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The San Bartolo lava flow field is the most recent flank eruption occurred at Stromboli volcano about 2 ka ago on the NE flank of the island. Despite its importance in being the most recent example of flank activity outside the barren Sciara del Fuoco slope, where the recent activity concentrated, the eruption duration, its volume, and the sequence of events has not yet been reconstructed. In this paper, we present a new survey of the lava flow field, carried out both on the field and photogrammetric and LIDAR surveys from UASs, in order to estimate the erupted lava volume and to reconstruct the sequence of events and infer a possible duration and impact of the eruption. The analysis of the surveys allowed us to verify the contact with previous lava flow fields, allowing a more precise lateral extension of the lava delta along the coast, as well as an estimation of the thickness and volume, at least for the subaerial portion of the lava flow field. The morphology analysis of the lava flow field allowed us to recognize structures suggesting inflation and then stationing of the lava flow fronts, features indicating a long-lasting eruption and a complex interaction with the sea. Our results can provide a useful scenario should a flank eruption occur in the future, a possibility that was close to happening in 1998, when the ground deformation stations revealed a lateral intrusion in the shallow supply system of the volcano.

This study, conducted in the frame of the Pianeta Dinamico project funded by Istituto Nazionale di Geofisica e Vulcanologia, aims to improve the knowledge of radon concentration dissolved in several different waters from some of the Italian volcanic areas and its relationships with lithological and structural settings, fluid chemistry and circulation, volcano dynamics.The study mainly focuses on 222Rn variations over time in thermal waters of the Campi Flegrei caldera at NW of Naples, an active volcanic field hosting an important geothermal system and one of the most dangerous calderas in the world. The caldera, part of the SW-NE trending fissure-like feeding system of the Phlegraean Volcanic District including also Ischia island, lastly erupted in 1538 and, since 2000, has been under a permanent unrest with up 1 metres of uplift, thousands of earthquakes and tons of CO2 emissions.25 sites were sampled and analysed for dissolved 222Rn levels at least twice per year since October 2021; starting from October 2022, 5 waters were then selected for monthly monitoring with the goal of unravelling exogenous (e.g., temperature or rainfall) versus endogenous processes relationships.In order to compare radon concentrations in the caldera with those in the volcanic context of southern Italy, we sampled and analysed as follows: a) 23 cold waters at Somma-Vesuvius, the stratovolcano placed at the intersection of regional NW–SE and NE–SW fault systems east of Naples, showing mild gaseous emissions after the 1944 eruption; b) 8 cold waters from the north of Campi Flegrei caldera, i.e. 7 from a multi-layer aquifer at the base of the extinct Roccamonfina stratovolcano and 1 water at Minturno (northern edge of Roccamonfina); c) 1 thermal water belonging to Ischia at the NW corner of the Gulf of Naples; d) 3 thermal waters of the Vulcano island from the Sicilian Aeolian Arc, characterised by vigorous seismic and fumarolic degassing activities that has shown an abrupt increase on August 2021.The waters are springs, lakes, pools, and groundwater; two are from Le Fumose (Campi Flegrei) and Porto Ponente (Vulcano) submerged emissions.Measurements have been performed by a Radon-in-air detector (RAD7®, Durridge Co.) equipped with Big Bottle RAD H2O and DRYSTIK accessories and processed using the CAPTURE program.Campi Flegrei reaches the highest radon concentrations, varying from 0.20 ± 0.03 to ~1887 ± 13 Bq/L. Somma-Vesuvius shows from almost no radon to 24 ± 1 Bq/L, and Ischia is at 54 ± 2 Bq/L.Roccamonfina area has a discrete variability from 0.2 ± 0.1 to ~ 71 ± 7 Bq/L at SE, being 9.0 ± 0.4 Bq/L at Minturno.Vulcano island attains the lowest detected concentrations, less than 2.4 ± 1.0 Bq/L.Dealing with different areas, the presented results lay the groundwork for better understanding radon behaviour and evaluating the implications on environmental and volcanic hazards assessment. At Campi Flegrei where, in 2012, the alert level was raised from base to warning, radon should be useful to investigate processes from which volcanic dynamics originates and to corroborate the monitoring outcomes.

