these shifts point to high-temperature water–rock interaction processes. Only a few thermal waters gave reliable geothermometric estimates, suggesting reservoir temperatures between 80 and 260 °C.

The Favara Grande is a geothermal area located on Pantelleria Island, Italy. The area is characterized high temperatures in the top layer of the soil (60°C), low pH (3–5) and hydrothermal gas emissions mainly composed of carbon dioxide (CO2), methane (CH4), and hydrogen (H2). These geothermal features may provide a suitable niche for the growth of chemolithotrophic thermoacidophiles, including the lanthanide-dependent methanotrophs of the phylum Verrucomicrobia. In this study, we started enrichment cultures inoculated with soil of the Favara Grande at 50 and 60°C with CH4 as energy source and medium containing sufficient lanthanides at pH 3 and 5. From these cultures, a verrucomicrobial methanotroph could be isolated via serial dilution and floating filters techniques. The genome of strain AP8 was sequenced and based on phylogenetic analysis we propose to name this new species Methylacidimicrobium thermophilum AP8. The transcriptome data at μmax (0.051 ± 0.001 h−1, doubling time ~14 h) of the new strain showed a high expression of the pmoCAB2 operon encoding the membrane-bound methane monooxygenase and of the gene xoxF1, encoding the lanthanide-dependent methanol dehydrogenase. A second pmoCAB operon and xoxF2 gene were not expressed. The physiology of strain AP8 was further investigated and revealed an optimal growth in a pH range of 3–5 at 50°C, representing the first thermophilic strain of the genus Methylacidimicrobium. Moreover, strain AP8 had a KS(app) for methane of 8 ± 1 μM. Beside methane, a type 1b [NiFe] hydrogenase enabled hydrogen oxidation at oxygen concentrations up to 1%. Taken together, our results expand the knowledge on the characteristics and adaptations of verrucomicrobial methanotrophs in hydrothermal environments and add a new thermophilic strain to the genus Methylacidimicrobium.

Twenty gas samples have been collected from the natural gas manifestations of Milos Island, the majority of which is found underwater along its coast. Furthermore, three anomalous degassing fumarolic areas (Kalamos, Paleochori and Adamas) have been recognized on-land. Almost all the gases are CO2-dominated with CO2 ranging from 88 to 99% vol for the samples taken underwater, while the on-land manifestations show a wider range (15–98%) due to air contamination. Methane reaches up to 1.0% vol, H2 up to 3.2% vol and H2S up to 3.5% vol indicating a hydrothermal origin of the gases. The isotope composition of He points out to mantle contributions up to 45%, while the C-isotope composition of CO2 (from −1.9 to +1.3‰ vs. V-PDB with most of the values around −0.5‰) suggests a prevailing limestone origin. Isotope composition of CH4, ranging from −18.4 to −5.0‰ vs. V-PDB for C and from −295 to +7‰ vs. V-SMOW for H, points to a geothermal origin with sometimes evident secondary oxidation processes. Additionally, CO2-flux measurements showed high values in the three fumarolic areas (up to 1100, 1500 and 8000 g/m2/d at Kalamos, Paleochori and Adamas respectively) with the highest CO2-flux values (up to about 23,000 g/m2/d) being measured in the sea at Kanavas with a floating chamber. The south-western part of the island was covered with a lower density prospection revealing only few anomalous CO2 flux values (up to 650 g/m2/d). The total output of the island (30.5 t/d) is typical of quiescent closed-conduit volcanoes and comparable to the other volcanic/geothermal systems of the south Aegean active volcanic arc (Nisyros, Kos, Nea Kameni, Methana and Sousaki).

