Volatile organic compounds (VOCs) from diffuse degassing areas: Interstitial soil gases as message bearers from deep hydrothermal reservoirs.

The chemical composition of volatile organic compounds (VOCs) in interstitial soil gases from hydrothermal areas is commonly shaped by both deep hydrothermal conditions (e.g., temperature, redox, sulfur fugacity) and shallow secondary processes occurring near the soil-atmosphere interface. Caldara di Manziana and Solfatara di Nepi, i.e., two hydrothermal systems characterized by diverse physicochemical conditions located in the Sabatini Volcanic District and Vicano-Cimino Volcanic District, respectively (Central Italy), were investigated to evaluate the capability of VOCs in soil gases to preserve information from the respective feeding deep fluid reservoirs. Hierarchical cluster analyses and robust principal component analyses allowed recognition of distinct groups of chemical parameters of soil gases collected from the two study areas. The compositional dissimilarities from the free-gas discharges were indeed reflected by the chemical features of soil gases collected from each site, despite the occurrence of shallow processes, e.g., air mixing and microbial degradation processes, affecting VOCs. Four distinct groups of VOCs were recognized suggesting similar sources and/or geochemical behaviors, as follows: (i) S-bearing compounds, whose abundance (in particular that of thiophenes) was strictly dependent on the sulfur fugacity in the feeding system; (ii) C4,5,7+ alkanes, n-hexane, cyclics and alkylated aromatics, related to relatively low-temperature conditions at the gas source; (iii) C2,3 alkanes, benzene, benzaldehyde and phenol, i.e., stable compounds and thermal degradation products; and (iv) aliphatic O-bearing compounds, largely influenced by shallow processes within the soil. However, they maintain a chemical speciation that preserves a signature derived from the supplying deep-fluids, with aldehydes and ketones becoming more enriched after intense interaction of the hypogenic fluids with shallow aquifers. Accordingly, the empirical results of this study suggest that the chemical composition of VOCs in soil gases from hydrothermal areas provides insights into both deep source conditions and fluid circulation dynamics, identifying VOCs as promising geochemical tracers for geothermal exploration.

Mercury distribution in plants and soils from the former mining area of Abbadia San Salvatore (Tuscany, Central Italy).

The distribution of heavy metals in plants (Castanea sativa, Sambucus nigra, Verbascum thapsus, Popolus spp., Salix spp., Acer pseudoplatanus, Robinia pseudoacacia) growing in soils from active and abandoned mining areas is of scientific significance as it allows to recognize their ability to survive in a hostile environment and provide useful indications for phytoremediation operations. In this work, soils from the former Hg-mining area of Abbadia San Salvatore (Tuscany, Central Italy) were analyzed for total, leached Hg, % of organic and inorganic-related Hg. The dehydrogenase enzyme activity (DHA) was also measured with the aim to evaluate the status of the soil, being characterized by high Hg contents (up to 1068 mg kg-1). Eventually, the concentration of Hg in the different parts of the plants growing on these soils was also determined. Most studied soils were dominated by inorganic Hg (up to 92%) while the DHA concentrations were < 151 µg TPF g-1 day-1, suggesting that the presence of Hg is not significantly affecting the enzymatic soil activity. This is also supported by the bioaccumulation factor (BF), being predominantly characterized by values < 1. Sambucus nigra and Verbascum thapsus had the highest Hg contents (39.42 and 54.54 mg kg-1, respectively). The plant leaves appear to be the main pathways of Hg uptake, as also observed in other mining areas, e.g., Almadèn (Spain), indicating that particulate-Hg and Hg0 are the main forms entering the plant system, the latter derived by the GEM emitted by both the edifices hosting the roasting furnaces and the soils themselves.

Mercury distribution in plants and soils from the former mining area of Abbadia San Salvatore (Tuscany, central Italy).

