Material sources of escaped gases from Tianchi volcanic geothermal area, Changbai Mountains

On the basis of the chemical components and stable isotopic compositions of escaped gases from the Tianchi volcanic geothermal area, the material sources of these gases are discussed, presenting that they are mainly derived from the residual mantle-derived magma in the crust; Changbai geothermal area may be directly interlinked with the eruption canal in history; there is a stable reservoir of the geothermal water and the deep-seated gases under the Changbai geothermal area, with water temperature of the reservoir being about (166 ± 9)°C. Project supported by the National Natural Science Foundation of China.     

Fumarolic activity of Avachinsky and Koryaksky volcanoes, Kamchatka, from 1993 to 1994

 Volcanic gas and condensate samples were collected in 1993–1994 from fumaroles of Koryaksky and Avachinsky, basaltic andesite volcanoes on the Kamchatka Peninsula near Petropavlovsk–Kamchatsky. The highest-temperature fumarolic discharges, 220  °C at Koryaksky and 473  °C at Avachinsky, are water-rich (940–985 mmol/mol of H₂O) and have chemical and isotopic characteristics typical of Kamchatka–Kurile, high- and medium-temperature volcanic gases. The temperature and chemical and water isotopic compositions of the Koryaksky gases have not changed during the past 11 years. They represent an approximate 2 : 1 mixture of magmatic and meteoric end members. Low-temperature, near-boiling-point discharges of Avachinsky Volcano are water poor (≈880 mmol/mol); Their compositions have not changed since the 1991 eruption, and are suggested to be derived from partially condensed magmatic gases at shallow depth. Based on a simple model involving mixing and single-step steam separation, low water and high CO₂ contents, as well as the observed Cl concentration and water isotopic composition in low-temperature discharges, are the result of near-surface boiling of a brine composed of the almost pure condensed magmatic gas. High methane content in low-temperature Avachinsky gases and the 220  °C Koryaksky fumarole, low C isotopic ratio in CO₂ at Koryaksky (–11.8‰), and water isotope data suggest that the "meteoric" end member contains considerable amounts of the regional methane-rich thermal water discovered in the vicinity of both volcanoes. Received: 2 May 1996 / Accepted: 5 November 1996     

Gas and hydrogen isotopic analyses of volcanic eruption clouds in Guatemala sampled by aircraft

Gas samples were collected by aircraft entering volcanic eruption clouds of three Guatemalan volcanoes. Gas chromatographic analyses show higher H₂ and S gas contents in ash eruption clouds and lower H₂ and S gases in vaporous gas plumes. H isotopic data demonstrate lighter isotopic distribution of water vapor in ash eruption clouds than in vaporous gas plumes. Most of the H₂O in the vaporous plumes is probably meteoric. The data are the first direct gas analyses of explosive eruptive clouds, and demonstrate that, in spite of atmospheric admixture, useful compositional information on eruptive gases can be obtained using aircraft.     

Origin of natural sulphur-bearing immiscible inclusions and H2S in oolite gas reservoir, Eastern Sichuan

Based on results of microscopic observation and laser Raman analysis about fluid inclusions, multiple special forms of immiscible inclusions that contain sulphur, liquid hydrocarbon, bitumen, etc. were discovered in samples collected from the H₂S gas reservoir-containing carbonates in the Lower Triassic Feixianguan Formation in the Jinzhu-Luojia area, Kai County, Sichuan Province. Based on the lithology and burial history of the strata involved as well as measurement results of homogenization temperature of fluid inclusions, bitumen reflectivity, etc., it is concluded that the H₂S in the gas reservoir resulted from the thermal reaction between hydrocarbons in reservoir and CaSO₄ in the gypsum-bearing dolostone section at the high temperature (140°C–17°C) oil-cracked gas formation stage in Late Cretaceous. Thereafter, research on a great number of immiscible inclusions in the reservoir reveals that elemental sulphur resulted from oxidation of part of the earlier-formed H₂S and further reaction between sulphates, hydrocarbons and H₂S in geological fluids in H₂S-bearing gas reservoir at a temperature of 86°C–89°C and a pressure of 340×10⁵Pa and during the regional uplift stage as characterized by temperature decrease and pressure decrease in Tertiary. Meanwhile, gypsum, anhydrite and calcite formed at this stage would trap particles like elemental sulphur and result in a variety of special forms of immiscible inclusions, and these inclusions would contain information concerning the complexity of the fluids in the reservoir and the origin of H₂S and natural sulphur in the gas reservoir.     

