Chemical and isotopic variations in fumarolic discharge and thermal waters at Vulcano Island (Aeolian Islands, Italy) during 1996: evidence of resumed volcanic activity

Gas samples from some fumaroles at ‘La Fossa' crater and Baia di Levante on Vulcano Island and from a diffuse soil gas emission were analysed during 1995–1996, along with water samples from thermal wells in the area of Vulcano Porto. During 1996, we observed a significant increase both in the gas/steam ratio and in the CO₂ concentration, as well as strong variations in δ¹³C_CO2, δD_H2O and δ¹⁸O_H2O of fumarolic gases. These variations are probably related to an increased inflow of deep fluids of magmatic origin. The temperatures of fumaroles did not show remarkable variations except for fumarole F11. In this case, temperature increased by about 80°C from February to August 1996. During the same period, remarkable variations in temperature, phreatic level and chemical and isotopic composition of water were also recorded in one of the geothermal wells in the Vulcano Porto area (Camping Sicilia; T60°C). The observed variations in this well are probably related to a pressure build-up, occurring at least in the surficial part of the system, because of increased gas flux and/or decreased permeability of the fumarolic degassing system. Chemical and isotopic composition of the water showed that during this evolutionary phase, the content of fumarolic condensate in this well was about 80 to 90%. Based on the observation of physical and chemical variables of the Camping Sicilia fluids, during this phase of activity, it is concluded that this area is affected by a phreatic eruption hazard if a volcanic episode with high energy discharge in a limited time span occurs. It follows that this well may be considered as a preferential point for volcanic activity monitoring, both in the case of normal routine surveillance and in the case of inaccessibility to the crater area.     

Guagua pichincha volcano, Ecuador: fluid geochemistry in volcanic surveillance

The densely populated metropolitan area of Quito is located on the slopes of the active Guagua Pichincha volcano at only 10 km from the crater. Recently, the Italian Ministry of Foreign Affairs sponsored a project for the mitigation of volcanic hazard in this area. The geochemical study carried out as part of this project was aimed at constructing a geochemical model of the zone for use in volcanic surveillance.According to this geochemical model, a hydrothermal aquifer (T = 200–240°C), fed both by meteoric waters and by fluids released by a magma body, lies at shallow levels beneath Guagua Pichincha crater. The crater fumaroles are essentially fed by steam boiled off from the hydrothermal aquifer. The high flow rate fumaroles located in the dome area show significant SO₂ contents, which suggest a relatively high contribution of magmatic fluids in the zone of the aquifer feeding them. The absence of SO₂ in the fumarolic discharges near the southern crater wall indicates instead that the magmatic fluids dissolve entirely into the aquifer here. The hot springs located at the western end of the crater represent the lateral discharge of the hydrothermal aquifer.On the basis of this model, it is likely that an increment in the flux of both the magmatic fluids and the heat from a magma body produces an increase, albeit small, of the pressure-temperature conditions of the hydrothermal system and consequent changes in flow rate and fluid chemistry of the fumarolic vents. In particular, total sulphur and possibly hydrochloric acid may increase in all the vents and sulphur dioxide may appear in other fumarolic discharges. The varying thermodynamic conditions in the hydrothermal aquifer can be evaluated on the basis of the equilibria among carbon species and hydrogen. Only minor delayed changes are expected in the physical-chemical characteristics of the springs located at the western end of the crater.     

