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.     

Restoration of new volcanic gas analyses from basalts of the afar region: Further evidence of CO2 -degassing trends

The restored compositions for approximately 70 new analyses reported recently for Erta'Alelava lake (LeGuern et al., 1979) are in good agreement with restored compositions (Gerlach, 1980a) based on previously published data. The results confirm earlier indications that gas collections taken at different times from the lava lake are related principally by variations in CO₂ content. Restored compositions for gas samples collected in the final stages of a November 1978 Ardoukoba eruption along the Asal Rift spreading axis resemble the Erta'Ale gases except for a much lower CO₂ content. The Ardoukoba gases fall close to a CO₂-decreasing control line for gases with initial compositions similar to the 1971–1973 Erta'Ale gases. These results suggest that gases released from basaltic lava along zones of crustal spreading follow compositional trends dominated by changes in CO₂ content.     

Sulfur and chlorine degassing from primitive arc magmas: temporal changes during the 1982–1983 eruptions of Galunggung (West Java, Indonesia)

The 1982–1983 eruptions of Galunggung represent a nine-month period of intermittent volcanic activity with significant changes in explosivity and emission of volatiles. Eruptions started with Vulcanian explosions but changed gradually to Strombolian activity. Compositions of juvenile material changed from basaltic andesite to high-Mg basalt, which are among the most primitive rock types known in the Indonesian arc system. Although bulk compositions suggest a single evolution trend, we infer from the compositions of melt inclusions in olivine phenocrysts that the magmas represent derivatives of a complex spectrum of primary melts. Primitive inclusions in olivine phenocrysts from magma erupted during the Strombolian phase contain up to 2000 ppm sulfur, but concentrations decrease rapidly with increasing SiO₂ down to matrix glass values (50–100 ppm). ‘Vulcanian’ inclusions appear to be degassed before eruption (200 ppm S). Chlorine concentrations increase from 750 to 2200 ppm in Strombolian, and from 800 to 1500 in Vulcanian magmas, whereas matrix glass contains about 1000 ppm in both cases. Ash leachates show two cycles of decreasing S/Cl ratios: from 9.7 to 5.6 at the start of the activity, and from 12.2 to 2.0 after four months. As the second cycle follows upon increased seismic activity at shallow depth, it probably reflects degassing of fresh sulfur-rich magma arriving in the shallow Galunggung reservoir. In contrast to the degassed state of Vulcanian magma, the significant amounts of adsorbed sulfur on the ashes point to an excess source of sulfur, which was most likely derived from intruding Strombolian magma. Hence, the observed sulfur flux of 2 Mt is not in accordance with a petrologic estimate of 0.09 Mt. Using a published value of 550 Mt of erupted material about 0.34 km³ fresh undegassed magma is needed to account for the observed sulfur flux. This is close to the erupted volume of Vulcanian magma (0.26 km³), which presumably was replaced completely by Strombolian magma during the eruption. Using the petrologic method, we calculate a total release of 0.3 Mt chlorine, which agrees well with an output of 0.47 Mt estimated independently from S/Cl ratios of the ash leachates and TOMS sulfur yields. Ash leachates show that about 35% of the sulfur and 30% of the chlorine was scavenged from the eruption plumes. Our results suggest that sulfur and chlorine were largely decoupled during degassing, which resulted in considerable variations in S/Cl ratios during the Galunggung eruptions. We infer that sulfur degassing reflects the arrival of fresh magma at shallow depth, whereas chlorine is largely derived from simultaneously erupted material. As a consequence, the petrologic estimates are more consistent with observed emissions for chlorine than for sulfur.     

