Development and testing of a new flexible, easily and widely applicable chemical water quality index (CWQI).

Water quality indices (WQIs) are numeric parameters that summarize the overall quality status of freshwaters compared to quality standards by aggregating multiple physicochemical data into a single value. Among the available WQIs in the literature, several criticalities were recognized including: (a) mathematical complexity of the computation, (b) lack of inclusivity, (c) arbitrary weight assignment method, and (d) site-specificity of most of the indexes. The proposed index, the Chemical Water Quality Index (CWQI), aims to overcome these flaws and provides a computation based on simple mathematic equations that are easily manageable on spreadsheet software. The computation is divided into two steps: (i) parametrization of the variables and (ii) index determination. The parametrization consists of assigning a score (s) from ∼1 to 10 to each chemical variable based on (i) measured concentrations and (ii) quality targets (e.g., the limits provided by the European legislation for drinking waters). In the second step, a weight (w), directly proportional to the score (s), is assigned to each parameter, allowing to overcome any bias related to subjective assignments from the user. The resulting CWQI ranges from ∼1 (very good quality) to 10 (extremely poor quality). The reliability and accuracy of the CWQI were assessed by (i) applying the computation to 1,810 waters and (ii) comparing our results with another available WQI. The CWQI outputs showed an optimal response with the number of variables exceeding the quality target with high correlation coefficients (r = 0.94; R2 = 0.89). Due to the simplicity of its computation, the absence of arbitrariness in the weightage of selected variables, and the independence of the proposed approach regarding the choice of the chemical parameters, CWQI can be easily and universally applied.

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.

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.

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.

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.

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.

Distribution of gaseous Hg in the Mercury mining district of Mt. Amiata (Central Italy): a geochemical survey prior the reclamation project.

The Mt. Amiata volcano is the youngest and largest volcanic edifice in Tuscany (central-northern Italy) and is characterized by a geothermal field, exploited for the production of electrical energy. In the past Mt. Amiata was also known as a world-class Hg district whose mining activity was mainly distributed in the central-eastern part of this silicic volcanic complex, and particularly in the municipality of Abbadia San Salvatore. In the present work we report a geochemical survey on Hg(0) measurements related to the former mercury mine facilities prior the reclamation project. The Hg(0) measurements were carried out by car for long distance regional surveys, and on foot for local scale surveys by using two LUMEX (915+ and M) devices. This study presents the very first Hg(0) data obtained with this analytical technique in the Mt. Amiata area. The facilities related to the mining areas and structures where cinnabar was converted to metallic Hg are characterized by high Hg values (>50,000ngm(-3)), although the urban center of Abbadia San Salvatore, few hundred meters away, does not appear to be receiving significant pollution from the calcine area and former industrial edifices, all the recorded values being below the values recommended by the issuing Tuscany Region authorities (300ngm(-3)) and in some cases approaching the Hg background levels (3-5ngm(-3)) for the Mt. Amiata area.

Mercury accumulation efficiency of different biomonitors in indoor environments: the case study of the Central Italian Herbarium (Florence, Italy).

Biomonitoring studies are often employed to track airborne pollutants both in outdoor and indoor environments. In this study, the mercury (Hg) sorption by three biomonitors, i.e., Pinus nigra bark, Pseudovernia furfuracea lichen, and Hypnum cupressiforme moss, was investigated in controlled (indoor) conditions. In comparison to outdoor environments, controlled conditions offer the opportunity to investigate more in detail the variables (humidity, temperature, pollutants speciation, etc.) that control Hg uptake. The biomonitors were exposed in two distinct periods of the year for 2 and 12 months respectively, in the halls of the Central Italian Herbarium (Natural History Museum of the University of Florence, Italy), which are polluted by Hg, due to past plant sample treatments. The Hg sorption trend was monitored every 3 weeks by recording: (i) the Hg content in the substrata, (ii) gaseous elemental mercury (GEM) concentrations in the exposition halls, (iii) temperature, (iv) humidity, and (v) particulate matter (PM) concentrations. At the end of the experiment, Hg concentrations in the biomonitors range from 1130 ± 201 to 293 ± 45 µg kg-1 (max-min) in barks, from 3470 ± 571 to 648 ± 40 µg kg-1 in lichens, and from 3052 ± 483 to 750 ± 127 µg kg-1 in mosses. All the biomonitors showed the highest Hg accumulation after the first 3 weeks of exposure. Mercury concentrations increased over time showing a continuous accumulation during the experiments. The biomonitors demonstrated different Hg accumulation trends in response to GEM concentrations and to the different climatic conditions (temperature and humidity) of the Herbarium halls. Barks strictly reflected the gaseous Hg pollution, while lichen and moss accumulation was also influenced by the climatic conditions of the indoor environment. Mercury bound to PM seemed to provide a negligible contribution to the biomonitors final uptake.

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.

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.

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.

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.

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.

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.

Environmental impact assessment on the stone decay in the archaeological site of Hierapolis (Denizli, Turkey).

The archaeological site of Hierapolis (Denizli province, Turkey) is unique in terms of the conservation of marbles and travertines. Environmental factors (i.e. interaction with thermal waters, high thermal stress, CO2 degassing) and geological aspects (presence of seismic faults, frequent earthquakes, formation of travertine) play a fundamental role in the durability and conservation state of the stone materials. This paper presents a multi-analytical approach aimed to identify the phenomena and causes of stone decay related to environmental conditions. The analyses of alteration and decay phenomena are discussed together with the monitoring of the main environmental parameters and with analyses of waters and gases present in the archaeological site. Finally, the need of a continuous monitoring of the environmental parameters affecting the archaeological site is stressed.

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.

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.

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.

Geosphere-biosphere interactions in bio-activity volcanic lakes: evidences from Hule and Rìo Cuarto (Costa Rica).

Hule and Río Cuarto are maar lakes located 11 and 18 km N of Poás volcano along a 27 km long fracture zone, in the Central Volcanic Range of Costa Rica. Both lakes are characterized by a stable thermic and chemical stratification and recently they were affected by fish killing events likely related to the uprising of deep anoxic waters to the surface caused by rollover phenomena. The vertical profiles of temperature, pH, redox potential, chemical and isotopic compositions of water and dissolved gases, as well as prokaryotic diversity estimated by DNA fingerprinting and massive 16S rRNA pyrosequencing along the water column of the two lakes, have highlighted that different bio-geochemical processes occur in these meromictic lakes. Although the two lakes host different bacterial and archaeal phylogenetic groups, water and gas chemistry in both lakes is controlled by the same prokaryotic functions, especially regarding the CO2-CH4 cycle. Addition of hydrothermal CO2 through the bottom of the lakes plays a fundamental priming role in developing a stable water stratification and fuelling anoxic bacterial and archaeal populations. Methanogens and methane oxidizers as well as autotrophic and heterotrophic aerobic bacteria responsible of organic carbon recycling resulted to be stratified with depth and strictly related to the chemical-physical conditions and availability of free oxygen, affecting both the CO2 and CH4 chemical concentrations and their isotopic compositions along the water column. Hule and Río Cuarto lakes were demonstrated to contain a CO2 (CH4, N2)-rich gas reservoir mainly controlled by the interactions occurring between geosphere and biosphere. Thus, we introduced the term of bio-activity volcanic lakes to distinguish these lakes, which have analogues worldwide (e.g. Kivu: D.R.C.-Rwanda; Albano, Monticchio and Averno: Italy; Pavin: France) from volcanic lakes only characterized by geogenic CO2 reservoir such as Nyos and Monoun (Cameroon).