The distribution of heavy metals in plants growing in soils from active and abandoned mining areas is of scientific significance as it allows one to recognize their ability to survive in a hostile environment and to provide useful indications for phytoremediation operations. In this work, soils developed in the former Hg-mining area of Abbadia San Salvatore (Tuscany, Central Italy) were analyzed for total, leached Hg, % of organic- and inorganic-related Hg. The dehydrogenase enzyme activity (DHA) was also measured with the aim to evaluate the status of the soil, being characterized by high Hg content. Eventually, the concentration of Hg in the different parts of the plants growing on these soils was analyzed. The soils showed Hg content up to 1068 mg kg - 1 and in most of them is dominated by inorganic Hg (up to 92%). The DHA concentrations were < 151 µg TPF g - 1 day - 1 , suggesting that the presence of Hg is not significantly affecting the enzymatic soil activity. This is also supported by the bioaccumulation factor (BF) that is < 1 in most of the studied plants. Generally speaking, the plant leaves appear to be one of the main pathways of Hg uptake, as also observed in other mining areas, e.g. Almaden (Spain), suggesting that particulate-Hg and Hg 0 are the main forms entering the plant system, the latter derived by the GEM emitted by both the edifices hosting the roasting furnaces and the soils themselves.

Contamination Assessment and Temporal Evolution of Nitrates in the Shallow Aquifer of the Metauro River Plain (Adriatic Sea, Italy) after Remediation Actions.

Over the last decades, groundwater resources at global level have suffered a significant deterioration due to nitrate pollution, mainly related to the input of agricultural fertilizers, manure, sewage, and untreated urban and industrial effluents. The most impacted waters are those forming surface and shallow reservoirs, which usually play a key role in supplying waters to civil, agricultural, and industrial activities. The terminal portion of the Metauro River plain, located in central Italy along the Adriatic Sea coastline, hosts a strategic phreatic aquifer that, along with the surface water of the Metauro River, supplies water to the local population (i.e., about 60,000 people). This shallow coastal aquifer experiences a long-lasting story of nitrate contamination since the 1970s when the increase in the use of agricultural fertilizers contributed to very high levels of pollution (NO3- > 100 mg/L). This fact prompted the local authorities to carry out remediation actions that involve a pumping system to inject the NO3--poor waters from the Metauro River course directly into the shallow aquifer. The present work was aimed at defining the contamination of nitrates in this important water resource. The main geochemical characteristics and the temporal evolution of NO3- concentrations (between 2009 and 2020), in the shallow coastal aquifer of the Metauro River plain, were analyzed by means of classical geochemical analyses and multivariate methods accounting for the compositional nature of the data, to assess the efficiency of the in-situ remediation over time.

Interplay between abiotic and microbial biofilm-mediated processes for travertine formation: Insights from a thermal spring (Piscine Carletti, Viterbo, Italy).

Active hydrothermal travertine systems are ideal environments to investigate how abiotic and biotic processes affect mineralization mechanisms and mineral fabric formation. In this study, a biogeochemical characterization of waters, dissolved gases, and microbial mats was performed together with a mineralogical investigation on travertine encrustations occurring at the outflow channel of a thermal spring. The comprehensive model, compiled by means of TOUGHREACT computational tool from measured parameters, revealed that mineral phases were differently influenced by either abiotic conditions or microbially driven processes. Microbial mats are shaped by light availability and temperature gradient of waters flowing along the channel. Mineralogical features were homogeneous throughout the system, with euhedral calcite crystals, related to inorganic precipitation induced by CO2 degassing, and calcite shrubs associated with organomineralization processes, thus indicating an indirect microbial participation to the mineral deposition (microbially influenced calcite). The microbial activity played a role in driving calcite redissolution processes, resulting in circular pits on calcite crystal surfaces possibly related to the metabolic activity of sulfur-oxidizing bacteria found at a high relative abundance within the biofilm community. Sulfur oxidation might also explain the occurrence of gypsum crystals embedded in microbial mats, since gypsum precipitation could be induced by a local increase in sulfate concentration mediated by S-oxidizing bacteria, regardless of the overall undersaturated environmental conditions. Moreover, the absence of gypsum dissolution suggested the capability of microbial biofilm in modulating the mobility of chemical species by providing a protective envelope on gypsum crystals.

Geochemical and microbiological profiles in hydrothermal extreme acidic environments (Pisciarelli Spring, Campi Flegrei, Italy).

