Forecast of volcanic eruptions by chemical methods

From the magmatic emanations differentiation point of view it is possible to calculate some ratios such as F/CO₂, Cl/CO₂, SO₂/CO₂, SO₂/H₂S, H₂S/CO₂ and CO₂/N₂ in the tumarolic gases for the forecasting of volcanic activity. In order to predict the cruptions of a volcano it is needed to select several fumaroles or hot springs having different regimes of variation of the above ratios. The study of some fumaroles composition at the Asama. Mihara, Kirishima and other volcanoes in Japan showed a close connection between volcanic gas compositions and state of the volcanoes.     

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.     

The effect of variations in rainfall on the chemical composition of vulcano fumaroles (Italy)

Analytical data for samples collected over a period of 17 months at the crater fumaroles of Vulcano are given. Fluids are both condensed and absorbed in KOH solutions, thus providing a complete analysis of acid and condensable species. Variations in H₂O, CO₂, SO₂, H₂S, HCl, B, F, Br, NH₄ concentrations are taken into account. Rainwater represents an important modifying facor of the basic chemical composition of the investigated discharges, which do not seem to have undergone any other significant change during the above mentioned span of time. While acting essentially as a diluting factor for CO₂ and SO₂, the inflow of meteoric water can introduce substantial modifications in concentrations of other constituents. As a consequence, any correct comparison of fumaroles compositions either for different systems or for different samplings at the same system should take into consideration the influence of meteorological conditions.     

Fumarole/plume and diffuse CO2 emission from Sierra Negra caldera, Galapagos archipelago

Measurements of visible and diffuse gas emission were conducted in 2006 at the summit of Sierra Negra volcano, Galapagos, with the aim to better characterize degassing after the 2005 eruption. A total SO₂ emission of 11?±?2?t day^?1 was derived from miniature differential optical absorption spectrometer (mini-DOAS) ground-based measurements of the plume emanating from the Mini Azufral fumarolic area, the most important site of visible degassing at Sierra Negra volcano. Using a portable multigas system, the H₂S/SO₂, CO₂/SO₂, and H₂O/SO₂ molar ratios in the Mina Azufral plume emissions were found to be 0.41, 52.2, and 867.9, respectively. The corresponding H₂O, CO₂, and H₂S emission rates were 562, 394, and 3?t day^?1, respectively. The total output of diffuse CO₂ emissions from the summit of Sierra Negra volcano was 990?±?85?t day^?1, with 605?t day^?1 being released by a deep source. The diffuse-to-plume CO₂ emission ratio was about 1.5. Mina Azufral fumaroles released gasses containing 73.6?mol% of H₂O; the main noncondensable components amounted to 97.4?mol% CO₂, 1.5?mol% SO₂, 0.6?mol% H₂S, and 0.35?mol%?N₂. The higher H₂S/SO₂ ratio values found in 2006 as compared to those reported before the 2005 eruption reveal a significant hydrothermal contribution to the fumarolic emissions. ³He/⁴He ratios measured at Mina Azufral fumarolic discharges showed values of 17.88?±?0.25?R _A , indicating a mid-ocean ridge basalts (MORB) and a Galapagos plume contribution of 53 and 47?%, respectively.     

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

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

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.     

Etude de la phase gazeuse occluse dans les laves de «l’Ardoukôba», volcan éphémère d’une dorsale émergée (Afar)

Gases trapped in lavas of three main flows of the Ardoukôba eruption (8 to 15 November, 1978) have been analysed by mass spectrometry. These analyses concern both plagioclase phenocrysts and microcrystalline mesostasis. Fluids are released between 500°C and 1200°C, and consist of H₂O, CO₂, CO, N₂, SO₂, HCl, H₂, CH₄ with traces of hydrocarbons and H₂S. The total content is less than 0.3–0.4 wt. % of samples with about 0.1–0.15 wt % of H₂O. No significant variation among the three flows is observed. Plagioclase phenocrysts are less abundant in fluids than the mesostasis (～2/3). The gases trapped in these phenocrysts are richer in CO and organic compounds, whereas mesostasis contain more H₂O, CO₂ and SO₂. CO is likely produced by reduction of CO₂ and H₂O with carbon during either analyses or eruption itself, or is of primary origin. In the latter case, gas composition suggests an entrapment temperature of about 1200°C ± 75°C. Kinetic study of the water and carbon dioxide release allows to calculate the diffusion characteristics of these fluids. Water and carbon dioxide behave rather similarly. Plagioclase gives a single activation energy value (8 Kcal/mole), while mesostasis gives two values (8 Kcal/mole, 15 Kcal/mole). Diffusion coefficients at 20°C are estimated to fall in the range 10^?13 · 10^?12 cm² · sec^?1.     