Diffuse CO<Subscript>2</Subscript> degassing at Vesuvio,Italy

At Vesuvio, a significant fraction of the rising hydrothermal–volcanic fluids is subjected to a condensation and separation process producing a CO₂–rich gas phase, mainly expulsed through soil diffuse degassing from well defined areas called diffuse degassing structures (DDS), and a liquid phase that flows towards the outer part of the volcanic cone. A large amount of thermal energy is associated with the steam condensation process and subsequent cooling of the liquid phase. The total amount of volcanic–hydrothermal CO₂ discharged through diffuse degassing has been computed through a sequential Gaussian simulation (sGs) approach based on several hundred accumulation chamber measurements and, at the time of the survey, amounted to 151 t d^–1. The steam associated with the CO₂ output, computed assuming that the original H₂O/CO₂ ratio of hydrothermal fluids is preserved in fumarolic effluents, is 553 t d^–1, and the energy produced by the steam condensation and cooling of the liquid phase is 1.47×10¹² J d^–1 (17 MW). The location of the CO₂ and temperature anomalies show that most of the gas is discharged from the inner part of the crater and suggests that crater morphology and local stratigraphy exert strong control on CO₂ degassing and subsurface steam condensation. The amounts of gas and energy released by Vesuvio are comparable to those released by other volcanic degassing areas of the world and their estimates, through periodic surveys of soil CO₂ flux, can constitute a useful tool to monitor volcanic activity.Editorial responsibility: H. Shinohara     

Genesis and evolution of the fumaroles of vulcano (Aeolian Islands,Italy): a geochemical model

A geochemical model explaining the presence of fumaroles having different gas composition and temperature at the top of the crater and along the northeastern coast of Vulcano island is proposed. A pressurized biphase (liquid-vapor) reservoir at the depth of about 2 km is hypothesized. Energy and mass balance sheets controlP-T conditions in the system.P-T must vary along a boiling curve of brine as liquid is present. The CO₂ content in the steam is governed by the thermodynamic properties of the fluids in the H₂-NaCl-CO₂ system. On the assumption that oxygen fugacity in the system is between the HM-FMQ oxygen buffers, observed SO₂/H₂S, CO₂/CO, CO/CH₄ ratios in the fumarolic gases at the Fossa crater appear in equilibrium with a temperature higher than that observed, such as may exist at depth. The more reduced gas phases present on the sea-side may result from re-equilibrium processes in shallower aquifers. The suggested model would help in monitoring changes in volcanic activity by analyzing fumarolic gases.     

Chemical evolution and volcanic activity of the active crater lake of Poás volcano, Costa Rica, 1993–1997

Concentrations of chloride and sulfate and pH in the hot crater lake (Laguna Caliente) at Poás volcano and in acid rain varied over the period 1993–1997. These parameters are related to changes in lake volume and temperature, and changes in summit seismicity and fumarole activity beneath the active crater. During this period, lake level increased from near zero to its highest level since 1953, lake temperature declined from a maximum value of 70°C to a minimum value of 25°C, and pH of the lake water increased from near zero to 1.8. In May 1993 when the lake was nearly dry, chloride and sulfate concentrations in the lake water reached 85,400 and 91,000 mg l⁻¹, respectively. Minimum concentrations of chloride and sulfate after the lake refilled to its maximum volume were 2630 and 4060 mg l⁻¹, respectively. Between January 1993 and May 1995, most fumarolic activity was focused through the bottom of the lake. After May 1995, fumarolic discharge through the bottom of the lake declined and reappeared outside the lake within the main crater area. The appearance of new fumaroles on the composite pyroclastic cone coincided with a dramatic decrease in type B seismicity after January 1996. Between May 1995 and December 1997, enhanced periods of type A seismicity and episodes of harmonic tremor were associated with an increase in the number of fumaroles and the intensity of degassing on the composite pyroclastic cone adjacent to the crater lake. Increases in summit seismic activity (type A, B and harmonic tremor) and in the height of eruption plumes through the lake bottom are associated with a period of enhanced volcanic activity during April–September 1994. At this time, visual observations and remote fumarole temperature measurements suggest an increase in the flux of heat and gases discharged through the bottom of the crater lake, possibly related to renewed magma ascent beneath the active crater. A similar period of enhanced seismic activity that occurred between August 1995 and January 1996, apparently caused fracturing of sealed fumarole conduits beneath the composite pyroclastic cone allowing the focus of fumarolic degassing to migrate from beneath the lake back to the 1953–1955 cone. Changes in the chemistry of summit acid rain are correlated changes in volcanic activity regardless of whether fumaroles are discharging into the lake or are discharging directly into the atmosphere.     

