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.     

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.     

Sulfur isotopic effects in the disproportionation reaction of sulfur dioxide in hydrothermal fluids: implications for the δS variations of dissolved bisulfate and elemental sulfur from active crater lakes

Sulfur isotope effects during the SO₂ disproportionation reaction to form elemental sulfur (3SO₂+3H₂O→2HSO₄⁻+S+2H⁺) at 200–330°C and saturated water vapor pressures were experimentally determined. Initially, a large kinetic isotopic fractionation takes place between HSO₄⁻ and S, followed by a slow approach to equilibrium. The equilibrium fractionation factors, estimated from the longest run results, are expressed by 1000 ln α_HSO4⁻–S=6.21×10⁶/T²+3.62. The rates at which the initial kinetic fractionation factors approach the equilibrium ones were evaluated at the experimental conditions.δ³⁴S values of HSO₄⁻ and elemental sulfur were examined for active crater lakes including Noboribetsu and Niseko, (Hokkaido, Japan), Khloridnoe, Bannoe and Maly Semiachik (Kamchatka), Poás (Costa Rica), Ruapehu (New Zealand) and Kawah Ijen and Keli Mutu (Indonesia). Δ_HSO4⁻–S values are 28‰ for Keli Mutu, 26‰ for Kawah Ijen, 24‰ for Ruapehu, 23‰ for Poás, 22‰ for Maly Semiachik, 21‰ for Yugama, 13‰ for Bannoe, 9‰ for Niseko, 4‰ for Khloridonoe, and 0‰ for Noboribetsu, in the decreasing order. The SO₂ disproportionation reaction in the magmatic hydrothermal system below crater lakes where magmatic gases condense is responsible for high Δ_HSO4⁻–S values, whereas contribution of HSO₄⁻ produced through bacterial oxidation of reduced sulfur becomes progressively dominant for lakes with lower Δ_HSO4⁻–S values. Currently, Noboribetsu crater lake contains no HSO₄⁻ of magmatic origin. A 40-year period observation of δ³⁴S_HSO4⁻ and δ³⁴S_S values at Yugama indicated that the isotopic variations reflect changes in the supply rate of SO₂ to the magmatic hydrothermal system. This implies a possibility of volcano monitoring by continuous observation of δ³⁴S_HSO4⁻ values. The δ¹⁸O values of HSO₄⁻ and lake water from the studied lakes covary, indicating oxygen isotopic equilibration between them. The covariance gives strong evidence that lake water circulates through the sublimnic zone at temperatures of 140±30°C.     

Geochemistry of the acid Kawah Putih lake, Patuha Volcano, West Java, Indonesia

Kawah Putih is a summit crater of Patuha volcano, West Java, Indonesia, which contains a shallow, 300 m-wide lake with strongly mineralized acid–sulfate–chloride water. The lake water has a temperature of 26–34°C, pH=<0.5–1.3, S^tot=2500–4600 ppm and Cl=5300–12 600 ppm, and floating sulfur globules with sulfide inclusions are common. Sulfur oxyanion concentrations are unusually high, with S₄O₆²⁻+S₅O₆²⁻+S₆O₆²⁻=2400 – 4200 ppm. Subaerial fumaroles (<93°C) on the lake shore have low molar SO₂/H₂S ratios (<2), which is a favorable condition to produce the observed distribution of sulfur oxyanion species. Sulfur isotope data of dissolved sulfate and native sulfur show a significant ³⁴S fractionation (ΔSO₄–S_e of 20‰), probably the result of SO₂ disproportionation in or below the lake. The lake waters show strong enrichments in ¹⁸O and D relative to local meteoric waters, a result of the combined effects of mixing between isotopically heavy fluids of deep origin and meteoric water, and evaporation-induced fractionation at the lake surface. The stable-isotope systematics combined with energy-balance considerations support very rapid fluid cycling through the lake system. Lake levels and element concentrations show strong seasonal fluctuations, indicative of a short water residence time in the lake as well.Thermodynamic modeling of the lake fluids indicates that the lake water is saturated with silica phases, barite, pyrite and various Pb, Sb, Cu, As, Bi-bearing sulfides when sulfur saturation is assumed. Precipitating phases predicted by the model calculations are consistent with the bulk chemistry of the sulfur-rich bottom sediments and their identified mineral phases. Much of the lake water chemistry can be explained by congruent rock dissolution in combination with preferential enrichments from entering fumarolic gases or brines and element removal by precipitating mineral phases, as indicated by a comparison of the fluids, volcanic rocks and lake bed sediment.Flank springs on the mountain at different elevations vary in composition, and are consistent with local rock dissolution as a dominant factor and pH-dependent element mobility. Discharges of warm sulfate- and chloride-rich water at the highest elevation and a near-neutral spring at lower level may contain a small contribution of crater-lake water. The acid fluid-induced processes at Patuha have led to the accumulation of elements that are commonly associated with volcano-hosted epithermal ore deposits. The dispersal of heavy metals and other potentially toxic elements from the volcano via the local drainage system is a matter of serious environmental concern.     

