Sr isotope diversity of hot spring and volcanic lake waters from Zao volcano,Japan

The ratio of ⁸⁷Sr/⁸⁶Sr was measured from different water samples of thermal/mineral (hot spring as well as crater lake) and meteoric origins, in order to specify the location and to verify the detailed model of a volcano-hydrothermal system beneath Zao volcano. The ratio showed a trimodal distribution for the case of thermal/mineral water: 0.7052–0.7053 (Type A, Zao hot spring), 0.7039–0.7043 (Type B, Okama crater lake and Shin-funkiko hot spring), and 0.7070–0.7073 (Type C, Gaga, Aone, and Togatta hot springs), respectively. However, in comparison, the ratio was found to be higher for meteoric waters (0.7077–0.7079). The water from the central volcanic edifice (Type B) was found to be similar to that of nearby volcanic rocks in their Sr isotopic ratio. This indicates that the Sr in water was derived from shallow volcanic rocks. The ⁸⁷Sr/⁸⁶Sr ratio for water from the Zao hot spring (Type A) was intermediate between those of the pre-Tertiary granitic and the Quaternary volcanic rocks, thus suggesting that the water had reacted with both volcanic and granitic rocks. The location of the vapor–liquid separation was determined as the boundary of the pre-Tertiary granitic and the Quaternary volcanic rocks by comparing the results of this strontium isotopic study with those of Kiyosu and Kurahashi [Kiyosu, Y., Kurahashi, M., 1984. Isotopic geochemistry of acid thermal waters and volcanic gases from Zao volcano in Japan. J. Volcanol. Geotherm. Res. 21, 313–331.].     

Coseismic changes in the chemical composition of volcanic gases from the Owakudani geothermal area on Hakone volcano,Japan

The chemical and isotopic compositions of volcanic gases at a borehole and a natural fumarole in the Owakudani geothermal area, Hakone volcano, Japan, have been repeatedly measured since 2001, when a seismic swarm occurred in the area. The CO₂/H₂O and CO₂/H₂S ratios were high in 2001. It increased in 2006 and again in 2008 when seismic swarms occurred beneath the geothermal area. The observed increases suggest the injection of CO₂- and SO₂-rich magmatic gas into the underlying hydrothermal reservoir, implying that the magmatic gas was episodically supplied to the hydrothermal system in 2006 and 2008. The earthquake swarms probably resulted from the injection of gas through the shallow crust accompanying the break of the sealing zone.     

The geochemistry of thermal waters and fumarolic gases on Shiashkotan I., Kuril Islands

Based on geochemical studies we have updated our knowledge of the generation conditions and discharge of thermal waters on Shiashkotan Island. The thermal springs, which are abundant on the island, are surface expressions of the North Shiashkotan and Kuntomintar hydrothermal systems. The North Shiashkotan hydrothermal system shows the classical hydrochemical zonality. The discharge of the Kuntomintar hydrothermal system is confined within two thermal fields that are situated in the central and northeastern craters of the eponymous volcano. The high temperature of the gases that are issuing from Kuntomintar Volcano to the ground surface and the higher predictive ratios S/Cl, S/C, and CO₂/H₂ in its composition provide evidence of a possible renewal of its fumarole activity.     

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.     

Continuous chemical monitoring of volcanic gas in Izu-Oshima volcano, Japan

A new continuous monitoring system has been developed for the measurement of volcanic gas from the steam well located 3 km north from the summit of Izu-Oshima volcano, Japan. After removing the water vapor using three sequential dehydration methods, CO₂ and SO₂ contents are measured using IR sensors, and O₂ and H₂ using a zirconia sensor and a semiconductor sensor, respectively. This system has been in operation without any significant trouble for 3 years.The dehydrated volcanic gas from the well consists of a mixture of CO₂, O₂ and N₂. A decreasing trend of the CO₂ content was observed from 1995 to 1998 together with a decrease of volcanic activity. Seasonal changes have also been observed in CO₂ and O₂ contents, CO₂ being higher and O₂ lower in summer, which suggests larger contribution of magmatic components in summer. While changes in short-term variation in CO₂ and O₂ are influenced by atmospheric pressure changes; the CO₂ content correlates inversely with atmospheric pressure unlike O₂ with some hours delay. In contrast, the H₂ content increased intermittently up to 1200 ppm one to several hours after a sudden drop in the atmospheric pressure and without any apparent correlation with seasonal changes.This system allows us to study temporal variation in chemical composition of volcanic gas during quiescent periods of volcanic activity of Izu-Oshima volcano, and might help us detect anomalous changes before future eruptive events.     

Studies on volcanic gases and gases from hydrothermal fields in Kamchatka

This paper describes the main lines of investigation for the volcanic and geothermal research in Kamchatka. Methods of gas sampling in the field and gas extraction from rocks are also described.     