This article presents findings from two episodes of seismicity and gas emission that occurred on 7 October 2015 and 6 December 2019 in Campi Flegrei caldera. This caldera has been affected by long-term unrest since 2004. The 6 December 2019 episode, consisting of a swarm of 38 earthquakes (maximum duration magnitude 3.1, the largest between 1984 and March 2020), occurred at the end of a one month period characterized by an increase in the ground uplift rate from 0.19±0.01 to 0.72±0.05 mm/day. A sudden increase in the fumarolic tremor amplitude, which is a proxy of gas emission-related parameters recorded at Solfatara–Pisciarelli hydrothermal area (e.g., CO2 air concentration), was observed during the seismicity episode. The uplift rate decreased immediately after the swarm (0.10±0.01 mm/day), whereas the fumarolic tremor amplitude remained higher than that observed prior to the swarm. Through analyzing the time series of uplift recorded in Pozzuoli (central area of the caldera) from differential measurements on tide gauges, we were able to identify the 2015 episode. This episode was characterized by increasing uplift rates that culminated in a seismic swarm of 33 earthquakes on 7 October, which was followed by decreasing uplift rates. We computed double-difference locations of earthquakes from the two swarms and found that they located along a conduit-like path, coinciding with a high-resistivity contrast zone, previously identified by audiomagnetotelluric measurements. The focal mechanisms of the major earthquakes of both swarms indicate fault planes radial with respect to the maximum uplift area. These phenomena can be interpreted as episodes of the volcanic and (or) hydrothermal system pressurization that culminate in an injection of fluids along the conduit-like path, which behaves as a valve that allows fluid discharge and the temporary depressurization of the source region.

Radon is an inert radioactive and radiogenic gas whose exposure is considered harmful for human health. Radon migrates in the hydrogeological systems and discharge into air when water is exposed to the atmosphere. In hydrothermal and geothermal settings of quiescent volcanoes, the surveillance of dissolved 222Rn can be useful to define the hydrological setting and to track fluids’ dynamics. The quantity of dissolved 222Rn depends on different factors such as the characteristics of the aquifer, water-rock-gas interactions, water residence time, radioactive supply. The present study provides measurements of radon concentration levels in 20 thermal waters at the Campi Flegrei volcanic caldera, an important geothermal system with hydrothermal manifestations in the Neapolitan area. We used a Radon-in-air detector (RAD7®, Durridge Co.) equipped with Big Bottle RAD H2O and DRTYSTICK accessories. Water samples are taken from subsurface thermal groundwater, springs, lakes, pools and one submerged thermal spring with different chemical-physical conditions. They are mostly chlorine to bicarbonate waters, with the exception of few sulphate, sampled nearby gas vents of Solfatara and Pisciarelli, with temperature and pH values ranging from 18.1 to 91.3 °C and from 2 to 8 respectively. The hottest and most acidic sulphate waters refer to a small boiling pool at the hydrothermal discharge area of Pisciarelli and have nearly zero Rn levels.Dissolved radon concentrations vary from 0.1 ± 0.1 to 910 ± 9 Bq/L with an average value of 122.7 Bq/L, using the CAPTURE program, the default RAD7 data acquisition program. Similar values in radon concentration are obtained using the method proposed in De Simone et al. (2015), ranging between 0.1 ± 0.1 and 1037± 60 Bq/L with an average value of 133.0 Bq/L.The 222Rn levels from this study not exceed the additional reference level of 1000 Bq/L that can be used in specific situations for the protection of human health.No correlation has been observed between temperature, pH, major anions and radon concentration values, nor between rock composition since it is almost homogeneous at the study sites. Rn levels therefore appear to reflect the local sedimentological, structural or hydrogeological setting.These results are the first of our investigation of dissolved Rn at the Campi Flegrei caldera, acquired in the ongoing “Pianeta Dinamico” project focused on the hydrothermal system functioning of the quiescent volcanoes and financed by the Istituto Nazionale di Geofisica e Vulcanologia. The final goal will be to define the natural Rn fluctuations in relation to the background levels and eventual anomalies in the hydrogeological system, also for public health safety monitoring. Therefore, a future step in this framework will be integrating more dissolved radon measurements in the Campania territory using the same research approach adopted in this study. De Simone G., Galli G., Lucchetti C., Tuccimei P. (2015) Calibration of Big Bottle RAD H2O set-up for radon in water using HDPE bottles Radiat. Meas., 76, pp. 1-7.

Bagni San Filippo area is characterized by the discharge of thermal waters and deeply produced CO2-rich gases both from vents and soil diffuse degassing. The thermal waters are the results of the mixing between meteoric waters and hot fluids deriving from the condensation, at depth, of vapours uprising from a deep hydrothermal reservoir. This process gives rise to a relatively shallow thermal system at temperature close to 50°C, characterized by SO4-rich and Cl-poor waters and elevated PCO2 (~7 bar). Most of the incondensable gas of deep originated vapour is released as a free gas phase forming cold gas vents and localized spots of anomalous CO2 diffuse degassing. The location and the shape of these degassing zones are strongly controlled by the main tectonic structures of the area. Through detailed soil diffuse degassing surveys and hydrogeochemical modelling, we estimate at 226-326 t d-1 and at 965 t d-1 the deep CO2 emission and the amount of condensates discharged by the thermal springs, respectively. The thermal energy associated to the process results at ~ 29 MW, most of which (~ 25 MW) is associated with condensation occurring at depths greater than groundwater circulation.

