Chemical composition of fumarolic gases and spring discharges from El Chichòn volcano, Mexico: causes and implications of the changes detected over the period 1998–2000

Since the March–April 1982 eruption of El Chichòn volcano, intense hydrothermal activity has characterised the 1-km-wide summit crater. This mainly consists of mud and boiling pools, fumaroles, which are mainly located in the northwestern bank of the crater lake. During the period 1998–2000, hot springs and fumaroles discharging inside the crater and from the southeastern outer flank (Agua Caliente) were collected for chemical analyses. The observed chemical fluctuations suggest that the physico-chemical boundary conditions regulating the thermodynamic equilibria of the deep rock/fluid interactions have changed with time. The chemical composition of the lake water, characterised in the period 1983–1997 by high Na⁺, Cl⁻, Ca²⁺ and SO₄²⁻ contents, experienced a dramatic change in 1998–1999, turning from a Na⁺–Cl⁻- to a Ca²⁺–SO₄²⁻-rich composition. In June 2000, a relatively sharp increase in Na⁺ and Cl⁻ contents was observed. At the same time, SO₂/H₂S ratios and H₂ and CO contents in most gas discharges increased with respect to the previous two years of observations, suggesting either a new input of deep-seated fluids or local variations of the more surficial hydrothermal system. Migration of gas manifestations, enhanced number of emission spots and variations in both gas discharge flux and outlet temperatures of the main fluid manifestations were also recorded. The magmatic-hydrothermal system of El Chichòn is probably related to interaction processes between a deep magmatic source and a surficial cold aquifer; an important role may also be played by the interaction of the deep fluids with the volcanic rocks and the sedimentary (limestone and evaporites) basement. The chemical and physical changes recorded in 1998–2000 were possibly due to variations in the permeability of the conduit system feeding the fluid discharges at surface, as testified by the migration of gas and water emanations. Two different scenarios can be put forward for the volcanic evolution of El Chichòn: (1) build-up of an infra-crater dome that may imply a future eruption in terms of tens to hundreds of years; (2) minor phreatic–phreatomagmatic events whose prediction and timing is more difficult to constrain. This suggests that, unlike the diminished volcanic activity at El Chichòn after the 1982 paroxistic event, the volcano-hydrothermal fluid discharges need to be more constantly monitored with regular and more frequent geochemical sampling and, at the same time, a permanent network of seismic stations should be installed.     

Generation of Icelandic rhyolites: silicic lavas from the Torfajökull central volcano

The Torfajökull central volcano in south-central Iceland contains the largest volume of exposed silicic extrusives in Iceland (225 km³). Within SW-Torfajökull, postglacial mildly alkalic to peralkalic silicic lavas and lava domes (67–74 wt.% SiO₂) have erupted from a family of fissures 1–2.5 km apart within or just outside a large caldera (12×18 km). The silicic lavas show a fissure-dependent variation in composition, and form five chemically distinct units. The lavas are of low crystallinity (0–7 vol.%) and contain phenocrysts in the following order of decreasing abundance: plagioclase (An_10-40), Na-rich anorthoclase (<Or₂₃), clinopyroxene (Fs_37-20), FeTi oxides (Usp_32-60; Ilm_93-88), hornblende (edenitic–ferroedenitic) and olivine (Fo_22-37), with apatite, pyrrhotite and zircon as accessory phases. The phenocryst assemblage (0.2–4.0 mm) consistently exhibits pervasive disequilibrium with the host melt (glass). Xenoliths include sparse, disaggregated, and partially fused leucocratic fragments as well as amphibole-bearing rocks of broadly intermediate composition. The values of the silicic lavas are in the range 3.6–4.4, and these are lower than the values of comagmatic, contemporaneous basaltic extrusives within SW-Torfajökull, implying that the former can not be derived from the latter by simple fractional crystallization. FeTi-oxide geothermometry reveals temperatures as low as 750–800°C. To explain the fissure-dependent chemical variations, depletions, low FeTi-oxide temperatures and pervasive crystal-melt disequilibrium, we propose the extraction and collection of small parcels of silicic melt from originally heterogeneous basaltic crustal rock through heterogeneous melting and wall rock collapse (solidification front instability, SFI). The original compositional heterogeneity of the source rock is due to (1) silicic segregations, in the form of pods and lenses characteristically formed in the upper parts of gabbroic intrusives, and (2) extreme isostatic subsidence of the earlier, less differentiated lavas of the Torfajökull central volcano. Ridge migration into older crustal terranes, coupled with establishment of concentrated volcanism at central volcanoes like Torfajökull due to propagating regional fissure swarms, supplies the heat source for this overall process. Continued magmatism in these fissures promotes extensive prograde heating of older crust and the progressive vitality and rise of the central volcano magmatic system that leads to, respectively, SFI and subsidence melting. The ensuing silicic melts (with relict crystals) are extracted, collected and extruded before reaching complete internal equilibrium. Chemically, this appears as a two-stage process of crystal fractionation. In general, the accumulation of high-temperature basaltic magmas at shallow depths beneath the Icelandic rift zones and major central volcanoes, coupled with unique tectonic conditions, allows large-scale reprocessing and recycling of the low- , hydrothermally altered Icelandic crust. The end result is a compositionally bimodal proto-continental crust.     