Although terrestrial hydrothermal systems are considered among the most fascinating environments, how their unique and extreme conditions can affect microorganisms selection and the role in biogeochemical cycles has not yet been well elucidated. A combined geochemical and microbiological exploration in waters and sediments from 10 sampling points along a sharp temperature gradient (15-90°C) within an extremely acidic hydrothermal system (Pisciarelli Spring, Campi Flegrei area, southern Italy) displayed how hydrothermal fluids influence the microbial dynamics. This area was characterized by high levels of reduced gaseous species (e.g. H2S, H2, CH4, CO) and very low pH values (<2.3). Thermodynamic calculations revealed a high microbial catabolic potential in oxidation/reduction reactions of N-, S- and Fe-bearing species. Overall, an increase of the archaeal/bacterial abundance ratio was observed by decreasing temperature and pH values. In particular, Archaea and Bacteria were present in almost equal cell abundance (up to 1.1 × 109 and 9.3 × 108 cell/g, respectively) in the <70°C sampling points (average pH = 2.09); on the contrary, the highest temperature waters (85-90°C; average pH = 2.26) were characterized by a low abundance of archaeal cells. The high-throughput sequencing of the 16S rRNA genes indicated strong differences in archaeal and bacterial communities composition along the temperature gradient. However, the microbiome in this extreme environment was mainly constituted by chemoautotrophic microorganisms that were likely involved in N-, S- and Fe-bearing species transformations (e.g. Acidianus infernus, Ferroplasma acidarmanus, Acidithiobacillus,Sulfobacillus,Thaumarchaeota), in agreement with thermodynamic calculations.

Mercury and Arsenic Discharge from Circumneutral Waters Associated with the Former Mining Area of Abbadia San Salvatore (Tuscany, Central Italy).

Dissolved and suspended toxic elements in water discharged from abandoned and active mining areas pose several critical issues, since they represent a threat to the environment. In this work, we investigated the water, suspended particulates, and stream sediments of a 2.1 km long creek (Fosso della Chiusa) that is fed by waters draining the galleries of the abandoned Hg mining area of Abbadia San Salvatore (Mt. Amiata, Tuscany, central Italy). The geochemical results show evidence that the studied matrices are characterized by relatively high concentrations of Hg and As, whereas those of Sb are generally close to or below the instrumental detection limit. Independent of the matrices, the concentration of As decreases from the emergence point to the confluence with the Pagliola creek. In contrast, Hg concentrations display more complex behavior, as water and sediment are mainly characterized by concentrations that significantly increase along the water course. According to the geoaccumulation index (Igeo), sediments belong to Class 6 (extremely contaminated) for Hg. The Igeo of As varies from Class 6, close to the emergence, to Class 2 (moderately contaminated), dropping to Class 0 (uncontaminated) at the confluence with the Pagliola creek. Finally, the total mass load of Hg and As entering the Pagliola creek was computed to be 1.3 and 0.5 kg/year, respectively, when a mean flow rate of 40 L/s was considered. The calculated loads are relatively low, but, when the Fosso della Chiusa drainage basin is taken into account, the specific load is comparable to, or even higher than, those of other mining areas.

Insights into the Porretta Terme (northern Apennines, Italy) hydrothermal system revealed by geochemical data on presently discharging thermal waters and paleofluids.

This study focuses on the geochemical features of the presently discharging thermal and cold springs and on paleofluids from the upstream portion of the Reno river basin (Alto Reno; central-northern Italy). The aim is investigating the primary sources of the modern and fossil fluids and the interactions between deep and shallow aquifers. Paleofluids are from fluid inclusions hosted within euhedral and hopper quartz crystals and consist of a two-phase, liquid-vapor aqueous fluid and a unary CH4 fluid. The aqueous inclusions have constant phase ratios and a calculated salinity of ~ 1.5 wt% NaCleq. They homogenize by bubble disappearance at 100-200 °C, whereas the estimated entrapment depth is ~ 3-5.5 km. The paleofluids likely represent the vestiges of the deep and hot, CH4-rich, Na+-Cl- fluids produced by the interaction between meteoric waters and Triassic and Miocene formations. The modern Na+-Cl-(HCO3-) thermal waters originate from meteoric waters infiltrating SW of the study area, at elevation > 800 m a.s.l., circulating within both the Triassic evaporites and the overlying Miocene turbiditic formations, where salt dissolution/precipitation, sulfate reduction, and production of thermogenic CH4 occur. The equilibrium temperature of the deep fluid source is ~ 170 °C, corresponding to > 5 km depth. Cold springs are Ca2+-HCO3- type and show low amounts of biogenic CO2 and CH4 with no inputs of deep-originated fluids excepting in the immediate surroundings of the thermal area, confirming the lack of significant hydraulic connection between shallow and deep aquifers. We propose a genetic link between the quartz-hosted paleofluid and the thermal waters present in the area.

