Francesco Capecchiacci

Origin and Distribution of Thiophenes and Furans in Gas Discharges from Active Volcanoes and Geothermal Systems

The composition of non-methane organic volatile compounds (VOCs) determined in 139 thermal gas discharges from 18 different geothermal and volcanic systems in Italy and Latin America, consists of C2–C20 species pertaining to the alkanes, alkenes, aromatics and O-, S- and N-bearing classes of compounds. Thiophenes and mono-aromatics, especially the methylated species, are strongly enriched in fluids emissions related to hydrothermal systems. Addition of hydrogen sulphide to dienes and electrophilic methylation involving halogenated radicals may be invoked for the formation of these species. On the contrary, the formation of furans, with the only exception of C4H8O, seems to be favoured at oxidizing conditions and relatively high temperatures, although mechanisms similar to those hypothesized for the production of thiophenes can be suggested. Such thermodynamic features are typical of fluid reservoirs feeding high-temperature thermal discharges of volcanoes characterised by strong degassing activity, which are likely affected by conspicuous contribution from a magmatic source. The composition of heteroaromatics in fluids naturally discharged from active volcanoes and geothermal areas can then be considered largely dependent on the interplay between hydrothermal vs. magmatic contributions. This implies that they can be used as useful geochemical tools to be successfully applied in both volcanic monitoring and geothermal prospection.

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.

Volatile organic compounds (VOCs) in air from Nisyros Island (Dodecanese Archipelago, Greece): Natural versus anthropogenic sources

This study presents the chemical composition of VOCs in air and gas discharges collected at Nisyros Island (Dodecanese Archipelago, Greece). The main goals are i) to discriminate between natural and anthropogenic VOC sources and ii) to evaluate their impact on local air quality. Up to 63 different VOCs were recognized and quantitatively determined in 6 fumaroles and 19 air samples collected in the Lakki caldera, where fumarolic emissions are located, and the outer ring of the island, including the Mandraki village and the main harbor. Air samples from the crater area show significant concentrations of alkanes, alkenes, cyclic, aromatics, and S- and O-bearing heterocycles directly deriving from the hydrothermal system, as well as secondary O-bearing compounds from oxidation of primary VOCs. At Mandraki village, C6H6/Σ(methylated aromatics) and Σ(linear)/Σ(branched) alkanes ratios <1 allow to distinguish an anthropogenic source related to emissions from outlet pipes of touristic and private boats and buses.

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).

Flux measurements of benzene and toluene from landfill cover soils

Carbon dioxide and CH 4, C6H6 and C7H8 fluxes from the soil cover of Case Passerini landfill site (Florence, Italy) were measured using the accumulation and static closed chamber methods, respectively. Results show that the CH4/CO2, CH4/ C 6H6 and CH4/C7H8 ratios of the flux values are relatively low when compared with those of the ‘pristine’ biogas produced by degradation processes acting on the solid waste material disposed in the landfill. This suggests that when biogas transits through the cover soil, CH4 is affected by degradation processes activated by oxidizing bacteria at higher extent than both CO2 and mono-aromatics. Among the investigated hydrocarbons, C6H6 has shown the highest stability in a wide range of redox conditions. Toluene behaviour only partially resembles that of C6H6, possibly because de-methylation processes require less energy than that necessary for the degradation of C6H6, the latter likely occurring via benzoate at anaerobic conditions and/or through various aerobic metabolic pathways at relatively shallow depth in the cover soil where free oxygen is present. According to these considerations, aromatics are likely to play an important role in the environmental impact of biogas released into the atmosphere from such anthropogenic emission sites, usually only ascribed to CO2 and CH4. In this regard, flux measurements using accumulation and static closed chamber methods coupled with gas chromatography and gas chromatography—mass spectrometry analysis may properly be used to obtain a dataset for the estimation of the amount of volatile organic compounds dispersed from landfills.

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.

The Geothermal Resource in the Guanacaste Region (Costa Rica): New Hints From the Geochemistry of Naturally Discharging Fluids

The Guanacaste Geothermal Province (GGP) encompasses the three major volcanoes of northern Costa Rica, namely from NW to SE: Rincon de la Vieja, Miravalles and Tenorio. The dominant occurrence of (i) SO4-rich acidic fluids at Rincon de la Vieja, (ii) Cl-rich mature fluids at Miravalles and (iii) HCO3--rich and low-temperature fluids at Tenorio was previously interpreted as due to a north-to-south general flow of thermal waters and a magmatic gas upwelling mostly centered at Rincon de la Vieja, whereas Miravalles volcano was regarded as the typical geothermal system. The uniformity in chemical and isotopic (R/Ra and 34S) compositions of the neutral Cl-rich waters suggested to state that all the thermal discharges in the GGP are linked at depth to a single, regional geothermal reservoir. In this scenario, the thermal manifestations related to Tenorio volcano were regarded as a distal and diluted fluid outflow. In this study, a new gas geochemical dataset, including both chemical and isotopic (13C-CO2 and R/Ra) parameters of fluid discharges from the three volcanoes, is presented and discussed. Particular attention was devoted to the Tenorio thermal manifestations, since they were poorly studied in the past because this area has been considered of low geothermal potential. The aim is to provide insights into the magmatic-hydrothermal fluid circulation and, to verify the spatial distribution of the heat fluid source feeding the fluid manifestations. Our results only partially confirm the previously depicted model, because the geochemical and isotopic features (e.g. relatively high concentrations of temperature-dependent gases and high R/Ra values) shown by fluids seeping out from the southern sector of Tenorio volcano are more representative of medium-to-high enthalpy volcanic systems than those typically occurring in distal areas. This implies that the geothermal potential in the south of the GGP is higher than previously thought.