Geochemical Changes in Spring Water Associated with the 2000 Eruption of the Miyakejima Volcano, Japan

Water was sampled from eight springs and a lake in volcanic Miyakejima Island of Japan after the 2000 eruption. Major chemical and isotopic compositions of the water were analyzed. Significant increases of sulfate ion are observed in several springs where the thickness of ejecta exceeds 32 mm. A good relationship of Cl/S mole ratios between spring water and leachate of the ejecta is observed. Sulfur isotopic compositions of the spring water become close to that of leachate of the ejecta as time elapses after the eruption. Consequently the sources of the added sulfate ion in the spring water after the eruption are interpreted to be anhydrite and adhered sulfur of the ejecta.     

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.     

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

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

Implication of the temporal sulphur isotopic variation during the 2000 eruption of Miyakejima Volcano, Japan

Abstract   The variation of sulphur isotopic composition during the 2000 eruption of the Miyakejima Volcano was examined in order to monitor the temporal change of the volcanic activity. The δ³⁴S values of water-soluble sulphate leached from volcanic ash effused during intermittent eruptions from July to September 2005 range from +5 to +11‰ with a fluctuation of ca 3‰ within a single eruption. The δ³⁴S value of sulphuric acid mist collected with 'Cu-metal trap' placed on the flank of the volcano from December 2000 to January 2001 is +6.2‰. These sulphur isotopic compositions of sulphate, which were isotopically equilibrated in the subvolcanic hydrothermal system, indicate that the temperature of the hydrothermal system beneath the caldera increased after the period of intermittent phreatic and phreatomagmatic eruptions. Then, the δ³⁴S value of sulphuric acid trapped from January to March 2001 was +9.0‰ and the δ³⁴S value of water-soluble sulphate on volcanic ash emitted with minor eruption in May 2001 was +11.0‰, suggesting a decrease in temperature of the subvolcanic hydrothermal system.     

Geochemistry of gases and waters discharged by the mud volcanoes at Paternò, Mt. Etna (Italy)

 Approximately 20 km south of Mt. Etna craters, at the contact between volcanic and sedimentary formations, three mud volcanoes discharge CO₂-rich gases and Na–Cl brines. The compositions of gas and liquid phases indicate that they are fed by a hydrothermal system for which temperatures of 100–150  °C were estimated by means of both gas and solute geothermometry. The hydrothermal system may be associated with CO₂-rich groundwaters over a large area extending from the central part of Etna to the mud volcanoes. Numerous data on the He, CH₄, CO₂ composition of the gases of the three manifestations, sampled over the past 5 years, indicate clearly that variations are due to separation processes of a CO₂-rich gas phase from the liquid. The effects of these processes have to be taken into account in the interpretation of the monitoring data collected for the geochemical surveillance of Etna volcano. Received: 4 September 1995 / Accepted: 14 February 1996     

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.     

East Pacific Rise at latitude 21°N: isotopic composition and origin of the hydrothermal sulphur

The sulphur isotope composition of 16 pyrite and chalcopyrite samples from recent sulphide deposits (“Cyana”—project RITA) and active sulphide mineralisation (“Alvin”—project RISE) associated with hydrothermal sources at 380±30°C on the East Pacific Rise at latitude 21°N have been measured. The³⁴S/³²S ratios are relatively uniform and essentially identical for both sites: δ³⁴S=+1.4to3.0%. (CDT), mean +2.1‰. The sulphides were analysed after the majority of the very numerous micro-inclusions of anhydrite had been removed.Two independent physico-chemical analyses of the data demonstrate that about 90% of the sulphur was leached from the basaltic host rocks by the circulating seawater-hydrothermal fluids.     