Interpretation of volcanic gas data from tholeiitic and Alkaline Mafic Lavas

The analyses of approximately 100 high temperature gas samples from erupting lavas of Surtsey, Erta Ale, Ardoukoba, Kilauea, Mount Etna and Nyiragongo exhibit erratic compositions resulting from analytical errors, condensation effects, reactions with sampling devices, and contamination by atmospheric gases, meteoric water and organic material. Computational techniques have been devised to restore reported analyses to compositions representative of the erupted gases. The restored analyses show little evidence of short-term variations. The principal species are H₂O, CO₂, SO₂, H₂, CO, H₂S, S₂, and HCl. The O₂ fugacities range from nickel-nickel oxide to a half order of magnitude below quartz-magnetite-fayalite. There is no evidence for a unique magmatic gas composition; instead, the erupted gases show regular compositional trends characterized by decreasing CO₂ with progressive outgassing. The gases from more alkaline lavas (Etna, Nyiragongo) are distinctly richer in CO₂, while those from less alkaline (Surtsey) or tholeiitic lavas (Erta Ale, Ardoukoba) tend to be richer in H₂O. Kilauean gases range from CO₂-rich to H₂O-rich. The total sulfur contents of the erupted gases show an excellent positive correlation with lava O₂ fugacity. All restored analyses are significantly lower in H₂O and enriched in sulfur and CO₂ compared to the «excess volatiles».     

The stable isotope geochemistry of volcanic lakes, with examples from Indonesia

Stable isotope compositions (δD, δ¹⁸O and δ³⁴S) of volcanic lake waters, gas condensates and spring waters from Indonesia, Italy, Japan, and Russia were measured. The spring fluids and gas samples plot in a broad array between meteoric waters and local high-temperature volcanic gas compositions. The δD and δ¹⁸O data from volcanic lakes in East Indonesia plot in a concave band ranging from local meteoric waters to evaporated fluids to waters heavier than local high-temperature volcanic gases. We investigated isotopic fractionation processes in volcanic lakes at elevated temperatures with simultaneous mixing of meteoric waters and volcanic gases. An elevated lake water temperature gives enhanced kinetic isotope fractionation and changes in equilibrium fractionation factors, providing relatively flat isotope evolution curves in δ¹⁸O–δD diagrams. A numerical simulation model is used to derive the timescales of isotopic evolution of crater lakes as a function of atmospheric parameters, lake water temperature and fluxes of meteoric water, volcanic gas input, evaporation, and seepage losses. The same model is used to derive the flux magnitude of the Keli Mutu lakes in Indonesia. The calculated volcanic gas fluxes are of the same order as those derived from energy budget models or direct gas flux measurements in open craters (several 100 m³ volcanic water/day) and indicate a water residence time of 1–2 decades. The δ³⁴S data from the Keli Mutu lakes show a much wider range than those from gases and springs, which is probably related to the precipitation of sulfur in these acid brine lakes. The isotopic mass balance and S/Cl values suggest that about half of the sulfur input in the hottest Keli Mutu lake is converted into native sulfur.     

Role of magma mixing during the recent activity of La Fossa di vulcano (Aeolian Islands, Italy)

Relatively homogeneous trachytes have been erupted for approximately 3800 years at la Fossa di Vulcano. From the Punte Nere eruptive cycle up to the Palizzi cycle the products varied little, while after the Palizzi cycle (1600 + 1000 a B.P.) to the latest eruption, 1888–1890 AD, a spectrum of compositions, with rhyolite dominating, characterized the erupted products.A stratigraphic sequence, starting with the Palizzi lava flow, has been studied, focussing the attention on lavas and volcanic bombs, to define the role that magma mixing processes have played in the recent history of La Fossa di Vulcano. Textural and chemical analyses of whole rocks, glass, groundmass, and mineral phases indicate that only the breadcrust bombs, erupted during the 1888–1890, show evidence of mixing between trachytic and rhyolitic end-members. Interestingly, in the deposits of the same eruption, trachytic bombs also occur.The lava flows erupted before 1888–1890 display general features suggesting that they entrained crystals and lava fragments during magma ascent. During the 1888–1890 eruption the trachytic bombs were erupted before the breadcrust bombs, which have a more evolved and hybrid composition. These characteristics, together with the change of the nature of the products after the Palizzi cycle, require a complex volcanological model for the recent history of la Fossa di Vulcano.     