The complex geology of Greece includes two important parallel running ophiolitic belts. The Othrys Massif in central Greece belongs to the westernmost of them. In the current study, 33 water samples from cold hyperalkaline and hypothermal (T < 40°C) alkaline springs and 30 gas samples (either dissolved or free) were collected at 17 different sites in and around this wide ophiolite outcrop, aiming to determine the origin of fluids and evidence gas-water-rock interaction processes taking place in the area. Water samples were analysed for their chemical (major ions and trace elements) and isotope (d18O-H2O, d2H-H2O) composition. They can be subdivided into alkaline (pH 11 and Ca-OH composition). Trace elements generally showed very low concentrations and mostly inversely correlated with pH. Gases were analysed for their chemical (He, Ne, Ar, H2, O2, N2, CH4, C2H6, CO2 and H2S) and isotope (d13C-CH4, d2H-CH4, d13C-CO2) composition. Samples from alkaline waters were mainly dominated by CH4 (from 128,000 to 915,000 μmol/mol), while hyperalkaline waters showed a N2-rich composition (from 727,000 to 977,000 μmol/mol). Methane had a wide range of isotope compositions (d13C-CH4 from -74.5 to -14.5 and d2H-CH4 from -343 to -62 ). Alkaline waters present the most negative isotope values for CH4, evidencing a biogenic (both thermogenic and microbial) origin. Many of the hyperalkaline waters had CH4 isotope values compatible with an abiogenic origin through serpentinization processes but occasionaly very negative values were recorded, indicating sometimes a clear biogenic contribution. Finally, few samples both from alkaline and hyperalkaline waters showed some evidence of secondary oxidation processes.

Samples of efflorescences and encrustations of hydrothermal origin were collected at Sousaki (Greece) and analysed for their mineralogical (XRD) and chemical composition. Solutions obtained both from mineralization with HNO3 and from leaching with deionised water were analysed for major (ICP-OES), minor and trace metals (ICP-MS) and sulfate contents (IC). Results evidence the dependence of the chemical and mineralogical composition on micro-environmental conditions i.e. humidity, oxygen-rich or -poor environment, exposed or sheltered from meteoric agents. In fact, the presence of highly soluble sulfate minerals with elevated contents of many metals (e.g. Mg, Al, Fe, Mn, Cr, Ni, etc.) further underscores the important influence of hydrothermal activity on elements' mobility, whilst the sometimes very high concentrations in toxic elements like Al, Cr, Ni suggest also possible environmental impacts.

The Favara Grande nature reserve on the volcanic island of Pantelleria (Italy) is known for its geothermal gas emissions and high soil temperatures. These volcanic soil ecosystems represent “hot spots” of greenhouse gas emissions. The unique community might be shaped by the hostile conditions in the ecosystem, and it is involved in the cycling of elements such as carbon, hydrogen, sulfur, and nitrogen. Our metagenome study revealed that most of the microorganisms in this extreme environment are only distantly related to cultivated bacteria. The results obtained profoundly increased the understanding of these natural hot spots of greenhouse gas production/degradation and will help to enrich and isolate the microbial key players. After isolation, it will become possible to unravel the molecular mechanisms by which they adapt to extreme (thermo/acidophilic) conditions, and this may lead to new green enzymatic catalysts and technologies for industry., Volcanic and geothermal environments are characterized by low pH, high temperatures, and gas emissions consisting of mainly CO2 and varied CH4, H2S, and H2 contents which allow the formation of chemolithoautotrophic microbial communities. To determine the link between the emitted gases and the microbial community composition, geochemical and metagenomic analysis were performed. Soil samples of the geothermic region Favara Grande (Pantelleria, Italy) were taken at various depths (1 to 50 cm). Analysis of the gas composition revealed that CH4 and H2 have the potential to serve as the driving forces for the microbial community. Our metagenomic analysis revealed a high relative abundance of Bacteria in the top layer (1 to 10 cm), but the relative abundance of Archaea increased with depth from 32% to 70%. In particular, a putative hydrogenotrophic methanogenic archaeon, related to Methanocella conradii, appeared to have a high relative abundance (63%) in deeper layers. A variety of [NiFe]-hydrogenase genes were detected, showing that H2 was an important electron donor for microaerobic microorganisms in the upper layers. Furthermore, the bacterial population included verrucomicrobial and proteobacterial methanotrophs, the former showing an up to 7.8 times higher relative abundance. Analysis of the metabolic potential of this microbial community showed a clear capacity to oxidize CH4 aerobically, as several genes for distinct particulate methane monooxygenases and lanthanide-dependent methanol dehydrogenases (XoxF-type) were retrieved. Analysis of the CO2 fixation pathways showed the presence of the Calvin-Benson-Bassham cycle, the Wood-Ljungdahl pathway, and the (reverse) tricarboxylic acid (TCA) cycle, the latter being the most represented carbon fixation pathway. This study indicates that the methane emissions in the Favara Grande might be a combination of geothermal activity and biological processes and further provides insights into the diversity of the microbial population thriving on CH4 and H2. IMPORTANCE The Favara Grande nature reserve on the volcanic island of Pantelleria (Italy) is known for its geothermal gas emissions and high soil temperatures. These volcanic soil ecosystems represent “hot spots” of greenhouse gas emissions. The unique community might be shaped by the hostile conditions in the ecosystem, and it is involved in the cycling of elements such as carbon, hydrogen, sulfur, and nitrogen. Our metagenome study revealed that most of the microorganisms in this extreme environment are only distantly related to cultivated bacteria. The results obtained profoundly increased the understanding of these natural hot spots of greenhouse gas production/degradation and will help to enrich and isolate the microbial key players. After isolation, it will become possible to unravel the molecular mechanisms by which they adapt to extreme (thermo/acidophilic) conditions, and this may lead to new green enzymatic catalysts and technologies for industry.