Origin of a native sulfur chimney in the Kueishantao hydrothermal field, offshore northeast Taiwan

Analyses of rare earth and trace element concentrations of native sulfur samples from the Kueishantao hydrothermal field were performed at the Seafloor Hydrothermal Activity Laboratory of the Key Labo-ratory of Marine Geology and Environment, Institute of Oceanology, Chinese Academy of Sciences. Using an Elan DRC II ICP-MS, and combining the sulfur isotopic compositions of native sulfur samples, we studied the sources and formation of a native sulfur chimney. The results show, when comparing them with native sulfur from crater lakes and other volcanic areas, that the native sulfur content of this chimney is very high (99.96%), the rare earth element (REE) and trace element constituents of the chimney are very low (ΣREE<21×10?9), and the chondrite-normalized REE patterns of the native sulfur samples are similar to those of the Kueishantao andesite, implying that the interaction of subseafloor fluid-andesite at the Kueishantao hydrothermal field was of short duration. The sulfur isotopic compo-sitions of the native sulfur samples reveal that the sulfur of the chimney, from H2S and SO2, originated by magmatic degassing and that the REEs and trace elements are mostly from the Kueishantao ande-site and partly from seawater. Combining these results with an analysis of the thermodynamics, it is clear that from the relatively low temperature (<116 ℃ ), the oxygenated and acidic environment is favorable for formation of this native sulfur chimney in the Kueishantao hydrothermal field.     

Geochemical evidence for mixing of magmatic fluids with seawater,Nisyros hydrothermal system,Greece

The chemical and isotopic compositions (δD_H2O, δ¹⁸O_H2O, δ¹⁸O_CO2, δ¹³C_CO2, δ³⁴S, and He/N₂ and He/Ar ratios) of fumarolic gases from Nisyros, Greece, indicate that both arc-type magmatic water and local seawater feed the hydrothermal system. Isotopic composition of the deep fluid is estimated to be +4.9±0.5‰ for δ¹⁸O and ?11±5‰ for δD corresponding to a magmatic water fraction of 0.7. Interpretation of the stable water isotopes was based on liquid–vapor separation conditions obtained through gas geothermometry. The H₂–Ar, H₂–N₂, and H₂–H₂O geothermometers suggest reservoir temperatures of 345±15 °C, in agreement with temperatures measured in deep geothermal wells, whereas a vapor/liquid separation temperature of 260±30 °C is indicated by gas equilibria in the H₂O–H₂–CO₂–CO–CH₄ system. The largest magmatic inputs seem to occur below the Stephanos–Polybotes Micros crater, whereas the marginal fumarolic areas of Phlegeton–Polybotes Megalos craters receive a smaller contribution of magmatic gases.     

Seismicity and fluid geochemistry at Lassen Volcanic National Park,California: Evidence for two circulation cells in the hydrothermal system

Seismic analysis and geochemical interpretations provide evidence that two separate hydrothermal cells circulate within the greater Lassen hydrothermal system. One cell originates south to SW of Lassen Peak and within the Brokeoff Volcano depression where it forms a reservoir of hot fluid (235–270 °C) that boils to feed steam to the high-temperature fumarolic areas, and has a plume of degassed reservoir liquid that flows southward to emerge at Growler and Morgan Hot Springs. The second cell originates SSE to SE of Lassen Peak and flows southeastward along inferred faults of the Walker Lane belt (WLB) where it forms a reservoir of hot fluid (220–240 °C) that boils beneath Devils Kitchen and Boiling Springs Lake, and has an outflow plume of degassed liquid that boils again beneath Terminal Geyser. Three distinct seismogenic zones (identified as the West, Middle, and East seismic clusters) occur at shallow depths (< 6 km) in Lassen Volcanic National Park, SW to SSE of Lassen Peak and adjacent to areas of high-temperature (≤ 161 °C) fumarolic activity (Sulphur Works, Pilot Pinnacle, Little Hot Springs Valley, and Bumpass Hell) and an area of cold, weak gas emissions (Cold Boiling Lake). The three zones are located within the inferred Rockland caldera in response to interactions between deeply circulating meteoric water and hot brittle rock that overlies residual magma associated with the Lassen Volcanic Center. Earthquake focal mechanisms and stress inversions indicate primarily N–S oriented normal faulting and E–W extension, with some oblique faulting and right lateral shear in the East cluster. The different focal mechanisms as well as spatial and temporal earthquake patterns for the East cluster indicate a greater influence by regional tectonics and inferred faults within the WLB. A fourth, deeper (5–10 km) seismogenic zone (the Devils Kitchen seismic cluster) occurs SE of the East cluster and trends NNW from Sifford Mountain toward the Devils Kitchen thermal area where fumarolic temperatures are ≤ 123 °C. Lassen fumaroles discharge geothermal gases that indicate mixing between a N₂-rich, arc-type component and gases derived from air-saturated meteoric recharge water. Most gases have relatively weak isotopic indicators of upper mantle or volcanic components, except for gas from Sulphur Works where δ¹³C–CO₂, δ³⁴S–H₂S, and δ¹⁵N–N₂ values indicate a contribution from the mantle and a subducted sediment source in an arc volcanic setting.     

