Occurrence of Halogen-rich Phlogopite in Late Cenozoic Volcanic Rocks in the Japanese Arcs

Abstract. Halogen-rich phlogopite occurs in the groundmass of andesite and dacite lavas from Late Tertiary to Quaternary volcanoes associated with native sulfur and limonite deposits (Shiretoko-Iwozan, Hachimantai, Adatara, Omeshidake, Masaki) and hydrothermal ore deposits (Harukayama, Muineyama, Hishikari) in Japan. The F contents of the halogen-rich phlogopite range from 3.6 to 5.7 wt%, corresponding to atomic F/(F+C1+OH) ratios ranging from 0.45 to 0.69. On the other hand, the Cl contents of the halogen-rich phlogopite are around 0.2 wt%. The atomic Mg/(Mg+Fe) ratios range from 0.69 to 0.83.
The fluorine intercept value [IV(F)] defined by Munoz (1984) of the phlogopites ranges from 0.79 to 3.17, and the chlorine intercept value [IV(Cl)] ranges from -7.11 to -7.77. The observed IV(F) of the phlogopites broadly overlap the range of the IV(F) for biotites from porphyry copper deposits. On the other hand, the observed IV(Cl) are significantly lower than the IV(Cl) for biotites from porphyry copper deposits. Whereas the F contents of the phlogopite appear more prominent compared to the Cl contents, the calculation of halogen intercept values revealed that the phlogopites are enriched in Cl with respect to the element distribution effect of Mg-Fe substitution. Since the degree of Cl enrichment of the phlogopite is more significant compared to that of biotite in porphyry copper deposits, the phlogopites are considered to have formed under the condition of significantly high activity of halogens. Hydrothermal ore deposits may be formed in magmatic hydrothermal system associated with volcanoes where halogen-rich phlogopite is formed by hypersaline fluid.     

Sulfur Isotopic Study of the Toyoha Deposit, Hokkaido, Japan Comparison between the Earlier-Stage and the Later-Stage Veins

Abstract: The sulfur isotopic ratios (δ³⁴S) of ore minerals from the Toyoha deposit, Hokkaido, one of the largest Pb–Zn–Ag polymetallic vein-type deposits in Japan, were studied. More than 90% of the δ³⁴S values of the studied sulfide minerals collected from the Toyoha deposit range from +5 to +9%, with an average of approximately +7% irrespective of the mineral species, veins, elevations, depth, mineralization stages and mineral assemblages. Relatively uniform δ³⁴S values obtained in this study suggest that the reduced aqueous sulfur species predominated over the oxidized sulfur in the ore solution throughout the mineralization stages. Thus, the source of sulfur for the ore sulfides is postulated to be magmatic.
The temperature obtained from the fluid inclusion study and the temperature of the sulfur isotopic geothermometer are not consistent. This suggests that each mineral precipitated under disequilibrated conditions with respect to the sulfur isotope.
The change in redox conditions presumably encountered between the mineralization stages did not account for the isotopic fluctuations since the isotopic exchanges between the oxidized and reduced aqueous sulfurs are much slower than the rate of oxidation of the ore solution.     

Secondary‐volatiles linked metallic iron in eucrites: The dual‐origin metals of Camel Donga