Geochemistry of gases and waters discharged by the mud volcanoes at Paternò, Mt. Etna (Italy)

 Approximately 20 km south of Mt. Etna craters, at the contact between volcanic and sedimentary formations, three mud volcanoes discharge CO₂-rich gases and Na–Cl brines. The compositions of gas and liquid phases indicate that they are fed by a hydrothermal system for which temperatures of 100–150  °C were estimated by means of both gas and solute geothermometry. The hydrothermal system may be associated with CO₂-rich groundwaters over a large area extending from the central part of Etna to the mud volcanoes. Numerous data on the He, CH₄, CO₂ composition of the gases of the three manifestations, sampled over the past 5 years, indicate clearly that variations are due to separation processes of a CO₂-rich gas phase from the liquid. The effects of these processes have to be taken into account in the interpretation of the monitoring data collected for the geochemical surveillance of Etna volcano. Received: 4 September 1995 / Accepted: 14 February 1996     

Geochemistry of the magmatic–hydrothermal system of Kawah Ijen volcano, East Java, Indonesia

Samples from Kawah Ijen crater lake, spring and fumarole discharges were collected between 1990 and 1996 for chemical and isotopic analysis. An extremely low pH (<0.3) lake contains SO₄–Cl waters produced during absorption of magmatic volatiles into shallow ground water. The acidic waters dissolve the rock isochemically to produce “immature” solutions. The strong D and ¹⁸O enrichment of the lake is mainly due to enhanced evaporation at elevated temperature, but involvement of a magmatic component with heavy isotopic ratios also modifies the lake D and ¹⁸O content. The large Δ_SO4–S⁰ (23.8–26.4‰) measured in the lake suggest that dissolved SO₄ forms during disproportionation of magmatic SO₂ in the hydrothermal conduit at temperatures of 250280°C. The lake δ¹⁸O_SO4 and δ¹⁸O_H2O values may reflect equilibration during subsurface circulation of the water at temperatures near 150°C. Significant variations in the lake's bulk composition from 1990 to 1996 were not detected. However, we interpret a change in the distribution and concentration of polythionate species in 1996 as a result of increased SO₂-rich gas input to the lake system.Thermal springs at Kawah Ijen consist of acidic SO₄–Cl waters on the lakeshore and neutral pH HCO₃–SO₄–Cl–Na waters in Blawan village, 17 km from the crater. The cation contents of these discharges are diluted compared to the crater lake but still do not represent equilibrium with the rock. The SO₄/Cl ratios and water and sulfur isotopic compositions support the idea that these springs are mixtures of summit acidic SO₄–Cl water and ground water.The lakeshore fumarole discharges (T=170245°C) have both a magmatic and a hydrothermal component and are supersaturated with respect to elemental sulfur. The apparent equilibrium temperature of the gas is 260°C. The proportions of the oxidized, SO₂-dominated magmatic vapor and of the reduced, H₂S-dominated hydrothermal vapor in the fumaroles varied between 1979 and 1996. This may be the result of interaction of SO₂-bearing magmatic vapors with the summit acidic hydrothermal reservoir. This idea is supported by the lower H₂S/SO₂ ratio deduced for the gas producing the SO₄–Cl reservoir feeding the lake compared with that observed in the subaerial gas discharges. The condensing gas may have equilibrated in a liquid–vapor zone at about 350°C.Elemental sulfur occurs in the crater lake environment as banded sediments exposed on the lakeshore and as a subaqueous molten body on the crater floor. The sediments were precipitated in the past during inorganic oxidation of H₂S in the lake water. This process was not continuous, but was interrupted by periods of massive silica (poorly crystallized) precipitation, similar to the present-day lake conditions. We suggest that the factor controlling the type of deposition is related to whether H₂S- or silica-rich volcanic discharges enter the lake. This could depend on the efficiency with which the lake water circulates in the hydrothermal cell beneath the crater. Quenched liquid sulfur products show δ³⁴S values similar to those found in the banded deposits, suggesting that the subaqueous molten body simply consists of melted sediments previously accumulated at the lake bottom.     

