Sampling and analytical procedures for the determination of VOCs released into air from natural and anthropogenic sources: A comparison between SPME (Solid Phase Micro Extraction) and ST (Solid Trap) methods

In the present study, two sampling and analytical methods for VOC determination in fumarolic exhalations related to hydrothermal-magmatic reservoirs in volcanic and geothermal areas and biogas released from waste landfills were compared: (a) Solid Traps (STs), consisting of three phase (Carboxen B, Carboxen C and Carbosieve S111) absorbent stainless steel tubes and (b) Solid Phase Micro Extraction (SPME) fibers, composed of DiVinylBenzene (DVB), Carboxen and PolyDimethylSiloxane. These techniques were applied to pre-concentrate VOCs discharged from: (i) low-to-high temperature fumaroles collected at Vulcano Island, Phlegrean Fields (Italy), and Nisyros Island (Greece), (ii) recovery wells in a solid waste disposal site located near Florence (Italy). A glass condensing system cooled with water was used to collect the dry fraction of the fumarolic gases, in order to allow more efficient VOC absorption avoiding any interference by water vapor and acidic gases, such as SO₂, H₂S, HF and HCl, typically present at relatively high concentrations in these fluids. Up to 37 organic species, in the range of 40–400 m/z, were determined by coupling gas chromatography to mass spectrometry (GC–MS). This study shows that the VOC compositions of fumaroles and biogas determined via SPME and ST are largely consistent and can be applied to the analysis of VOCs in gases released from different natural and anthropogenic environments. The SPME method is rapid and simple and more appropriate for volcanic and geothermal emissions, where VOCs are present at relatively high concentrations and prolonged gas sampling may be hazardous for the operator. The ST method, allowing the collection of large quantities of sample, is to be preferred to analyze the VOC composition of fluids from diffuse emissions and air, where these compounds are present at relatively low concentrations.     

Fluorine speciation in topsoils of three active volcanoes of Sicily (Italy)

Fluorine is one of the many environmental harmful elements released by volcanic activity. The content of total oxalate-extractable and water-extractable fluorine was determined in 96 topsoils of three active volcanic systems of southern Italy (Mt Etna, Stromboli and Vulcano). Total fluorine (F) content (F _TOT) ranges from 112 to 7,430 mg kg⁻¹, F extracted with oxalate (F _OX) ranges from 16 to 2,320 mg kg⁻¹ (2–93% of F _TOT) and F extracted with distilled water ( ) ranges from 1.7 to 159 mg kg⁻¹ (0.2–40 % of F _TOT). Fluorine in the sampled topsoils derives both from the weathering of volcanic rocks and ashes and from the enhanced deposition due to volcanic gas emissions either from open-conduit passive degassing (Mt Etna and Stromboli) or from a fumarolic field (Vulcano). Fluorine accumulation in the studied soils does not generally present particular environmental issues except for a few anomalous sites at Vulcano, where measured contents could be dangerous both for vegetation and for grazing animals.     

Lichens as bioindicators in volcanic areas: Mt. Etna and Vulcano Island (Italy)

 The aim of this paper is to verify whether lichens have the capacity to accumulate atmospheric contaminators linked to volcanic activity. About 100 lichens were collected in 1994 and 1995 from two active volcanic areas in Italy: Mount Etna and Vulcano Island. Twenty-seven elements were analyzed for each individual lichen using Instrumental Neutronic Activation Analysis and Inductively Coupled Plasma-Mass Spectrometry. Lichen composition reflects the contribution of the volcanic particulate material, and the two areas investigated can be distinguished on the basis of the concentration of some lithophile elements. Moreover, the distribution in lichens of the elements (As, Sb, Br, Pb) – derived from gas emissions (plume, fumaroles) – also shows different geochemical trends on Mt. Etna and Vulcano. Received: 20 April 1998 · Accepted: 4 July 1998     