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.     

Genesis of chlorine and sulphur in fumarolic emissions at Vulcano Island (Italy): assessment of pH and redox conditions in the hydrothermal system

Chlorine- and sulphur-bearing compounds in fumarole discharges of the La Fossa crater at Vulcano Island (Italy) can be modelled by a mixing process between magmatic gases and vapour from a boiling hydrothermal system. This allows estimating the compounds in both endmembers. Magma degassing cannot explain the time variation of sulphur and HCl concentrations in the deep endmember, which are more probably linked to reactions of solid phases at depth, before mixing with the hydrothermal vapours. Based on the P–T conditions and speciation of the boiling hydrothermal system below La Fossa, the HCl and S_tot contents in the hydrothermal vapours were used to compute the redox conditions and pH of the aqueous solution. The results suggest that the haematite–magnetite buffer controls the hydrothermal fO₂ values, while the pH has increased since the end of the 1970s. The main processes affecting pH values may be linked to Na–Ca exchanges between evolved seawater, feeding the boiling hydrothermal system, and local rocks. While Na is removed from water, calcium enters the solution, undergoes hydrolysis and produces HCl, lowering the pH of the water. The increasing water–rock ratio within the hydrothermal system lowers the Ca availability, so the aqueous solution becomes less acidic. Seawater flowing towards the boiling hydrothermal brine dissolves a large quantity of pyrite along its path. In the boiling hydrothermal system, dissolved sulphur precipitates as pyrite and anhydrite, and becomes partitioned in vapour phase as H₂S and SO₂. These results are in agreement with the paragenesis of hydrothermal alteration minerals recovered in drilled wells at Vulcano and are also in agreement with the isotopic composition of sulphur emitted by the crater fumaroles.     

Lattice-Boltzmann simulations of the capillary pressure–saturation–interfacial area relationship for porous media

Hysteresis in the relationship between capillary pressure (P_c), wetting phase saturation (S_w) and nonwetting–wetting interfacial area per volume (a_nw) is investigated using multiphase lattice-Boltzmann simulations of drainage and imbibition in a glass bead porous system. In order to validate the simulations, the P_c–S_w and a_nw–S_w main hysteresis loops were compared to experimental data reported by Culligan et al. [Culligan KA, Wildenschild D, Christensen BS, Gray WG, Rivers ML, Tompson AB. Interfacial area measurements for unsaturated flow through porous media. Water Resour Res 2004;40:W12413]. In general, the comparison shows that the simulations are reliable and capture the important physical processes in the experimental system. P_c–S_w curves, a_nw–S_w curves and phase distributions (within the pores) show good agreement during drainage, but less satisfactory agreement during imbibition. Drainage and imbibition scanning curves were simulated in order to construct P_c–S_w–a_nw surfaces. The root mean squared error (RMSE) and mean absolute error (MAE) between drainage and imbibition surfaces was 0.10 mm⁻¹ and 0.03 mm⁻¹, respectively. This small difference indicates that hysteresis is virtually nonexistent in the P_c–S_w–a_nw relationship for the multiphase system studied here. Additionally, a surface was fit to the main loop (excluding scanning curves) of the drainage and imbibition P_c–S_w–a_nw data and compared to the surface fit to all of the data. The differences between these two surfaces were small (RMSE = 0.05 mm⁻¹ and MAE = 0.01 mm⁻¹) indicating that the P_c–S_w–a_nw surface is adequately represented without the need for the scanning curve data, which greatly reduces the amount of data required to construct the non-hysteretic P_c–S_w–a_nw surface for this data.     

