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.     

Erta'ale lava lake: heat and gas transfer to the atmosphere

Data on uncontaminated samples of volcanic gases can be counted on the fingers of one hand, yet estimation of total volcanic gas flow cannot be made without such data. In this paper the flux of gas from the lava lake to the atmosphere is calculated by a heat budget based on the excess heat loss caused by combustion of H₂ and CO and by the mass rate of loss of other gases on the basis of their ratios to H₂ and CO in the unoxidized gas samples. The estimated rates of loss of H₂O, CO₂, SO₂ and HCl are consistent with the rate of loss of heat if this heat is generated by crystallization and if the initial magma contains concentrations of gas appropriate for submarine basalt from oceanic ridges. The moderate activity of permanent degassing from the two active lava ponds studied gives a lower flux than that of other volcanoes.     

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.     

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».     

A new technique to estimate volcanic gas composition: plume measurements with a portable multi-sensor system

A portable multi-sensor system was developed to measure volcanic plumes in order to estimate the chemical composition and temperature of volcanic gases. The multi-sensor system consists of a humidity–temperature sensor, SO₂ electrochemical sensor, CO₂ IR analyzer, pump and flow control units, pressure sensor, data logger, and batteries; the whole system is light (∼5 kg) and small enough to carry in a medium-size backpack. Volcanic plume is a mixture of atmosphere and volcanic gas; therefore volcanic gas composition and temperature can be estimated by subtracting the atmospheric gas background from the plume data. In order to obtain the contrasting data of the plume and the atmosphere, measurements were repeated in and out of the plume. The multi-sensor technique was applied to measure the plume of Tarumae, Tokachi, and Meakan volcanoes, Hokkaido, Japan. Repeated measurements at each volcano gave a consistent composition with ±10–30% errors, depending on the stability of the background atmospheric conditions. Fumarolic gas samples were also collected at the Tokachi volcano by a conventional method, and we found a good agreement (the difference <10%) between the composition estimated by the multi-sensor technique and conventional method. Those results demonstrated that concentration ratios of major volcanic gas species (i.e., H₂O, CO₂, and SO₂) and temperature can be estimated by the new technique without any complicated chemical analyses even for gases emitted from an inaccessible open vent. Estimation of a more detailed gas composition can be also achieved by the combination of alkaline filter techniques to measure Cl/F/S ratios in the plume and other sensors for H₂S and H₂.     

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.     

Field measurements of volcanic gases. Vulcano Island (Italy), Kilauea (Hawaii,U.S.A.), Merapi (Java,Indonesia)

A field gas chromatograph, built in 1978, was used in the field to directly analyse volcanic gases before water vapor condensation. Tested in Vulcano (Italy), Kilauea (Hawaii) and Merapi (Indonesia), this field measurement technique provides the actual composition of the volcanic gas mixture. The technique avoids the depletion of sulfur gases and the dissolution of the acid gases in the condensed water during the cooling. Thus the mixture of H₂S and SO₂ in fumarolic and high temperature gases (up to 819°C) in equilibrium at the emission temperature was examined.     

Magmatic degassing at Erta 'Ale volcano,Ethiopia

Here we report measurements of the chemical composition and flux of gas emitted from the central lava lake at Erta 'Ale volcano (Ethiopia) made on 15 October 2005. We determined an average SO₂ flux of ∼ 0.69 ± 0.17 kg s^− 1 using zenith sky ultraviolet spectroscopy of the plume, and molar proportions of magmatic H₂O, CO₂, SO₂, CO, HCl and HF gases to be 93.58, 3.66, 2.47, 0.06, 0.19 and 0.04%, respectively, by open-path Fourier transform infrared (FTIR) spectrometry. Together, these data imply fluxes of 7.3, 0.7, 0.008, 0.03 and 0.004 kg s^− 1 for H₂O, CO₂, CO, HCl and HF, respectively. These are the first FTIR spectroscopic observations at Erta 'Ale, and are also some of the very few gas measurements made at the volcano since the early 1970s (Gerlach, T.M., 1980b. Investigation of volcanic gas analyses and magma outgassing from Erta 'Ale lava lake, Afar, Ethiopia. Journal of Volcanology and Geothermal Research, 7(3–4): 415–441). We identify significant increases in the proportion of H₂O in the plume with respect to both CO₂ and SO₂ across this 30-year interval, which we attribute to the depletion of volatiles in magma that sourced effusive eruptions during the early 1970s and/or to fractional magma degassing between the two active pit craters located in the summit caldera.     