The eruption of Mt. Etna which occurred on December 24th 2018 was characterized by strombolian activity and fire fountains, emitted by the New South-East Crater and along a fissure that propagated towards the SE. The influence of volcanic emissions on atmospheric deposition was clearly detectable at several kilometres from the source. Wet and dry (bulk) deposition samples were collected each month, through a network of eleven collectors, in the areas of Milazzo, and Priolo between June 2018 and June 2019. They were analysed for major ions and trace elements concentrations. The pH values range from 3.9 to 8.3, while the EC values range from 7 to 396 μS cm-1. An extensive neutralization of the acidity has been recognised mainly due to the suspended alkaline dust particles, which have a buffering role in rainwater. A high load of Na+ and Cl- was observed at all sites, related to the closeness of the study areas to the coast, showing a high positive correlation (R2 = 0.989) along the line of Na+/Cl- ratio in seawater. During the eruption, the volcanic plume was carried by the winds for long distance (more than 300 km) affecting the area of Priolo but not that of Milazzo, which was upwind with respect to Mt. Etna. The impact of volcanic HF was clearly recognised in the samples collected after the eruption. Volcanic SO2 and HCl had a lower impact due to the overwhelming input of anthropogenic sulfate and marine chloride. On the contrary, the signature of the Mt. Etna eruption can be well recognised in the high concentrations of certain trace elements in the samples collected immediately after the eruption. The strongest contrast between affected and non-affected samples was recognised in Al, Cd, and especially in the volatile elements Tl and Te, which are typically enriched in volcanic emissions. The results showed that volcanic eruptions might have a relevant effect on the atmospheric chemistry and on the composition of rainwater up to distances of 80 km from the emission vents.

In this study, hydrogen sulfide (H2S) measurements in air carried out using (a) passive/diffusive samplers (Radiello® traps) and (b) a high-frequency (60 s) real-time analyzer (Thermo® 450i) were compared in order to evaluate advantages and limitations of the two techniques. Four different sites in urban environments (Florence, Italy) and two volcanic areas characterized by intense degassing of H2S-rich fluids (Campi Flegrei and Vulcano Island, Italy) were selected for such measurements. The concentrations of H2S generally varied over 5 orders of magnitude (from 101e103 mg/m3), the H2S values measured with the Radiello® traps (H2SR) being significantly higher than the average values measured by the Thermo® 450i during the trap exposure (H2STa), especially when H2S was