High concentrations of dissolved biogenic methane associated with cyanobacterial blooms in East African lake surface water.

The contribution of oxic methane production to greenhouse gas emissions from lakes is globally relevant, yet uncertainties remain about the levels up to which methanogenesis can counterbalance methanotrophy by leading to CH4 oversaturation in productive surface waters. Here, we explored the biogeochemical and microbial community variation patterns in a meromictic soda lake, in the East African Rift Valley (Kenya), showing an extraordinarily high concentration of methane in oxic waters (up to 156 µmol L-1). Vertical profiles of dissolved gases and their isotopic signature indicated a biogenic origin of CH4. A bloom of Oxyphotobacteria co-occurred with abundant hydrogenotrophic and acetoclastic methanogens, mostly found within suspended aggregates promoting the interactions between Bacteria, Cyanobacteria, and Archaea. Moreover, aggregate sedimentation appeared critical in connecting the lake compartments through biomass and organic matter transfer. Our findings provide insights into understanding how hydrogeochemical features of a meromictic soda lake, the origin of carbon sources, and the microbial community profiles, could promote methane oversaturation and production up to exceptionally high rates.

Unveiling the changes in urban atmospheric CO2 in the time of COVID-19 pandemic: A case study of Florence (Italy).

The outbreak of COVID-19 pandemic was accompanied by global mobility restrictions and slowdown in manufacturing activities. Accordingly, cities experienced a significant decrease of CO2 emissions. In this study, continuous measurements of CO2 fluxes, atmospheric CO2 concentrations and δ13C-CO2 values were performed in the historical center of Florence (Italy) before, during and after the almost two-month long national lockdown. The temporal trends of the analyzed parameters, combined with the variations in emitting source categories (from inventory data), evidenced a fast response of flux measurements to variations in the strength of the emitting sources. Similarly, the δ13C-CO2 values recorded the change in the prevailing sources contributing to urban atmospheric CO2, confirming the effectiveness of carbon isotopic data as geochemical tracers for identifying and quantifying the relative contributions of emitting sources. Although the direct impact of restriction measurements on CO2 concentrations was less clear due to seasonal trends and background fluctuations, an in-depth analysis of the daily local CO2 enhancement with respect to the background values revealed a progressive decrease throughout the lockdown phase at the end of the heating season (>10 ppm), followed by a net increase (ca. 5 ppm) with the resumption of traffic. Finally, the investigation of the shape of the frequency distribution of the analyzed variables revealed interesting aspects concerning the dynamics of the systems.

Are geochemical regime shifts identifiable in river waters? Exploring the compositional dynamics of the Tiber River (Italy).

Rivers are dynamic and sensitive systems that change their chemical composition from source to mouth. This is due to the influence of a set of variables controlled by hydro-litho-eco-atmospheric processes and anthropic pressures which are, in turn, affected by catchment attributes. This work proposes a new way of thinking about river geochemistry focused on environmental interconnections rather than single chemical variables. Abrupt changes in the system state (composition) of a certain environmental media, driven by perturbations, may trigger Geochemical Regime Shifts (GRSs). This eventuality is explored in the Tiber River (central Italy) chemistry by Compositional Data Analysis, robust Principal Component Analysis and score-distance graphs. Data variability and the interlinks between response and forcing variables are investigated for different drained areas. A potential GRS is detected for major elements in the lower reaches resulting from a threshold-like state response caused by lithological forcing. On the contrary, trace elements respond gradually to environmental drivers, showing no abrupt changes. The findings outline mechanisms and factors influencing the river's self-restoring capability at a basin-wide scale, providing a better comprehension of the circumstances controlling the equilibrium dynamics of river water systems.

100 years of high GEM concentration in the Central Italian Herbarium and Tropical Herbarium Studies Centre (Florence, Italy).