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».     

Fumarole compositions and mercury emissions from the Tatun Volcanic Field,Taiwan: Results from multi-component gas analyser,portable mercury spectrometer and direct sampling techniques

Gas emissions from Tatun volcanic group, northern Taiwan, were studied for the first time using a multi-component gas analyser system (Multi-GAS) in combination with Giggenbach flask methods at fumaroles and mud pools at Da-you-keng (DYK) and Geng-tze-ping (GZP). CO₂/S molar ratios observed at DYK ranged from 3–17, similar ratios were observed using a Multi-GAS sensor box of 8–16. SO₂ at GZP was low, higher concentrations were observed at DYK where SO₂/H₂S ratios were close to 1 for both methods. A lower CO₂/H₂S ratio was measured via Giggenbach flask sampling (7.2) than was found in the plume using the gas sensor at GZP (9.2). This may reflect rapid oxidation of H₂S as it mixes with background air. Gaseous elemental mercury (GEM) levels were observed in the fumarole gases using a portable mercury spectrometer. These are the first such measurements of mercury at Tatun. Mean GEM concentrations in the fumarole plumes were ∼ 20 ng m^− 3, with much higher concentrations observed close to the ground (mean [GEM] 130 and 290 ng m^− 3 at DYK and GZP, respectively). The GEM in the fumarole plume was elevated above concentrations in industrial/urban air in northern Taiwan and the increase in GEM observed when the instrument was lowered suggests high levels of mercury are present in the surrounding ground surface. The GEM/CO₂ (10^− 8) and GEM/S (10^− 6) ratios observed in the fumarole gases were comparable to those observed at other low-temperature fumaroles. Combining the Hg/CO₂ ratio with a previous CO₂ flux value for the area, the annual GEM flux from the Tatun field is estimated as 5–50 kg/year.     

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

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

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

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

Equilibrium calculations in volcanic gaseous systems

Equilibria calculations of high-temperature volcanic gases from lava lakes are carried out on the basis of best volcanic gas samples. The equilibrium gas composition at temperatures from 800° to 1400°K and pressures up to 25 kilobars (in ideal gas system) was calculated using the free energy minimization model as well as the Newton-Raphson methods. It is shown that the juvenile «magmatic gas » of basaltic magma consists of three components: H₂O, SO₂, CO₂; the water vapor being about 60%. The increase of temperature under constant pressure results in the increase of the SO₂ concentration and in the simultaneous decrease of H₂S. Under the same conditions the ratios CO/CO₂ and H₂/H₂O are found to increase. Methane cannot be a component of «magmatic gas» corresponding to the elemental composition of basaltic lava gases. The calculated values of \(P_{O_2 } \) are in good agreement with the experimental data obtained from direct measurements of \(P_{O_2 } \) in lava lakes and experiments with basaltic melts.     

Fumaroles in ice caves on the summit of Mount Rainier—preliminary stable isotope, gas, and geochemical studies