Leakage of Active Crater lake brine through the north flank at Rincón de la Vieja volcano, northwest Costa Rica, and implications for crater collapse

The Active Crater at Rincón de la Vieja volcano, Costa Rica, reaches an elevation of 1750 m and contains a warm, hyper-acidic crater lake that probably formed soon after the eruption of the Rio Blanco tephra deposit approximately 3500 years before present. The Active Crater is buttressed by volcanic ridges and older craters on all sides except the north, which dips steeply toward the Caribbean coastal plains. Acidic, above-ambient-temperature streams are found along the Active Crater's north flank at elevations between 800 and 1000 m. A geochemical survey of thermal and non-thermal waters at Rincón de la Vieja was done in 1989 to determine whether hyper-acidic fluids are leaking from the Active Crater through the north flank, affecting the composition of north-flank streams.Results of the water-chemistry survey reveal that three distinct thermal waters are found on the flanks of Rincón de la Vieja volcano: acid chloride–sulfate (ACS), acid sulfate (AS), and neutral chloride (NC) waters. The most extreme ACS water was collected from the crater lake that fills the Active Crater. Chemical analyses of the lake water reveal a hyper-acidic (pH0) chloride–sulfate brine with elevated concentrations of calcium, magnesium, aluminum, iron, manganese, copper, zinc, fluorine, and boron. The composition of the brine reflects the combined effects of magmatic degassing from a shallow magma body beneath the Active Crater, dissolution of andesitic volcanic rock, and evaporative concentration of dissolved constituents at above-ambient temperatures. Similar cation and anion enrichments are found in the above-ambient-temperature streams draining the north flank of the Active Crater. The pH of north-flank thermal waters range from 3.6 to 4.1 and chloride:sulfate ratios (1.2–1.4) that are a factor of two greater than that of the lake brine (0.60). The waters have an ACS composition that is quite different from the AS and NC thermal waters that occur along the southern flank of Rincón de la Vieja.The distribution of thermal water types at Rincón de la Vieja strongly indicates that formation of the north-flank ACS waters is not due to mixing of shallow, steam-heated AS water with deep-seated NC water. More likely, hyper-acidic brines formed in the Active Crater area are migrating through permeable zones in the volcanic strata that make up the Active Crater's north flank. Dissolution and shallow subsurface alteration of north-flank volcanoclastic material by interaction with acidic lake brine, particularly in the more permeable tephra units, could weaken the already oversteepened north flank of the Active Crater. Sector collapse of the Active Crater, with or without a volcanic eruption, represents a potential threat to human lives, property, and ecosystems at Rincón de la Vieja volcano.     

Seismic activity accompanying the outbreak of the 1991–1993 eruption of Mt. Etna (Italy)

The character and location of seismic activity accompanying the onset of the 1991–1993 eruption at Mt. Etna are compatible with the surface evidence of the volcanic pile rupture. Both the epicentral distribution and the focal mechanisms of a swarm that occurred on December 14, 1991, agree with magma ascent occurring along the main NNW-SSE-trending structure of the volcano and the consequent opening of a system of effusive fissures with the same trend. A typical mainshock-aftershock sequence, recorded the day after and indicating transcurrent displacement occurring along the second-principal structure of Etna (NE-SW), depicts the tectonic response of the volcanic pile and the underlying basement to major stresses applied by the magma push.     

The storage and release of magma on Mount Etna

The eruptive history of Etna during the past 450 years provides data on effusion rates, volumes of magma involved, and the nature of the eruptive conduits. These data are interpreted in terms of a two-part intravolcanic magma reservoir which feeds the flank eruptions through dike-like conduits. The structural framework of the volcano which controls the spatial distribution of eruptive sites is partly inherited from the basement and partly controlled by the central magma column and the surrounding caldera boundary faults. Hydraulic fracturing theory predicts that the central magma column will fail at depths below 1 km if the tensile strength of the conduit rocks is about 100 bars and that a peak fracturing capability will be reached between 1 and 2 km depth. This inference agrees well with the peak of flank eruptive activity at 1.4 km below the summit observed in the data on the loci of eruptions. The average flank-eruption feeding dike is defined and shown to be capable of the observed maximum effusion rates (20–100 m³ s⁻¹) from magmatic pressure differences of 30–150 bars     