Estimates of heat and pyroclast discharge by volcanic eruptions based upon the eruption cloud and steady plume observations

Fumarolic steam plumes and eruption clouds rise like convetive turbulent columns into the atmosphere. Formulae are presented here for estimating the heat power of plumes, the production rate of juvenile pyroclasts ejected during eruptions and the heat output of fumaroles. Their accuracy is tested using the well-studied examples of eruptions of Kamchatkan volcanoes.The Briggs (1969) formula may be used in observing the ascending part of a plume in crosswinds. The best results have been obtained using the CONCAWE formula which permits estimation of the heat power in crosswinds based on the axis height of a horizontal part of a maintained plume. Three connected equations have been suggested for a stable atmosphere and calm weather conditions. The first one, which is applicable for heights ranging from 100 m to 1 km, is the formula proposed by Morton et al. (1956). This equation changes for higher layers of the troposphere (1–10 km) and stratosphere (10–55 km).A classification scale was constructed allowing us to compare volcanic eruptions and fumarolic activity in terms of the intensity of their plumes.The described method is useful for volcano surveillance; it helps in the study of the energetics and mechanics of volcanic and magmatic processes.     

The magmatic- and hydrothermal-dominated fumarolic system at the Active Crater of Lascar volcano,northern Chile

Low-to-high temperature fumaroles discharging from the Active Crater of Lascar volcano (northern Chile) have been collected in November 2002, May 2005 and October 2006 for chemical and isotopic analysis to provide the first geochemical survey on the magmatic-hydrothermal system of this active volcano. Chemical and isotopic gas composition shows direct addition of high-temperature fluids from magmatic degassing, mainly testified by the very high contents of SO₂, HCl and HF (up to 87,800, 29,500 and 2,900 μmol/mol) and the high R/Ra values (up to 7.29). Contributions from a hydrothermal source, mainly in gas discharges of the Active Crater rim, has also been detected. Significant variations in fluid chemistry, mainly consisting of a general decrease of magmatic-related compounds, i.e. SO₂, have affected the fumarolic system during the period of observation, indicating an increase of the influence of the hydrothermal system surrounding the ascending deep fluids. The chemical composition of Active Crater fumaroles has been used to build up a geochemical model describing the main processes that regulate the fluid circulation system of Lascar volcano to be utilized in volcanic surveillance.     

Thermal anomalies in fumaroles at Vulcano island (Italy) and their relationship with seismic activity

Fumarole thermal monitoring is a useful tool in the evaluation of volcanic activity, since temperatures strongly relate to the upward flux of magmatic volatiles. Once depurated from meteorological noise, their variations can reflect permeability changes due to crustal stress dynamics eventually associated to seismic activity. In this work, we discuss a fumarole temperature record acquired in the period September 2009–May 2012 at Vulcano island (Italy), during which changes of volcanic state, local seismic activity and teleseisms occurred. Apart from positive thermal anomalies driven by increments in volcanic activity, we observed 3 episodes at least of concurrence between tectonic earthquakes and fumarole temperature increments, with particular reference to the local August 16th, 2010 Lipari earthquake, the March 11th, 2011 Sendai–Honshu (Japan) earthquake and a seismic swarm occurred along the Tindari-Letojanni fault in July–August 2011. We interpreted the seismic-related anomalies as “crustal fluid transients”, i.e. signals of volcanogenic vapour flow variations induced by stress-induced permeability changes. From this perspective fumarolic activity can be considered as a tracer of geodynamic instability but, since seismic and volcanic phenomena are in mutual cause-effect relationships, a multidisciplinary observation system is mandatory for correctly addressing thermal data interpretation.     