International audience; The Dead Sea Transform (DST) fault system, where a lateral displacement between the African and Arabian plates occurs, is characterised by anomalous heat flux in the Israeli area close to the border with Syria and Jordan. The concentration of He and CO2, and isotopic composition of He and total dissolved inorganic carbon were studied in cold and thermal waters collected along the DST, in order to investigate the source of volatiles and their relationship with the tectonic framework of the DST. The waters with higher temperature (up to 57.2 °C) are characterised by higher amounts of CO2 and helium (up to 55.72 and 1.91 * 10-2 cc l-1, respectively). Helium isotopic data (R/Ra from 0.11 to 2.14) and 4He/20Ne ratios (0.41-106.86) show the presence of deep-deriving fluids consisting of a variable mixture of mantle and crust end-members, with the former reaching up to 35%. Carbon isotope signature of total dissolved carbon from hot waters falls within the range of magmatic values, suggesting the delivery of deep-seated CO2. The geographical distribution of helium isotopic data and isotopic carbon (CO2) values coupled with (CO2/3He ratios) indicate a larger contribution of mantle-derived fluids affecting the northern part of the investigated area, where the waters reach the highest temperature. These evidences suggest the occurrence of a favourable tectonic framework, including a Moho discontinuity up-rise and/or the presence of a deep fault system coupled with the recent magmatic activity recognised in the northern part of Israel.

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 (

Volcanic and geothermal systems emit endogenous gases by widespread degassing from soils, including CH4, a greenhouse gas twenty-five times as potent as CO2. Recently, it has been demonstrated that volcanic or geothermal soils are not only a source of methane, but are also sites of methanotrophic activity. Methanotrophs are able to consume 10–40 Tg of CH4 a−1 and to trap more than 50% of the methane degassing through the soils. We report on methane microbial oxidation in the geothermally most active site of Pantelleria (Italy), Favara Grande, whose total methane emission was previously estimated at about 2.5 Mg a−1 (t a−1). Laboratory incubation experiments with three top-soil samples from Favara Grande indicated methane consumption values of up to 59.2 nmol g−1 soil d.w. h−1. One of the three sites, FAV2, where the highest oxidation rate was detected, was further analysed on a vertical soil profile, the maximum methane consumption was measured in the top-soil layer, and values greater than 6.23 nmol g−1 h−1 were still detected up to a depth of 13 cm. The highest consumption rate was measured at 37 °C, but a still detectable consumption at 80 °C (> 1.25 nmol g−1 h−1) was recorded. The soil total DNA extracted from the three samples was probed by Polymerase Chain Reaction (PCR) using standard proteobacterial primers and newly designed verrucomicrobial primers, targeting the unique methane monooxygenase gene pmoA; the presence of methanotrophs was detected at sites FAV2 and FAV3, but not at FAV1, where harsher chemical–physical conditions and negligible methane oxidation were detected. The pmoA gene libraries from the most active site (FAV2) pointed to a high diversity of gammaproteobacterial methanotrophs, distantly related to Methylocaldum-Metylococcus genera, and the presence of the newly discovered acido-thermophilic Verrucomicrobia methanotrophs. Alphaproteobacteria of the genus Methylocystis were isolated from enrichment cultures under a methane-containing atmosphere at 37 °C. The isolates grow at a pH range of 3.5 to 8 and temperatures of 18–45 °C, and consume 160 nmol of CH4 h−1 mL−1 of culture. Soils from Favara Grande showed the largest diversity of methanotrophic bacteria detected until now in a geothermal soil. While methanotrophic Verrucomicrobia are reported as dominating highly acidic geothermal sites, our results suggest that slightly acidic soils, in high-enthalpy geothermal systems, host a more diverse group of both culturable and uncultivated methanotrophs.