Airborne measurements of particle and gas emissions from the December 1994–January 1995 eruption of Popocatépetl volcano (Mexico)

Airborne and ground-based (correlation spectrometer, cascade impactor, and photoelectric counter together with intake filter probes) measurements are described for the volcanic emissions from Popocatépetl volcano (Mexico) from December 23, 1994 to January 28, 1995. Measurements of SO₂ restarted 48 h after the eruption onset of December 21, 1994. Maximum sulfur dioxide (4560 t d⁻¹) plus 3.8×10⁴ t d⁻¹ of particulate matter were ejected on December 24, 1994. The maximum rate of ejection occurred coincidentally with the maximum amplitude of harmonic tremor and the maximum number of seismic type B events. Sulfur dioxide emission rates ranged from 1790 to 2070 t d⁻¹ (December 23–24, 1994). Afterwards, sulfur dioxide emission rates clearly indicated a consistent decline. However, frequent gas and ash emission puffs exhibited SO₂ fluxes reaching values as high as 3060 t d⁻¹. The emission SO₂ baseline for the period of study (February 1994–January 1995) was about 1000 t d⁻¹. Ejection velocity of particulate matter was approximately 270 m s⁻¹ reaching a height of about 2.5 km over the summit. The immediate aerosol dispersion area was estimated at 6.0×10⁴ km² maximum. The microscopic structure of particles (aerosol and tephra) showed a fragile material, probably coming from weathered crustal layers. X-ray fluorescence and neutron-activation analysis from the impactor samples found the following elements: Si, Al, Ca, S, P, Cl, K, Ni, Fe, Ti, Sc, Cu, Zn, Mn, Sr, Cr, Co, Y, Br, Se, Ga, Rb, Hg and Pb. Morphological analysis shows that ash samples might be from pulverized basaltic rock indicating that the Popocatépetl eruption of December 21, 1994 was at low temperature. The microscopic structure of puff material showed substance aggregates consisted of fragile rock, water and adsorbed SO₂. These aggregates were observed within water droplets of approximately 1 mm and even larger. Sulfur transformations in the droplets occurred intensively. Volcanic ash contained 5–6% of sulfur during the first expulsion hours. Elemental relative concentrations with respect to Al show that both Si and S have relative concentrations >1, i.e., 13.73 and 2.17, respectively in agreement with the photoelectric counter and COSPEC measurements.     

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.     

Hydrothermal vent waters at 13°N on the East Pacific Rise: isotopic composition and gas concentration