A water flow model of the active crater lake at Aso volcano,Japan: fluctuations of magmatic gas and groundwater fluxes from the underlying hydrothermal system

The first crater of Nakadake, peak of Aso volcano, Japan, contains a hot water lake that shows interesting variations in water level and temperature. These variations were discovered by precise, continuous observations of the lake independent of precipitation. We developed a numerical model of a hot crater lake and compared with observational data for the period from July 2006 to January 2009. The numerical model revealed seasonal changes in mass flux (75–132 kg/s) and enthalpy (1,840–3,030 kJ/kg) for the fluid supplied to the lake. The relation between the enthalpy and mass flux indicates that the bottom input fluid is a mixture of high- and low-temperature fluids. Assuming a mixture of high-temperature steam at 800°C and liquid water at 100°C, we evaluated the liquid and steam fluxes. The liquid water flux shows a seasonal increase lagging behind the rainy season by 2 months, suggesting that the liquid water is predominantly groundwater. The fluctuation pattern in the flux of the high-temperature steam shows a relation with the amplitude of volcanic tremor, suggesting that heating of the hydrothermal system drives the tremor. Consequently, precise observations of a hot crater lake represent a potential method of monitoring volcanic hydrothermal systems in the shallow parts of the volcanoes.     

First <Superscript>13</Superscript>C/<Superscript>12</Superscript>C isotopic characterisation of volcanic plume CO<Subscript>2</Subscript>

We describe analytical details and uncertainty evaluation of a simple technique for the measurement of the carbon isotopic composition of CO₂ in volcanic plumes. Data collected at Solfatara and Vulcano, where plumes are fed by fumaroles which are accessible for direct sampling, were first used to validate the technique. For both volcanoes, the plume-derived carbon isotopic compositions are in good agreement with the fumarolic compositions, thus providing confidence on the method, and allowing its application at volcanoes where the volcanic component is inaccessible to direct sampling. As a notable example, we applied the same method to Mount Etna where we derived a δ¹³C of volcanic CO₂ between −0.9 ± 0.27‰ and −1.41 ± 0.27‰ (Bocca Nuova and Voragine craters). The comparison of our measurements to data reported in previous work highlights a temporal trend of systematic increase of δ¹³C values of Etna CO₂ from ~ −4‰, in the 1970’s and the 1980’s, to ~ −1‰ at the present time (2009). This shift toward more positive δ¹³C values matches a concurrent change in magma composition and an increase in the eruption frequency and energy. We discuss such variations in terms of two possible processes: magma carbonate assimilation and carbon isotopic fractionation due to magma degassing along the Etna plumbing system. Finally, our results highlight potential of systematic measurements of the carbon isotopic composition of the CO₂ emitted by volcanic plumes for a better understanding of volcanic processes and for improved surveillance of volcanic activity.     

Fumarolic pipes in the Tshirege Member of the Bandelier Tuff on the Pajarito Plateau, Jemez Mountains, New Mexico

The objective of this study is to demonstrate the relationships among devitrification, vapor phase alteration, localization of gas emanations into fumarolic pipes, and initial deformation of the ash flow sheet during cooling and lithification. Utilizing a unique and temporary exposure of the Tshirege Member of the Bandelier Tuff near Los Alamos, New Mexico, we identify several zones of distinctly preserved fossil fumarolic activity. The fumarolic zones vary in width from a few centimeters to more than a meter. Almost ubiquitously, these zones demonstrate fines-depletion, induration of the margins, upward-flaring geometries, and intense fracturing of overlying geologic units. The fumaroles were preferentially located on post welding, early formed cooling joints that vented to the surface after the vapor phase alteration stage. The pipes were regularly spaced at distances of approximately 4.5?m (N–S) to 7?m (E–W). In turn the pipes were covered by a surge deposit and overlying tuff which rapidly lithified. The overlying tuff was then brecciated during continued fumarolic pipe emissions. Geochemical evaluations confirm the presence of high-temperature mineral (scapolite) indicative of transport of hot volcanic gases through these zones. The pipe centers and walls are depleted in SiO₂, and enriched in Al₂O₃ and FeO. The overlying tuff breccia zones are enriched in Al₂O₃, FeO and MgO, and depleted in SiO₂, NaO, and K₂O. From comparison to other ignimbrite cooling histories, the fissures, fumaroles, and structures observed all likely formed in the first few decades after the deposition of the upper Tshirege subunits. This may have significant implications as to timing of initial cooling fractures and subsequent consolidation of gas emission pathways.     