Shallow submarine gas vents in Levante Bay, Vulcano Island (Italy), emit around 3.6t CO2 per day providing a natural laboratory for the study of biogeochemical processes related to seabed CO2 leaks and ocean acidification. The main physico-chemical parameters (T, pH and Eh) were measured at more than 70 stations with 40 seawater samples were collected for chemical analyses. The main gas vent area had high concentrations of dissolved hydrothermal gases, low pH and negative redox values all of which returned to normal seawater values at distances of about 400 m from the main vents. Much of the bay around the vents is corrosive to calcium carbonate; the north shore has a gradient in seawater carbonate chemistry that is well suited to studies of the effects of long-term increases in CO2 levels. This shoreline lacks toxic compounds (such as H2S) and has a gradient in carbonate saturation states.

The geochemical behaviour of Rare Earth Elements, Zr and Hf was investigated in the thermal waters of Nevado del Ruiz volcano system. A wide range of pH, between 1.0 and 8.8, characterizes these fluids. The acidicwaters are sulphate dominatedwith different Cl/SO4 ratios. The important role of the pH and the ionic complexes for the distribution of REE, Zr a nd Hf in the aqueous phase was evidenced. The pH rules the precipitation of authigenic Fe and Al oxyhydroxides producing changes in REE, Zr, Hf amounts and strong anomalies of Cerium. The precipitation of alunite and jarosite removes LREE from the solution, changing the REE distribution in acidic waters. Y-Ho and Zr-Hf (twin pairs) have a different behaviour in strong acidic waterswith respect to the water with pH near-neutral. Yttrium and Ho behave as Zr and Hf in waters with pH near neutral-to-neutral, showing superchondritic ratios. The twin pairs showed to be sensitive to the co-precipitation and/or adsorption onto the surface of authigenic particulate (Fe-, Al-oxyhydroxides), suggesting an enhanced scavenging of Ho and Hf with respect to Y and Zr, leading to superchondritic values. In acidic waters, a different behaviour of twin pairs occurs with chondritic Y/Ho ratios and sub-chondritic Zr/Hf ratios. For the first time, Zr and Hf were investigated in natural acidic fluids to understand the behaviour of these elements in extreme acidic conditions and different major anion chemistry. Zr/Hf molar ratio changes from 4.75 to 49.29 in water with pH < 3.6. In strong acidic waters the fractionation of Zr and Hf was recognized as function of major anion contents (Cl and SO4), suggesting the formation of complexes leading to sub-chondritic Zr/Hf molar ratios.

Alkaline lakes like the hydrothermally affected lake Specchio di Venere (Pantelleria Island, Central Mediterranean) are typical geological settings harbouring calcified microbial mats. The present work is focused on the discrimination between biotic and abiotic processes driving carbonate precipitation in this lake, using hydrochemical, mineralogical and isotopic data. Hydrochemical analyses demonstrate that the lake is nearly 10−fold supersaturated with regard to aragonite and seasonally reaches hydromagnesite supersaturation. Microscopic observations depict organosedimentary laminated structures consisting of microbial communities and aragonitic precipitates, which are rather disseminated in pores than directly linked to microorganisms. Oxygen isotopic data indicate that authigenic carbonate crystallisation from evaporating water is the dominant precipitation process, further suggested by the absence of textural evidence of diagenetic processes. Conversely, the observed δ13C values reflect an influence of extracellular polymeric substances (EPS) on carbon fractionation during the precipitation process, due to the selective sequestration of 12C in the biomass. The above considerations suggest that at lake Specchio di Venere the carbonate precipitation is mainly of inorganic nature, but a minor role played by biologically influenced processes in microbial mats is not excluded.

