Chemistry and isotope ratios of sulfur in basalts and volcanic gases at Kilauea volcano,Hawaii

Eighteen basalts and some volcanic gases from the submarine and subaerial parts of Kilauea volcano were analyzed for the concentration and isotope ratios of sulfur. By means of a newly developed technique, sulfide and sulfate sulfur in the basalts were separately but simultaneously determined. The submarine basalt has 700 ± 100 ppm total sulfur with δ³⁴S_Σs of $\text{0.7 ± 0.1 ‰}$. The sulfate/sulfide molar ratio ranges from 0.15 to 0.56 and the fractionation factor between sulfate and sulfide is $\text{+7.5 ± 1.5‰}$. On the other hand, the concentration and δ³⁴S_Σs values of the total sulfur in the subaerial basalt are reduced to 150 ± 50 ppm and $\text{?0.8 ± 0.2‰}$, respectively. The sulfate to sulfide ratio and the fractionation factor between them are also smaller, 0.01 to 0.25 and +3.0‰, respectively. Chemical and isotopic evidence strongly suggests that sulfate and sulfide in the submarine basalt are in chemical and isotopic equilibria with each other at magmatic conditions. Their relative abundance and the isotope fractionation factors may be used to estimate the $\text{?o}{}_2$ and temperature of these basalts at the time of their extrusion onto the sea floor. The observed change in sulfur chemistry and isotopic ratios from the submarine to subaerial basalts can be interpreted as degassing of the SO₂ from basalt thereby depleting sulfate and ³⁴S in basalt.The volcanic sulfur gases, predominantly SO₂, from the 1971 and 1974 fissures in Kilauea Crater have δ³⁴S values of 0.8 to 0.9%., slightly heavier than the total sulfur in the submarine basalts and definitely heavier than the subaerial basalts, in accord with the above model. However, the δ³⁴S value of sulfur gases (largely SO₂) from Sulfur Bank is 8.0%., implying a secondary origin of the sulfur. The δ³⁴S values of native sulfur deposits at various sites of Kilauea and Mauna Loa volcanos, sulfate ions of four deep wells and hydrogen sulfide from a geothermal well along the east rift zone are also reported. The high δ³⁴S values (+5 to +6%._o) found for the hydrogen sulfide might be an indication of hot basaltseawater reaction beneath the east rift zone.     

Oxygen isotope study of metamorphic and granitic rocks of the Yanai district in the Ryoke belt,Japan

¹⁸O/¹⁶O ratios have been obtained for 134 whole-rocks and minerals from metamorphic and granitic rocks of the Yanai district in the Ryoke belt, Southwest Japan. The ¹⁸O/¹⁶O ratios of pelitic rocks of the marginal metamorphic zone decrease progressively with increasing metamorphic grade. In the gneiss-granite complex (zone of migmatite [1]), the most characteristic feature of the rocks is that oxygen isotopic homogenization proceeds on both local and regional scales in parallel with “granitization” or chemical homogenization. Granitic rocks of various origin are fairly uniform in isotopic composition with δ ¹⁸O of quartz of 12 to 14‰ (SMOW) and δ ¹⁸O of biotite of 7 to 9‰ and are about 3 to 4‰ enriched in ¹⁸O compared to other Cretaceous granites of non-metamorphic terranes in Japan. The high ¹⁸O/¹⁶O ratios of granitic rocks of this district were discussed in relation to the ¹⁸O-depletion in metasediments. Oxygen isotopic fractionations among coexisting minerals from various rock-types of the gneiss-granite complex indicate that these minerals were formed under near isotopic equilibrium at a temperature of about 600 to 700° C. Some abnormal fractionations of quartz-biotite pairs also were obtained for rocks which had undergone a progressive ¹⁸O-depletion or ¹⁸O-enrichment. This is due to high resistivity of quartz and contrastive susceptibility of biotite to isotopic exchange during metamorphism and “granitization”.     

Measurement of elastic properties of single-crystal CaO up to 1200 K

The elastic moduli of a single-crystal calcium oxide, CaO, are measured in the temperature range from 300 to 1200 K (1.8 times of the Debye temperature) by the resonant sphere technique (RST). The lowest 18 modes are identified in the frequency range from 0.6 to 1.4 MHz for the vibrating spherical specimen, which is 5.6564 mm in diameter and 3.3493 g/cm³ in density at room temperature, and the resonant frequencies are traced as a function of temperature. The adiabatic elastic moduli are determined in the present temperature range from the observed frequencies by inversion calculations. Most of the elastic moduli, except forC ₁₂ modulus, decrease as temperature increases. The temperature curves ofC _s andC ₄₄ moduli cross at 372 K. This means that the CaO specimen has an isotropic elasticity at the temperature. The temperature derivatives (?C ₁₁/?T) _P and (?C _s/?T) _P become slightly less negative with temperature increase and (?C _s /?T) _P and (?C ₄₄/?T) _P are almost constant. Combining the present elastic data with thermal expansion and specimen heat capacity data of CaO, we present the temperature dependence of thermodynamic parameters important in the studies of earth's interior.     

Meteoric hydrothermal origin of calcites in “Green Tuff” formations,Miocene age,Japan

Oxygen and carbon isotope compositions were determined for calcites from the Green Tuff formations of Miocene age in Japan. Values of ¹⁸O from 24 calcites in altered rocks from 5 districts range from –2 to +16_SMOW, in most cases from 0 to +8_SMOW. The low ¹⁸O values rule out the possibility of their low-temperature origin or any significant contribution of magmatic fluid in the calcite precipitation. These values, coupled with their mineral assemblages, suggest that the calcites formed from meteoric hydrothermal solutions which caused propylitic alteration after the submarine strata became emergent.Values of ¹³C from the calcites show a wide variation from –17 to 0_PDB. Calcites from different districts have different ranges of ¹³C values, indicating that there was no homogeneous reservoir of carbon at the time the calcite formed, and that the carbon had local sources. Carbon isotopic compositions of calcite within ore deposits in the Green Tuff formations range from –19 to 0_PDB, similar to those of calcite in the altered rocks in the same district, suggesting that the carbon in ore calcites was likely supplied from the surrounding rocks through activity of meteoric hydrothermal solutions.     