Volcanic CO2 flux measurement at Campi Flegrei by tunable diode laser absorption spectroscopy

Near-infrared room temperature tunable diode lasers (TDL) have recently found increased usage in atmospheric chemistry and air monitoring research, but applications in volcanology are still limited to a few examples. Here, we explored the potential of a commercial infrared laser unit (GasFinder 2.0 from Boreal Laser Ltd) for measurement of volcanic CO₂ mixing ratios, and ultimately for estimating the volcanic CO₂ flux. Our field tests were conducted at Campi Flegrei near Pozzuoli, Southern Italy, where the GasFinder was used during three campaigns in October 2012, January 2013 and May 2013 to repeatedly measure the path-integrated mixing ratios of CO₂ along cross sections of the atmospheric plumes of two major fumarolic fields (Solfatara and Pisciarelli). By using a tomographic post-processing routine, we resolved, for each of the two fields, the contour maps of CO₂ mixing ratios in the atmosphere, from the integration of which (and after multiplication by the plumes’ transport speeds) the CO₂ fluxes were finally obtained. We evaluate a total CO₂ output from the Campi Flegrei fumaroles of ～490 Mg/day, in line with independent estimates based on in situ (Multi-GAS) observations. We conclude that TDL technique may enable CO₂ flux quantification at other volcanoes worldwide.     

Magma-hydrothermal system interaction inferred from volcanic gas measurements obtained during 2003–2008 at Meakandake volcano,Hokkaido, Japan

Phreatic eruptions occurred at the Meakandake volcano in 1988, 1996, 1998, 2006, and 2008. We conducted geochemical surveillance that included measurements of temperature, SO₂ emission rates, and volcanic gas composition from 2003 to 2008 at the Nakamachineshiri (NM), Northwest (NW), and Akanuma (AK) fumarolic areas, and the 96–1 vent, where historical eruptions had occurred. The elemental compositions of the gases discharged from the different areas are similar compared with the large variations observed in volcanic gases discharged from subduction zones. All the gases showed high apparent equilibrium temperatures, suggesting that all these gases originated from a common magmatic gas. The gases discharged from each area also exhibited different characteristics, which are probably the results of differences in the conditions of meteoric water mixing, quenching of chemical reactions, and vapor-liquid separation. The highest apparent equilibrium temperatures (about 500°C) were observed in the case of NW fumarolic gases, despite the low outlet temperature of about 100°C at these fumaroles. Since the NW fumaroles were formed as a result of the 2006 phreatic eruption, the high-temperature gas supply to the NW fumarole suggests that the phreatic eruption was caused by the ascent of high-temperature magmatic gases. The temperatures, compositions, and emission rates of the NM and 96–1 gases did not show any appreciable change after the 2006 eruption, indicating that each fumarolic system had a separate magmatic-hydrothermal system. The temperatures, compositions, and emission rates of the NM fumarolic gases were apparently constant, and these fumaroles are inferred to be formed by the evaporation of a hydrothermal system with a constant temperature of about 300°C. The 96–1 gas compositions showed large changes during continuous temperature decrease from 390° to 190°C occurred from 2003 to 2008, but the sulfur gas emission rates were almost constant at about four tons/day. At the 96–1 vent, the SO₂/H₂S ratio decreased, while the H₂/H₂O ratio remained almost constant; this was probably caused by the rock-buffer controlled chemical reaction during the temperature decrease.     