Volcanic emissions represent one of the most relevant natural sources of trace elements to the troposphere. Due to their potential toxicity, they may have important environmental impacts from local to global scale. They can also severely affect the atmospheric and terrestrial environment at timescales ranging from a few to millions of years. Mt. Etna volcano is known as one of the largest global contributors of magmatic gases (CO2, SO2 and halogens) and particulate matter, including some toxic trace elements. The aim of this study is to characterize the chemical composition and the mineralogical features of the volcanogenic aerosol passively emitted from Mt. Etna. Twenty-five samples were collected by filtration technique from different sites between 2008 and 2014. Chemical and mineralogical analyses allowed to discriminate two main constituents: the first is mainly referable to the silicate component in the volcanic plume, like lithic, juvenile fragments or glass shards and crystals (e.g. plagioclases, pyroxenes, oxides); the second constituent consists of soluble compounds like sulphosalts or halide minerals (sulphates, chlorides and fluorides). Fluxes of major and trace metals emitted in the atmosphere have been estimated. By comparing the Etnean trace elements with those from European anthropic emissions, we conclude that Mt. Etna is the main persistent point source of major and trace metals in the Mediterranean region. Results gathered from this investigation is of fundamental importance due to the exposure and potential impact of harmful chemical compounds for hundred thousand tourist visits each year to the summit of Mt. Etna.

This paper documents arsenic concentrations in 157 groundwater samples from the island of Ischia and the Phlegrean Fields, two of the most active volcano-hosted hydrothermal systems from the Campanian Volcanic Province (Southern Italy), in an attempt to identify the environmental conditions and mineral-solution reactions governing arsenic aqueous cycling. On Ischia and in the Phlegrean Fields, groundwaters range in composition from NaCl brines, which we interpret as the surface discharge of deep reservoir fluids, to shallow-depth circulating fluids, the latter ranging from acid-sulphate steam-heated to hypothermal, cold, bicarbonate groundwaters. Arsenic concentrations range from 1.6 to 6900 μg·l- 1 and from 2.6 to 3800 μg·l- 1 in the Phlegrean Fields and on Ischia, respectively. They increase with increasing water temperature and chlorine contents, and in the sequence bicarbonate groundwaters < steam-heated groundwaters < NaCl brines. According to thermochemical modeling, we propose that high As concentrations in NaCl brines form after prolonged water-rock interactions at reservoir T, fO2 and fH2S conditions, and under the buffering action of an arsenopyrite + pyrite + pyrrhotite rock assemblage. On their ascent toward the surface, NaCl brines become diluted by As-depleted meteoric-derived bicarbonate groundwaters, giving rise to hybrid water types with intermediate to low As contents. Steam-heated groundwaters give their intermediate to high As concentrations to extensive rock leaching promoted by interaction with As-bearing hydrothermal steam. © 2005 Elsevier B.V. All rights reserved.

International audience; The geochemical behaviour of Rare Earth Elements, Zr and Hf was investigated in the thermal waters of Nevado del Ruiz volcano system. A wide range of pH, between 1.0 and 8.8, characterizes these fluids. The acidic waters are sulphate dominated with different Cl/SO4 ratios. The important role of the pH and the ionic complexes for the distribution of REE, Zr and Hf in the aqueous phase was evidenced. The pH rules the precipitation of authigenic Fe and Al oxyhydroxides producing changes in REE, Zr, Hf amounts and strong anomalies of Cerium. The precipitation of alunite and jarosite removes LREE from the solution, changing the REE distribution in acidic waters.Y–Ho and Zr–Hf (twin pairs) have a different behaviour in strong acidic waters with respect to the water with pH near-neutral. Yttrium and Ho behave as Zr and Hf in waters with pH near neutral-to-neutral, showing super-chondritic ratios. The twin pairs showed to be sensitive to the co-precipitation and/or adsorption onto the surface of authigenic particulate (Fe-, Al-oxyhydroxides), suggesting an enhanced scavenging of Ho and Hf with respect to Y and Zr, leading to superchondritic values. In acidic waters, a different behaviour of twin pairs occurs with chondritic Y/Ho ratios and sub-chondritic Zr/Hf ratios. For the first time, Zr and Hf were investigated in natural acidic fluids to understand the behaviour of these elements in extreme acidic conditions and different major anion chemistry. Zr/Hf molar ratio changes from 4.75 to 49.29 in water with pH < 3.6. In strong acidic waters the fractionation of Zr and Hf was recognized as function of major anion contents (Cl and SO4), suggesting the formation of complexes leading to sub-chondritic Zr/Hf molar ratios.

