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Hydrothermal systems with active surface expressions are important natural source of atmospheric mercury. Here we report on the first simultaneous assessment of gaseous elemental mercury (GEM) and major volatiles (H2S and CO2) fluxes from the fumarolic system of Pisciarelli, currently the most active at the Campi Flegrei caldera (CFc), Naples (Italy). This was achieved via a GPS-synchronized Lumex and MultiGAS survey which extends similar investigations reported elsewhere. GEM concentrations measured in the fumarolic emissions were consistently above background air level close to the degassing area (mean ~ 8 ± 3 ng m−3 on average) and ranged up to 12,000 ng m−3. Our data evidenced pulsed sequences of GEM increases in the fumarole plume, closely matched by temporally consistent increases in CO2 and H2S (r2 = 0.9), supporting the idea that major volatiles, such as CO2 acts as potential carrier in transporting GEM within the magmatic/hydrothermal systems. The slope of the best fit calculated for the dispersion of our data provides a GEM/CO2 molar ratio of 1.1 × 10−8 and a GEM/H2S of 5 × 10−6, respectively. These ratios are comparable to those reported for both low (~ 100 °C) and high-T (~ 250 °C) fumaroles from non-explosive volcanic/hydrothermal degassing systems elsewhere. We adopted an ad-hoc method that combines video footages and gas measurements to obtain high precision concentration maps of gas emissions used to estimate the total atmospheric GEM, CO2 and H2S flux of about 0.0113, 225059 and 511 t y−1, respectively. The human health risk assessment related to the GEM emissions at Pisciarelli, confirms that, except for the degassing fumarolic area, all the main sites affected by the plume dispersion, always remain well below the safe threshold recommended by the health authorities.

Detailed surveys of diffuse CO2 flux, soil temperature, thermal gradients, and sampling of high-T fumaroles were carried out in the Favare area and Lake Specchio di Venere on Pantelleria Island. Spatial patterns of diffuse CO2 emissions in the Favare area reflect structural discontinuities (faults, fractures or cracks in the soil) associated with the volcano-tectonic structures of the young Monastero Caldera (NNE–SSW to NE–SW trending). The estimated diffuse CO2 output from two adjacent sites in the Favare area (~ 93,000 m2) is 7.8 t d− 1 (equivalent to 2.62 kt a− 1), whereas that from the west shore of the lake (450 m2) is 0.041 t d− 1 (or 0.015 kt a− 1). The extrapolation of diffuse CO2 fluxes across the entire altered area of Favare suggests that CO2 emissions are ~ 19.3 t d− 1. The diffuse CO2 flux correlates with shallow soil temperatures, indicating a similar source for both the heat and volatiles from the underlying geothermal reservoir. Gas equilibria applied to fumarolic effluents define P–T conditions for this reservoir at 2–6 bar and 120–160 °C, in good agreement with measurements from exploratory wells in these areas (e.g., 135 °C at a depth of 290 m). Using the CO2 flux as a tracer for steam output, and consequently for heat flow, the calculated thermal energy for the shallow reservoir is 10–12 MW; this represents the minimum geothermal potential of the reservoir on Pantelleria island.

Our study is aimed to develop a 3D physical model of the Campi Flegrei geothermal system, in order to achieve a more accurate and comprehensive representation of the hydrothermal processes occurring in the caldera. The new model, developed by using the TOUGH2 code simulator, accounts for the caldera rocks' physical properties, bathymetry and water table topography. In particular, the computational domain is constrained by density values obtained by tomographic inversion of gravity data collected during several surveys at CF both onshore and offshore the caldera. Empirical relations between density and porosity and between porosity and permeability, derived by published data on samples cored in deep wells or collected in outcrops, allowed us to characterize the main rocks physical parameters controlling the dynamic of the CF geothermal system. We have performed and compared several simulations investigating the effects of the injection at depth, underneath Solfatara crater, of a hot gaseous mixture rich in CO 2 . We show that, with respect to the available literature on 2D axisymmetric models, the effects of the water table topography together with the bathymetry and the heterogeneous distribution of the rocks' physical properties, lead to important differences in the hydrothermal circulation of fluids at CF. These constraints allow the activation of convective cells with different behaviors, which produce variable patterns of temperature inside the hydrothermal system. As a consequence, the predominant effect is again represented by a central plume below the Solfatara crater, but with a non-axisymmetric structure and a wider extension. Additionally, high temperature zones are present near the coastline and in the middle part of the submerged area of the caldera with a SE–NW alignment. Moreover, our results indicate that, the submerged part of the CF caldera would deserve a more accurate study and survey, being affected by phenomenon of heating and degassing. This information could be very useful in terms of hazard assessment and volcanic risk mitigation in such an active and densely inhabited volcanic and geothermal area.