Magmatic gas scrubbing: implications for volcano monitoring

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

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.     

Gas composition of Popocatépetl Volcano between 2007 and 2008: FTIR spectroscopic measurements of an explosive event and during quiescent degassing

On December 1, 2007, the solar absorption infrared spectra of the Popocatépetl volcanic plume was recorded during an eruptive event and complementarily on November 17, 2008, the passive quiescent degassing was measured from the same site. A portable FTIR spectrometer with a scanning mirror for fast tracking of the sun provided the flexibility, quality, and simplicity needed for field deployment. Slant columns of the gases SO₂, HCl, HF, and SiF₄ were retrieved and strong differences could be observed when comparing gas ratios in both time periods. During the explosive eruption, the SO₂/HCl ratio was three times greater and the HF/HCl ratio was slightly smaller than during passive degassing.While the ratios among SO₂, HCl, HF, and SiF₄ describe the chemical composition of the volcanic gas mixture, the SiF₄/HF ratio provides information about the equilibrium temperatures of the stored gases which in this study were calculated at 150° and 185 °C for the explosive and quiescent degassing episodes, respectively. We conclude that cooling of lava domes in the crater precedes Vulcanian explosions as suggested by Schaaf et al (2005). Based on SO₂ flux (Grutter et al., 2008) and measurements and data from the November 2008 event, the average fluxes for HCl, HF, SiF₄, and F through quiescent degassing are estimated to be 204, 22.7, 9.8, and 31.7 tons/day, respectively. These values are similar to those reported by Love et al. (1998) more than 10 yrs ago.     

Volcanic gases and sublimates from Showashinzan

Volcanic gases from Showashinzan are qualitatively the same as those liberated from igneous rocks when they are heated in vacuum. Their main components are H₂O, CO₂, and H₂. Then follow HCl, HF, N₂, SO₂, H₂S, S, CH₄, CO, Ar, Si, B, Mg, Na, K, Ca, Al, Fe, P, Br, NH₃, As, Zn, Sr, Ba, Cu, Pb, Sn, Sb, Bi, Ge, Ag, Cr, Ni, Mo, Rn, Ra, etc. They come through fumaroles of high temperature (～750°C.). Metallic compounds deposit as sublimates around the outlet of fumaroles. They are fractionated there according to their thermodynamic properties. When the temperature of gases falls, heavy metal elements deposit before reaching the surface of the earth. Ra is among them. Owing to the contribution of Ra thus depositted, Rn content of vapor is larger in low temperature fumaroles than in high temperature ones. Chemical compounds of H, C, N, O, and S vary their composition according to the condition of temperature and pressure. Sulfur exists as SO₂ more than H₂S. As the temperature of gases falls, SO₂ and H₂ decrease and H₂S increases. Mutual relation among them is ruled by the chemical equilibrium: SO₂+3H₂=H₂S+2H₂O. The structure of Showashinzan is not simple. Some deviations from the general rule are explained in connection with ground water.     

A magmatic source for fumaroles and diffuse degassing from the summit crater of Teide Volcano (Tenerife, Canary Islands): a geochemical evidence for the 2004–2005 seismic–volcanic crisis