Gas concentrations and isotopic compositions of water have been measured in hydrothermal waters from 13°N on the East Pacific Rise. In the most Mg-depleted samples ( 5 × 10⁻³ moles/kg) the gas concentrations are: 3–4.5 × 10⁻⁵ cm³ STP/kg helium, 0.62–1.24 cm³ STP/kg CH₄, 10.80–16.71 × 10⁻³ moles/kg CO₂. The samples contain large quantities (95–126 cm³/kg) of H₂ and some carbon monoxide (0.26–0.36 cm³/kg) which result from reaction with the titanium sampling bottles. δ¹³C in methane and CO₂ (−16.6 to −19.5 and −4.1 to −5.5 respectively) indicate temperatures between 475 and 550°C, whereas δ¹³C_CO is compatible with formation by reduction of CO₂ on Ti at 350°C close to the sampling temperature.³He/⁴He are very homogeneous at (7.5 ± 0.1)R_A(³He/⁴He = 1.0 × 10⁻⁵) and very similar to already published data as well as CH₄/³He ratios between 1.4 and 2.1 × 10⁶.¹⁸O and D in water show enrichments from 0.39 to 0.69‰ and from 0.62 to 1.49‰ respectively. These values correspond to W/R ratios of 0.4–7. The distinct¹⁸O enrichments indicate that the isotopic composition of the oceans is not completely buffered by the hydrothermal circulations. The³He-enthalpy relationship is discussed in terms of both hydrothermal heat flux and³He mantle flux.     

Genesis of high-magnesium andesites and associated basalts from Saga–Futagoyama, northwest Kyushu, southwest Japan

High-magnesium andesites associated with basalts erupted after the opening of the Sea of Japan are present at Saga–Futagoyama in northwest Kyushu, southwest Japan. High Mg/(Mg + Fe) [=0.84] of orthopyroxene phenocrysts and bulk rock Mg–Fe–Ni compositions suggest that these high-magnesium andesites were originally primitive melts insignificantly modified in crustal magma chambers. K_D^Ca–Na [= (Ca/Na)_pl/(Ca/Na)_{bulk rock}] ranges from 1.21 to 0.97 and suggests that the high-magnesium andesite magmas would originally have contained H₂O less than 1.8 wt.%. Nb/La does not show a negative correlation with respect to SiO₂. These lines of evidence indicate that hydrous components derived from the subducting slab would not have played a significant role in the genesis of the high-magnesium andesite magmas. Instead, the normative olivine − quartz − [CaTs + Jd] compositions and a negative correlation between Sr/Nd and SiO₂ indicate that the basalt-high-magnesium andesite association would have been formed by multi-stage partial melting of relatively anhydrous source at pressure ranging from 1.5 to 0.5 GPa.     

Geochemistry of fluids associated with the 1995–1996 eruption of Mt. Ruapehu, New Zealand: signatures and processes in the magmatic-hydrothermal system

The 1995–1996 eruption of Mt. Ruapehu has provided a number of insights into the geochemical processes operating within the magmatic-hydrothermal system of this volcano. Both pre-eruption degassing of the rising magma and its eventual intrusion into the convective zone of the hydrothermal system beneath the lake were clearly reflected in lake water compositions. The eruptions of September–October 1995 expelled the lake, and provided the first-ever opportunity to characterise gas discharges from this volcano. The fumarolic discharges revealed compositions typical of andesite volcanoes and strong interaction with the enclosing meteoric and hydrothermal system fluids. Some 1.1 MT of SO₂ gas was released from the volcano between September 1995 and December 1996, whereas ca. twice this amount (2.2 MT equivalent SO₂) was erupted as soluble (i.e. leachable) oxyanions of sulphur. Significantly more sulphur was released from the volcano over this period than can be accounted for from the magma volume actually erupted. The evidence suggests that a sizable component of the evolved sulphur was remobilised from the long-lived hydrothermal system within the volcano during the 1995–1996 activity.     

Morphology and composition of spinel in Pu’u ’O’o lava (1996–1998), Kilauea volcano, Hawaii