Up to 1980s, the most used preservative for herbaria specimens was HgCl2, sublimating at ambient air conditions; ionic Hg then reduces to Hg0 (gaseous elemental mercury, GEM) and diffuses throughout poor ventilated environments. High GEM levels may indeed persist for decades, representing a health hazard. In this study, we present new GEM data from the Central Italian Herbarium and Tropical Herbarium Studies Centre of the University of Florence (Italy). These herbaria host one of the largest collection of plants in the world. Here, HgCl2 was documented as plant preservative up to the 1920s. GEM surveys were conducted in July 2013 and July and December 2017, to account for temporal and seasonal variations. Herbaria show GEM concentrations well above those of external locations, with peak levels within specimen storage cabinets, exceeding 50,000 ng/m3. GEM concentrations up to ~7800 ng/m3 were observed where the most ancient collections are stored and no ventilation systems were active. On the contrary, lower GEM concentrations were observed at the first floor. Here, lower and more homogeneously distributed GEM concentrations were measured in 2017 than in 2013 since the air-conditioning system was updated in early 2017. GEM concentrations were similar to other herbaria worldwide and lower than Italian permissible exposure limit of 20,000 ng/m3 (8-hr working day). Our results indicate that after a century from the latest HgCl2 treatment GEM concentrations are still high, i.e., the treatment itself is almost irreversible. Air conditioning and renewing is probably the less expensive and more effective method for GEM lowering.

Microbiomes in Soils Exposed to Naturally High Concentrations of CO2 (Bossoleto Mofette Tuscany, Italy).

Direct and indirect effects of extremely high geogenic CO2 levels, commonly occurring in volcanic and hydrothermal environments, on biogeochemical processes in soil are poorly understood. This study investigated a sinkhole in Italy where long-term emissions of thermometamorphic-derived CO2 are associated with accumulation of carbon in the topsoil and removal of inorganic carbon in low pH environments at the bottom of the sinkhole. The comparison between interstitial soil gasses and those collected in an adjacent bubbling pool and the analysis of the carbon isotopic composition of CO2 and CH4 clearly indicated the occurrence of CH4 oxidation and negligible methanogenesis in soils at the bottom of the sinkhole. Extremely high CO2 concentrations resulted in higher microbial abundance (up to 4 × 109 cell g-1 DW) and a lower microbial diversity by favoring bacteria already reported to be involved in acetogenesis in mofette soils (i.e., Firmicutes, Chloroflexi, and Acidobacteria). Laboratory incubations to test the acetogenic and methanogenic potential clearly showed that all the mofette soil supplied with hydrogen gas displayed a remarkable CO2 fixation potential, primarily due to the activity of acetogenic microorganisms. By contrast, negligible production of acetate occurred in control tests incubated with the same soils, under identical conditions, without the addition of hydrogen. In this study, we report how changes in diversity and functions of the soil microbial community - induced by high CO2 concentration - create peculiar biogeochemical profile. CO2 emission affects carbon cycling through: (i) inhibition of the decomposition of the organic carbon and (ii) promotion of CO2-fixation via the acetyl-CoA pathway. Sites naturally exposed to extremely high CO2 levels could potentially represent an untapped source of microorganisms with unique capabilities to catalytically convert CO2 into valuable organic chemicals and fuels.

Assessment, control, and prevention of microbiological and chemical hazards in seasonal swimming pools of the Versilia district (Tuscany, central Italy).

Although in Europe the quality of swimming pools (SPs) is dictated by regulations, microbiological and chemical hazards are described in the literature. Environmental bacteria or toxic disinfection by-product (DBP) compounds may indeed be recovered in waters even after disinfection. We evaluated the water quality from 26 outdoor seasonal SPs of the Versilia district, according to requirements of Regional Decree 54R/2015. In spring 2017, supply and reinstatement waters were collected after shock hyperchlorination (10 mg/L) while in summertime, a second sampling of waters before entering the pools, as well as in the pools, was performed after SPs were open to the public. In all samples, microbiological and chemical parameters were determined as defined by Directive 98/83/EC and the Italian Health Ministry. Microbiological data were within suggested limits. The first chemical analyses showed that in 35% of the feeding-pool seawater samples, the halogenated organic compounds were higher than the maximum permissible concentrations (30 µg/L). Pool waters were then dechlorinated and re-treated with hydrogen peroxide (10 mg/L) to ensure the abatement of DBPs (from 164 ± 107 to 0.9 ± 0.8 µg/L; p = 0.002). Results highlighted the need of self-controlled procedures for the SPs waters to prevent waterborne diseases and suggested hydrogen peroxide as the most appropriate disinfection method.