New Perspectives on Water Chemistry and Compositional Data Analysis

Water chemistry is commonly investigated to determine the suitability of water for various uses. With increased knowledge of aqueous chemistry, it has become possible to interpret the evolutionary processes that determine water composition and quality. This paper presents procedures for exploring and modeling the environment using compositional data from water analysis, utilizing statistical tools in an appropriate sample space. Our procedures build on a methodology based on log-ratios initiated by John Aitchison in the early 1980's. They are not only useful for interpreting the structure of the data, but also for characterizing and modeling the influence of geochemical processes acting on the environment. The geochemistry of water samples collected from wells on Vulcano Island (one of the Aeolian Islands of the Italian province of Sicily) will be used to illustrate the techniques, although an exhaustive overview would require many different examples. Vulcano island is a quiescent volcanic area where mobilization of chemical species by weathering of volcanic rocks and input of gaseous components from fumarolic activity has produced environmental changes expressed in the composition of phreatic waters at the surface and in the shallow subsurface. Changes in the chemical composition of waters in unconfined aquifers of the northwestern part of the island around the active crater appear to be useful in understanding the natural processes at work.     

Reactions governing the chemistry of crater fumaroles from Vulcano Island,Italy, and implications for volcanic surveillance

More than 200 chemical and isotope analyses of fumarolic fluids collected at the Fossa Grande crater, Vulcano Island, during the 1980s show that the main process controlling these fluids is mixing between the gas released by a magma body and the vapour produced through evaporation of brines of marine origin. Large variations in the relative contribution of these two sources have been observed during the last 10 a. The main species (H₂O and CO₂), the inert gases (He and N₂), and the D content of steam are fixed by the mixing processes; they are therefore the best tracers the fraction of the deep magmatic component in the fumarolic fluids discharged at the surface. In contrast, the “fast” species (H₂ and CO) equilibrate at T,P values close to the outlet temperature and atmospheric pressure, and under redox conditions governed by the SO₂H₂S buffer, as indicated by thermodynamic calculations.Acid gases (HCl, HF, H₂S and SO₂) are partly contributed by the magmatic component and partly produced by the reactions between hot rocks, steam and salts which take place in the “dry” zones surrounding the central magmatic gas column, as suggested by the good agreement between their analytical and theoretical contents.     

Boron isotopic variations in fumarolic condensates and thermal waters from Vulcano Island, Italy: Implications for evolution of volcanic fluids

Temporal variation in the isotopic composition of boron has been monitored in fumarolic condensates collected over an extended time period (1970-1996) from La Fossa crater, Volcano Island. We also report comparative boron isotopic data for representative Vulcano lavas and for shallow hydrologic samples (seawater, wells, thermal springs) from the north flank of La Fossa. Combined with concurrent chemical and isotopic (δ¹⁸O, δD) data for the fumaroles, these results indicate that the fumarolic fluids record mixing relations between three distinct fluid end members: (1) a dominantly magmatic fluid (EM1); (2) a mixture of modified seawater with magmatic fluid (EM2); and (3) an aqueous fluid produced from seawater by extensive wall-rock reaction, evaporation, and boiling (AF). Differences between the latter two end members are most clearly accentuated on the basis of the boron isotopic data. Long-term compositional variations for crater fumaroles were dominated by EM1-AF mixing between 1979-88, with progressive decrease in EM1 contribution with time, and by EM2-AF mixing between 1988-96. The exact spatial distribution of these fluid reservoirs remains unclear, but all must have been present throughout the monitoring period to account for the observed variations. Moreover, the combined B-O-H data seem to preclude important contributions from shallow meteoric reservoirs. Marked short-term variations in δ¹¹B closely coincide with episodes of local seismicity, which presumably triggered reorganization of hydrothermal circulation patterns; gradual variations over periods up to 3-4 years are associated with relatively low seismicity during which fluid circulation was likely influenced by effects of mineral precipitation on permeability of the hydrologic system.     

Arsenic in volcanic gases

 Total arsenic contents were determined in volcanic gases by analysis of fumarolic condensates collected in the period 1984–1992 from different volcanoes around the world. Arsenic concentrations range from <0.006 to 30 μg/g. The highest values (1.2–30 μg/g) were found at Vulcano, Aeolian Islands (southern Italy). The analytical data show that volcanic gases have a large variability of arsenic contents possibly related to both the different physicochemical features of magma source and rock properties within the volcanic system. Received: 2 October 1996 · Accepted: 29 January 1997     