In this chapter, we review the state-of-the-art of the Campi Flegrei caldera (Naples) hydrothermal system, and its behaviour during the last decades. The Campi Flegrei caldera has been undergoing unrest since 1950, as evidenced by recurrent bradyseismic episodes accompanied by manifest changes in the degassing budget, degassing patterns and in the composition of the fumarolic fluids. In-depth analysis of geochemical and geophysical datasets acquired over decades has allowed identification of the mechanisms driving volcanic unrest at the Campi Flegrei caldera. We propose a conceptual model of the hydrothermal system feeding Solfatara fumaroles, where geochemical information is integrated with Audio Magneto Telluric measurements, which yields a realistic picture of the geometry of the system up to a depth of 2.5km. The model identifies a ~2km elongated vertical high resistivity structure in axis with the Solfatara fumaroles, which represents a relatively high permeability zone allowing hot fluid ascent from depth to the shallower portions of the hydrothermal system. Pulsed injections of hot magmatic fluids (CO2-rich and CH4-poor oxidised fluids) at the bottom of the hydrothermal system is thought to be one of the key processes that has controlled the evolution of the system during the last 40years. The episodes of injection of magmatic fluids changed in frequency and intensity during time, ultimately causing an overall heating and pressurisation of the system since the early 2000s, as reflected by escalating degassing flux, increase in areal extension of the degassing areas, and in the composition of the fumaroles. In particular, the CO2/CH4 and He/CH4 ratios of fumarolic fluids exhibited recurrent peaks, marking the episodes of injection of magmatic fluids. Moreover, the quasi-monotonic increasing trend of the fumarolic CO2/H2O ratio, from 0.15 to 0.18 in 2000 to ~0.4 in 2018–2019, has been interpreted as due to the combined action of partial steam condensation, and CO2 addition from a magmatic source and possibly from de-carbonation of hydrothermal calcite favoured by the heating of the hydrothermal reservoir. These changes strongly suggest that the ongoing (since 2000) unrest is triggered by a degassing magma source, but also that the system’s response is modulated by dynamics and structures of the overlying hydrothermal envelope. This evolution clearly requires careful scientific scrutiny and intensified monitoring in the years to come.

Comprehensive hydrogeochemical studies have been conducted in the Campi Flegrei volcanic aquifer since late 20th century due to the volcanic unrest. In the last decade, groundwater samples were grouped based on the dominant anion species (i.e. bicarbonate, sulfate and chloride) to explain the general hydrogeochemical processes. In this article, 44 groundwater samples are collected from Campi Flegrei aquifer to geochemically and spatially capture the main characteristics of the groundwater body. The hierarchical clustering algorithm is then performed on proportion of bicarbonate, sulfate and chloride, and the optimum number of clusters are determined regarding the results of deep hydrogeochemical investigations published in the past. The collected samples are categorized in the following groups: (1) bicarbonate-rich groundwater; (2) chlorine-rich groundwater; (3) sulfate-rich groundwater; and (4) mixed groundwater. The first group (As = 158.2 ± 169 μg/l, electric conductivity = 1,732.1 ± 1,086 μS/cm and temperature = 25.6 ± 8 °C) is mainly derived from poor arsenic meteoric water, but there is significant thermal/seawater contribution in the second one (As = 1,457.8 ± 2,210 μg/l, electric conductivity = 20,118.3 ± 11,139 μS/cm and temperature = 37.1 ± 20 °C). Interaction of the bicarbonate-rich groundwater and hydrothermal vapors gives rise to the sulfate-rich groundwater (As = 847.2 ± 679 μg/l, electric conductivity = 3,940.0 ± 540 μS/cm and temperature = 82.8 ± 3 °C) around Solfatara volcano. The mixed groundwater (As = 451.4 ± 388 μg/l, electric conductivity = 4,482.9 ± 4,027 μS/cm and temperature = 37.1 ± 16 °C) is observed where the three main groundwater groups undergo a mixing process, depending on the hydrogeology of the volcanic aquifer. Contrary to the bicarbonate- and sulfate-rich groundwater, the chlorine-rich and mixed groundwater generally occurs at low piezometric levels (approximately

Fluids supplied by stored magma at depth are causal factors of volcanic unrest, as they can cause pressurization/heating of hydrothermal systems. However, evidence for links between hydrothermal pressurization, CO2 emission and volcano seismicity have remained elusive. Here, we use recent (2010−2020) observations at Campi Flegrei caldera (CFc) to show hydrothermal pressure, gas emission and seismicity at CFc share common source areas and well-matching temporal evolutions. We interpret the recent escalation in seismicity and surface gas emissions as caused by pressure-temperature increase at the top of a vertically elongated (0.3–2 km deep) gas front. Using mass (steam) balance considerations, we show hydrothermal pressurization is causing energy transfer from the fluids to the host rocks, ultimately triggering low magnitude earthquakes within a seismogenetic volume containing the hydrothermal system. This mechanism is probably common to other worldwide calderas in similar hydrothermal activity state., Journal of Volcanology and Geothermal Research, 414, ISSN:0377-0273