Lake Averno is situated in the homonymous crater in the northwestern sector of the Campi Flegrei active volcanic system in Campania region, Italy. In February 2005 a fish kill event was observed in the lake, prompting a geochemical survey to ascertain the possible cause. In February 2005 a geochemical survey revealed that the lake water was unstratified chemically and isotopically, presumably, as a result of lake overturn. This fish kill phenomenon was recorded at least two other times in the past. In contrast to the February 2005 results, data collected in October 2005, shows the Lake Averno to be stratified, with an oxic epilimnion (surface to 6 m) and an anoxic hypolimnion (6 m to lake bottom at about 33 m). Chemical and isotopic compositions of Lake Averno waters suggest an origin by mixing of shallow waters with a Na–Cl hydrothermal component coupled with an active evaporation process. The isotopic composition of Dissolved Inorganic Carbon, as well as the composition of the non-reactive dissolved gas species again supports the occurrence of this mixing process. Decreasing levels of SO 4 and increasing levels of H 2 S and CH 4 contents in lake water with depth, strongly suggests anaerobic bacterial processes are occurring through decomposition of organic matter under anoxic conditions in the sediment and in the water column. Sulfate reduction and methanogenesis processes coexist and play a pivotal role in the anaerobic environment of the Lake Averno. The sulfate reducing bacterial activity has been estimated in the range of 14–22 μmol m − 2 day − 1 . Total gas pressure of dissolved gases ranges between 800 and 1400 mbar, well below the hydrostatic pressure throughout the water column, excluding the possibility, at least at the survey time, of a limnic eruption. Vertical changes in the density of lake waters indicate that overturn may be triggered by cooling of epilimnetic waters below 7 °C. This is a possible phenomenon in winter periods if atmospheric temperatures remain frosty for enough time, as occurred in February 2005. The bulk of these results strongly support the hypothesis that fish kill was caused by a series of events that began with the cooling of the epilimnetic waters with breaking of the thermal stratification, followed by lake overturn and the rise of toxic levels of H 2 S from the reduced waters near the lake bottom.

Fumarolic fluid compositions and diffuse soil emissions of hydrothermal fluids of the Donna Rachele area (0.86 km 2 , western flank of Mt. Epomeo, Ischia Island) have been studied in order to develop a conceptual geochemical model of the hydrothermal system. The degassing area was mapped and the total release of hydrothermal gas and heat associated with the diffuse emission of hydrothermal fluids was estimated. A mesostructural study was carried out in order to investigate the relations between the brittle structures and the main pathways of the uprising vapor. The fumarolic compositions are typical of hydrothermal fluids and water (>99%) represents the major component. All gas species in the H 2 O–H 2 –CO–CH 4 –CO 2 –H 2 S system are close to equilibrium concentrations at temperatures of ∼300°C and at redox conditions slightly more oxidizing than expected. The compositions of the Donna Rachele fumarolic gas approach the pure liquid equilibrium composition. This indicates a high fraction of separated vapor and suggests the presence of a highly energetic hydrothermal system at depth. The pure liquid equilibrium compositions of the Donna Rachele fumaroles, along with the historical records of shallow seismicity, the ‘explosion’ of a well in 1995, the occurrence of intense acoustic phenomena and of shallow wells discharging vapor indicate that the internal pressure of the hydrothermal system is occasionally larger than the hydrostatic pressure. To quantify the energy dissipated in the Donna Rachele area by the emission of fumarolic fluids, the hydrothermal diffuse degassing was studied by means of 336 soil CO 2 flux measurements. The highest CO 2 fluxes were measured in hydrothermally altered areas along the faults that border Mt. Epomeo. Structural data indicate that the vapor rises up along NW–SE striking normal faults related to gravity-induced stresses and affecting highly fractured lavas. The older faults, which are related to the Mt. Epomeo resurgence, act as a permeability barrier and bound the Donna Rachele diffuse degassing structure. The total hydrothermal CO 2 output was estimated to be ∼9 t d −1 . Assuming that the H 2 O/CO 2 ratio of the fluids that feed the diffuse degassing is the same as that of fumarolic effluents, the calculated heat flux is ∼40 MW. This value, which represents an important energy release, is only a part of the total thermal energy release of Ischia, where other fumarolic areas occur. The results obtained at Ischia indicate the importance of thermal energy released by diffuse degassing structures in the energy balance of quiescent volcanoes. Values of the thermal energy release from the Ischia hydrothermal system are comparable with those estimated on other quiescent volcanoes.