The morphology and composition of spinel in rapidly quenched Pu’u ’O’o vent and lava tube samples are described. These samples contain glass, olivine phenocrysts (3–5 vol.%) and microphenocrysts of spinel (0.05 vol.%). The spinel surrounded by glass occurs as idiomorphic octahedra 5–50 μm in diameter and as chains of octahedra that are oriented with respect to each other. Spinel enclosed by olivine phenocrysts is sometimes rounded and does not generally form chains. The temperature before quenching was calculated from the MgO content of the glass and ranges from 1150°C to 1180°C. The oxygen fugacity before quenching was calculated by two independent methods and the log f_O2 ranged from −9.2 to −9.9 (delta QFM=−1). The spinel in the Pu’u ’O’o samples has a narrow range in composition with Cr/(Cr+Al)=0.61 to 0.73 and Fe²⁺/(Fe²⁺+Mg)=0.46 to 0.56. The lower the calculated temperature for the samples, the higher the average Fe²⁺/(Fe²⁺+Mg), Fe³⁺ and Ti in the spinel. Most zoned spinel crystals decrease in Cr/(Cr+Al) from core to rim and, in the chains, the Cr/(Cr+Al) is greater in the core of larger crystals than in the core of smaller crystals. The occurrence of chains and hopper crystals and the presence of Cr/(Cr+Al) zoning from core to rim of the spinel suggest diffusion-controlled growth of the crystals. Some of the spinel crystals may have grown rapidly under the turbulent conditions of the summit reservoir and in the flowing lava, and the crystals may have remained in suspension for a considerable period. The rapid growth may have caused very local (μm) gradients of Cr in the melt ahead of the spinel crystal faces. The crystals seem to have retained the Cr/(Cr+Al) ratio that developed during the original growth of the crystal, but the Fe²⁺/(Fe²⁺+Mg) ratio may have equilibrated fairly rapidly with the changing melt composition due to olivine crystallization. Six of the samples were collected on the same day at various locations along a 10-km lava tube and the calculated pre-collection temperatures of the samples show a 5°C drop with distance from the vent. The average Fe²⁺/(Fe²⁺+Mg) of the spinel in these samples shows a weak positive correlation with decreasing MgO in the glass of these samples. The range in Cr₂O₃ (0.041–0.045 wt.%) of the glass for these six samples is too small to distinguish a consistent change along the lava tube. The spinel in the Pu’u ’O’o samples shows a zoning trend in a Cr–Al–Fe³⁺ diagram almost directly away from the Cr apex. This compares with a zoning trend in rapidly quenched MORB samples away from Cr coupled with decreasing Fe³⁺. The trend away from Cr displayed by spinel in rapidly quenched samples is in marked contrast to the trend of increasing Fe³⁺ shown by spinel in slowly cooled lava.     

Chromite in the Paricutin lava flows (1943–1952)

Small euhedral chromite crystals are found in olivine macrophenocrysts (Fo_80–84) from the basaltic andesites (150 ppm Cr) erupted in 1943–1947, and in orthopyroxene macrophenocrysts of the andesites (75 ppm Cr) erupted in 1947–1952. The majority of the chromite octahedra are 5–20 μm in diameter, and some are found in clusters and linear chains of three or more oriented chromite crystals. The composition of the majority of the chromite grains within olivine and orthopyroxene macrophenocrysts is Fe²⁺/(Fe²⁺+Mg)=0.5–0.6, Cr/(Cr+Al)=0.5–0.6 and Fe³⁺/(Fe³⁺+Al+Cr)=0.2–0.3. The chromite crystals in contact with the groundmass are larger, subhedral, and grade in composition from chromite cores to magnetite rims. Comparison of the composition of chromite with those of other volcanic rocks shows that the most primitive Paricutin chromite is richer in total iron and higher in Fe³⁺/(Fe³⁺+Al+Cr) than primary chromite in most lavas. The linear chains of oriented chromite octahedra are found in olivine and orthopyroxene macrophenocrysts, and in the groundmass. These chromite chains are thought to result from diffusion-controlled crystallization because of the very high partition coefficient (1000) of Cr between chromite and melt. We conclude that chromite was a primary phase in the lavas at the time of extrusion and that magnetite only crystallized after extrusion during cooling of the lava flows. The presence of chromite microphenocrysts in andesitic lavas containing as little as 70 ppm Cr can be explained by dissolved H₂O in the melt depressing the liquidus temperature for orthopyroxene such that chromite becomes a liquidus phase. The influence of dissolved H₂O can also explain the lack of plagioclase macrophenocrysts in most of the lavas and the relatively high partition coefficient (20) of Ni between olivine and melt and the high partition coefficient (40) of Cr between orthopyroxene and melt. The liquidus temperature of the basaltic andesite is estimated to have been less than 1140°C, assuming H₂O>1 wt.%, and the log f_O2 to have been above that of the QFM buffer. The chromite and orthopyroxene liquidus temperature of the andesites, assuming H₂O>1 wt.%, is estimated to have been 1100°C or less. The derivation of the later andesites from the earlier basaltic andesites has been explained by a combination of fractional crystallization of olivine, orthopyroxene and plagioclase, and assimilation of xenoliths. The significantly lower Cr, Ni and Mg of the andesites may have been in part due to the separation of olivine macrophenocrysts plus enclosed chromite crystals from the earlier basaltic andesites.     