UV camera measurements of fumarole field degassing (La Fossa crater,Vulcano Island)

The UV camera is becoming an important new tool in the armory of volcano geochemists to derive high time resolution SO₂ flux measurements. Furthermore, the high camera spatial resolution is particularly useful for exploring multiple-source SO₂ gas emissions, for instance the composite fumarolic systems topping most quiescent volcanoes. Here, we report on the first SO₂ flux measurements from individual fumaroles of the fumarolic field of La Fossa crater (Vulcano Island, Aeolian Island), which we performed using a UV camera in two field campaigns: in November 12, 2009 and February 4, 2010. We derived ~ 0.5 Hz SO₂ flux time-series finding fluxes from individual fumaroles, ranging from 2 to 8.7 t d^?1, with a total emission from the entire system of ~ 20 t d^?1 and ~ 13 t d^?1, in November 2009 and February 2010 respectively. These data were augmented with molar H₂S/SO₂, CO₂/SO₂ and H₂O/SO₂ ratios, measured using a portable MultiGAS analyzer, for the individual fumaroles. Using the SO₂ flux data in tandem with the molar ratios, we calculated the flux of volcanic species from individual fumaroles, and the crater as a whole: CO₂ (684 t d^?1 and 293 t d^?1), H₂S (8 t d^?1 and 7.5 t d^?1) and H₂O (580 t d^?1 and 225 t d^?1).     

Geochemistry of volcanic and hydrothermal gases of Mutnovsky volcano,Kamchatka: evidence for mantle,slab and atmosphere contributions to fluids of a typical arc volcano

We report chemical compositions (major and trace components including light hydrocarbons), hydrogen, oxygen, helium and nitrogen isotope ratios of volcanic and geothermal fluids of Mutnovsky volcano, Kamchatka. Several aspects of the geochemistry of fluids are discussed: chemical equilibria, mixing of fluids from different sources, evaluation of the parent magmatic gas composition and contributions to magmatic vapors of fluids from different reservoirs of the Kamchatkan subduction zone. Among reactive species, hydrogen and carbon monoxide in volcanic vapors are chemically equilibrated at temperatures >300°C with the SO₂-H₂S redox-pair. A metastable equilibrium between saturated and unsaturated light hydrocarbons is attained at close to discharge temperatures. Methane is disequilibrated. Three different sources of fluids from three fumarolic fields in the Mutnovsky craters can be distinguished: (1) magmatic gas from a large convecting magma body discharging through Active Funnel, a young crater with the hottest fumaroles (up to 620°C) contributing ~80% to the total volcanic gas output; (2) volcanic fluid from a separate shallow magma body beneath the Bottom Field of the main crater (96–280°C fumaroles); and (3) hydrothermal fluid with a high relative and absolute concentrations of CH₄ from the Upper Field in the main crater (96–285°C fumaroles). The composition of the parent magmatic gas is estimated using water isotopes and correlations between He and other components in the Active Funnel gases. The He-Ar-N₂ systematics of volcanic and hydrothermal fluids of Mutnovsky are consistent with a large slab-derived sedimentary nitrogen input for the nitrogen inventory, and we calculate that only ~1% of the magmatic N₂ has a mantle origin and <<1% is derived from the arc crust.     

18O/16O studies of fossil fissure fumaroles from the Valley of Ten Thousand Smokes, Alaska