Evaluation of volcanic gas analysis from surtsey volcano, iceland 1964–1967

Methods used previously to remove compositional modifications from volcanic gas analyses for Mount Etna and Erta'Ale lava lake have bean employed to estimate the gas phase composition at Nyiragongo lava lake, based on samples obtained in 1959. H₂O data were not reported in 11 of the 13 original analyses. The restoration methods have been used to estimate the H₂O contents of the samples and to correct the analyses for atmospheric contamination, loss of sulfur and for pre- and pest-collection oxidation of H₂S, S₂, and H₂. The estimated gas compositions are relatively CO₂-rich, low in total sulfur and reduced. They contain approximately 35–50% CO₂ 45–55% H₂O, 1–2% SO₂, 1–2% H₂., 2–3% CO, 1.5–2.5% H₂S, 0.5% S₂ and 0.1% COS over,he collection temperature range 102° to 960° C. The oxygen fugacities of the gases are consistently about half an order of magnitude below quartz-magnetite-fayalite. The low total sulfur content and resulting low atomic S/C of the Nyiragongo gases appear to be related to the relatively low f_O2 of the crystallizing lava. At temperatures above 800°C and pressures of 1–1.5 k bar, the Nyiragongo gas compositions resemble those observed in primary fluid inclusions believed to have formed at similar temperatures and pressures in nephelines of intrusive alkaline rocks. Cooling to 300°C, with f_O2 buffered by the rock, results in gas compositions very rich in CH₄ (50–70%) and resembling secondary fluid inclusions formed at 200–500°C in alkaline rocks. Below 600°C the gases become supersaturated in carbon as graphite. These inferences are corroborated by several reports of hydrocarbons in plutonic alkaline rocks, and by the presence of CH₄-rich waters in Lake Kivu — a lake on the flanks of Nyiragongo volcano.     

Radionuclides and sulfur content in Mount Etna plume in 1983–1995: new constraints on the magma feeding system

Radionuclide activities (²¹⁰Pb, ²¹⁰Bi, ²¹⁰Po) were investigated in Mount Etna plume from 1983 to 1995. At SE crater the long-term observation (12 years) of the ²¹⁰Po/²¹⁰Pb ratio shows that it can behave as a degassing vent not directly related to the main magma reservoir depending on the magma level inside the volcano. Since 1992, the simultaneous determination of radionuclides and sulfur in the main plume results in new constraints on the degassing model of Lambert et al. (Earth Planet. Sci. Lett., 76 (1986) 185). The ²¹⁰Po/SO₂ and ²¹⁰Pb/SO₂ ratios enable us to identify two sources of ²¹⁰Po in the plume: one is magmatic, correlated with SO₂, the other one is an additional component issued from the decay of ²¹⁰Pb in the shallow degassing cell, and depends directly on the residence time of the gases before their emission. Estimations of the volume of degassing magma, the residence time of the gases and the proportion of undegassed magma renewing the shallow degassing cell are given for the period 1992–1995. During the 1992 eruption, the rate of degassing magma volume is estimated to have been as high as 5×10⁶ m³/day, and the volume of the shallow degassing magma reservoir about 0.5 km³. In 1994 and 1995 the rate of non-erupted degassing magma volume was estimated to have been about 0.18 km³/year. During the entire 1983–1995 period, only 15–20% of the degassed magma was erupted.     

Chemical and isotopic compositions of thermal springs,fumaroles and bubbling gases at Tacaná Volcano (Mexico–Guatemala): implications for volcanic surveillance