The present work reports the results of 15 studies of diffuse CO₂ degassing performed at Teide Volcano crater (Canary Island, Spain) and the chemical and isotopic compositions of fluids discharged from a fumarolic field located at the top of the volcano as measured between 1991 and 2010. A higher contribution of magmatic gases accompanied by enhanced total diffuse CO₂ emissions were observed in relation with a seismic crisis that occurred in Tenerife Island between 2001 and 2005, with the main peak of seismic activity between April and June 2004. A significant pulse in total diffuse CO₂ emission was observed at the crater of Teide (up to 26.3?t day^?1) in 2001. In December 2003, the chemical composition of the Teide fumarole changed significantly, including the appearance of SO₂, an increase in the HCl and CO concentrations and in the C₂H₆/C₂H₄ and C₃H₈/C₃H₆ ratios, and a decrease in the H₂S, CH₄, and C₆H₆ concentrations and in the gas/steam ratio. A few months after a drastic decrease in seismic activity, the SO₂, HCl, and CO concentrations and the C₂H₆/C₂H₄ and C₃H₈/C₃H₆ ratios strongly decreased, whereas the CH₄ and C₆H₆ concentrations and the gas/steam ratios increased. According to the trends shown by both the geochemical parameters and the seismic signals late in the observation period, the risk of a rejuvenation of volcanic activity at Teide is considered to be low. The associated temporal changes in seismic activity and magmatic degassing indicate that geophysical and fluid geochemistry signals in this system are related. Future monitoring programs aimed at mitigating volcanic hazard on Tenerife Island should involve coupled geophysical and geochemical studies.     

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.     

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.     

IDOAS: A new monitoring technique to study the 2D distribution of volcanic gas emissions

Imaging Differential Optical Absorption Spectroscopy (IDOAS) is an optical remote-sensing method using scattered sunlight as light source. It combines a “pushbroom” imaging spectrometer with the DOAS technique and thus allows imaging two-dimensional trace gas distributions, e.g., in volcanic plumes. The highly sensitive and specific detection of many trace gases simultaneously (specific molecules, not just elements, e.g. SO₂, BrO, NO₂, O₃, HCHO, etc.) is possible, and the temporal and spatial variation of these gases can be measured. The IDOAS system presented here enables the taking of two-dimensional images of trace gas distributions in a volcanic plume with a spatial resolution of 100 pixels horizontally × 64 pixels vertically, each with a field of view of 0.087° in horizontal and 0.208° in vertical directions. Therefore, IDOAS provides useful information about the chemical composition and chemical variability in a volcanic plume and allows studying plume dispersal and chemical transformations. The technique was applied to map the SO₂ distribution in the plume of Mt. Etna volcano for the first time in October 2003.     

Magmatic gases extracted and analysed from ocean floor volcanics

Magmatic gases extracted and analysed from basaltic rocks collected in the FAMOUS area near 36°50′ N in the Atlantic ocean show that the total amount of gas included in the samples varies between about 500 ppm to 1600 ppm. The main gaseous phases included in the various types of basalts consist of CO₂ (270–700 ppm), CO (150–800 ppm), HCl (100–1000 ppm), H₂ (0–50 ppm), SO₂ (up to 175 ppm), N₂ (up to about 213 ppm) and traces of hydrocarbons (up to about 24 ppm). The relative amount of CO, CO₂ and SO₂ varies with both the degree of crystallinity of the rock and with fractional crystallization and/or fractional melting. The glassy margin of pillow lavas have a higher CO/CO₂ ratio than the more crystalline interior. The most fractionated rocks of the series rich in clinopyroxene are depleted in the CO/CO₂ ratio and have a higher SO₂ content than do the most mafic end members rich in olivine. Early-formed olivine was crystallized in a reducing environment rich in CO and H₂ with respect to later formed mineral associations. It is likely that the carbon and sulfur oxidation is taking place at a relatively shallow depth during magmatic ascent or during volcanism. The ocean floor volcanics when compared to subaerial basalts are depleted in SO₂ and have on the average ten times more H₂.     

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.     

Différenciation de l’émanation magmatique: réactions H2S + SO2 dans les gaz volcaniques. Vulcano (Italie), 1923–1979

Different systems of gas collection were tested on Vulcano Island (Italy). Sampling flasks do not keep the real H₂S/SO₂ ratio. Warm chemical traps (Sicardi, 1940) and warm field gas chromatography keep the gas samples in equilibrium. A mixture of H₂S and SO₂ is emitted at the crater but at the sea shore H₂S is predominant. Such difference is interpreted as due to the percolation across near-surface water tables. The same gas composition was observed within magmatic gases (Merapi) using identical techniques and the difference of composition at the shore and at the crater can be used to explain different aerosols compositions.     

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.