Microbiome profiling in extremely acidic soils affected by hydrothermal fluids: the case of the Solfatara Crater (Campi Flegrei, southern Italy).

An integrated geochemical and microbiological investigation of soils from the Solfatara Crater (Campi Flegrei, southern Italy) demonstrated that interstitial soil gases dominated by CO2 and other typical hydrothermal gaseous species (e.g. H2S, CH4, ethane, benzene, alkenes and S-bearing organic compounds) influenced the composition of microbial communities. The relatively high concentrations of hydrothermal fluids permeating the soil produced acidic conditions and whitish deposits that characterize the Solfatara Crater floor. Archaea and Bacteria showed almost equal cell abundance (up to 3.2 × 107 and 4.2 × 107 cell/g, respectively) with relatively low levels of biodiversity and equitability in sites characterized by elevated temperatures (up to 70°C), very low pH values (up to 2.2) and reducing conditions. In these sites, high-throughput sequencing showed the marked selection of microorganisms, mainly affiliated with the genera Thermoplasma, Ferroplasma and Acidithiobacillus. A relatively high biodiversity and concomitant distinctive structure of the microbial community were observed in soils poorly affected by fumarolic emissions that were oxic and rich in organic matter.

The biogeochemical vertical structure renders a meromictic volcanic lake a trap for geogenic CO2 (Lake Averno, Italy).

Volcanic lakes are characterized by physicochemical favorable conditions for the development of reservoirs of C-bearing greenhouse gases that can be dispersed to air during occasional rollover events. By combining a microbiological and geochemical approach, we showed that the chemistry of the CO2- and CH4-rich gas reservoir hosted within the meromictic Lake Averno (Campi Flegrei, southern Italy) are related to the microbial niche differentiation along the vertical water column. The simultaneous occurrence of diverse functional groups of microbes operating under different conditions suggests that these habitats harbor complex microbial consortia that impact on the production and consumption of greenhouse gases. In the epilimnion, the activity of aerobic methanotrophic bacteria and photosynthetic biota, together with CO2 dissolution at relatively high pH, enhanced CO2- and CH4 consumption, which also occurred in the hypolimnion. Moreover, results from computations carried out to evaluate the dependence of the lake stability on the CO2/CH4 ratios, suggested that the water density vertical gradient was mainly controlled by salinity and temperature, whereas the effect of dissolved gases was minor, excepting if extremely high increases of CH4 are admitted. Therefore, biological processes, controlling the composition of CO2 and CH4, contributed to stabilize the lake stratification of the lake. Overall, Lake Averno, and supposedly the numerous worldwide distributed volcanic lakes having similar features (namely bio-activity lakes), acts as a sink for the CO2 supplied from the hydrothermal/magmatic system, displaying a significant influence on the local carbon budget.

Lake Afrera, a structural depression in the Northern Afar Rift (Red Sea).

The boundary between the African and Arabian plates in the Southern Red Sea region is displaced inland in the northern Afar rift, where it is marked by the Red Sea-parallel Erta Ale, Alaita, and Tat Ali volcanic ridges. The Erta Ale is offset by about 20 and 40 km from the two en echelon ridges to the south. The offset area is highly seismic and marked by a depression filled by lake Afrera, a saline body of water fed by hydrothermal springs. Acoustic bathymetric profiles show ≈80 m deep canyons parallel to the NNW shore of the lake, part of a system of extensional normal faults striking parallel to the Red Sea. This system is intersected by oblique structures, some with strike-slip earthquakes, in what might evolve into a transform boundary. Given that the lake's surface lies today about 112 m below sea level, the depressed (minus ≈190 m below sea level) lake's bottom area may be considered the equivalent of the "nodal deep" in slow-slip oceanic transforms. The chemistry of the lake is compatible with the water having originated from hydrothermal liquids that had reacted with evaporites and basalts, rather than residual from evaporation of sea water. Bottom sediments include calcitic grains, halite and gypsum, as well as ostracod and diatom tests. The lake's level appears to have dropped by over 10 m during the last ≈50 years, continuing a drying up trend of the last few thousand years, after a "wet" stage 9,800 and 7,800 years before present when according to Gasse (1973) Lake Afrera covered an area several times larger than at present. This "wet" stage corresponds to an early Holocene warm-humid climate that prevailed in Saharan and Sub Saharan Africa. Lake Abhé, located roughly 250 km south of Afrera, shows similar climate-driven oscillations of its level.