The edifice of Mount Rainier, an active stratovolcano, has episodically collapsed leading to major debris flows. The largest debris flows are related to argillically altered rock which leave areas of the edifice prone to failure. The argillic alteration results from the neutralization of acidic magmatic gases that condense in a meteoric water hydrothermal system fed by the melting of a thick mantle of glacial ice. Two craters atop a 2000-year-old cone on the summit of the volcano contain the world's largest volcanic ice-cave system. In the spring of 1997 two active fumaroles (T=62°C) in the caves were sampled for stable isotopic, gas, and geochemical studies.Stable isotope data on fumarole condensates show significant excess deuterium with calculated δD and δ¹⁸O values (−234 and −33.2‰, respectively) for the vapor that are consistent with an origin as secondary steam from a shallow water table which has been heated by underlying magmatic–hydrothermal steam. Between 1982 and 1997, δD of the fumarole vapor may have decreased by 30‰.The compositions of fumarole gases vary in time and space but typically consist of air components slightly modified by their solubilities in water and additions of CO₂ and CH₄. The elevated CO₂ contents (δ¹³C_CO2=−11.8±0.7‰), with spikes of over 10,000 ppm, require the episodic addition of magmatic components into the underlying hydrothermal system. Although only traces of H₂S were detected in the fumaroles, most notably in a sample which had an air δ¹³C_CO2 signature (−8.8‰), incrustations around a dormant vent containing small amounts of acid sulfate minerals (natroalunite, minamiite, and woodhouseite) indicate higher H₂S (or possibly SO₂) concentrations in past fumarolic gases.Condensate samples from fumaroles are very dilute, slightly acidic, and enriched in elements observed in the much higher temperature fumaroles at Mount St. Helens (K and Na up to the ppm level; metals such as Al, Pb, Zn Fe and Mn up to the ppb level and volatiles such as Cl, S, and F up to the ppb level).The data indicate that the hydrothermal system in the edifice at Mount Rainier consists of meteoric water reservoirs, which receive gas and steam from an underlying magmatic system. At present the magmatic system is largely flooded by the meteoric water system. However, magmatic components have episodically vented at the surface as witnessed by the mineralogy of incrustations around inactive vents and gas compositions in the active fumaroles. The composition of fumarole gases during magmatic degassing is distinct and, if sustained, could be lethal. The extent to which hydrothermal alteration is currently occurring at depth, and its possible influence on future edifice collapse, may be determined with the aid of on site analyses of fumarole gases and seismic monitoring in the ice caves.     

浙江省珊溪水库地区土壤Rn和H2地球化学特征

在浙江省珊溪水库地区布设5条断层土壤气Rn和H₂测线,并选取15个溶解水氡采样测点。测量结果显示,其中有3条土壤气测线上的Rn浓度均值超过70 Bq/L,土壤H₂测值最高达1 377 ppm,水样中溶解氡浓度最高值为68.3 Bq/L。通过珊溪水库地区历史地震活动和地质构造情况分析,发现该地区土壤Rn、H₂和溶解水氡的高值分布区均与双溪—焦溪垟断裂F_11-3分支的空间位置密切相关,该断裂分支是珊溪水库地区小震活动的发震断裂。另外通过研究发现,历史震群活动距今时间以及震群活动的频度和强度是影响珊溪水库地区土壤气Rn和H₂地球化学特征的重要因素。     

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.     

Volatile emissions and gas geochemistry of Hot Spring Basin,Yellowstone National Park,USA

We characterize and quantify volatile emissions at Hot Spring Basin (HSB), a large acid-sulfate region that lies just outside the northeastern edge of the 640 ka Yellowstone Caldera. Relative to other thermal areas in Yellowstone, HSB gases are rich in He and H₂, and mildly enriched in CH₄ and H₂S. Gas compositions are consistent with boiling directly off a deep geothermal liquid at depth as it migrates toward the surface. This fluid, and the gases evolved from it, carries geochemical signatures of magmatic volatiles and water–rock reactions with multiple crustal sources, including limestones or quartz-rich sediments with low K/U (or ^40?Ar/^4?He). Variations in gas chemistry across the region reflect reservoir heterogeneity and variable degrees of boiling. Gas-geothermometer temperatures approach 300 °C and suggest that the reservoir feeding HSB is one of the hottest at Yellowstone. Diffuse CO₂ flux in the western basin of HSB, as measured by accumulation-chamber methods, is similar in magnitude to other acid-sulfate areas of Yellowstone and is well correlated to shallow soil temperatures. The extrapolation of diffuse CO₂ fluxes across all the thermal/altered area suggests that 410 ± 140 t d^− 1 CO₂ are emitted at HSB (vent emissions not included). Diffuse fluxes of H₂S were measured in Yellowstone for the first time and likely exceed 2.4 t d^− 1 at HSB. Comparing estimates of the total estimated diffuse H₂S emission to the amount of sulfur as SO₄²⁻ in streams indicates ~ 50% of the original H₂S in the gas emission is lost into shallow groundwater, precipitated as native sulfur, or vented through fumaroles. We estimate the heat output of HSB as ~ 140–370 MW using CO₂ as a tracer for steam condensate, but not including the contribution from fumaroles and hydrothermal vents. Overall, the diffuse heat and volatile fluxes of HSB are as great as some active volcanoes, but they are a small fraction (1–3% for CO₂, 2–8% for heat) of that estimated for the entire Yellowstone system.     