Chemical and optical studies of glass shards in Pleistocene and Pliocene ash layers from DSDP site 192, Northwest Pacific Ocean

Thirty-four ash layers of Pleistocene and Pliocene age from DSDP Site 192, northwestern Pacific Ocean, have been subjected to detailed chemical and optical study to evaluate: (1) the chemical and optical variability in glass shards from deep-sea ash layers, and (2) secondary changes brought about by prolonged exposure to seawater. Glass shards from approximately half of the ash layers studied were found to have uniform compositions which approach the precision of the microprobe chemical analyses, whereas the remainder are compositionally diverse (e.g., SiO₂, variations of 5–15% among shards from the same ash layer) and appear to be the eruptive products of compositionally zoned magma chambers. Optical studies of glass shards confirm the absence of devitrification or the formation of pervasive secondary alteration products. By contrast, chemical studies suggest that the glass shards have experienced progressive hydration with possible minor ion exchange of K, Mg, Ca and Si. The hydration occurs rapidly and leads to a rather uniform water content of 4.5–5% after several hundred thousands of years exposure to seawater. Step-wise heating dehydration experiments, optical effects, and published'oxygen isotope studies indicate that the water of hydration is incorporated uniformly within the glass. Systematic chemical differences between electron microprobe analyses of glass shard interiors and corresponding bulk chemical study by atomic absorption lead us to postulate that glass shard margins have undergone a minor chemical exchange with major cations in seawater. They have gained 0.10–0.20 wt. % K₂0, MgO, and CaO while losing a corresponding amount of Si₂O. Although the glass shards from DSDP Site 192 are hydrated and may have experienced subtle, surficial ion exchange, we stress that they are the most chemically representative samples available of magmas that were explosively erupted from volcanic arcs.     

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.     

Isotopic geochemistry of acid thermal waters and volcanic gases from Zaō volcano in Japan

The chemical composition and D/H, and ratios have been determined for the acid hot waters and volcanic gases discharging from Zaō volcano in Japan. The thermal springs in Zaō volcano issue acid sulfate-chloride type waters (Zaō) and acid sulfate type waters (Kamoshika). Gases emitted at Kamoshika fumaroles are rich in CO₂, SO₂ and N₂, exclusive of H₂O. Chloride concentrations and oxygen isotope data indicate that the Zaō thermal waters issue a fluid mixture from an acid thermal reservoir and meteoric waters from shallow aquifers. The waters in the Zaō volcanic system have slight isotopic shifts from the respective local meteoric values. The isotopic evidence indicates that most of the water in the system is meteoric in origin. Sulfates in Zaō acid sulfate-chloride waters with δ³⁴S values of around +15‰, are enriched in ³⁴S compared to Zaō H₂S, while the acid sulfate waters at Kamoshika contain supergene light sulfate (δ³⁴S = + 4‰) derived from volcanic sulfur dioxide from the volcanic exhalations. The sulfur species in Zaō acid waters are lighter in δ³⁴S than those of other volcanic areas, reflecting the difference in total pressure.     

Rates of sulfur dioxide and particle emissions from White Island volcano,New Zealand,and an estimate of the total flux of major gaseous species

Airborne correlation spectrometry (COSPEC) was used to measure the rate of SO₂ emission at White Island on three dates, i.e., November 1983, 1230 ± 300 t/d; November 1984, 320 ± 120 t/d; and January 1985, 350 ± 150 t/d (t = metric tons). The lower emission rates are likely to reflect the long-term emission rates, whereas the November 1983 rate probably reflects conditions prior to the eruption of December 1983. The particle flux in the White Island plume, as determined with a quartz crystal microbalance/cascade in November 1983, was 1.3 t/d, unusually low for volcanic plumes. The observed plume particles, as shown from scanning electron microscopy, include halite, native sulfur, and silicates and are broadly similar to other volcanic plumes.Gas analyses from high-temperature volcanic fumaroles collected from June 1982 through November 1984 werde used together with the COSPEC data to estimate the flux of other gas species from White Island. The rates estimated are indicative of the long-term volcanic emission, i.e., 8000–9000 t/d H₂O, 900–1000 t/d CO₂, 70–80 t/d HCl, 1.5–2 t/d HF, and about 0.2 t/d NH₃. The long-term thermal power output at White Island is estimated at about 400 MW.     