Erosion rates of waterfalls in post‐volcanic fluvial systems around Aso volcano,southwestern Japan

Estimation of the recession rate of waterfalls is a crucial issue in bedrock river erosion because waterfall recession can cause a major impact on bedrock incision, especially when waterfall recession rates are high. Areas of active volcanoes are often characterized by many waterfalls in the volcanic edifice. This study examines recession rates of waterfalls in welded Aso‐1 ignimbrite from the Aso volcano in southwestern Japan using an empirical equation, which comprises a force/resistance index composed of measurable geomorphic parameters. The estimated recession rates are on the order of 0·01–0·07 m a^?1. The estimated rates are then validated by examining the duration and distance of their recession. The duration of waterfall recession is derived from eruptive ages of the Aso ignimbrites, giving waterfall recession distances of approximately 10 km. Although the original locations of the waterfalls suggested by the recession distances exceed the downstream limit of the present Aso‐1 ignimbrite remnants along valley floors, features of the surrounding topography are consistent with these localities being where the waterfalls formed. The use of an equation to estimate recession rates is therefore considered to be valid and practical. The contrast between the highly dissected landforms downstream of the present waterfalls and the gentle landscapes upstream of the waterfalls suggests that the rapid recession of the waterfalls is the major cause of post‐eruptive fluvial erosion into ignimbrites. Copyright © 2007 John Wiley & Sons, Ltd.     

Isotope geochemistry of minerals and fluids from Newberry volcano, Oregon

Isotopic compositions were determined for hydrothermal quartz, calcite, and siderite from core samples of the Newberry 2 drill hole, Oregon. The δ¹⁵O values for these minerals decrease with increasing temperatures. The values indicate that these hydrothermal minerals precipitated in isotopic equilibrium with water currently present in the reservoirs. The δ¹⁸O values of quartz and calcite from the andesite and basalt flows (700–932 m) have isotopic values which require that the equilibrated water δ¹⁸O values increase slightly (− 11.3 to −9.2‰) with increasing measured temperatures (150–265°C). The lithic tuffs and brecciated lava flows (300–700 m) contain widespread siderite. Calculated oxygen isotopic compositions of waters in equilibrium with siderite generally increase with increasing temperatures (76–100°C). The δ¹⁸O values of siderite probably result from precipitation in water produced by mixing various amounts of the deep hydrothermal water (− 10.5 ‰) with meteoric water (− 15.5 ‰) recharged within the caldera. The δ¹³C values of calcite and siderite decrease with increasing temperatures and show that these minerals precipitated in isotopic equilibrium with CO₂ of about −8 ‰.The δ¹⁸O values of weakly altered (<5% alteration of plagioclase) whole-rock samples decrease with increasing temperatures above 100°C, indicating that exchange between water and rock is kinetically controlled. The water/rock mass ratios decrease with decreasing temperatures. The δ¹⁸O values of rocks from the bottom of Newberry 2 show about 40% isotopic exchange with the reservoir water.The calculated δ¹⁸O and δD values of bottom hole water determined from the fluid produced during the 20 hour flow test are −10.2 and −109‰, respectively. The δD value of the hydrothermal water indicates recharge from outside the caldera.     

Evaluation of gases,condensates, and SO2 emissions from Augustine volcano,Alaska: the degassing of a Cl-rich volcanic system

After the March–April 1986 explosive eruption a comprehensive gas study at Augustine was undertaken in the summers of 1986 and 1987. Airborne COSPEC measurements indicate that passive SO₂ emission rates declined exponentially during this period from 380±45 metric tons/day (T/D) on 7/24/86 to 27±6 T/D on 8/24/87. These data are consistent with the hypothesis that the Augustine magma reservoir has become more degassed as volcanic activity decreased after the spring 1986 eruption. Gas samples collected in 1987 from an 870°C fumarole on the andesitic lava dome show various degrees of disequilibrium due to oxidation of reduced gas species and condensation (and loss) of H₂O in the intake tube of the sampling apparatus. Thermochemical restoration of the data permits removal of these effects to infer an equilibrium composition of the gases. Although not conclusive, this restoration is consistent with the idea that the gases were in equilibrium at 870°C with an oxygen fugacity near the Ni–NiO buffer. These restored gas compositions show that, relative to other convergent plate volcanoes, the Augustine gases are very HCl rich (5.3–6.0 mol% HCl), S rich (7.1 mol% total S), and H₂O poor (83.9–84.8 mol% H₂O). Values of D and ¹⁸O suggest that the H₂O in the dome gases is a mixture of primary magmatic water (PMW) and local seawater. Part of the Cl in the Augustine volcanic gases probably comes from this shallow seawater source. Additional Cl may come from subducted oceanic crust because data by Johnston (1978) show that Cl-rich glass inclusions in olivine crystals contain hornblende, which is evidence for a deep source (>25km) for part of the Cl. Gas samples collected in 1986 from 390°–642°C fumaroles on a ramp surrounding the inner summit crater have been oxidized so severely that restoration to an equilibrium composition is not possible. H and O isotope data suggest that these gases are variable mixtures of seawater, FMW, and meteoric steam. These samples are much more H₂O-rich (92%–97% H₂O) than the dome gases, possibly due to a larger meteoric steam component. The 1986 samples also have higher Cl/S, S/C, and F/Cl ratios, which imply that the magmatic component in these gases is from the more degassed 1976 magma. Thus, the 1987 samples from the lava dome are better indicators than the 1986 samples of degassing within the Augustine magma reservoir, even though they were collected a year later and contain a significant seawater component. Future gas studies at Augustine should emphasize fumaroles on active lava domes. Condensates collected from the same lava-dome fumarole have enrichments ot 10⁷–10² in Cl, Br, F, B, Cd, As, S, Bi, Pb, Sb, Mo, Zn, Cu, K, Li, Na, Si, and Ni. Lower-temperature (200°–650°C) fumaroles around the volcano are generally less enriched in highly volatile elements. However, these lower-termperature fumaroles have higher concentration of rock-forming elements, probably derived from the wall rock.     