This study presents baseline data for future geochemical monitoring of the active Tacaná volcano–hydrothermal system (Mexico–Guatemala). Seven groups of thermal springs, related to a NW/SE-oriented fault scarp cutting the summit area (4,100m a.s.l.), discharge at the northwest foot of the volcano (1,500–2,000m a.s.l.); another one on the southern ends of Tacaná (La Calera). The near-neutral (pH from 5.8 to 6.9) thermal (T from 25.7°C to 63.0°C) HCO₃–SO₄ waters are thought to have formed by the absorption of a H₂S/SO₂–CO₂-enriched steam into a Cl-rich geothermal aquifer, afterwards mixed by Na/HCO₃-enriched meteoric waters originating from the higher elevations of the volcano as stated by the isotopic composition (δD and δ¹⁸O) of meteoric and spring waters. Boiling temperature fumaroles (89°C at ~3,600m a.s.l. NW of the summit), formed after the May 1986 phreatic explosion, emit isotopically light vapour (δD and δ¹⁸O as low as −128 and −19.9‰, respectively) resulting from steam separation from the summit aquifer. Fumarolic as well as bubbling gases at five springs are CO₂-dominated. The δ¹³C_CO2 for all gases show typical magmatic values of −3.6 ± 1.3‰ vs V-PDB. The large range in ³He/⁴He ratios for bubbling, dissolved and fumarolic gases [from 1.3 to 6.9 atmospheric ³He/⁴He ratio (R _A)] is ascribed to a different degree of near-surface boiling processes inside a heterogeneous aquifer at the contact between the volcanic edifice and the crystalline basement (⁴He source). Tacaná volcano offers a unique opportunity to give insight into shallow hydrothermal and deep magmatic processes affecting the CO₂/³He ratio of gases: bubbling springs with lower gas/water ratios show higher ³He/⁴He ratios and consequently lower CO₂/³He ratios (e.g. Zarco spring). Typical Central American CO₂/³He and ³He/⁴He ratios are found for the fumarolic Agua Caliente and Zarco gases (3.1 ± 1.6 × 10¹⁰ and 6.0 ± 0.9 R _A, respectively). The L/S (5.9 ± 0.5) and (L + S)/M ratios (9.2 ± 0.7) for the same gases are almost identical to the ones calculated for gases in El Salvador, suggesting an enhanced slab contribution as far as the northern extreme of the Central American Volcanic Arc, Tacaná.     

Chemistry and mineralogy of high-temperature gas discharges from Colima volcano, Mexico. Implications for magmatic gas–atmosphere interaction

Gases, condensates and silica tube precipitates were collected from 400°C (Z2) and 800°C (Z3) fumaroles at Colima volcano, Mexico, in 1996–1998. Volcanic gases at Colima were very oxidized and contain up to 98% air due to mixing with air inside the dome interior, close to the hot magmatic body. An alkaline trap method was used to collect gas samples, therefore only acidic species were analysed. Colima volcanic gases are water-rich (95–98 mol%) and have typical S/C/Cl/F ratios for a subduction type volcano. δD-values for the high-temperature Z3 fumarolic vapour vary from −26 to −57‰. A negative δD–Cl correlation for the Z3 high-temperature fumarole may result from magma degassing: enrichment in D and decrease in the Cl concentration in condensates are likely a consequence of input of “fresh” batches of magma and an increasing of volcanic activity, respectively.The trace element composition of Colima condensates generally does not differ from that of other volcanoes (e.g. Merapi, Kudryavy) except for some enrichment in V, Cu and Zn. Variations in chemical composition of precipitates along the silica tube from the high-temperature fumarole (Colima 1, fumarole Z3), in contrast to other volcanoes, are characterized by high concentrations of Ca and V, low concentration of Mo and a lack of Cd. Mineralogy of precipitates differs significantly from that described for silica tube experiments at other volcanoes with reduced volcanic gas. Thermochemical modelling was used to explain why very oxidized gas at Colima does not precipitate halite, sylvite, and Mo- and Cd-minerals, but does precipitate V-minerals and native gold, which have not been observed before in mineral precipitates from reduced volcanic gases.     

Explosive silicic volcanism in Iceland and the Jan Mayen area during the last 6 Ma: sources and timing of major eruptions

Fifty-three major explosive eruptions on Iceland and Jan Mayen island were identified in 0–6-Ma-old sediments of the North Atlantic and Arctic oceans by the age and the chemical composition of silicic tephra. The depositional age of the tephra was estimated using the continuous record in sediment of paleomagnetic reversals for the last 6 Ma and paleoclimatic proxies (δ¹⁸O, ice-rafted debris) for the last 1 Ma. Major element and normative compositions of glasses were used to assign the sources of the tephra to the rift and off-rift volcanic zones in Iceland, and to the Jan Mayen volcanic system. The tholeiitic central volcanoes along the Iceland rift zones were steadily active with the longest interruption in activity recorded between 4 and 4.9 Ma. They were the source of at least 26 eruptions of dominant rhyolitic magma composition, including the late Pleistocene explosive eruption of Krafla volcano of the Eastern Rift Zone at about 201 ka. The central volcanoes along the off-rift volcanic zones in Iceland were the source of at least 19 eruptions of dominant alkali rhyolitic composition, with three distinct episodes recorded at 4.6–5.3, 3.5–3.6, and 0–1.8 Ma. The longest and last episode recorded 11 Pleistocene major events including the two explosive eruptions of Tindfjallajökull volcano (Thórsmörk, ca. 54.5 ka) and Katla volcano (Sólheimar, ca. 11.9 ka) of the Southeastern Transgressive Zone. Eight major explosive eruptions from the Jan Mayen volcanic system are recorded in terms of the distinctive grain-size, mineralogy and chemistry of the tephra. The tephra contain K-rich glasses (K₂O/SiO₂>0.06) ranging from trachytic to alkali rhyolitic composition. Their normative trends (Ab–Q–Or) and their depleted concentrations of Ba, Eu and heavy-REE reflect fractional crystallisation of K-feldspar, biotite and hornblende. In contrast, their enrichment in highly incompatible and water-mobile trace elements such as Rb, Th, Nb and Ta most likely reflect crustal contamination. One late Pleistocene tephra from Jan Mayen was recorded in the marine sequence. Its age, estimated between 617 and 620 ka, and its composition support a common source with the Borga pumice formation at Sør Jan in the south of the island.     