GPS Measurements in the Neapolitan volcanic area

The surveillance of the Neapolitan volcanic area (Mt. Vesuvius, the Phlegrean Fields and the island of Ischia) represents the principal activity of the Osservatorio Vesuviano. Such an activity is carried out also through the study of ground deformations. This study deals with the use of the GPS as a powerful topographic technique. In the last two years, three GPS networks in the above mentioned area were established, with 8 vertices at Mt. Vesuvius, 20 vertices in the Island of Ischia and 30 vertices in the Phlegrean Fields. In Mt. Vesuvius area a GPS test was carried out, in order to verify the possibility of the installation of a network of GPS permanent stations. In the island of Ischia, three different GPS techniques (Static, Fast Static and RTK-Real Time Kinematics) have been used to get a first set of coordinates and to carry out a comparison between these in small extension areas. GPS data of the Phlegrean Fields are still in processing. The results for Mt. Vesuvius area and the island of Ischia are hereby presented and discussed.     

The behavior of chlorine and sulfur during differentiation of the Mt. Somma-Vesuvius magmatic system

Summary Reheated silicate melt inclusions in volcanic rock samples from Mt. Somma-Vesuvius, Italy, have been analyzed for 29 constituents including H₂O, S, Cl, F, B, and P₂O₅. This composite volcano consists of the older Mt. Somma caldera, formed between 14 and 3.55 ka before present, and the younger Vesuvius cone. The melt inclusion compositions provide important constraints on pre-eruptive magma geochemistry, identify relationships that relate to eruption behavior and magma evolution, and provide extensive evidence for magmatic fluid exsolution well before eruption. The melt inclusion data have been categorized by groups that reflect magma compositions, age, and style of eruptions. The data show distinct differences in composition for eruptive products older than 14.0 ka (pre-caldera rocks) versus eruptive products younger than 3.55 ka. Moreover, pre-caldera eruptions were associated with magmas relatively enriched in SiO₂, whereas eruptions younger than 3.55 ka (i.e., the syn- and post-caldera magmas which generated the Somma caldera and the Vesuvius cone) were derived from magmas comparatively enriched in S, Cl, CaO, MgO, P₂O₅, F, and many lithophile trace elements. Melt inclusion data indicate that eruptive behavior at Vesuvius correlates with pre-eruptive volatile enrichments. Most magmas associated with explosive plinian and subplinian events younger than 3.55 ka contained more H₂O, contained significantly more S, and exhibited higher (S/Cl) ratios than syn- and post-caldera magmas which erupted during relatively passive interplinian volcanic phenomena. Received January 10, 2000 Revised version accepted July 17, 2000     

Magma-derived gas influx and water-rock interactions in the volcanic aquifer of Mt. Vesuvius, Italy

We report in this paper a systematic investigation of the chemical and isotopic composition of groundwaters flowing in the volcanic aquifer of Mt. Vesuvius during its current phase of dormancy, including the first data on dissolved helium isotope composition and tritium content. The relevant results on dissolved He and C presented in this paper reveal that an extensive interaction between rising magmatic volatiles and groundwaters currently takes place at Vesuvius.Vesuvius groundwaters are dilute (mean TDS ∼ 2800 mg/L) hypothermal fluids ( mean T = 17.7°C) with a prevalent alkaline-bicarbonate composition. Calcium-bicarbonate groundwaters normally occur on the surrounding Campanian Plain, likely recharged from the Apennines. δD and δ¹⁸O data evidence an essentially meteoric origin of Vesuvius groundwaters, the contribution from either Tyrrhenian seawater or ¹⁸O-enriched thermal water appearing to be small or negligible. However, the dissolution of CO₂-rich gases at depth promotes acid alteration and isochemical leaching of the permeable volcanic rocks, which explains the generally low pH and high total carbon content of waters. Attainment of chemical equilibrium between the rock and the weathering solutions is prevented by commonly low temperature (10 to 28°C) and acid-reducing conditions.The chemical and isotope (C and He) composition of dissolved gases highlights the magmatic origin of the gas phase feeding the aquifer. We show that although the pristine magmatic composition may vary upon gas ascent because of either dilution by a soil-atmospheric component or fractionation processes during interaction with the aquifer, both ¹³C/¹²C and ³He/⁴He measurements indicate the contribution of a magmatic component with a δ¹³C ∼ 0‰ and R/R_a of ∼2.7, which is consistent with data from Vesuvius fumaroles and phenocryst melt inclusions in olivine phenocrysts.A main control of tectonics on gas ascent is revealed by data presented in this paper. For example, two areas of high CO₂ release and enhanced rock leaching are recognized on the western (Torre del Greco) and southwestern (Torre Annunziata-Pompeii) flanks of Vesuvius, where important NE-SW and NW-SE tectonic structures are recognized. In contrast, waters flowing through the northern sector of the volcano are generally colder, less saline, and CO₂ depleted, despite in some cases containing significant concentrations of magma-derived helium. The remarkable differences among the various sectors of the volcano are reconciled in a geochemical interpretative model, which is consistent with recent structural and geophysical evidences on the structure of Somma-Vesuvius volcanic complex.     