The volcanic system of Ischia is characterized by an intense hydrothermal activity, documented since the early 16th century by the study of Iasolino (1588), which represents the first systematic analysis of the thermal springs of the island for therapeutic purposes. Later studies partially contributed to the enhancement of knowledge on the volcanic, hydrogeological and hydrothermal features of the island, highlighting the strong interaction between hydrothermal flowpaths and volcano-tectonic processes . The reconstruction of the hydrothermal system becomes, therefore, a fundamental element for territorial planning, not only in terms of management of the huge water and geothermal resource, but also and above all in a perspective of prevention and mitigation of volcanic risk. Thermal springs, fumaroles and clay deposits due to the hydrothermal alteration of volcanic products testifies for the existence of an active deep hydrothermal system. Commonly, the geochemical characterization of fluids and groundwater has been used for the definition of the origin and structure of hydrothermal systems, when hydrogeological information is incomplete. However, volcanic hydrothermal systems, such as that characterizes the island of Ischia, are particularly difficult to analyze and outline, as the groundwater resources are the result of an articulated and dynamic interaction among meteoric water, sea water and fluids of deep origin. In such cases, the need for an interdisciplinary approach is evident, involving knowledge and research methods ranging from geology to volcanology, geophysics, geochemistry and hydrogeology. With particular reference to the functional and structural representation of the geothermal system of the island of Ischia and the resulting correlations with the volcano-tectonic processes, the examination of previous information highlights the need to update and improve the knowledge on groundwater hydrodynamics and mineralization processes.Therefore, this study represents the result of a strong interdisciplinary action that, starting from the design and implementation of a database on the existing geological/volcanological and hydrogeological information, contributes to highlight the critical issues, defines an operating scheme of the hydro-geo-thermal system of the island of Ischia, and aims at upgrade its hydrogeological, geochemical and volcanic monitoring system, in order to contribute to the mitigation of natural risks.Moreover, this study well fits into the framework of the ongoing researches on volcanic hazard at Ischia and is integrated with the actions planned by the Italian Department of Civil Defense. The knowledge of groundwater dynamics and pathways is of fundamental importance for understanding the water/magma interaction processes in case of re-alimentation of the shallow magmatic system, and the assessment of the possibility of phreatic explosions occurrence.

The Italian Apennines are among the most important sources of freshwater for several Italian regions. With evidences of deep CO2-rich fluids intruding into aquifers in the nearby central-southern Apennines, a thorough investigation into the geochemistry of groundwater became critical to ensure the water quality in the area. Here, we show the main hydrogeochemical processes occurring in the Matese Massif (MM) aquifer through the investigation of 98 water samples collected from springs and water wells. All waters were classified as HCO3 type with Ca dominance (from 50% up to 97%) and variable amount of Mg (from 1% up to 49%). A multivariate statistical approach through the application of the factor analysis (FA) highlighted three main hydrogeochemical processes: (i) water-carbonate rock interactions mostly enhanced in peripheral areas of the MM by CO2 deep degassing; (ii) addition of NaCl-rich components linked to recharging process and to water mixing processes of the groundwater with a thermal component relatively rich in Cl, Na, and CO2; (iii) anthropogenic activities influencing groundwater composition at the foothills of MM. Furthermore, the first detailed TDIC, pCO2, and δ13C-TDIC distribution maps of the MM area have been created, which track chemical and isotopic anomalies in several peripheral areas (Pratella, Ailano, and Telese) throughout the region. These maps systematically highlight that the greater the amount of dissolved carbon occurs the heavier the C isotope enrichment, especially in the peripheral areas. Conversely, spring waters emerging at higher altitudes within MM are only slightly mineralized and associated with δ13C-TDIC values mainly characterized by recharging processes with the addition of biogenic carbon during the infiltration process through the soil.

Understanding the formation of biogenic molecules in abiotic conditions is a prerequisite in the origin-of-life studies. Determining the conditions allowing an efficient one-pot synthesis of the largest possible panel of biogenic compounds may shed light on the plausible scenario in which the processes that kick-started life might have occurred. We report a set of experiments describing the syntheses taking place from formamide (NH2CHO) and thermal water in the presence of meteorites, in the hydrothermal physical-chemical environment of the Phlegrean Fields. The results show that meteorites catalyse the synthesis of a large panel of organic compounds of biological relevance, including carboxylic acids, nucleobases, amino acids and sugars. The simplicity of the system (a one-carbon molecule as starting compound, a volcanic hydrothermal environment, meteorites as catalysts) hints to a possible extension of the results to similar environments present in other planetary bodies and space objects.