Volatile metal(loid)s are known to be emitted from volcanoes worldwide. We tested the suitability of active moss monitoring for tracking volatile metal(loid)s released from the fumarolic field on Vulcano Island, Italy, and differentiated fumaroles from other sources of gaseous and particulate trace elements such as sea spray and soil. Metal(loid) accumulation on the mosses per day did depend neither on the state of the exposed moss (dead or living) nor exposure time (3, 6, or 9 weeks). After collection, mosses were digested with either HNO3/H2O2 or deionized water and analyzed by ICP-MS. While for most elements both extraction methods yielded similar concentrations, higher concentrations were observed e.g. for Pb in the stronger HNO3/H2O2 extracts, indicating the presence of particles, which were not digested and removed by filtration in deionized water extracts. Due to their ubiquitous detection in comparable concentrations at all 23 moss monitoring stations all over the island, Li, Mg and Sr were attributed to sea spray origin. Iron, Co, W, V, Pb, Cr, Mo, and Ba occurred predominantly at the crater, where the soil was not covered by vegetation, and thus likely represent soil-borne particulate transport. Arsenic, Sb, S, Se, Tl, Bi, and I showed a clear concentration maximum within the fumarolic field. Concentrations gradually decreased along a transect in wind direction from the fumaroles, which confirms their volcanic origin. Active moss monitoring thus proved to be an inexpensive and easy-to-apply tool for investigations of volcanic metal(loid) emissions and distributions enabling differentiation of trapped elements by their source of origin.

International audience; The significant amounts of selenium (Se) emitted by volcanoes may have important impact on human health due to the narrow range between nutrition requirement and toxic effects for living organisms upon Se exposure. Although soils play a key role in determining the level in food and water and thereby human health, little is known about the behaviour of Se in volcanic soils. In this work we evaluated the Se release during rainwater–soil interaction under controlled conditions using soils collected on the flanks of Etna volcano and synthetic rain. Selenium concentrations in soil leachate solutions displayed a spatial distribution, which cannot be explained by plume deposition, total Se soil concentrations or the presence of Fe oxides. Instead, Al compounds and to a minor extent SOM were identified as the active phases controlling the selenate mobilization during interaction with sulphate-containing rainwater. This shows the importance of soils as reactive interfaces. Selenium is mobilized when volcanic-derived acid rain interacts with poorly developed soils close to the crater. This geogenic process might influence the chemical composition of groundwater and as a result, human health.

Water samples collected from public drinking water supplies in Sicily were analysed for electric conductivity and for their chloride, sulphate and nitrate contents. The samples were collected as uniformly as possible from throughout the Sicilian territory, with an average sampling density of about one sample for every 7,600 inhabitants. Chloride contents that ranged from 5.53 to 1,302 mg/l were correlated strongly with electric conductivity, a parameter used as a proxy for water salinity. The highest values are attributable to seawater contamination along the coasts of the island. High chloride and sulphate values attributable to evaporitic rock dissolution were found in the central part of Sicily. The nitrate concentrations ranged from 0.05 to 296 mg/l, with 31 samples (4.7% of the total) exceeding the maximum admissible concentration of 50 mg/l. Anomalous samples always came from areas of intensive agricultural usage, indicating a clear anthropogenic origin. The same parameters were also measured in bottled water sold in Sicily, and they all were within the ranges for public drinking water supplies. The calculated mean nitrate intake from consuming public water supplies (16.1 mg/l) did not differ significantly from that of bottled water (15.2 mg/l). Although the quality of public water supplies needs to be improved by eliminating those that do not comply with the current drinking water limits, at present it does not justify the high consumption of bottled water (at least for nitrate contents).