Magmatic gas scrubbing: implications for volcano monitoring

Despite the abundance of SO_2(g) in magmatic gases, precursory increases in magmatic SO_2(g) are not always observed prior to volcanic eruption, probably because many terrestrial volcanoes contain abundant groundwater or surface water that scrubs magmatic gases until a dry pathway to the atmosphere is established. To better understand scrubbing and its implications for volcano monitoring, we model thermochemically the reaction of magmatic gases with water. First, we inject a 915°C magmatic gas from Merapi volcano into 25°C air-saturated water (ASW) over a wide range of gas/water mass ratios from 0.0002 to 100 and at a total pressure of 0.1 MPa. Then we model closed-system cooling of the magmatic gas, magmatic gas-ASW mixing at 5.0 MPa, runs with varied temperature and composition of the ASW, a case with a wide range of magmatic–gas compositions, and a reaction of a magmatic gas–ASW mixture with rock. The modeling predicts gas and water compositions, and, in one case, alteration assemblages for a wide range of scrubbing conditions; these results can be compared directly with samples from degassing volcanoes. The modeling suggests that CO_2(g) is the main species to monitor when scrubbing exists; another candidate is H₂S_(g), but it can be affected by reactions with aqueous ferrous iron. In contrast, scrubbing by water will prevent significant SO_2(g) and most HCl_(g) emissions until dry pathways are established, except for moderate HCl_(g) degassing from pH<0.5 hydrothermal waters. Furthermore, it appears that scrubbing will prevent much, if any, SO_2(g) degassing from long-resident boiling hydrothermal systems. Several processes can also decrease or increase H_2(g) emissions during scrubbing making H_2(g) a poor choice to detect changes in magma degassing.We applied the model results to interpret field observations and emission rate data from four eruptions: (1) Crater Peak on Mount Spurr (1992) where, except for a short post-eruptive period, scrubbing appears to have drastically diminished pre-, inter-, and post-eruptive SO_2(g) emissions, but had much less impact on CO_2(g) emissions. (2) Mount St. Helens where scrubbing of SO_2(g) was important prior to and three weeks after the 18 May 1980 eruption. Scrubbing was also active during a period of unrest in the summer of 1998. (3) Mount Pinatubo where early drying out prevented SO_2(g) scrubbing before the climactic 15 June 1991 eruption. (4) The ongoing eruption at Popocatépetl in an arid region of Mexico where there is little evidence of scrubbing.In most eruptive cycles, the impact of scrubbing will be greater during pre- and post-eruptive periods than during the main eruptive and intense passive degassing stages. Therefore, we recommend monitoring the following gases: CO_2(g) and H₂S_(g) in precursory stages; CO_2(g), H₂S_(g), SO_2(g), HCl_(g), and HF_(g) in eruptive and intense passive degassing stages; and CO_2(g) and H₂S_(g) again in the declining stages. CO_2(g) is clearly the main candidate for early emission rate monitoring, although significant early increases in the intensity and geographic distribution of H₂S_(g) emissions should be taken as an important sign of volcanic unrest and a potential precursor. Owing to the difficulty of extracting SO_2(g) from hydrothermal waters, the emergence of >100 t/d (tons per day) of SO_2(g) in addition to CO_2(g) and H₂S_(g) should be taken as a criterion of magma intrusion. Finally, the modeling suggests that the interpretation of gas-ratio data requires a case-by-case evaluation since ratio changes can often be produced by several mechanisms; nevertheless, several gas ratios may provide useful indices for monitoring the drying out of gas pathways.     