The roots of Mt. Vesuvius deduced from gravity anomalies

Summary The structures of the Somma-Vesuvius volcanic complex are modelled on the basis of the interpretation of gravity anomalies obtained from data available in the literature and acquired along a new profile along the coastline from Naples to Castellammare di Stabia. In order to highlight the contribution of shallow crustal structures, the residual anomalies were considered. A marked gravity low was recognised in the eastern sector of Vesuvius. Furthermore data interpretation was carried out along two profiles centred on the low gravity region in question: a first profile crossing the Vesuvius crater in direction WNW-ESE, and a second one in NNE-SSW direction. The 2 ? D model obtained reveals a crustal structure characterised by sediments of 2.3 Mg/m³ density, overlying bedrock with a density of 2.6 Mg/m³. Near the volcanic system the model becomes more complex due to the presence of light sediments with a density of 2.1 Mg/m³ overlying a body with a density of 2.4 Mg/m³ which extends into depth. The latter is thought to be closely related to the zone of magma ascent developed along the volcanic axis. Along the coast the volcanic component is reduced and the model shows that the layer with a density of 2.3 Mg/m³ ranges in thickness from 0 to about 3500 m. An additional body between 1500 and 3000 m with a density of 2.4 Mg/m³ was considered in order to account for the slight rise in the residual anomaly in the area in the vicinity of Mt. Vesuvius. The analysis of the gravity anomaly pattern coincides with the complex system of faults and fractures intersecting the carbonate basement and the volcanic area in question, which developed as a consequence of extensional processes at the continental edge of the Italian Peninsula due to the opening of the Tyrrhenian basin. This extensional tectonics has created favourable conditions for the collapse of the south-western slope of Mt. Vesuvius and the development of eruptive vents and cracks on its flanks. Received May 18, 2000; revised version accepted March 6, 2001     

Experimental simulation of magma–carbonate interaction beneath Mt. Vesuvius, Italy

We simulated the process of magma–carbonate interaction beneath Mt. Vesuvius in short duration piston-cylinder experiments under controlled magmatic conditions (from 0 to 300 s at 0.5 GPa and 1,200 °C), using a Vesuvius shoshonite composition and upper crustal limestone and dolostone as starting materials. Backscattered electron images and chemical analysis (major and trace elements and Sr isotopes) of sequential experimental products allow us to identify the textural and chemical evolution of carbonated products during the assimilation process. We demonstrate that melt–carbonate interaction can be extremely fast (minutes), and results in dynamic contamination of the host melt with respect to Ca, Mg and ⁸⁷Sr/⁸⁶Sr, coupled with intense CO₂ vesiculation at the melt–carbonate interface. Binary mixing between carbonate and uncontaminated melt cannot explain the geochemical variations of the experimental charges in full and convection and diffusion likely also operated in the charges. Physical mixing and mingling driven by exsolving volatiles seems to be a key process to promote melt homogenisation. Our results reinforce hypotheses that magma–carbonate interaction is a relevant and ongoing process at Mt. Vesuvius and one that may operate not only on a geological, but on a human timescale.     