The Pleistocene cinder cones surrounding Volcán Colima, Mexico re-visited: eruption ages and volumes, oxidation states, and sulfur content

Located at the volcanic front in the western Mexican arc, in the Colima Rift, is the active Volcán Colima, which lies on the southern end of the massive (∼450 km³) Colima-Nevado volcanic complex. Along the margins of this andesitic volcanic complex, is a group of 11 scoria cones and associated lavas, which have been dated by the ⁴⁰Ar/³⁹Ar method. Nine scoria cones erupted ∼1.3 km³ of alkaline magma (basanite, leucite-basanite, minette) between 450 and 60 ka, with >99% between 240 and 60 ka. Two additional cones (both the oldest and calc-alkaline) erupted <0.003 km³ of basalt (0.5 Ma) and <0.003 km³ of basaltic andesite (1.2 Ma), respectively. Cone and lava volumes were estimated with the aid of digital elevation models (DEMs). The eruption rate for these scoria cones and their associated lavas over the last 1.2 Myr is ∼1.2 km³/Myr, which is more than 400 times smaller than that from the andesitic Colima-Nevado edifice. In addition to these alkaline Colima cones, two other potassic basalts erupted at the volcanic front, but ∼200 km to the ESE (near the historically active Volcán Jorullo), and were dated at 1.06 and 0.10 Ma. These potassic suites reflect the tendency in the west-central Mexican arc for magmas close to the volcanic front to be enriched in K₂O relative to those farther from the trench.Ferric-ferrous analyses on pristine samples from the alkaline cones adjacent to V. Colima and V. Jorullo indicate that their oxygen fugacities relative to the nickel-nickel oxide buffer are significantly higher (ΔNN0=2–4) than those for the calc-alkaline magma types (0–1.5). These ΔNNO values correlate positively with Ba concentrations and likely reflect the influence of a slab-derived fluid. As a result of the high oxidation states, the solubility of sulfur in these potassic magmas is enhanced. Indeed the sulfur content of both the whole rock and the apatite phenocrysts (and in olivine melt inclusions reported in the literature) suggest that part of their pre-eruptive sulfur gas (SO₂) concentrations could have been discharged to the atmosphere in amounts comparable to the 1982 eruption of El Chichón, although over a prolonged period spanning thousands of years (not per eruption).Electronic Supplementary Material Supplementary material is available for this article at Editorial responsibility: J. Donnelly-Nolan     

The eruptive history of the Tequila volcanic field, western Mexico: ages, volumes, and relative proportions of lava types