Gaseous Elemental Mercury and Total and Leached Mercury in Building Materials from the Former Hg-Mining Area of Abbadia San Salvatore (Central Italy).

Mercury has a strong environmental impact since both its organic and inorganic forms are toxic, and it represents a pollutant of global concern. Liquid Hg is highly volatile and can be released during natural and anthropogenic processes in the hydrosphere, biosphere and atmosphere. In this study, the distribution of Gaseous Elemental Mercury (GEM) and the total and leached mercury concentrations on paint, plaster, roof tiles, concrete, metals, dust and wood structures were determined in the main buildings and structures of the former Hg-mining area of Abbadia San Salvatore (Siena, Central Italy). The mining complex (divided into seven units) covers a surface of about 65 ha and contains mining structures and managers' and workers' buildings. Nine surveys of GEM measurements were carried out from July 2011 to August 2015 for the buildings and structures located in Units 2, 3 and 6, the latter being the area where liquid mercury was produced. Measurements were also performed in February, April, July, September and December 2016 in the edifices and mining structures of Unit 6. GEM concentrations showed a strong variability in time and space mostly depending on ambient temperature and the operational activities that were carried out in each building. The Unit 2 surveys carried out in the hotter period (from June to September) showed GEM concentrations up to 27,500 ng·m-3, while in Unit 6, they were on average much higher, and occasionally, they saturated the GEM measurement device (>50,000 ng·m-3). Concentrations of total (in mg·kg-1) and leached (in µg·L-1) mercury measured in different building materials (up to 46,580 mg·kg-1 and 4470 mg·L-1, respectively) were highly variable, being related to the edifice or mining structure from which they were collected. The results obtained in this study are of relevant interest for operational cleanings to be carried out during reclamation activities.

Seafloor doming driven by degassing processes unveils sprouting volcanism in coastal areas.

We report evidences of active seabed doming and gas discharge few kilometers offshore from the Naples harbor (Italy). Pockmarks, mounds, and craters characterize the seabed. These morphologies represent the top of shallow crustal structures including pagodas, faults and folds affecting the present-day seabed. They record upraise, pressurization, and release of He and CO2 from mantle melts and decarbonation reactions of crustal rocks. These gases are likely similar to those that feed the hydrothermal systems of the Ischia, Campi Flegrei and Somma-Vesuvius active volcanoes, suggesting the occurrence of a mantle source variously mixed to crustal fluids beneath the Gulf of Naples. The seafloor swelling and breaching by gas upraising and pressurization processes require overpressures in the order of 2-3 MPa. Seabed doming, faulting, and gas discharge are manifestations of non-volcanic unrests potentially preluding submarine eruptions and/or hydrothermal explosions.

New occurrence of reed bed decline in southern Europe: do permanent flooding and chemical parameters play a role?

Based on the experimental design proposed in similar studies, macromorphological and ecological traits of common reed beds were analysed at Lake Chiusi (Central Italy), together with selected chemical parameters in sediments and interstitial waters and aerial images of the site, in order to investigate reed decline and search for possible correlations among data. Typical symptoms of the reed dieback syndrome were detected, thus enlarging the occurrence of this phenomenon in southern Europe. Permanently dry, permanently flooded and partially flooded stands show different levels of decline, with the permanent flooding always co-occurring with reed dieback. Only few of the considered chemical parameters seem to play a role in reed decline (nitrates, rubidium, nickel, barium, manganese), although no clear pattern was identified. Data suggest that the co-occurrence of some chemicals with stressing conditions might affect the growth even of an efficient metal accumulator, as reed is generally considered.