Environmental impact of the acid fumarolic plume of a passively degassing volcano (Vulcano Island,Italy)

This paper investigates the role played by the fumarolic plume of a passive degassing volcano in the genesis of rock coatings (RC) and in the introduction and re-distribution of metals and trace elements in the surficial environment. At La Fossa active volcano (Vulcano Island) and in the surrounding environment RC develop owing to exposure of the ground surface to the volcanic acid plume produced by the passive degassing of La Fossa. Significant positive anomalies of a wide variety of metals and trace elements (including Bi, Ag, Se, Te, Sb, Pb, As, Cu, Tl and Cd) were observed either in distal and proximal RC. Most of these anomalies are interpreted to be the result of the transport and subsequent deposition of trace elements, likely to form volatile compounds, in the fumarolic plume. Two main processes seem to control the geochemistry of RC: one is represented by the leaching and subsequent deposition of elements from the proximal toward the distal RC; the other is the direct input of trace elements carried by the emitted volcanic aerosol. The fact that most of the trace elements (particularly Pb, As, Tl, Bi, Te, Se, Cd) enriched in the RC of Vulcano are highly toxic and potentially dangerous to health in high concentration, indicates that the atmospheric metal injection by the quiescently degassing La Fossa volcano together with the subsequent deposition and remobilization by means of surficial waters may represent an environmental hazard that should be taken into account in evaluating the potential impact of volcanic air pollution on human health.     

Genesis of fumarolic emissions as inferred by isotope mass balances: CO2 and water at Vulcano Island, Italy

We have developed a quantitative model of CO₂ and H₂O isotopic mixing between magmatic and hydrothermal gases for the fumarolic emissions of the La Fossa crater (Vulcano Island, Italy). On the basis of isotope balance equations, the model takes into account the isotope equilibrium between H₂O and CO₂ and extends the recent model of chemical and energy two-end-member mixing by Nuccio et al. (1999). As a result, the H₂O and CO₂ content and the δD, δ¹⁸O, and δ¹³C isotope compositions for both magmatic and hydrothermal end-members have been assessed. Low contributions of meteoric steam, added at a shallow depth, have been also recognized and quantified in the fumaroles throughout the period from 1988 to 1998. Nonequilibrium oxygen isotope exchange also seems to be occurring between ascending gases and wall rocks along some fumarolic conduits.The δ¹³C_CO2 of the magmatic gases varies around −3 to 1‰ vs. Peedee belemnite (PDB), following a perfect synchronism with the variations of the CO₂ concentration in the magmatic gases. This suggests a process of isotope fractionation because of vapor exsolution caused by magma depressurization. The hydrogen isotopes in the magmatic gases (−1 to −‰ vs. standard mean ocean water [SMOW]), as well as the above δ¹³C_CO2 value, are coherent with a convergent tectonic setting of magma generation, where the local mantle is widely contaminated by fluids released from the subducted slab. Magma contamination in the crust probably amplifies this effect.The computed isotope composition of carbon and hydrogen in the hydrothermal vapors has been used to calculate the δD and δ¹³C of the entire hydrothermal system, including mixed H₂O-CO₂ vapor, liquid water, and dissolved carbon. We have computed values of about 10‰ vs. SMOW for water and −2 to −6.5‰ vs. PDB for CO₂. On these grounds, we think that Mediterranean marine water (δD_H2O ≈ 10‰) feeds the hydrothermal system. It infiltrates at depth throughout the local rocks, reaching oxygen isotope equilibrium at high temperatures. Interaction processes between magmatic gases and the evolving seawater also seem to occur, causing the dissolution of isotopically fractionated aqueous CO₂ and providing the source for hydrothermal carbon. These results have important implications concerning fluid circulation beneath Vulcano and address the more convenient routine of geochemical surveillance.     

Seismic assessment of phreatic-explosion hazard at ‘La Fossa’ Volcano (Island of Vulcano,Italy)

Active volcanic areas are sometimes affected by phreatic eruptions, which are explosions due to the outbreak of a confined pocket of steam and gas without the direct involvement of molten magma. Eruptive activity at La Fossa Volcano, Island of Vulcano (Italy), typically starts with a phreatic explosion, continues as phreatomagmatic and turns into a late magmatic stage, depending on the reduction in the efficiency of magma-water interaction. The present risk is mainly related to a village located at the very foot of the active volcanic cone, which in summer seasons is inhabited by more than 10,000 people. Because the last eruptive episode occurred in 1888–1890, when no local instrumental control was performed, the scientific community does not have any information about the seismic phenomena which could precede the initial phreatic blast. Inferences from similar monitored volcanoes, which awakened in the last few years after more or less long quiescence, are therefore made to tentatively depict possible pre-eruptive seismic scenarios and also to evaluate the most appropriate surveillance and alert criteria to adopt. Appreciable signs of volcanic unrest have been detected in recent years, mainly related to modifications in the physical and chemical features of fumarolic fluids discharged at the active crater. Following the classification of local seismic shocks, the recording oflong-period events (peak frequency 2 Hz) should be taken into account as a realistic seismic warning of volcanic hazard enhancement. A likely short-term seismic precursor may be finally given by the appearance of the so-calledbanded tremor, a seismic signal likely produced by intermittent hydrothermal boiling accompanying the hydraulic fracturing of rocks at the top of a pressurized aquifer. Real-time recognition of tremor can be therefore very useful to avoid, at least, injuries to volcanologists and visitors working or staying on the most dangerous sectors of the volcano.     