Mechanism of energy transfer in the lava lake of Niragongo (Zaire), 1959–1977

Heat and mass transfer rates were studied at the Niragongo lava lake during two expeditions directed by H. Tazieff in 1959 and 1972. The results of this study are as follows:Heat is transferred to the surface of the lake by the movement of lava; gas discharge is a result and not the cause of convection. The chemical composition of the gases and magma has changed very little between 1959 and 1972, whereas the mass and energy outputs differ by an order of magnitude. In 1977 a catastrophic explosion seems to have been caused by tectonic factors, stopping the slow convection of magma under the volcano and hence reducing surface manifestations in the form of the lava lake and escaping fumarolic and magmatic gases. The gas discharge was, in tons day⁻¹, 5000 for H₂O, 11,000 for CO₂, 1000 for SO₂ in 1959, and in 1972 7700 for H₂O, 180,000 for CO₂ and 23,000 for SO₂. These values correspond to an energy transfer of 0.9 × 10⁹ W in 1959 and 16 × 10⁹ W in 1972.     

Sulfur dioxide emissions from Popocatépetl volcano (Mexico): case study of a high-emission rate, passively degassing erupting volcano

Popocatépetl volcano in central Mexico has been erupting explosively and effusively for almost 4 years. SO₂ emission rates from this volcano have been the largest ever measured using a COSPEC. Pre-eruptive average SO₂ emission rates (2–3 kt/d) were similar to the emission rates measured during the first part of the eruption (up to August 1995) in contrast with the effusive–explosive periods (March 1996–January 1998) during which SO₂ emission rates were higher by a factor of four (9–13 kt/d). Based on a chronology of the eruption and the average SO₂ emission rates per period, the total SO₂ emissions (up to 1 January 1998) are estimated to be about 9 Mt, roughly half as much as the SO₂ emissions from Mount Pinatubo in a shorter period. Popocatépetl volcano is thus considered as a high-emission rate, passively degassing eruptive volcano. SO₂ emission rates and SO₂ emissions are used here to make a mass balance of the erupted magma and related gases. Identified excess SO₂ is explained in terms of continuous degassing of unerupted magma and magma mixing. Fluctuations in SO₂ emission rate may be a result of convection and crystallization in the chamber or the conduits, cleaning and sealing of the plumbing system, and/or SO₂ scrubbing by the hydrothermal system.     

The occurrence of Mt Barca flank eruption in the evolution of the NW periphery of Etna volcano (Italy)

Geological surveys, tephrostratigraphic study, and ⁴⁰Ar/³⁹Ar age determinations have allowed us to chronologically constrain the geological evolution of the lower NW flank of Etna volcano and to reconstruct the eruptive style of the Mt Barca flank eruption. This peripheral sector of the Mt Etna edifice, corresponding to the upper Simeto valley, was invaded by the Ellittico volcano lava flows between 41 and 29 ka ago when the Mt Barca eruption occurred. The vent of this flank eruption is located at about 15 km away from the summit craters, close to the town of Bronte. The Mt Barca eruption was characterized by a vigorous explosive activity that produced pyroclastic deposits dispersed eastward and minor effusive activity with the emission of a 1.1-km-long lava flow. Explosive activity was characterized by a phreatomagmatic phase followed by a magmatic one. The geological setting of this peripheral sector of the volcano favors the interaction between the rising magma and the shallow groundwater hosted in the volcanic pile resting on the impermeable sedimentary basement. This process produced phreatomagmatic activity in the first phase of the eruption, forming a pyroclastic fall deposit made of high-density, poorly vesicular scoria lapilli and lithic clasts. Conversely, during the second phase, a typical strombolian fall deposit formed. In terms of hazard assessment, the possible occurrence of this type of highly explosive flank eruption, at lower elevation in the densely inhabited areas, increases the volcanic risk in the Etnean region and widens the already known hazard scenario.     