The unique occurrence of abundant (~1 vol%) near‐pure‐Fe metal in the Camel Donga eucrite is more complicated than previously believed. In addition to that component of groundmass metal, scattered within the meteorite are discrete nodules of much higher kamacite abundance. We have studied the petrology and composition of two of these nodules in the form of samples we call CD2 and CD3. The nodules are ovoids 11 (CD2) to 15 (CD3) mm across, with metal, or inferred preweathering metal, abundances of 12–17 vol% (CD2 is unfortunately quite weathered). The CD3 nodule also includes at its center a 5 mm ovoid clumping (6 vol%) of F‐apatite. Both nodules are fine‐grained, so the high Fe metal and apatite contents are clearly not flukes of inadequate sampling. The metals within the nodules are distinctly Ni‐rich (0.3–0.6 wt%) compared to the pure‐Fe (Ni generally 0.01 wt%) groundmass metals. Bulk analyses of three pieces of the CD2 nodule show that trace siderophile elements Ir, Os, and Co are commensurately enriched; Au is enriched to a lesser degree. The siderophile evidence shows the nodules did not form by in situ reduction of pyroxene FeO. Moreover, the nodules do not show features such as silica‐phase enrichment or pyroxene with reduced FeO (as constrained by FeO/MgO and especially FeO/MnO) predicted by the in situ reduction model. The oxide minerals, even in groundmass samples well away from the nodules, also show little evidence of reduction. Although the nodule boundaries are generally sharp, groundmass‐metal Ni content is anti‐correlated with distance from the CD3 nodule. We infer that the nodules represent materials that originated within impactors into the Camel Donga portion of the eucrite crust, but probably were profoundly altered during later metamorphism/metasomatism. Origin of the pure‐Fe groundmass metal remains enigmatic. In situ reduction probably played an important role, and association in the same meteorite of the Fe‐nodules is probably significant. But the fluid during alteration was probably not (as previously modeled) purely S and O, of simple heat‐driven internal derivation. We conjecture a two‐stage metasomatism, as fluids passed through Camel Donga after impact heating of volatile‐rich chondritic masses (survivors of gentle accretionary impacts) within the nearby crust. First, reduction to form troilite may have been triggered by fluids rich in S₂ and CO (derived from the protonodules?), and then in a distinct later stage, fluids were (comparatively) H₂O‐rich, and thus reacted with troilite to form pure‐Fe metal along with H₂S and SO₂. The early eucrite crust was in places a dynamic fluid‐bearing environment that hosted complex chemical processes, including some that engendered significant diversity among metal+sulfide alterations.     

Temporal variations in the current structure and volume transport of the Coastal Oyashio revealed by direct current measurement

Direct current measurements by a shipboard and bottom-mounted acoustic Doppler current profiler and concurrent hydrographic observations with a CTD were conducted off southeastern Hokkaido, Japan, between January and May 2005 to reveal temporal variations in the current structure and volume transport of the Coastal Oyashio (CO). The CO, which has a baroclinic jet structure with southwestward speeds exceeding 90 cm s^?1 and a width of 7–8 km, was associated with a surface-to-bottom density front and was formed on the offshore side of the shelf break. The volume transport of CO (T _CO) was estimated by integrating the fluxes of lower-density water that was trapped against the coast along the density front represented by the 26.2 σ _θ isopycnal line. This transport decreased monotonously from 0.79 Sv (1 Sv = 10⁶ m³ s^?1) in January to 0.21 Sv in March and subsequently to 0.12 Sv in May, possibly due to the decay of the East Sakhalin Current Water in the Okhotsk Sea. Accompanied by a decrease in T _CO, the location of the jet structure associated with the density front moved toward the coast while the maximum speed of the jet decreased and the tilt of the front became more horizontal. Consequently, more saline offshore Oyashio water flowed into the deep part of the shelf area, and the current structure altered from relatively barotropic in winter to baroclinic in spring. This study is the first to estimate the observed volume transport of the CO from direct current measurements.     

Spinifex-like textured metaperidotites from the Higo Metamorphic Rocks,Japan, a possible high-pressure dehydration product of antigorite serpentinite

Spinifex-like textured metaperidotites from the Higo Metamorphic Rocks (HMR), west-central Kyushu, Japan, may be formed by high-pressure dehydration of antigorite, and may indicate deep subduction of serpentinite reaching a pressure–temperature condition of 1.6 GPa and 740–750 °C. Three rock types have been identified based on mineral assemblage and rock texture: Type I (L) consisting of medium-grained (1–5 cm long) olivine + enstatite + chromite ±tremolite with secondary talc and anthophyllite that occurs in low-grade metamorphic rocks of the biotite zone, Type I (H) of coarse-grained (up to 10 cm long) olivine + enstatite (with clinoenstatite lamella) + chromite ±tremolite with secondary talc that occurs in high-grade metamorphic rocks of the garnet-cordierite zone, and Type II composed of Al-spinel + chlorite + olivine + apatite + ilmenite with minor sodic gedrite in the garnet-cordierite zone together with Type I (H). Olivines in all rock types are mostly serpentinized during exhumation. The chromite-olivine thermometer gives 560–690 °C for Type I (L) rocks, and the spinel-olivine thermometer gives 610–740 °C for Type II rocks. The peak metamorphic pressure will be higher than 1.6 GPa based on the location of the experimentally determined invariant point (P = 1.6 GPa and T = 670 °C) of antigorite + forsterite + enstatite + talc + H₂O. This estimate is consistent with the occurrence of chlorite in Type II rocks, which is stable up to 890 °C at 2.0 GPa. The spinifex-like textured metaperidotites occur as small bodies in the low P/T type gneisses, implying tectonic juxtaposition of them probably during exhumation of the HMR. Recent findings of medium pressure (0.9–1.2 GPa) granulites and gneisses from the HMR may indicate that the HMR has a deep root into the wedge mantle from which the spinifex-like textured metaperidotites have derived.     