At three sample sites where there are good exposures of the upper 15 m of the 1912 ash-flow sheet in the Valley of Ten Thousand Smokes (VTTS), Alaska, ¹⁸O/¹⁶O studies indicate that fumarolic activity produced a very wide range of δ¹⁸O values (?0.1 to +12.6; n=32) in the groundmass adjacent to fossil fissure fumaroles. This contrasts sharply with the uniformity of δ¹⁸O in the groundmass away from fumarolic conduits (δ¹⁸O=+5.9 to +7.1; n=7) and in all of the feldspar phenocrysts (δ¹⁸O=+6.11 to +7.5 1 for 11 samples from this study and Hildreth 1987), independent of whether these were collected from fossil fumaroles or from unaltered tuff. Only one sample contained feldspars that were even slightly ¹⁸O-enriched relative to the others (cloudy plagioclase δ¹⁸O=+8.45). and this sample also contained the most ¹⁸0-enriched groundmass of any of those analyzed (δ¹⁸O=+12.6). This preservation of primary magmatic δ¹⁸O values in the VTTS feldspar phenocrysts is clearly a consequence of the extremely short time span (i.e., 1912 to ≈1923) of vigorous, high-temperature, fumarolic activity in the 1912 ash-flow sheet. These ¹⁸O/^l6O systematica are strikingly similar to those discovered in the 2.8-Ma intracaldera Chegem Tuff (Gazis et al. 1996) and in the fossil fumaroles in the outflow sheet of the 0.76 Ma Bishop Tuff (Holt and Taylor 1998), thus confirming that a similar type of fumarolic meteoric-hydro-thermal activity occurred above the zone of intense welding in all three of these ash-flow tuffs. This is particularly important, because it provides a direct linkage between the older tuffs and the actual observations at the VTTS of steam chemistry, water/rock interaction, circulation geometry, flow velocities, and fumarolic temperatures (up to 645°C). The ¹⁸O/^l6O effects in the VTTS can all be explained in terms of a two-stage history: (a) an early, 10- to 15-year-long, high-temperature (τ;450°C), fumarolic ¹⁸O-depletion event (groundmass δ¹⁸O=?0.1 to +4.8); and (b) a subsequent, much longer-lived, low-temperature (<150°C), ¹⁸O-enrichment episode (groundmass as high as δ¹⁸O=+12.6). Steam in these low-temperature fumaroles probably passed through various parts of the same hydrothermal system associated with the earlier, higher-temperature, fumarolic activity, and a weakened form of this low-temperature hydrothermal circulation continues to the present day (Keith et al. 1992; Lowell and Keith 1991). This low-temperature ¹⁸O/¹⁶O exchange probably occurred in combination with mineralogical alteration of both the groundmass and the calcium-rich portions of feldspar phenocrysts during the waning (<150°C) stages of fumarolic activity (Spilde et al. 1993). The slight ¹⁸O enrichment of apparently pristine, transparent feldspar phenocrysts (δ¹⁸O=+7.51) in one of the ¹⁸O-depleted, meteoric-hydrothermally altered fumarolic samples (whole-rock δ¹⁸O=+4.8) probably indicates that this sample was incipiently altered at low temperatures as fumarolic activity waned, and thus may have had a whole-rock δ¹⁸O value much lower than +4.87‰ prior to 1923.     

Incrustations and fumarolic condensates at kilauea volcano, Hawaii: field, drill-hole and laboratory observations

Hawaiian volcanoes characteristically have but few of the many types of minerals found in incrustations of other volcanic areas. In Hawaii sulfates resulting from air oxidation of volatiles predominate, and fluorides produced during rock alteration by fumarolic gases are prominent. Halides are generally found where reducing conditions exist in fumaroles and lava lake drill holes. The most common mineral types are sulfur, opaline silica, gypsum, ralstonite, and thenardite. Minerals from the same deposit are found to vary markedly in the content of the less abundant components. Condensates from vapor issuing from fumaroles show little quantitative relationship in component content to incrustations deposited at the same fumaroles. It is believed that an energetically favorable isomorphic substitution of some elements in the crystal lattice of a depositing mineral may lead to the build-up of a high concentration of an element from a lean vapor. Equilibrium calculations applied to condensate studies give a good quantitative approximation to the concentrations of the elements found in natural systems, but when applied to incrustations they serve only to indicate general compositional relations. Laboratory studies have shown the important role of chlorides in metal transfer in the gas phase in high-temperature aqueous systems, but only in the absence of oxygen. These studies also demonstrated the important role of HF in rock alteration and in the transfer of silica.     

Fumarole monitoring with a handheld infrared camera: Volcán de Colima,Mexico, 2006–2007