Hydrogen, Oxygen and Sulfur Isotope Studies of Seafloor Hydrothermal System at the Desmos Caldera, Manus Back-arc Basin, Papua New Guinea: An Analogue of Terrestrial Acid Hot Crater-lake

Abstract. The Onsen site is an active submarine hydrothermal system hosted by the Desmos caldera in the Eastern Manus Basin, Papua New Guinea. The hydrothermal fluid is very acidic (pH=1.5) and abundant native sulfur is deposited around the vent. The δ³⁴S values of native sulfur range from -6.5 to -9.3 %o. δ³⁴S values of H₂S and SO₄ in the hydrothermal fluid are -4.3 to -9.9 %o and +18.6 to +20.0 %o, respectively. These δ³⁴S values are significantly lower than those of the other hydrothermal systems so far reported. These low δ³⁴S values and the acidic nature of the vent fluids suggest that volcanic SO₂ gas plays an important role on the sulfur isotope systematic of the Onsen hydrothermal system. Relationship among the δ³⁴S values of S-bearing species can be successively explained by the model based on the disproportionation reaction starting from the volcanic SO₂ gas. The predicted δ³⁴S values of SO₂ agree with the measured whole rock δ³⁴S values. δD and δ¹⁸O values of clay minerals separated from the altered rock samples also suggest the contribution of the magmatic fluid to the hydrothermal system. Present stable isotopic study strongly suggests that the Onsen hydrothermal site in the Desmos caldera is a magmatic submarine hydrothermal system.     

Spatiotemporal characteristics of the displacement field revealed with principal component analysis and the mode-rotation technique

Principal component analysis (PCA) was applied to the displacement field recorded at 147 GPS stations in the Kanto-Tokai district, Japan, for the period from January 1999 to February 2003. Some prominent geophysical events occurred during this period. Using PCA, we attempted to decompose the displacement field into some representative spatial modes and their corresponding temporal modes to quantitatively extract the primary geophysical events that have caused rapid crustal deformation in this region. The displacement field was roughly decomposed into modes corresponding to the following three major events: (1) The Miyake-Kozu volcanic event, which occurred in the region south of Tokyo in 2000. It included large-scale dyke intrusion and intensive earthquake swarm between the Miyakejima and Kozushima islands. (2) The Tokai slow-slip event, which is considered to have begun just after the Miyake-Kozu volcanic event and is ongoing as of November 2005. It occurred on the boundary between the subducting Philippine Sea Plate and the overriding Eurasian (Amurian) Plate in the Tokai district. (3) The Boso slow-slip event, which lasted for approximately 10 days in October 2002. It occurred on the boundary between the subducting Pacific Plate and the overriding North American Plate near the Boso Peninsula. In the decomposition process, we combined the mode-rotation technique with ordinary PCA. This is because PCA causes contamination between modes, i.e., a mode obtained with PCA is contaminated by other modes. For example, the first principal mode corresponding to the Miyake-Kozu volcanic event, which is by far the largest in magnitude, was clearly seen in many other modes. In order to remove such contamination, we applied the mode-rotation technique, in which the principal axes derived from PCA are rotated so as to minimize the correlation coefficients between different temporal modes for a time period in which some prominent change occurs. Combining the mode-rotation technique with PCA exhibited a better performance in separating the displacement field.     

New discoveries in dynamics of an M8 earthquake-phenomena and their implications from the 2003 Tokachi-oki earthquake using a long term monitoring cabled observatory

At the 2003 Tokachi-oki earthquake of M8, seafloor phenomena such as a generation process of tsunami, seafloor uplifts, turbidity current, etc., were observed using a cabled observatory installed on the seafloor. The turbidity current was observed as a benthic storm caused presumably by the mainshock. The seafloor uplifts were observed at the mainshock and continuously after the mainshock. The uplifts were 0.35, 0.37, and 0.12 m for epicentral distances of 25.5, 31.4, and 81.7 km, respectively. After the mainshock, a continuous uplift of the seafloor is observed at all three pressure gauge locations indicating that there was a change in the state of friction on the plate boundary interface by the mainshock. In this paper, we first show what was observed using the cabled observatory installed right above the focal area of the earthquake, and then we discuss to summarize these phenomena associated with the earthquake, its possible causes, and future directions in long term monitoring of seismogenic processes.     

Underground storage of carbon dioxide in depleted natural gas reservoirs and in useless aquifers

Depleted reservoirs of natural gas and petroleum can provide excellent traps for carbon dioxide. Deep aquifers, which are not used due to high salinity, can host larger amount of the carbon dioxide under their high formation pressure than natural gas and oir reservoirs. Small fraction of aquifers in sedimentary basins in the world are enough to host about 87 gigaton-C of carbon dioxide.

A preliminary technical and economical survey on the carbon dioxide injection system suggests that the energy requirement for carbon dioxide injection into subterranean aquifers is about 269 kWh/ton-C and that the investment and operation costs for system are 79 $/ton-C. By our preliminary cost estimation in Japan, the CO₂-emission-free electricity generation may become possible with a cost increase of 35% for natural-gas-fired power station, and of 60% for coal-fired-power station.