The eruptive history of the Tequila volcanic field (1600 km²) in the western Trans-Mexican Volcanic Belt is based on ⁴⁰Ar/³⁹Ar chronology and volume estimates for eruptive units younger than 1 Ma. Ages are reported for 49 volcanic units, including Volcán Tequila (an andesitic stratovolcano) and peripheral domes, flows, and scoria cones. Volumes of volcanic units 1 Ma were obtained with the aid of field mapping, ortho aerial photographs, digital elevation models (DEMs), and ArcGIS software. Between 1120 and 200 kyrs ago, a bimodal distribution of rhyolite (~35 km³) and high-Ti basalt (~39 km³) dominated the volcanic field. Between 685 and 225 kyrs ago, less than 3 km³ of andesite and dacite erupted from more than 15 isolated vents; these lavas are crystal-poor and show little evidence of storage in an upper crustal chamber. Approximately 200 kyr ago, ~31 km³ of andesite erupted to form the stratocone of Volcán Tequila. The phenocryst assemblage of these lavas suggests storage within a chamber at ~2–3 km depth. After a hiatus of ~110 kyrs, ~15 km³ of andesite erupted along the W and SE flanks of Volcán Tequila at ~90 ka, most likely from a second, discrete magma chamber located at ~5–6 km depth. The youngest volcanic feature (~60 ka) is the small andesitic volcano Cerro Tomasillo (~2 km³). Over the last 1 Myr, a total of 128±22 km³ of lava erupted in the Tequila volcanic field, leading to an average eruption rate of ~0.13 km³/kyr. This volume erupted over ~1600 km², leading to an average lava accumulation rate of ~8 cm/kyr. The relative proportions of lava types are ~22–43% basalt, ~0.4–1% basaltic andesite, ~29–54% andesite, ~2–3% dacite, and ~18–40% rhyolite. On the basis of eruptive sequence, proportions of lava types, phenocryst assemblages, textures, and chemical composition, the lavas do not reflect the differentiation of a single (or only a few) parental liquids in a long-lived magma chamber. The rhyolites are geochemically diverse and were likely formed by episodic partial melting of upper crustal rocks in response to emplacement of basalts. There are no examples of mingled rhyolitic and basaltic magmas. Whatever mechanism is invoked to explain the generation of andesite at the Tequila volcanic field, it must be consistent with a dominantly bimodal distribution of high-Ti basalt and rhyolite for an 800 kyr interval beginning ~1 Ma, which abruptly switched to punctuated bursts of predominantly andesitic volcanism over the last 200 kyrs.Electronic Supplementary Material Supplementary material is available in the online version of this article at Editorial responsility: J. Donnelly-NolanThis revised version was published online in January 2005 with corrections to Tables 1 and 3.An erratum to this article can be found at     

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

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

Pre-eruptive and syn-eruptive conditions in the Black Butte, California dacite: Insight into crystallization kinetics in a silicic magma system

A series of experiments and petrographic analyses have been run to determine the pre-eruption phase equilibria and ascent dynamics of dacitic lavas composing Black Butte, a dome complex on the flank of Mount Shasta, California. Major and trace element analyses indicate that the Black Butte magma shared a common parent with contemporaneously erupted magmas at the Shasta summit. The Black Butte lava phenocryst phase assemblage (20 v.%) consists of amphibole, plagioclase (core An_77.5), and Fe–Ti oxides in a fine-grained (< 0.5 mm) groundmass of plagioclase, pyroxene, Fe–Ti oxides, amphibole, and cristobalite. The phenocryst assemblage and crystal compositions are reproduced experimentally between 890 °C and 910 °C, ≥ 300 MPa, X_H2O = 1, and oxygen fugacity = NNO + 1. This study has quantified the extent of three crystallization processes occurring in the Black Butte dacite that can be used to discern ascent processes. Magma ascent rate was quantified using the widths of amphibole breakdown rims in natural samples, using an experimental calibration of rim development in a similar magma at relevant conditions. The majority of rims are 34 ± 10 μm thick, suggesting a time-integrated magma ascent rate of 0.004–0.006 m/s among all four dome lobes. This is comparable to values for effusive samples from the 1980 Mount St. Helens eruption and slightly faster than those estimated at Montserrat. A gap between the compositions of plagioclase phenocryst cores and microlites suggests that while phenocryst growth was continuous throughout ascent, microlite formation did not occur until significantly into ascent. The duration of crystallization is estimated using the magma reservoir depth and ascent rate, as determined from phase equilibria and amphibole rim widths, respectively. Textural analysis of the natural plagioclase crystals yields maximum growth rates of plagioclase phenocryst rims and groundmass microlites of 8.7 × 10^− 8 and 2.5 × 10^− 8 mm/s, respectively. These rates are comparable to values determined from time-sequenced samples of dacite erupted effusively from Mount St. Helens during 1980 and indicate that syneruptive crystallization processes were important during the Black Butte eruptive cycle.     

