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.     

Experimental determination of the rate and equilibrium fractionation factors of sulfur isotope exchange between sulfate and sulfide in slightly acid solutions at 300°C and 1000 bars

A sulfur isotope fractionation of 20.0 ± 0.2‰ was measured between aqueous sulfide and sulfate at 300°C and 1000 bars using gold-cell hydrothermal solution equipment. The value is 2‰ smaller than previously published values. Rates of exchange were determined as a function of pH and total sulfur content. Initial mean ³⁴S concentration was changed to approach equilibrium from two directions. Half-times ranged from 3.4 to 8.2 days, with shorter times obtained for more acid and more concentrated solutions.The sulfate-sulfide isotope temperature scale based on theory should be revised according to this new fractionation factor. The rate data permit assessment of the extent to which equilibrium may be attained in some natural systems. For example, the lack of agreement between temperatures based on sulfide mineral pairs and sulfide-sulfate mineral pairs from Kuroko ore deposits of Japan might imply that the residence time of sulfate and sulfide in Kuroko solutions was not longer than 1000 years, if the present kinetic data are correct. Geothermal systems such as the Wairakei system of New Zealand may reach sulfur isotope equilibrium between sulfate and sulfide in 300 years at 300°C, but would be increasingly removed from equilibrium at lower temperatures if residence times were 300 years or less.     

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”.     

Origin of waters responsible for serpentinization of the Izu-Ogasawara-Mariana forearc seamounts in view of hydrogen and oxygen isotope ratios

Many serpentinite seamounts occur over a region 20–120 km west of the trench axis in the Izu-Ogasawara-Mariana forearc regions. The hydrogen and oxygen isotopic compositions of serpentine from these regions indicate that there are at least two kinds of waters responsible for serpentinization: seawater and water derived from dehydration of the descending slab. Serpentine from two Mariana and two Torishima samples with microscopically ductile and sheared texture (sheared-type) have lowerδD(−63to−52‰) and slightly higherδ18O values (+6.1 to +8.2‰) than that of other nine Ogasawara samples with mesh texture (mesh-type) (δD= −43to−49‰ andδ¹⁸O= +5.8to+6.7‰). This suggests that the sheared-type serpentine with lowerδD and slightly higherδ¹⁸O values was formed within the wedge mantle by interaction with water derived from a descending slab. The sheared texture is likely to have been produced during diapiric uplift. The unaltered portion of the ultramafic bodies later interacted with seawater after emplacement at or near the seafloor, resulting in formation of the mesh-type serpentine with higherδD values.     

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.     

3-D MHD SIMULATION OF X-TYPE COALESCENCE OF TWO CURRENT-LOOPS

We present simulation results of X-type coalescence of two current-loops, by using a 3-D resistive MHD code. The results are compared with the limb flare observed by Yohkoh on 2 August, 1993 at 08:30 UT, which is a good example of partial X-type coalescence. It is shown that the maximum temperature enhancement near the cross-point of the two loops, obtained from the simulation, agrees well with the observations when the plasma is 0.08.     

Lower crustal fluid distribution in the northeastern Japan arc revealed by high-resolution 3D seismic tomography

The Ou Backbone Range strikes northwards through the central northeastern Japan arc and is bounded on both sides by the active reverse Uwandaira and Sen'ya faults. We have applied a traveltime inversion method (seismic tomography) with spatial velocity correlation to active and passive seismic data in order to investigate a three-dimensional (3-D) velocity structure. The data set contains 33,993 P- and 18,483 S-wave arrivals from 706 natural sources and 40 blasts, as well as 2803 P-wave traveltime data from 10 explosions detonated during the 1997 controlled source experiment. The traveltime inversion reveals a zone beneath the Ou Backbone Range in which P-wave velocities (V_P) are approximately 6–8% lower than the average velocity at equivalent depths. The low V_P and a low V_P to S-wave velocity (V_S) ratio (V_P/V_S) of about 1.65 suggest the presence of aqueous fluids in the middle crust.     

Oxygen isotope variations in magmatic differentiation processes of the volcanic rocks in Japan

The ¹⁸O/¹⁶O ratios were analyzed for 35 volcanic rocks from the Izu-Hakone region, Oki-Dogo Island, Asama Volcano and Kiso-Ontake Volcano in the Japanese Islands. The ¹⁸O-enrichment in magma during crystallization differentiation is recognized in every rock series. The magnitude of solid-liquid isotope fractionation in the magma of tholeiite series is similar to that of alkali rock series, while the apparent isotope fractionation of calc-alkali rock series is larger than that of the above two series. The ¹⁸O value of the tholeiite magma in the Izu- Hakone region is +5.7 relative to SMOW, which suggests its origin from the fresh upper mantle material. The primary magma of the calc-alkali rock series in Asama Volcano is assumed to have the ¹⁸O value similar to or slightly higher than that of the Izu-Hakone primary magma. The alkali rock series of Oki-Dogo Island in the continental side of the island arc is by 1 heavier than the Izu-Hakone rock suite. This may imply that Oki-Dogo rock series might have exchanged their oxygen with ¹⁸O-rich crustal materials, or they might have originated from somewhat ¹⁸O-rich upper mantle material.     

Geology and age model of the Lower Pleistocene Nojima,Ofuna, and Koshiba Formations of the middle Kazusa Group,a forearc basin‐fill sequence on the Miura Peninsula,the Pacific side of central Japan

We present field and core observations, nannofossil biostratigraphy, and stable oxygen isotope fluctuations in foraminiferal tests to describe the geology and to construct an age model of the Lower Pleistocene Nojima, Ofuna, and Koshiba Formations (in ascending order) of the middle Kazusa Group, a forearc basin‐fill succession, exposed on the northern Miura Peninsula on the Pacific side of central Japan. In the study area, the Nojima Formation is composed of sandy mudstone and alternating sandy mudstone and mudstone, the Ofuna Formation of massive mudstone, and the Koshiba Formation of sandy mudstone, muddy sandstone, and sandstone. The Kazusa Group contains many tuff beds that are characteristic of forearc deposits. Thirty‐six of those tuff beds have characteristic lithologies and stratigraphic positions that allow them to be traced over considerable distances. Examination of calcareous nannofossils revealed three nannofossil datum planes in the sequences: datum 10 (first appearance of large Gephyrocapsa), datum 11 (first appearance of Gephyrocapsa oceanica), and datum 12 (first appearance of Gephyrocapsa caribbeanica). Stable oxygen isotope data from the tests of the planktonic foraminifer Globorotalia inflata extracted from cores were measured to identify the stratigraphic fluctuations of oxygen isotope ratios that are controlled by glacial–interglacial cycles. The observed fluctuations were assigned to marine isotope stages (MISs) 49–61 on the basis of correlations of the fluctuations with nannofossil datum planes. Using the age model obtained, we estimated the ages of 24 tuff beds. Among these, the SKT‐11 and SKT‐12 tuff beds have been correlated with the Kd25 and Kd24 tuff beds, respectively, of the Kiwada Formation on the Boso Peninsula. The Kd25 and Kd24 tuff beds are widely recognized in Pleistocene strata in Japan. We used our age model to date SKT‐11 at 1573 ka and SKT‐12 at 1543 ka.