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.     

Chemistry and metal contents of magmatic gases: the new Tolbachik volcanoes case (Kamchatka)

The gaseous products of new Tolbachik volcanoes were studied during 1975 to 1977 throughout all eruptive stages and during the post eruptive activity. In investigations the northern break-out gases emitted during the eruption from the moving and consolidated lava flows there have been detected H₂O (the main component), H₂, HF, HCl, SO₂ and H₂S, CO₂, CO, NH₃, CH₄ and other hydrocarbons, NH₄Cl predominated in compositions of condensates and subtimates on lava flows and the most characteristic microcomponents were Zn, Cu, Pb, Sn, Ag and others. Sampling of gases and condensates at the southern break-out was conducted immediately from the flowing melt. In gases there have been detected H₂O (98 mol. %). HCl and H₂ (0.9 mol. % each) as well as HF, SO₂, H₂S, CO₂ and in small quantities O₂ and N₂, Gases reached the equilibrium state atT andP sampling and were characteristic of gas composition of the southern break-out magma. HCl, HF and H₂SO₄ were predominant during condensate and sublimate mineralization. The major raicrocomponents were represented by Pt, Sb, As, Zn, Cu, Pb, Ni, Co and others. Comparison of compositions of gases and of products of their reactions at the northern and at the southern break-outs allows us to assume the presence of the deeper magma source at the northern break-out and of shallow magma source at the southern break-out.     

Temporal variations of gas compositions of fumaroles in the Tatun Volcano Group,northern Taiwan

Hydrothermal activity is common in the Tatun Volcano Group of northern Taiwan. Helium isotopic compositions of fumarolic samples show that mantle component occupies more than 60% in the previous study. Along with recent seismic results, a magma reservoir is inferred to have existed beneath the area of Da-you-keng, where fumarolic venting is the most active in Tatun Volcano Group. Progressive increases of HCl concentrations and SO₂/H₂S ratio in fumaroles from Da-you-keng have been observed since August 2004. The HCl concentration changed from almost the detection limit to thousands of ppm, even up to 30,000 ppm. SO₂/H₂S ratios varied from almost 0 to 3; hence SO₂ became the dominated S species in this area. These variations were accompanied by rising temperature of fumaroles in the Tatun Volcano Group, especially in the area of Da-you-keng (from boiling point to 131 °C). Meanwhile, ³He/⁴He ratios showed a decreasing trend but returned to normal values shortly thereafter. We propose two possible processes, 1) new magma supply and 2) recent opening of fractures in local area, to explain these observations. Based on the change of ³He/⁴He ratio and lack of ground deformation, we consider the latter might be more plausible.     

A simple method for the collection and analysis of volcanic gas samples

Investigations into the chemistry of volcanic gases depend on the availability of complete and accurate analyses of volcanic exhalations. The wide variety of sampling and analysis methods hitherto used, often supplying only partial analyses of low precision, made intercomparison, and thus a systematic study of volcanic gases, difficult. With the method proposed here, complete volcanic gas samples are obtained permitting the accurate determination of all major species by standard analytical methods without the need for highly specialised ancillary equipment. The samples are collected in evacuated 300 ml pyrex flasks through titanium tubes deeply inserted into the gas vent. Two types of flask are used, a single compartment flask allowing the easy determination of the major constituents and containing 50 ml 4 N NaOH, and a double compartment flask for the separate analysis of the sulfur species and containing 25 ml 0.1 N As₂O₃ in 1 N HClO₄ in the first, and 50 ml 4 N NaOH in the second compartment. Non-absorbed gases are determined by gas chromatography, the rest by standard analytical procedures. The determination of H₂O, CO₂, SO₂, SO₂, S₂, H₂S, HCl, HF, H₂, N₂, O₂, CH₄, CO and NH₂ is described.