The rheological evolution of alkaline Vesuvius magmas and comparison with alkaline series from the Phlegrean Fields, Etna, Stromboli and Teide

Somma-Vesuvius is considered one of the highest-risk volcanic systems in the world due to its high population density and record of highly destructive explosive activity. Eruptive style at Vesuvius varies greatly, alternating between effusive and explosive activities, and is likely strongly controlled by the evolution of the physical and chemical properties of the magma. Nevertheless, with the exception of the 1631 eruption, the rheological properties of Vesuvius magmas remain largely unconstrained. Here, we investigate the Newtonian shear viscosity (η) of dry and hydrous melts from the Mercato (plinian) and 1906 (violent strombolian) eruptions. These eruptions differ in size, eruptive style and magma chemistry (from phonolite to phono-tephrite). To evaluate the dry liquid viscosity variation covered by the eruptive products of the recent activity at Vesuvius, we measured the melt viscosities of bulk rock compositions and, for highly crystalline samples, of the separated groundmasses of tephras from the Pollena and 1906 eruptions. Hydrated samples with up to 4.24 wt% dissolved water were synthesised in a piston cylinder apparatus at confining pressure up to 10 kbar. The dry high temperature and the dry and hydrous low-temperature viscosities were obtained by combining the concentric cylinder and micropenetration techniques. The measured viscosities were parameterized by a modified Vogel-Fulcher-Tammann equation, accounting for the effect of water content, and were compared with previous measurements and models. At magmatic temperatures, the viscosities of Mercato samples are about four orders of magnitude higher than that of the least viscous investigated products from the 1906 eruption. Complex numerical models to forecast eruptive scenarios and their environmental impact are extremely sensitive to the accuracy of the input parameters and constitutive equations of magma properties. As a consequence, the numerical expressions obtained here are of particular relevance in the context of hazard assessment related to the different possible eruptive scenarios at Vesuvius through numerical simulation tools. The effect of composition on the liquid viscosities is compared to other high-Na (e.g., samples from Teide and Etna) and high-K (e.g., samples from Stromboli and Phlegrean Fields) alkaline magmas.     

Low-pH waters discharging from submarine vents at Panarea Island (Aeolian Islands,southern Italy) after the 2002 gas blast: Origin of hydrothermal fluids and implications for volcanic surveillance

A geochemical survey of thermal waters collected from submarine vents at Panarea Island (Aeolian Islands, southern Italy) was carried out from December 2002 to March 2007, in order to investigate (i) the geochemical processes controlling the chemical composition of the hydrothermal fluids and (ii) the possible relations between the chemical features of the hydrothermal reservoir and the activity of the magmatic system. Compositional data of the thermal water samples were integrated in a hydrological conceptual model, which describes the formation of the vent fluid by mixing of seawater, seawater concentrated by boiling, and a deep, highly-saline end-member, whose composition is regulated by water-rock interactions at relatively high temperature and shows clear clues of magmatic-related inputs. The chemical composition of concentrated seawater was assumed to be represented by that of the water sample having the highest Mg content. The composition of the deep end-member was instead calculated by extrapolation assuming a zero-Mg end-member. The Na–K–Ca geothermometer, when applied to the thermal end-member composition, indicated an equilibrium temperature of approximately 300 °C, a temperature in agreement with the results obtained by gas-geothermometry.     