Seismogenic stress field beneath Mt. Etna (South Italy) and possible relationships with volcano-tectonic features

Shallow shear-type seismic activity occurring beneath the Etna volcano during 1990–1995 has been analysed for hypocenter locations, focal mechanisms and stress tensor inversion. The results have been examined jointly with Electronic Distance Measurements and tiltmeter data collected in the same period and reported in the literature. Significant seismicity located in the upper 10 km was found to be confined to the time intervals in which ground deformation data indicated inflation of the volcano edifice (e.g., the periods preceding the December 1991–March 1993 and August 1995–March 1996 eruptive phases). The shocks mostly occurred in a sector approximately centered on the crater area and elongated in the East–West direction. The causative seismogenic stress shows a low-dip East–West orientation of σ₁. In agreement with existing knowledge on relationships between local fault systems and magma uprise processes, the shallow seismicity in question is tentatively explained as being due to lateral compression by magma inside a nearly North–South system. The volcano deflation phase revealed by Electronic Distance Measurements and tilt data during the 1991–1993 major eruption was not accompanied by any significant shear-type shallow event. Below the depth of 10 km, the North–South prevailing orientation of σ₁ reflects the dominant role of the regional stress.     

Temporal Variability of Major and Trace Element Concentrations in the Groundwaters of Mt. Etna (Italy): Effects of Transient Input of Magmatic Fluids Highlighted by Means of Cluster Analysis

Data for major, minor and trace elements in groundwaters from Mt. Etna volcano collected in 1994, 1995 and 1997 were analyzed using Cluster Analysis (CA). Two groups of sampling sites were identified (named clusters A and B), mainly on the basis of their different salinity and content of dissolved CO₂. The highest levels of both of these parameters were observed in the sites of cluster A, located in the lower south-western and central eastern flanks of the volcano. For both of the statistical groups CA was repeated, taking into account the mean values of each parameter in time, and the results allowed us to recognize four distinct groups of parameters for each group of sites on the basis of their temporal patterns. Four different types of temporal patterns were recognized: concave, convex, increasing, decreasing. The observed changes were basically interpreted as a result of the different response of dissolved chemical elements to changes in the aqueous environment and/or in their solubility/mobility in water due to different rates of input of magmatic gases to Etna’s aquifers. The main changes occurred in 1995, when Etna’s volcanic activity resumed after a two-year period of rest. The temporal changes of the majority of the studied parameters (water temperature, water conductivity, Eh, pH, Al, Mg, B, Ca, Cl⁻, Hg, Mn, Mo, Na, Ni, Se, Si, Sr, Cr Zn and pCO₂) were not cluster-dependent, therefore they were not apparently affected by differences in water salinity between the two groups of sampling sites. A limited number of parameters (Ti, K, Li, HCO₃⁻, As, Fe, SO₄²⁻, Cu and V), however, manifested different behaviors, depending on the cluster of sites to which they belonged, thus suggesting their apparent dependency on water salinity.     

Mercury concentration,speciation and budget in volcanic aquifers: Italy and Guadeloupe (Lesser Antilles)

Quantifying the contribution of volcanism to global mercury (Hg) emissions is important to understand the pathways and the mechanisms of Hg cycling through the Earth's geochemical reservoirs and to assess its environmental impacts. While previous studies have suggested that degassing volcanoes might contribute importantly to the atmospheric budget of mercury, little is known about the amount and behaviour of Hg in volcanic aquifers. Here we report on detailed investigations of both the content and the speciation of mercury in aquifers of active volcanoes in Italy and Guadeloupe Island (Lesser Antilles). In the studied groundwaters, total Hg (THg) concentrations range from 10 to 500 ng/l and are lower than the 1000 ng/l threshold value for human health protection fixed by the World Health Organization [WHO (1993): WHO Guidelines for Drinking Water Quality- http://www.who.int/water_sanitation_health/GDWQ/index.htlm]. Positive co-variations of (THg) with sulphate indicate that Hg-SO₄-rich acid groundwaters receive a direct input of magmatic/hydrothermal gases carrying mercury as Hg⁰_(gas). Increasing THg in a volcanic aquifer could thus be a sensitive tracer of magmatic gas input prior to an eruption. Since the complex behaviour and toxicity of mercury in waters depend on its chemical speciation, we carefully determined the different aqueous forms of this element in our samples. We find that dissolved elemental Hg⁰_(aq) and particulate-bound Hg (Hg_P) widely prevail in volcanic aquifers, in proportions that highlight the efficiency of Hg adsorption onto colloidal particles. Moreover, we observe that dissolved Hg⁰_aq and Hg(II) forms coexist in comparable amount in most of the waters, in stark contrast to the results of thermodynamic equilibrium modelling. Therefore, chemical equilibrium between dissolved mercury species in volcanic waters is either prevented by natural kinetic effects or not preserved in collected waters due to sampling/storage artefacts. Finally, we provide a first quantitative comparison of the relative intensity of aqueous transport and atmospheric emissions of mercury at Mount Etna, a very active basaltic volcano.     