This paper describes a methodology for the monitoring of fumarole temperatures at medium ranges (~ 6 km) using a handheld infrared camera (wavelength range: 8–13.5 µm). As a relationship between fumarole temperatures, gas flux and volcanic activity has been demonstrated by a number of studies, fumarole temperature data has a potential use as a monitoring tool. Volcán de Colima is an andesitic stratovolcano with a 300 m diameter summit crater formed by the destruction of the 2004 lava dome by a series of explosions in 2005. Between January 2006 and August 2007, sequences of thermal images were recorded from a viewpoint 6 km to the north during regular 24–48 hour monitoring excursions. The temperatures of fumaroles on the crater rim and the ground surface on the volcano's flanks were measured. A methodology was developed to remove data affected by clouds or volcanic water vapour based on rates of temperature change and scatter within the data. For the remaining data, it is demonstrated mathematically that at this range, typical variations in atmospheric transmissivity will affect the apparent temperatures by +/− 2 °C, while a 25% change in fumarole heat flux would change it by 5–10 °C. The mean night-time apparent temperature of the fumaroles was calculated for each excursion and showed an irregular decline over the 19 month period. Subtracting the radiant heat flux of flank rocks from those of the fumaroles removes seasonal variations and gives the clearest view of trends in the fumarole heat flux. A sharp drop in fumarole temperature during February 2007 coincided with the emergence of a lava dome in the crater. The declining fumarole temperature is interpreted to reflect decreasing gas flux from the crater in line with a change in eruptive regime from frequent, small, ash-rich explosions to slow effusion of lava.     

Signs of potential renewal of eruptive activity at La Fossa (Vulcano,Aeolian Islands)

Since the end of the last magmatic eruption (1890), activity of La Fossa (southern Tyrrhenian Sea, Italy) has consisted of fumarolic emissions of fluctuating intensity. Fluids are discharged principally at two fumarolic fields located in the northern rim of the active crater and at the beach sited at its northern foot. Increased thermal, seismic and geochemical activity has been recorded since 1978, when an earthquake of M=5.5 occurred in the region. This paper combines available geophysical and geochemical information in order to develop a tentative interpretation of two episodes of apparent unrest which occurred in 1985 and 1987–1988, enhancing the risk of renewal of the eruptive activity. The 1985 unrest consisted essentially of a sharp build up of the internal pressure in the shallow hydrothermal system, which was induced by the injection of hot gases of magmatic origin. The crater fumaroles displayed significant increases in CO₂ and other acid species, but their outlet temperature did not change. Conversely, the 1987–1988 episode was characterized by appreciable modifications at the crater fumaroles, with only secondary effects at the fumarole system of the beach. The sliding of part of the eastern flank of the La Fossa cone into the sea occurred on 20 April 1988, when the region was affected by crustal dilatation producing a seismic sequence of relatively high intensity. Both episodes of unrest were accompanied by increases of local microseismic activity, which affected the nothern sector of the island in 1985, and the southern one in 1988. Finally, a phase of appreciable areal contraction was detected in 1990, probably due to the effect of the cooling and crystallization of magma at relatively shallow depths, accompanying the increased thermal activity at the crater fumaroles. Regional tectonic stress seems to play an important role in the transition of the volcanic system from a phase of relative stability to a phase of apparent unrest, inducing the heating and the expansion of shallow hydrothermal fluids. Available information is insufficient to indicate whether or not the volcano is building towards the renewal of a magmatic eruption, and there is no evidence to hypothesize episodes of significant magma migration. The frequency of measurements of many parameters needs to be increased in order to learn more about the temporal relationships between geochemical and geophysical variations preceding and accompanying periods of increased thermal activity. This will probably be a valid tool for recognizing short-term precursors of a future eruption, reducing the risk of false alarms.     

The use of chemical indicators in the surveillance of volcanic activity affecting the Crater Lake on Mt Ruapehu,New Zealand

Between January 1966 and December 1973 approximately 100 water samples wert collected from the Crater Lake of Mt Ruapehu. From analyses of the samples, changes in chloride and magnesium concentrations and pH emerged as the most useful indicators for the occurrence of the two major processes associated with eruptive activity: Chloride concentrations vary in response to changes in fumarolic activity, arising from the degassing of magma; rises in magnesium concentrations are due to interaction of lake water with freshly injected, hot andesitic material. Similarly, variations in temperature, pH and the ratio Mg/Cl enable the effects of dilution and evaporation to be considered. The thermal power required to maintain elevated lake temperatures ～200 MW during quiet periods, reaching 1000 MW during active periods, is largely transferred by fumarolic steam.