The aquatic geochemistry of arsenic in volcanic groundwaters from southern Italy

This paper discusses the abundance, speciation and mobility of As in groundwater systems from active volcanic areas in Italy. Using literature data and new additional determinations, the main geochemical processes controlling the fate of As during gas–water–rock interaction in these systems are examined. Arsenic concentrations in the fluids range from 0.1 to 6940 μg/l, with wide differences observed among the different volcanoes and within each area. The dependence of As content on water temperature, pH, redox potential and major ions is investigated. Results demonstrate that As concentrations are highest where active hydrothermal circulation takes place at shallow levels, i.e. at Vulcano Island and the Phlegrean Fields. In both areas the dissolution of As-bearing sulphides is likely to be the main source of As. Mature Cl-rich groundwaters, representative of the discharge from the deep thermal reservoirs, are typically enriched in As with respect to SO₄-rich “steam heated groundwaters”. In the HCO₃⁻ groundwaters recovered at Vesuvius and Etna, aqueous As cycling is limited by the absence of high-temperature interactions and by high-Fe content of the host rocks, resulting in oxidative As adsorption. Thermodynamic modelling suggests that reducing H₂S-rich groundwaters are in equilibrium with realgar, whereas in oxidising environments over-saturation with respect to Fe oxy-hydroxides is indicated. Under these oxidising conditions, As solubility decreases controlled by As co-precipitation with, or adsorption on, Fe oxy-hydroxides. Consistent with thermodynamic considerations, As mobility in the studied areas is enhanced in intermediate redox environments, where both sulphides and Fe hydroxides are unstable.     

Interaction between seismic and volcanic deformation: a possible interpretation of ground deformation observed at Vulcano Island (1976–84)

Levelling measurements carried by Osservatorio Vesuviano over Vulcano Island (North Sicily) since June 1976 show a complex history of small but significant vertical movements which took place after the ‘Patti earthquake’ of 15/4/1978. Three phases can be identified in the time history of ground deformation: (I) co-seismic subsidence of the northern part of the Island with respect to the southern part, followed by (II) transient inflation of the central region surrounding ‘La Fossa’ volcano, and finally (III) deflation and subsidence to stationary values greater than phase I. Large variations in temperature and gas content of magmatic origin were also detected in fumaroles along the crater rim of ‘La Fossa’. The coincidence in time of the earthquake with the start of the deformation history, the proximity of the event to Vulcano Island and the favourable mechanism (right lateral) and orientation (NNW) of the fault strike, suggest that the earthquake triggered the observed deformation. Among the plausible models, one seems particularly able to reproduce the amplitude and time evolution of the geodetic data, in a manner consistent with the geochemical observations. According to this model the earthquake, while generating a compressive stress field in the quadrant of Vulcano Island, induced at first a relative coseismic subsidence of the northern part of the island, accompanied by a large increase of the mean stress within a magma chamber at ～ 6.5 km depth. Volatile fluids were then released from the top of the magma chamber and migrated towards the surface following the enhanced pressure gradient. As a result fluid pressure diffusion around the magma chamber induced a local transient uplift of ground that vanished after exhaustion of the overpressure at the source, and finally left a permanent dislocation deformation, possibly amplified by the post-seismic relaxation of the earthquake deviatoric stress. This interpretation is qualitatively consistent with the one suggested by Ferri et al. (1988).     

Transcrystalline melt migration in clinopyroxene

Glass inclusions in clinopyroxene phenocrysts from La Sommata (Vulcano Island, Aeolian Arc) were reheated and submitted to a sustained thermal gradient. Each remelted inclusion undergoes a transient textural and chemical reequilibration and concomitantly begins to migrate along a crystallographic direction, at a small angle with the thermal gradient. The completion of morphological evolution requires a characteristic time that is governed by chemical diffusion. Chemical reequilibration results in the formation of a colored halo that delineates the former location and shape of the inclusion after it has migrated away. Transcrystalline migration proceeds by dissolution of the host clinopyroxene ahead and precipitation astern. Its rate is not limited by Fick’s law, but by the crystal-melt interface kinetics. Clinopyroxene dissolution and growth are slower than for olivine in similar conditions but obey the same analytical law, which can be transposed to equally or more sluggish melting or crystallization events in nature. When a gas bubble is initially present, it responds to elastic forces by quickly shifting toward the cold end of the inclusion, where it soon becomes engulfed as an isolated fluid inclusion in the reprecipitated crystal. This study confirms that transcrystalline melt migration, beside its possible implications for small-scale melt segregation and fluid-inclusion generation in the Earth’s mantle, provides an experimental access to interfacial kinetic laws in near-equilibrium conditions.