Soil CO2 degassing on Mt Etna (Sicily) during the period 1989–1993: discrimination between climatic and volcanic influences

Wide variations were measured in the diffuse CO₂ flux through the soils in three selected areas of Mt Etna between August 1989 and March 1993. Degassing of CO₂ from the area of Zafferana Etnea-S. Venerina, on the eastern slope of the volcano, has been determined to be more strongly influenced by meteorological parameters than the other areas. The seasonal component found in the data from this area has been excluded using a filtering algorithm based on the best fitting equation calculated from the correlation between CO₂ flux values and those of air temperature. The filtered data appear to have variations temporally coincident with those from the other areas, thus suggesting a common and probably deep source of gas. The highest fluxes measured in the two most peripheral areas may correlate well with other geophysical and volcanological anomalous signals that preceded the strong eruption of 1991–1993 and that were interpreted as deep pressure increases. Anomalous decreases in CO₂ fluxes accompanied the onset and the evolution of that eruption and have been interpreted as a sign of upward migration of the gas source. The variations of CO₂ flux at the 1989 SE fracture have also given interesting information on the timing of the magmatic intrusion that has then fed the 1991–1993 eruption.     

Array analyses of volcanic earthquakes and tremor recorded at Las Cañadas caldera (Tenerife Island, Spain) during the 2004 seismic activation of Teide volcano

We analyze data from three seismic antennas deployed in Las Cañadas caldera (Tenerife) during May–July 2004. The period selected for the analysis (May 12–31, 2004) constitutes one of the most active seismic episodes reported in the area, except for the precursory seismicity accompanying historical eruptions. Most seismic signals recorded by the antennas were volcano-tectonic (VT) earthquakes. They usually exhibited low magnitudes, although some of them were large enough to be felt at nearby villages. A few long-period (LP) events, generally associated with the presence of volcanic fluids in the medium, were also detected. Furthermore, we detected the appearance of a continuous tremor that started on May 18 and lasted for several weeks, at least until the end of the recording period. It is the first time that volcanic tremor has been reported at Teide volcano. This tremor was a small-amplitude, narrow-band signal with central frequency in the range 1–6 Hz. It was detected at the three antennas located in Las Cañadas caldera. We applied the zero-lag cross-correlation (ZLCC) method to estimate the propagation parameters (back-azimuth and apparent slowness) of the recorded signals. For VT earthquakes, we also determined the S–P times and source locations. Our results indicate that at the beginning of the analyzed period most earthquakes clustered in a deep volume below the northwest flank of Teide volcano. The similarity of the propagation parameters obtained for LP events and these early VT earthquakes suggests that LP events might also originate within the source volume of the VT cluster. During the last two weeks of May, VT earthquakes were generally shallower, and spread all over Las Cañadas caldera. Finally, the analysis of the tremor wavefield points to the presence of multiple, low-energy sources acting simultaneously. We propose a model to explain the pattern of seismicity observed at Teide volcano. The process started in early April with a deep magma injection under the northwest flank of Teide volcano, related to a basaltic magma chamber inferred by geological and geophysical studies. The stress changes associated with the injection produced the deep VT cluster. In turn, the occurrence of earthquakes permitted an enhanced supply of fresh magmatic gases toward the surface. This gas flow induced the generation of LP events. The gases permeated the volcanic edifice, producing lubrication of pre-existing fractures and thus favoring the occurrence of VT earthquakes. On May 18, the flow front reached the shallow aquifer located under Las Cañadas caldera. The induced instability constituted the driving mechanism of the observed tremor.