Quiescent volcanoes dissipate a large part of their thermal energy through hot soils and ground degassing mainly in restricted areas called Diffuse Degassing Structures. La Solfatara crater represents the main spot of thermal release for the Campi Flegrei volcano (Italy) despite its reduced dimensions with regards to the whole caldera. The purpose of this study was to develop a method to measure thermal energy release extrapolating it from the ground surface temperature. We used imaging from thermal cameras at short distances (1 m) to obtain a mapping of areas with thermal anomalies and a measure of their temperatures. We built a conceptual model of the energy release from the ground to atmosphere, which well fits the experimental data taken in the La Solfatara crater. Using our model and data, we could estimate the average heat flux in a portion of the crater as q a v g = 220 ± 40 W / m 2 , compatible with other measurements in literature.

This short communication aims at providing an updated report on degassing activity and ground deformation variations observed during the ongoing (2012–2019) Campi Flegrei caldera unrest, with a particular focus on Pisciarelli, currently its most active fumarolic field. We show that the CO2 flux from the main Pisciarelli fumarolic vent (referred as “Soffione”) has increased by a factor > 3 since 2012, reaching in 2018–2019 levels (>600 tons/day) that are comparable to those typical of a medium-sized erupting arc volcano. A substantial widening of the degassing vents and bubbling pools, and a further increase in CO2 concentrations in ambient air (up to 6000 ppm), have also been detected since mid-2018. We interpret this escalating CO2 degassing activity using a multidisciplinary dataset that includes thermodynamically estimated pressures for the source hydrothermal system, seismic and ground deformation data. From this analysis, we show that degassing, deformation and seismicity have all reached in 2018–2019 levels never observed since the onset of the unrest in 2005, with an overall uplift of ~57 cm and ~448 seismic events in the last year. The calculated pressure of the Campi Flegrei hydrothermal system has reached ~44 bar and is rapidly increasing. Our results raise concern on the possible evolution of the Campi Flegrei unrest and reinforce the need for careful monitoring of the degassing activity at Pisciarelli, hopefully with the deployment of additional permanent gas monitoring units.

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.

The Campi Flegrei caldera is located in the metropolitan area of Naples (Italy) and has been undergoing different stages of unrest since 1950, evidenced by episodes of significant ground uplift followed by minor subsidence, increasing and fluctuating emission strengths of water vapor and CO2 from fumaroles, and periodic seismic crises. We deployed a scanning laser remote-sensing spectrometer (LARSS) that measured path-integrated CO2 concentrations in the Pisciarelli area in May 2017. The resulting mean CO2 flux is 578 ± 246 t d−1. Our data suggest a significant increase in CO2 flux at this site since 2015. Together with recent geophysical observations, this suggests a greater contribution of the magmatic source to the degassing and/or an increase in permeability at shallow levels. Thanks to the integrated path soundings, LARSS may help to give representative measurements from large regions containing different CO2 sources, including fumaroles, low-temperature vents, and degassing soils, helping to constrain the contribution of deep gases and their migration mechanisms towards the surface.

In volcanoes with active hydrothermal systems, diffuse CO2 degassing may constitute the primary mode of volcanic degassing. The monitoring of CO2 emissions can provide important clues in understanding the evolution of volcanic activity especially at calderas where the interpretation of unrest signals is often complex. Here, we report eighteen years of CO2 fluxes from the soil at Solfatara of Pozzuoli, located in the restless Campi Flegrei caldera. The entire dataset, one of the largest of diffuse CO2 degassing ever produced, is made available for the scientific community. We show that, from 2003 to 2016, the area releasing deep-sourced CO2 tripled its extent. This expansion was accompanied by an increase of the background CO2 flux, over most of the surveyed area (1.4 km2), with increased contributions from non-biogenic source. Concurrently, the amount of diffusively released CO2 increased up to values typical of persistently degassing active volcanoes (up to 3000 t d−1). These variations are consistent with the increase in the flux of magmatic fluids injected into the hydrothermal system, which cause pressure increase and, in turn, condensation within the vapor plume feeding the Solfatara emission.

Fumaroles are known to generate seismic and infrasonic tremor, but this fumarolic tremor has so far received little attention. Seismic records taken near the Pisciarelli fumarole, a vigorously degassing vent of the restless Campi Flegrei volcano in Italy, reveal a fumarolesourced tremor whose amplitude has recently intensified. We use independent geochemical evidence to interpret this fumarolic tremor for the first time quantitatively. We find that the temporal increase in fumarolic tremor RSAM (real-time seismic-amplitude measurement) quantitatively correlates with increases in independent proxies of fumarole activity, including the CO2concentrations in the fumarole's atmospheric plume, the fumarole composition (CO/CO2and H2/H2O ratios), and temperature (T) and pressure (P) conditions of the source hydrothermal system. This association between RSAM and geochemical data suggests that the current escalation in fumarolic tremor is driven by increased gas transport and venting from a hydrothermal system that evolves toward higher T-P conditions. More widely, our results suggest that monitoring the tremor generated by fumaroles can pave the way to real-time tracking and interpreting the evolution of an ongoing hydrothermal-magmatic unrest, thus complementing information from periodic gas surveys. Our novel method of fumarole monitoring, based on well-established seismic techniques, is potentially suitable for capturing signals of unrest at any active volcano, including those in remote regions.