Fine‐structures of planar deformation features in shocked olivine: A comparison between Martian meteorites and experimentally shocked basalts as an indicator for shock pressure

We performed shock recovery experiments on an olivine‐phyric basalt at shock pressures of 22.2–48.5 GPa to compare with shock features in Martian meteorites (RBT 04261 and NWA 1950). Highly shocked olivine in the recovered basalt at 39.5 and 48.5 GPa shows shock‐induced planar deformation features (PDFs) composed of abundant streaks of defects. Similar PDFs were observed in olivine in RBT 04261 and NWA 1950 while those in NWA 1950 were composed of amorphous lamellae. Based on the present results and previous studies, the width and the abundance of lamellar fine‐structures increased with raising shock pressure. Therefore, these features could be used as shock pressure indicators while the estimated pressures may be lower limits due to no information of temperature dependence. For Martian meteorites that experienced heavy shocks, the minimum peak shock pressures of RBT 04261 and NWA 1950 are estimated to be 39.5–48.5 GPa and 48.5–56 GPa, respectively, which are found consistent with those estimated by postshock temperatures expected by the presence of brown olivine. We also investigated shock‐recovered basalts preheated at 750 and 800 °C in order to check the temperature effects on shock features. The results indicate a reduction in vitrifying pressure of plagioclase and a pressure increase for PDFs formation in olivine. Further temperature‐controlled shock recovery experiments will provide us better constraints to understand and to characterize various features found in natural shock events.     

Velocity of finer fragments from impact

We describe the method and the result of a new experiment to obtain velocity distribution of fine ejecta fragments, from a few to a hundred microns in size, produced from basalt targets by impacts of nylon projectiles at a velocity of 3.7 km s⁻¹. The size distribution of holes perforated by the ejecta fragments on thin films and foils placed around the targets was investigated, and the size-velocity relation was determined with the aid of an empirical formula for threshold penetration (McDonnell and Sullivan, Hypervelocity Impacts in Space, Unit for Space Sciences, University of Kent, 1992). The velocity of the fastest fragments, at a given size, is from the extrapolation of the size-velocity relation for 1–100 mm fragments (Nakamura and Fujiwara, Icarus92, 132–146, 1991; Nakamura et al, Icarus100, 127–135, 1992). The laboratory results are also compared with those obtained from the study of secondary craters around large lunar craters (Vickery, Icarus67, 224–236, 1986, Geophys. Res. Lett. 14, 726–729, 1987). All these data provide a smooth size-velocity relationship in the normalized fragment size range of four orders of magnitude.     