Eruptive history of Fisher Caldera,Alaska, USA

New field, compositional, and geochronologic data from Fisher Caldera, the largest of 12 Holocene calderas in Alaska, provide insights into the eruptive history and formation of this volcanic system. Prior to the caldera-forming eruption (CFE) 9400 years ago, the volcanic system consisted of a cluster of several small (∼3 km³) stratocones, which were independently active between 66±144 and 9.4±0.2 ka. Fisher Caldera formed through a single eruption, which produced a thick dacitic fall deposit and two pyroclastic-flow deposits, a small dacitic flow and a compositionally mixed basaltic-dacitic flow. Thickness and grain-size data indicate that the fall deposit was dispersed primarily to the northeast, whereas the two flows were oppositely directed to the south and north. After the cataclysmic eruption, a lake filled much of the caldera during what may have been a significant quiescent period. Volcanic activity from intracaldera vents gradually resumed, producing thick successions of scoria fall interbedded with lake sediments. Several Holocene stratocones have developed; one of which has had a major collapse event. The caldera lake catastrophically drained when a phreatomagmatic eruption generated a large wave that overtopped and incised the southwestern caldera wall. Multiple accretionary-lapilli-bearing deposits inside and outside the caldera suggest significant Holocene phreatomagmatic activity. The most recent eruptive activity from the Fisher volcanic system was a small explosive eruption in 1826, and current activity is hydrothermal. Late Pleistocene to Holocene magma eruption rates range from 0.03 to 0.09 km³ ky⁻¹ km⁻¹, respectively. The Fisher volcanic system is chemically diverse, ∼48–72 wt.% SiO₂, with at least seven dacitic eruptions over the last 82±14 ka that may have become more frequent over time. Least squares calculations suggest that prior to the CFE, Fisher Volcano products were not derived from a single, large magma reservoir, and were likely erupted from multiple, compositionally independent magma reservoirs. After the CFE, the majority of products appear to have derived from a single reservoir in which magma mixing has occurred.     

An example of health hazard: People killed by gas during a phreatic eruption: Diëng plateau (Java,Indonesia), February 20th 1979

On February 20th, 1979, 142 inhabitants of Dieng Plateau (Indonesia) were asphyxiated by poisonous gases during a mild phreatic eruption. From later fields gas collection and analysis, the casualties are considered to be due to CO₂ rich volcanic gases.     

Geochemistry of the volcano-hydrothermal system of El Chichón Volcano, Chiapas, Mexico