Authigenic carbonates in sediments from the Gulf of Mexico

The carbon isotopic composition of diagenetic dolomite and calcite in some sediments of the Gulf of Mexico varies between “normal-marine” (δ¹³C ca. 0‰) and −14.6‰ which suggests that biogenic CO₂ contributed to the carbonate formation. The δ¹³O values of dolomite and coexisting calcite are very similar but variable down-core.Dolomite and calcite precipitated early from pore water where SO₄²⁻ was not reduced. However, during (and after?) SO₄²⁻ reduction dolomite and calcite still formed and there are at least two generations of carbonate minerals present.     

Chemical geothermometry and fluid–mineral equilibria for the Ömer–Gecek thermal waters, Afyon area, Turkey

Thermal waters of the Ömer–Gecek geothermal field, Turkey, with temperatures ranging from 32 to 92°C vary in chemical composition and TDS contents. They are generally enriched in Na–Cl–HCO₃ and suggest deep water circulation. Silica and cation geothermometers applied to the Ömer–Gecek thermal waters yield reservoir temperatures of 75–155°C. The enthalpy–chloride mixing model, which approximates a reservoir temperature of 125°C for the Ömer–Gecek field, accounts for the diversity in the chemical composition and temperature of the waters by a combination of processes including boiling and conductive cooling of deep thermal water and mixing of the deep thermal water with cold water. It is also determined that the solubility of silica in most of the waters is controlled by the chalcedony phase. Equilibrium states of the Ömer–Gecek thermal waters studied by means of the Na–K–Mg triangular diagram, Na–K–Mg–Ca diagram, K–Mg–Ca geoindicator diagram, activity diagrams in the systems composed of Na₂O–CaO–K₂O–Al₂O₃–SiO₂–CO₂–H₂O phases, log SI diagrams, and finally the alteration mineralogy indicate that most of the spring and low-temperature well waters in the area can be classified as shallow or mixed waters which are likely to be equilibrated with calcite, chalcedony and kaolinite at predicted temperature ranges similar to those calculated from the chemical geothermometers. It was also observed that mineral equilibrium in the Ömer–Gecek waters is largely controlled by CO₂ concentrations.     

S, O and Sr isotope systematics of active vent materials from the Mariana backarc basin spreading axis at 18°N

Stable isotope ratios of S, O and Sr have been measured for active vent materials which were first found and sampled in April 1987 from the Mariana backarc spreading axis at 18°N. Chimneys consisted mostly of barite with a lesser proportion of sulfide minerals such as sphalerite, galena, chalcopyrite and pyrite. Theδ³⁴S values of sphalerite and galena taken from several chimneys and various parts of a chimney showed a narrow range from 2.1 to 3.1‰, suggesting uniform conditions of fluid chemistry during chimney growth. The sulfur isotopic results imply a contribution of hydrogen sulfide reduced from seawater sulfate in the deep hydrothermal reaction zone, considering that fresh glasses of the Mariana Trough basalts haveδ³⁴S= −0.6 ± 0.3‰. Sulfur isotopic compositions of hydrogen sulfide in the high temperature vent fluids (δ³⁴S= 3.6–4.8‰) which are higher than those of the sulfide minerals suggest the secondary addition of hydrogen sulfide partially reduced from entrained seawater SO₄²⁻ at a basal part of the chimneys. This interpretation is consistent with theδ³⁴S values of barite (21–22‰) that are higher than those of seawater sulfate. The residence time of the entrained SO₄²⁻ was an order of an hour on a basis of oxygen isotopic disequilibrium of barite. Strontium isotopic variations of barite and vent waters indicated that Sr in barite was mostly derived from the Mariana Trough basalts with a slight contribution from Sr in circulating sea-water, and that 10–20% mixing of seawater with ascending hydrothermal fluids induced precipitation of barite at the sea-floor.     

