Jacopo Cabassi

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.

Biogeochemical processes involving dissolved CO2 and CH4 at Albano, Averno, and Monticchio meromictic volcanic lakes (Central–Southern Italy)

This paper focuses on the chemical and isotopic features of dissolved gases (CH4 and CO2) from four meromictic lakes hosted in volcanic systems of Central–Southern Italy: Lake Albano (Alban Hills), Lake Averno (Phlegrean Fields), and Monticchio Grande and Piccolo lakes (Mt. Vulture). Deep waters in these lakes are characterized by the presence of a significant reservoir of extra-atmospheric dissolved gases mainly consisting of CH4 and CO2. The δ13C-CH4 and δD-CH4 values of dissolved gas samples from the maximum depths of the investigated lakes (from −66.8 to −55.6 ‰ V-PDB and from −279 to −195 ‰ V-SMOW, respectively) suggest that CH4 is mainly produced by microbial activity. The δ13C-CO2 values of Lake Grande, Lake Piccolo, and Lake Albano (ranging from −5.8 to −0.4 ‰ V-PDB) indicate a significant CO2 contribution from sublacustrine vents originating from (1) mantle degassing and (2) thermometamorphic reactions involving limestone, i.e., the same CO2 source feeding the regional thermal and cold CO2-rich fluid emissions. In contrast, the relatively low δ13C-CO2 values (from −13.4 to −8.2 ‰ V-PDB) of Lake Averno indicate a prevalent organic CO2. Chemical and isotopic compositions of dissolved CO2 and CH4 at different depths are mainly depending on (1) CO2 inputs from external sources (hydrothermal and/or anthropogenic); (2) CO2–CH4 isotopic exchange; and (3) methanogenic and methanotrophic activity. In the epilimnion, vertical water mixing, free oxygen availability, and photosynthesis cause the dramatic decrease of both CO2 and CH4 concentrations. In the hypolimnion, where the δ13C-CO2 values progressively increase with depth and the δ13C-CH4 values show an opposite trend, biogenic CO2 production from CH4 using different electron donor species, such as sulfate, tend to counteract the methanogenesis process whose efficiency achieves its climax at the water–bottom sediment interface. Theoretical values, calculated on the basis of δ13C-CO2 values, and measured δ13CTDIC values are not consistent, indicating that CO2 and the main carbon-bearing ion species (HCO3−) are not in isotopic equilibrium, likely due to the fast kinetics of biochemical processes involving both CO2 and CH4. This study demonstrates that the vertical patterns of the CO2/CH4 ratio and of δ13C-CO2 and δ13C-CH4 are to be regarded as promising tools to detect perturbations, related to different causes, such as changes in the CO2 input from sublacustrine springs, that may affect aerobic and anaerobic layers of meromictic volcanic lakes.

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).

Geochemical characterization of the ground waters from the former Hg-mining area of Abbadia San Salvatore (Mt. Amiata, central Italy): criticalities and perspectives for the reclamation process

This study was aimed to geochemically characterize the groundwater system of the Abbadia San Salvatore (Mt. Amiata, Siena, central Italy) former Hg-mining area, whose activity closed at the end of the seventies, in order to accomplish the reclamation process after that the former ownership of the mining concession (E.N.I. National Agency for Hydrocarbons, AGIP Division) passed the property to the Munici pality of Abbadia San Salvatore in 2008. The study area covers a surface of about 65 ha and since February 2013 old and new piezometers were used to assess the main chemical features along with the concentrations of As, Hg and Sb. Four sampling campaigns were carried out up to January 2014 and a relatively large spatial and temporal geochemical variability was observed. Apparently, the working activities related to the construction of an artificial channel (commenced in March 2013 and terminated at the end of 2013), which crosscuts the whole mining area to drain the surface waters in order to minimize the interaction between the meteoric waters and the by-products deriving by the production of metallic mercury, did not affect the groundwater system. Slag, roasted material and other by-products deriving from the local and surrounding Hg mining activities were indeed used to fill the terrain where most of the mining structures lie. The dominating geochemical facies was Ca(Mg)-SO4 and, subordinately, Ca(Mg)-HCO3, while Na-HCO3 compositions were rarely found. Dissolution of gypsum/anhydrite and carbonates and hydrolysis of sulfide minerals are likely the main geochemical process that produced the observed geochemical compositions. The contents of As and Sb only sporadically exceeded the maximum allowable concentrations intended for human consumption (98/83 EC Directive 1998), i.e. 10 and 5 mg L-1. Conversely, those of Hg were constantly above the EC directive, e.g. 1 mg L-1, with the exception of those waters located up- and downstream the groundwater flow. This indicates that the exotic filling terrains in the mining area, mainly consisting of roasting products, likely play a pivotal role in regulating the concentrations of Hg, which reached values up 853 mg L-1. The construction of permeable reactive barriers, located downstream the water flow, appears to be the most promising solution for the removal of Hg, although, according to the literature, several materials, tested with laboratory experiments, can be used and, as a consequence, it is necessary to individuate specific piezometers with different Hg concentrations where pilot investigations are to be carried out before undertaking any remediation actions.

The gas membrane sensor (GMS) method: a new analytical approach for real-time gas concentration measurements in volcanic lakes

Abstract The primary goal of this study was to apply an innovative analytical method based on a gas membrane sensor (GMS) to quantify the concentrations of CO2 and CH4 gas in water columns from volcanic lakes. For this purpose, dissolved CO2 and CH4 from the Monticchio Grande and Piccolo (Mt Vulture, Italy) and Pavin (Massif Central, France) lakes, characterized by depths of 35, 38 and 92 m, respectively, were measured using two different approaches: GMS and SH (single hose), the latter being an independent conventional method. The CO2 and CH4 concentrations recorded via the GMS and SH techniques were within the analytical errors of the two methods. These test measurements demonstrated that the GMS method can be successfully used to produce highly accurate in situ measurements of dissolved gas composition along the vertical profiles of lakes.

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.

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.