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.

For the first time a physical model, constrained by monitoring data, is used to derive a quantitative estimate of the evolution in time of magmatic gases that enter a hydrothermal system of an active volcano. The site is Campi Flegrei (west of Naples, in Italy), a caldera that had a large ground inflation in 1982–1984 followed by 20 yr of subsidence. More recently the behavior of the system has changed: the magmatic component of fumaroles has increased, swarms of earthquakes are more frequent, and the ground has started a general uplifting trend, indicating that the hydrothermal system undergoes repeated injections of magmatic fluid. Physical simulations of the process show that total injected fluid masses are the same order of magnitude as those emitted during small to medium size volcanic eruptions, and their cumulative curve highlights a current period of increasing activity. Gas emission studies coupled with physical modeling can be extremely effective in predicting magmatic evolution and eruptive activity at volcanoes.

SUMMARY The Solfatara is one of the major volcanoes of the Phlegrean Fields (Campi Flegrei) volcanic complex, and it is located in a densely populated area a few kilometres west of the city of Naples. It is an active resurgent caldera that has been characterized by a rich history of surface–ground deformation and soil diffuse degassing and fumarolic emissions, which are indications of the top of a hydrothermal plume. A seismic survey was completed in May 2009 for the characterization of the main subsurface features of the Solfatara. Using the complete data set, we have carried out surface wave inversion with high spatial resolution. A classical minimization of a least-squares objective function was first computed to retrieve the dispersion curves of the surface waves. Then, the fitting procedure between the data and a three-sediment-layer forward model was carried out (to a depth of 7 m), using an improved version of the neighbourhood algorithm. The inversion results indicate a NE-SW fault, which is not visible at the surface. This was confirmed by a temperature survey conducted in 2010. A passive seismic experiment localized the ambient noise sources that correlate well with the areas of high CO2 flux and high soil temperatures. Finally, considering that the intrinsic attenuation is proportional to the frequency, a centroid analysis provides an overview of the attenuation of the seismic waves, which is closely linked to the petrophysical properties of the rock. These different approaches that merge complete active and passive seismic data with soil temperature and CO2 flux maps confirm the presence of the hydrothermal system plume. Some properties of the top of the plume are indicated and localized.

Carbon dioxide flux from the soil is regularly monitored in selected areas of Vesuvio and Solfatara (Campi Flegrei, Pozzuoli) with the twofold aim of i) monitoring spatial and temporal variations of the degassing process and ii) investigating if the surface phenomena could provide information about the processes occurring at depth. At present, the surveyed areas include 15 fixed points around the rim of Vesuvio and 71 fixed points in the floor of Solfatara crater. Soil CO2 flux has been measured since 1998, at least once a month, in both areas. In addition, two automatic permanent stations, located at Vesuvio and Solfatara, measure the CO2 flux and some environmental parameters that can potentially influence the CO2 diffuse degassing. Series acquired by continuous stations are characterized by an annual periodicity that is related to the typical periodicities of some meteorological parameters. Conversely, series of CO2 flux data arising from periodic measurements over the arrays of Vesuvio and Solfatara are less dependent on external factors such as meteorological parameters, local soil properties (porosity, hydraulic conductivity) and topographic effects (high or low ground). Therefore we argue that the long-term trend of this signal contains the “best” possible representation of the endogenous signal related to the upflow of deep hydrothermal fluids.

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.

An extensive campaign of diffuse CO2 soil flux was carried out at the cone of Vesuvio in October 2006 with two main objectives: 1) to provide an estimation of CO2 diffusely discharged through the soils in the summit area and 2) to evidence those sectors of the volcano where structural and morphological conditions could favour the gas output. The survey consisted of 502 measurements of soil CO2 flux homogenously distributed over an area of about 1.8 km2. Results of this survey were compared with those obtained during a similar campaign carried out by Frondini et al. in 2000, from which we have taken and reinterpreted a subset of data belonging to the common investigated area. Graphical statistical analysis showed three overlapping populations in both surveys, evidencing the contribution of three different sources feeding the soil CO2 degassing process. The overall CO2 emission pattern of 2006 is coherent with that observed in 2000 and suggests that a value between 120 and 140 t/day of CO2 is representative of the total CO2 discharged by diffuse degassing from the summit area of Vesuvio. The preferential exhaling area lies in the inner crater, whose contribution resulted in 45.3% of the total CO2 emission in 2006 (with 62.8 t/day) and in 57.4% (with 70.3 t/day) in 2000, although its extension is only 13% of the investigated area. This highly emissive area correlated closely with the structural discontinuities of Vesuvio cone, mainly suggesting that the NW-SE trending tectonic line is actually an active fault leaking deep gas to the bottom of the crater. The drainage action of the fault could be enhanced by the “aspiration” effect of the volcanic conduit.