Chemical variations of tephra-fall deposit leachates for three eruptions from Popocatépetl volcano

Leachates from ash samples of the Popocatépetl eruptions of April 30, 1996, May 12, 1997, and October 17, 1998 settled at different distances from the crater were analyzed for anions (SO₄²⁻, Cl⁻, F⁻) and some metals. This study is aimed at determining the causes of the compositional variations of the leachates, to assist the assessment of water, soil and crop contamination due to ash deposits. Different behavior was observed in the ion concentrations with distance for the three eruptions. On April 30, 1996, SO₄²⁻ and F⁻ concentrations increased with distance, and Cl⁻ remained almost constant. On May 12, 1997, concentrations of the three anions decreased with distance. On October 17, 1998, F⁻, Cl⁻ and SO₄²⁻ increased more than three-fold with distance. Tephra size distributions were also different for the three eruptions. The observed trends of the leachates’ anion concentrations may have different causes: the type and intensity of the eruptions, the distribution of the tephra sizes, the degree of interaction of the tephras with volcanic gases, humidity, static charge, the original characteristics of the solid material, the transport time from the crater to the site of settling, and the relative angle between the wind direction and the sampling line. Enrichment factors and concentration trends for metals with distance suggest that Co, Ni, Cu and Pb in the leachates resulted mostly from volcanic gas adsorption.     

Viscosity of a Teide phonolite in the welding interval

The viscosity of a natural phonolitic composition with variable amounts of H₂O has been experimentally determined. The starting materials were crystal-free phonolitic glasses from Montaña Blanca, situated within the Las Cañadas caldera of Teide. Dry phonolitic melt viscosities were determined using concentric cylinder viscometry in the low viscosity range. The glassy quench products of these runs were then hydrated by high pressure synthesis in a piston–cylinder apparatus to generate a suite of samples with water contents ranging from 0.02 to 3.75 wt%. Samples thus hydrated were quenched rapidly and prepared (cut and polished) for the determination of water contents by infrared spectroscopy before and after experimental viscometry. The viscosities of the melts (dry and hydrated) were determined at 1 bar using a micropenetration technique. Samples were stable under the measurement conditions up to 3.75 wt% H₂O. Homogeneity of water content was confirmed by infrared spectroscopy and total water contents were calculated using absorptivity coefficients for compositions extremely close to that investigated here. The variation of viscosity as a function of water content and temperature can be described in the high viscosity interval of relevance to many welding processes by the non-Arrhenian expression:

(1)

log₁₀ η=−5.900−0.286 ln (H₂O)+(10775.4−394.8(H₂O))/(T−148.7+21.65 ln (H₂O))

whereas the high viscosity range alone is adequately described by the Arrhenian expression

(2)

log₁₀ η=−10.622−0.738 ln (H₂O)+(17114.3−590.4(H₂O))×1/T

where η is the viscosity in Pa s, H₂O is the water content in wt% and T is the temperature in K.These results are particularly useful for the scaling of conditions extant during the welding of phonolitic products of Montaña Blanca. The welding of glassy phonolitic rocks is enhanced by the lower viscosity of these melts with respect to calcalkaline rhyolites. The ratio of viscosities of phonolitic to calcalkaline rhyolitic melts is a complex function of temperature and water content and reaches up to 10^4.5 at 0.1 wt% H₂O and 500°C. Abundant evidence of welding and remobilisation of pyroclastic and spatter products of Teide system volcanism are consistent with these experimental observations.