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.     

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.     

Petrology,geochemistry, and age of the Spurr volcanic complex,eastern Aleutian arc

The Spurr volcanic complex (SVC) is a calc-alkaline, medium-K, sequence of andesites erupted over the last 250000 years by the eastern-most currently active volcanic center in the Aleutian arc. The ancestral Mt. Spurr was built mostly of andesites of uniform composition (58%–60% SiO₂), although andesite production was episodically interrupted by the introduction of new batches of more mafic magma. Near the end of the Pleistocene the ancestral Mt. Spurr underwent avalanche caldera formation, resulting in the production of a volcanic debris avalanche with overlying ashflows. Immediately afterward, a large dome (the present Mt. Spurr) formed in the caldera. Both the ash flows and dome are made of acid andesite more silicic (60%–63% SiO₂) than any analyzed lavas from the ancestral Mt. Spurr, yet contain olivine and amphibole xenocrysts derived from more mafic magma. The mafic magma (53%–57% SiO₂) erupted during and after dome emplacement from a separate vent only 3 km away. Hybrid block-and-ash flows and lavas were also produced. The vents for the silicic and mafic lavas are in the center and in the breach of the 5-by-6-km horseshoe-shaped caldera, respectively, and are less than 4 km apart. Late Holocene eruptive activity is restricted to Crater Peak, and magmas continue to be relatively mafic. SVC lavas are plag ±ol+cpx±opx+mt bearing. All postcaldera units contain small amounts of high-Al₂O₃, high-alkali amphibole, and proto-Crater Peak and Crater Peak lavas contain abundant pyroxenite and anorthosite clots presumably derived from an immediately preexisting magma chamber. Ranges of mineral chemistries within individual samples are often nearly as large as ranges of mineral chemistries throughout the SVC suite, suggesting that magma mixing is common. Elevated Sr, Pb, and O isotope ratios and trace-element systematics incompatible with fractional crystallization suggest that a significant amount of continental crust from the upper plate has been assimilated by SVC magmas during their evolution.     

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 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.     

Petrology and geochemistry of lava and ash erupted from Volcán Colima, Mexico, during 1998–2005

Lava (n = 8) and bulk ash samples (n = 6) erupted between July 1999 and June 2005 were investigated to extend time-series compositional and textural studies of the products erupted from Volcán Colima since 1869. In particular, we seek to evaluate the possibility that the current activity will culminate in major explosive Plinian-style event similar to that in 1913. Lava samples continue to show relatively heterogeneous whole-rock compositions with some significant mafic spikes (1999, 2001) as have prevailed since 1976. Groundmass SiO₂ contents continue trends to lower levels that have prevailed since 1961, in the direction of the still lower groundmass SiO₂ contents found in 1913 scoriae. Importantly, ash samples from investigated Vulcanian-style explosive eruptions in 2005 are devoid of particles with micro-vesiculated groundmass textures; such textures characterized the 1913 scoriae, signifying expansion of in-situ magmatic gas as the propellant of the 1913 eruption. All magmas erupted since 1913 appear to have arrived in the upper volcanic conduit system in a degassed state. The small to moderate Vulcanian-style explosive eruptions, which have been common since 1999 (> 16,000 events), have blasted ash clouds as high as 11 km a.s.l. and sent pyroclastic flows out to distances of 5 km. These eruptions do not appear to be powered by expansion of in-situ magmatic gas. New small lava domes have been observed in the crater prior to many explosive eruptions. These plugs of degassed lava may temporarily seal the conduit and allow the build-up of magmatic gases streaming upward from below ahead of rising and degassing magma. In this interpretation, when gas pressure exceeds the strength of the plug seal in the upper conduit, an explosive Vulcanian-style eruption occurs. Alternatively these explosive eruptions may represent interactions of hot rock and groundwater (phreato-magmatic).