Color measurements of volcanic ash deposits from three different styles of summit activity at Sakurajima volcano,Japan: Conduit processes recorded in color of volcanic ash

We measured quantitatively colors of volcanic ash deposits erupted from three different styles of summit activity (Strombolian activity, Vulcanian explosions and continuous ash venting activity) at Sakurajima volcano from 1974 to 1985. Colors of Strombolian ash samples have larger yellow components of their visible spectra (b^? values) than those of explosion and continuous venting ash samples. Colors of explosion ash samples show larger variation in both red and yellow components of their visible spectra (a^? and b^? values, respectively), while colors of continuous venting ash samples are in the narrow ranges within colors of explosion ash samples. Colors of components with lower densities than 3.1 g/cm³ (groundmass and phenocrystic plagioclase) obtained by magnetic and heavy liquid separation methods are similar to the unseparated bulk ash samples. This result suggests that the color variations of ash deposits are mainly originated from the particles composed of groundmass. The particles can be classified into three different types of particles with different vesicularity and crystallinity (vesicular particle [VP], dense particle with vesicles [DPV] and dense particle without vesicles [DP]). Analytical results of component proportions, chemical compositions of groundmass glasses, ferrous iron contents and surface ferric materials show that (1) VP has larger yellow components of the visible spectrum (b^? values) and high ferrous iron content, and is less crystallized than the DP and DPV, (2) DP has larger red and yellow components of its visible spectrum (a^? and b^? values, respectively) and involves ferric materials on the surfaces produced by oxidation process, and (3) DPV has smaller red and yellow components of its visible spectrum (a^? and b^? values, respectively) and involves less ferric materials on the ash surfaces. Color differences of ash deposits from three different activity styles can be explained by the different mixing ratios of VP, DPV and DP. During the Strombolian activity, the VP is a main component in the ash, which is formed from relatively less degassed and crystallized magma. In the Vulcanian explosion and continuous ash venting activity, the proportions of DPV and DP in ash are larger than that in the Strombolian activity. The highly crystallized DP may correspond to a vent cap, and DPV to a magma below the cap. The color measurements of ash deposits provide information on the pre-eruptive processes at the shallower levels of a conduit.     

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.     

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.     

Halogen acids in fumarolic gases of Kilauea volcano

The water-rich condensates of fumarolic gases, obtained from degassing lavas of the 1959–60 eruption of Kilauea volcano, contain unexpectedly high concentrations of hydrofluoric and hydrochloric acids, and thereby suggest that halogens are significant constituents of basaltic magmas. Vents on the pumice hill of Kilauea Iki yielded one sample that contained, in parts per million, 21,000 HF (1.1 N) with 2,920 HCl, and another sample, 20 HF with 70,500 HCl (2.0 N). Samples from vents elsewhere on the volcano had from one-fortieth to one-thousandth as much of the two acids. A rough correlation exists between the temperature of the fumaroles (range 110 to 820°C) and the total concentration of the halogen acids. This correlation is mainly due to progressive dilution of the magmatic halogen acids by water of probable meteoric origin in fumaroles of lower temperatures. Variations in the HF/HCl ratio (range 0.0003 to 7.2) may be explained by means of two different processes whose relative importance cannot be assessed with the data at hand (1). In their migration to the surface, the acid gases may have reacted with the lava to a variable extent owing to the widely different configurations of the several vents (steaming areas in glassy pumice, glowing cracks, and drillhole in lava lake). In the reaction, relatively more HF could have reacted at temperatures around 300°C with the glassy pumice (2). There is some indication that the HF/HCl ratio increases with time,suggesting that the crystallizing lava may have released HCl early, with HF concentrated in the later exhalations. The Br/Cl ratio ranges from 0.0036 down to 0.0014, as compared to 0.0034 of seawater.