Epidermis micromorphology of in situ Erica arborea L. exposed for generations to long-term effect of volcanic gases in Pisciarelli and Solfatara di Pozzuoli areas have been studied by X-ray analyses, SEM and TEM observations. In particular, the aim of this study is to investigate the effects of volcanic gases on extant and possibly fossil plants. Plants of the same species living in a nearby control site were also studied for comparison. SEM coupled with EDX analysis was used to localize different elements within the leaves (mesophyll, cell wall and cuticle). After conventional and cryo preparation, SEM of mature leaves ascertained that the abaxial side is more serrate in fumigated leaves and hairs, epicuticular wax alterations have also been noted. Leaves experiencing chronic fumigation display stomata more sunken with respect to the epidermal surface. TEM of transverse and longitudinal sections of cuticle showed an outer A2 granular amorphous layer and external to a B1 fibrillous layer. Significant statistical variations of ultrastructural components of the cuticle revealed a response of E. arborea to this extreme environment. At the ultrastructural level, significant variations in thickness of the cell wall plus cuticle, cell wall and A2 layer among fumigated and non-fumigated leaves have been found. In the studied localities a positive correlation between atmospheric CO2 concentration and the thickness of A2 layer also exists. The results are of interest being applicable in the understanding of plant cuticle responses during periods of normal vs. volcanic activity. © 2012 Elsevier B.V.

We intercompare results of three independent approaches to quantify a vented CO2 release at a strongly non-uniform CO2 Earth degassing at Caldara di Manziana, central Italy. An integrated path differential absorption lidar prototype and a commercial open path FTIR system were measuring column averaged CO2 concentrations in parallel at two different paths. An Eulerian gas dispersion model simulated 3-D CO2 concentration maps in the same area, using in situ CO2 flux input data acquired at 152 different points. Local processes the model does not account for, such as small-scale and short-lived wind eddies, govern CO2 concentrations in the instrument measurement paths. The model, on the other hand, also considers atmospheric effects that are out of the field of view of the instruments. Despite this we find satisfactory agreement between modeled and measured CO2 concentrations under certain meteorological conditions. Under these conditions the results suggest that an Eulerian dispersion model and optical remote sensing can be used as an integrated, complementary monitoring approach for CO2 hazard or leakage assessment. Furthermore, the modeling may assist in evaluating CO2 sensing surveys in the future. CO2 column amounts from differential absorption lidar are in line with those from FTIR for both paths with a mean residual of the time series of 44 and 34 ppm, respectively. This experiment is a fundamental step forward in the deployment of the differential absorption lidar prototype as a highly portable active remote sensing instrument probing vented CO2 emissions, including volcanoes.

This paper documents arsenic concentrations in 157 groundwater samples from the island of Ischia and the Phlegrean Fields, two of the most active volcano-hosted hydrothermal systems from the Campanian Volcanic Province (Southern Italy), in an attempt to identify the environmental conditions and mineral-solution reactions governing arsenic aqueous cycling. On Ischia and in the Phlegrean Fields, groundwaters range in composition from NaCl brines, which we interpret as the surface discharge of deep reservoir fluids, to shallow-depth circulating fluids, the latter ranging from acid-sulphate steam-heated to hypothermal, cold, bicarbonate groundwaters. Arsenic concentrations range from 1.6 to 6900 μg·l- 1 and from 2.6 to 3800 μg·l- 1 in the Phlegrean Fields and on Ischia, respectively. They increase with increasing water temperature and chlorine contents, and in the sequence bicarbonate groundwaters < steam-heated groundwaters < NaCl brines. According to thermochemical modeling, we propose that high As concentrations in NaCl brines form after prolonged water-rock interactions at reservoir T, fO2 and fH2S conditions, and under the buffering action of an arsenopyrite + pyrite + pyrrhotite rock assemblage. On their ascent toward the surface, NaCl brines become diluted by As-depleted meteoric-derived bicarbonate groundwaters, giving rise to hybrid water types with intermediate to low As contents. Steam-heated groundwaters give their intermediate to high As concentrations to extensive rock leaching promoted by interaction with As-bearing hydrothermal steam. © 2005 Elsevier B.V. All rights reserved.