 The 1982 eruption of El Chichón volcano ejected more than 1 km³ of anhydrite-bearing trachyandesite pyroclastic material to form a new 1-km-wide and 300-m-deep crater and uncovered the upper 500 m of an active volcano-hydrothermal system. Instead of the weak boiling-point temperature fumaroles of the former lava dome, a vigorously boiling crater spring now discharges  / 20 kg/s of Cl-rich (∼15 000 mg/kg) and sulphur-poor ( / 200 mg/kg of SO₄), almost neutral (pH up to 6.7) water with an isotopic composition close to that of subduction-type magmatic water (δD=–15‰, δ¹⁸O=+6.5‰). This spring, as well as numerous Cl-free boiling springs discharging a mixture of meteoric water with fumarolic condensates, feed the crater lake, which, compared with values in 1983, is now much more diluted (∼3000 mg/kg of Cl vs 24 030 mg/kg), less acidic (pH=2.6 vs 0.56) and contains much lower amounts of S ( / 200 mg/kg of SO₄, vs 3550 mg/kg) with δ³⁴S=0.5–4.2‰ (+17‰ in 1983). Agua Caliente thermal waters, on the southeast slope of the volcano, have an outflow rate of approximately 100 kg/s of 71  °C Na–Ca–Cl water and are five times more concentrated than before the eruption (B. R. Molina, unpublished data). Relative N₂, Ar and He gas concentrations suggest extensional tectonics for the El Chichón volcanic centre. The ³He/⁴He and ⁴He/²⁰Ne ratios in gases from the crater fumaroles (7.3R_a, 2560) and Agua Caliente hot springs (5.3R_a, 44) indicate a strong magmatic contribution. However, relative concentrations of reactive species are typical of equilibrium in a two-phase boiling aquifer. Sulphur and C isotopic data indicate highly reducing conditions within the system, probably associated with the presence of buried vegetation resulting from the 1982 eruption. All Cl-rich waters at El Chichón have a common source. This water has the appearence of a "partially matured" magmatic fluid: condensed magmatic vapour neutralized by interaction with fresh volcaniclastic deposits and depleted in S due to anhydrite precipitation. Shallow ground waters emerging around the volcano from the thick cover of fresh pumice deposits (Red waters) are Ca–SO₄–rich and have a negative oxygen isotopic shift, probably due to ongoing formation of clay at low temperatures. Received: 21 July 1997 / Accepted: 4 December 1997     

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.     

Brownish discoloration of the summit crater lake of Mt. Shinmoe-dake,Kirishima Volcano,Japan: volcanic–microbial coupled origin

A drastic change in lake water color from blue-green to brown was observed in the summit crater lake of Mt. Shinmoe-dake, Kirishima Volcano about 8 months after its 2008 eruption. The color change lasted for about 2 months (April–June 2009). The discoloration was attributed to a brownish color suspension that had formed in the lake water. X-ray fluorescence and Fourier transform infrared analyses of a sample of the suspension identified schwertmannite (Fe₈O₈(OH)₆(SO₄)). A cultivation test of iron-oxidizing bacteria for the sampled lake water with lakebed sediment revealed that the crater lake hosts iron-oxidizing bacteria, which likely participated in schwertmannite formation. We suggest that pyrite (FeS₂) provided an energy source for the iron-oxidizing bacteria since the mineral was identified in hydrothermally altered tephra ejected by the August 2008 eruption. From consideration of these and other factors, the brownish discoloration of the summit crater lake of Mt. Shinmoe-dake was inferred to have resulted from a combined volcanic–microbial process.     

Rare gas isotopes and mass fractionation: An indicator of gas transport into or from a magma

A simple model of mass fractionation may explain the isotopic ratios of rare gases in volcanic materials. Single-stage mass fractionation of atmospheric rare gases predicts an upper limit for²⁰Ne/²²Ne of 10.3 and a lower limit for⁴⁰Ar/³⁶Ar of 280. The rare gas data in volcanic materials seem to support this interpretation.Relatively low⁴⁰Ar/³⁶Ar ratios, as low as 282, have been observed in recent Japanese volcanic rocks. Such a low⁴⁰Ar/³⁶Ar ratio may be explained by mass fractionation of the atmospheric value if the rare gases represent those which were transported into the magma chamber with other volatile elements.Both the amounts and the fractionated rare gas abundance pattern of lighter elements which are observed in pumices from the recent eruption of Mt. Usu, Southern Hokkaido, Japan, suggest the possibility of air injection into its magma chamber. Thus, the fractionation of rare gases in volcanic materials may be a common occurrence, and it must be considered in models for the origin of isotopic differences between rare gases in volcanic materials and the atmosphere.