[1] We report first data on chemical composition of the gas emitted by the geothermal system of Sousaki, Greece. Gas manifestations display typical geothermal gas composition with CO2 as the main component and CH4 and H2S as minor species. Soil gas composition derives from the mixing of two end-members (atmospheric air and geothermal gas). Soil CO2 fluxes range from

The S, halogen and NO 3 contents of rainwater samples from the Etnean area were studied in order to define the environmental impact of plume emissions on the local environment. Samples, collected on a network of 11 bulk rain gauges, show significant variability in anion content, which can be ascribed to different meteorological and environmental conditions at each sampling site and to a variable distance from the different source areas. Data analysis suggests that S, F, Cl and Br are mainly magma-derived, whereas NO 3 mainly originates from anthropogenic sources. Samples collected from sites close to craters display considerable temporal variability, with increased anion concentrations being recorded during periods of intense plume degassing. Variations in precipitation also induce significant modifications in the chemistry of the meteoric-derived Etnean groundwaters.

The genus Methylobacter is considered an important and often dominant group of aerobic methane-oxidizing bacteria in many oxic ecosystems, where members of this genus contribute to the reduction of CH4 emissions. Metagenomic studies of the upper oxic layers of geothermal soils of the Favara Grande, Pantelleria, Italy, revealed the presence of various methane-oxidizing bacteria, and resulted in a near complete metagenome assembled genome (MAG) of an aerobic methanotroph, which was classified as a Methylobacter species. In this study, the Methylobacter sp. B2 MAG was used to investigate its metabolic potential and phylogenetic affiliation. The MAG has a size of 4,086,539 bp, consists of 134 contigs and 3955 genes were found, of which 3902 were protein coding genes. All genes for CH4 oxidation to CO2 were detected, including pmoCAB encoding particulate methane monooxygenase (pMMO) and xoxF encoding a methanol dehydrogenase. No gene encoding a formaldehyde dehydrogenase was present and the formaldehyde to formate conversion follows the tetrahydromethanopterin (H4MPT) pathway. “Ca. Methylobacter favarea” B2 uses the Ribulose-Mono-Phosphate (RuMP) pathway for carbon fixation. Analysis of the MAG indicates that Na+/H+ antiporters and the urease system might be important in the maintenance of pH homeostasis of this strain to cope with acidic conditions. So far, thermoacidophilic Methylobacter species have not been isolated, however this study indicates that members of the genus Methylobacter can be found in distinct ecosystems and their presence is not restricted to freshwater or marine sediments.

Volcanic and geothermal areas are hot and often acidic environments that emit geothermal gasses, including H2, CO and CO2. Geothermal gasses mix with air, creating conditions where thermoacidophilic aerobic H2- and CO-oxidizing microorganisms could thrive. Here, we describe the isolation of two Kyrpidia spormannii strains, which can grow autotrophically by oxidizing H2 and CO with oxygen. These strains, FAVT5 and COOX1, were isolated from the geothermal soils of the Favara Grande on Pantelleria Island, Italy. Extended physiology studies were performed with K. spormannii FAVT5, and showed that this strain grows optimally at 55°C and pH 5.0. The highest growth rate is obtained using H2 as energy source (μmax 0.19 ± 0.02 h-1, doubling time 3.6 h). K. spormannii FAVT5 can additionally grow on a variety of organic substrates, including some alcohols, volatile fatty acids and amino acids. The genome of each strain encodes for two O2-tolerant hydrogenases belonging to [NiFe] group 2a hydrogenases and transcriptome studies using K. spormannii FAVT5 showed that both hydrogenases are expressed under H2 limiting conditions. So far no Firmicutes except K. spormannii FAVT5 have been reported to exhibit a high affinity for H2, with a Ks of 327 ± 24 nM. The genomes of each strain encode for one putative CO dehydrogenase, belonging to Form II aerobic CO dehydrogenases. The genomic potential and physiological properties of these Kyrpidia strains seem to be quite well adapted to thrive in the harsh environmental volcanic conditions.