The first measurements of volcanic/hydrothermal water vapor and heat flux using eddy covariance (EC) were made at Solfatara crater, Italy, June 8–25, 2001. Deployment at six different locations within the crater allowed areas of focused gas venting to be variably included in the measured flux. Turbulent (EC) fluxes of water vapor varied between 680 and 11 200 g H2O m− 2 d− 1. Heat fluxes varied diurnally with the solar input, and the volcanic component of sensible heat ranged from ∼25 to 238 W m− 2. The highest measurements of both sensible and latent heat flux were made downwind of hot soil regions and degassing pools and during mid-day. The ratio of average volcanic heat (both latent and sensible) to CO2 flux resulted in an equivalent H2O/CO2 flux ratio of 2.2 by weight, which reflects the deep source H2O/CO2 gas ratio. The amount latent heat flux/evaporation was determined to be consistent both with what would be expected from the magnitude of CO2 fluxes and the fumarolic H2O/CO2 ratio, as well as with observed surface temperatures and wind speeds given a moist soil. This suggests that the water vapor that condenses in the shallow subsurface is remobilized at the soil–atmosphere interface through variable evaporation dependent on the deep heat flux and surface temperature. The results suggest that EC provides a quick and easy method to monitor average H2O/CO2 ratios continuously in volcanic regions, providing another important tool for volcanic hazards monitoring.

A geochemical model is proposed for water evolution at Somma–Vesuvio, based on the chemical and isotopic composition of groundwaters, submarine gas emission and chemical composition of the dissolved gases. The active degassing processes, present in the highest part of the volcano edifice, strongly influence the groundwater evolution. The geological–volcanological setting of the volcano forces the waters infiltrating at Somma–Vesuvio caldera, enriched in volcanic gases, to flow towards the southern sector to an area of high pCO2 groundwaters. Reaction path modelling applied to this conceptual model, involving gas–water–rock interaction, highlights an intense degassing process in the aquifer controlling the chemical and isotopic composition of dissolved gases, total dissolved inorganic C (TDIC) and submarine gas emission. Mapping of TDIC shows a unique area of high values situated SSE of Vesuvio volcano with an average TDIC value of 0.039 mol/L, i.e., one order of magnitude higher than groundwaters from other sectors of the volcano. On the basis of TDIC values, the amount of CO2 transported by Vesuvio groundwaters was estimated at about 150 t/d. This estimate does not take into account the fraction of gas loss by degassing, however, it represents a relevant part of the CO2 emitted in this quiescent period by the Vesuvio volcanic system, being of the same order of magnitude as the CO2 diffusely degassed from the crater area.

Cuticle micromorphology together with epidermal and epistomatal wax, in both current- and first-year-old needles of conifer Pinus halepensis (Aleppo pine) trees growing under volcanic gas fumigation was analysed in Pisciarelli area, Campi Flegrei, Southern Italy. As a control, current- and first-year-old needles growing far from volcanic gas emission were also sampled. Using a multidisciplinary approach with SEM, TEM and X-ray, volcanic gases were shown to cause degradation on epicuticular and epistomatal waxes. Significant statistical variations of ultrastructural components of the cuticle, with 30 measurements, including total thickness of the cuticle, and details and proportions of all different layers, and use of confidence interval, revealed a high degree of sensitivity of Aleppo pine to this extreme environment. In the present study, non-significant thickness variations of the cell wall plus cuticle among current- and first-year-old needles of both fumigated and non fumigated trees have been found. However, at the ultrastructural level, significant variations in cell wall and total cuticle thickness, especially within the three zones of B1 fibrillar layer, revealed different equilibria for each of the four types of material. Using energy dispersive X-ray microanalysis, no sulphur was found in either cuticle or epidermal cells, but the presence of H 2 S in the fumarole gas is suspected to cause indirect and/or direct cuticle alterations of wax structure. Ultrastructural characters of plant cuticles related to emission of volcanic gases during the geological past are also discussed. Among these considerations, an identification key enabling distinction between non fumigated and fumigated materials with 9 characters, provides a good tool detecting the influence of volcanism for extant and fossil plants.

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.

An eddy covariance (EC) station was deployed at Solfatara crater, Italy, June 8–25, 2001 to assess if EC could reliably monitor CO2 fluxes continuously at this site. Deployment at six different locations within the crater allowed areas of focused gas venting to be variably included in the measured flux. Turbulent (EC) fluxes calculated in 30-min averages varied between 950 and 4460 g CO2 m−2 d−1; the highest measurements were made downwind of degassing pools. Comparing turbulent fluxes with chamber measurements of surface fluxes using footprint models in diffuse degassing regions yielded an average difference of 0% (±4%), indicating that EC measurements are representative of surface fluxes at this volcanic site. Similar comparisons made downwind of degassing pools yielded emission rates from 12 to 27 t CO2 d−1 for these features. Reliable EC measurements (i.e. measurements with sufficient and stationary turbulence) were obtained primarily during daytime hours (08:00 and 20:00 local time) when the wind speed exceeded 2 m s−1. Daily average EC fluxes varied by ±50% and variations were likely correlated to changes in atmospheric pressure. Variations in CO2 emissions due to volcanic processes at depth would have to be on the same order of magnitude as the measured diurnal variability in order to be useful in predicting volcanic hazard. First-order models of magma emplacement suggest that emissions could exceed this rate for reasonable assumptions of magma movement. EC therefore provides a useful method of monitoring volcanic hazard at Solfatara. Further, EC can monitor significantly larger areas than can be monitored by previous methods.