Genesis of the Mamut Porphyry Copper Deposit, Sabah, East Malaysia

Abstract: The Mamut deposit of Sabah, East Malaysia, is a porphyry type Cu‐Au deposit genetically related to a quartz monzonite (“adamellite”) porphyry stock associated with upper Miocene Mount Kinabalu plutonism. The genesis of the Mamut deposit is discussed based on petrology of the intrusives in the Mount Kinabalu area combined with ore– and alteration–petrography, fluid inclusion and sulfur isotope studies. Groundmass of the adamellite porphyry at Mamut is rich in K which suggests vapor transport of alkaline elements during the mineralizing magmatic process, while the groundmass of the post‐ore “granodiorite” porphyry at Mamut contains small amounts of normative corundum suggesting depletion in alkaline elements at the root zone of the magma column. Sub‐dendritic tremolitic amphibole rims on hornblende phenocrysts in the Mamut adamellite porphyry suggest interaction between the mineralizing magma and the exsolved fluids. Occurrences of clinopyroxene microphenocrysts and pseudomor‐phic aggregates of shredded biotite and clinopyroxene after hornblende phenocrysts in the barren intrusives imply lower water fugacity and decreasing in water fugacity, respectively. Compositional gap between the core of hornblende phenocrysts and the tremolitic amphibole rims and those in the groundmass of the Mamut adamellite porphyry suggests a decrease in pressure. Higher X_Mg (=Mg/(Mg+Fe) atomic ratio) in the tremolitic amphibole rims in the Mamut adamellite porphyry compared to those of the barren intrusions suggests high oxygen fugacity. High halogen contents of igneous hydrous minerals such as amphiboles, biotite and apatite in the Mamut adamellite porphyry suggest the existence of highly saline fluids during the intrusion and solidification of the mineralizing magma. Fluid inclusions found in quartz veinlet stockworks are characterized by abundant hypersaline polyphase inclusions associated with subordinate amounts of immiscible gaseous vapor. Both Cu and Au are dispersed in disseminated and quartz stockwork ores. Chalcopyrite and pyrrhotite as well as magnetite are the principal ore minerals in the biotitized disseminated ores. Primary assemblage of intermediate solid solution (iss) and pyrrhotite converted to the present assemblage of chalcopyrite and pyrrhotite during cooling. Subsequent to biotitization, quartz veinlet stockworks formed associated with retrograde chlorite alteration. The Cu‐Fe sul–fides associated with stockwork quartz veinlet are chalcopyrite and pyrite. Overlapping Pb and Zn and subsequent Sb mineralizations were spatially controlled by NNE‐trending fractures accompanying the phyllic and advanced argillic alteration envelope. Sulfur isotopic composition of ore sulfides are homogeneous (about +2%) throughout the mineralization stages. These are identical to those of the magmatic sulfides of Mount Kinabalu adamellitic rocks.     

Growth of ringwoodite reaction rims from MgSiO3 perovskite and periclase at 22.5 GPa and 1,800 °C

The growth rate of ringwoodite reaction rims between MgSiO₃ perovskite and periclase was investigated at 22.5 GPa and 1,800 °C for 1–24 h using the Kawai-type high-pressure apparatus. The reaction was likely to proceed by a diffusion-controlled mechanism in which the dominant diffusion mechanism was grain-boundary diffusion. The reaction constant (the width of the ringwoodite reaction rim squared divided by time) determined from these experiments was between 1.3 × 10^?15 and 5.6 × 10^?15 m²/s. A Pt inert marker experiment indicated that the MgO component migrated faster than the SiO₂ component in ringwoodite. Thus, either Mg or O having the slower diffusion rate controlled the reaction. Because previous diffusion studies have shown that diffusion rates of O are slower than those of Mg, O would be a rate-controlling element for ringwoodite formation from MgSiO₃ perovskite and periclase. The growth rate appeared to be too fast to explain the observed topographic rise (~10 km) inside mantle plumes at the 660-km discontinuity.     

Dissolution kinetics of plagioclase in the melt of the system diopside-albite-anorthite,and origin of dusty plagioclase in andesites

The textures and kinetics of reaction between plagioclase and melts have been investigated experimentally, and origin of dusty plagioclase in andesites has been discussed. In the experiments plagioclase of different compositions (An₉₆, An₆₁, An₅₄, An₂₃, and An₂₂) surrounded by glasses of six different compositions in the system diopside-albite-anorthite was heated at temperatures ranging from 1,200 to 1,410° C for 30 min to 88 h. Textures were closely related to temperature and chemical compositions. A crystal became smaller and rounded above the plagioclase liquidus temperature of the starting melt (glass) and remained its original euhedral shape below the liquidus. Whatever the temperature, the crystal-melt interface became rough and often more complicated (sieve-like texture composed of plagioclase-melt mixture in the scale of a few m was developed from the surface of the crystal inward; formation of mantled plagioclase) if the crystal is less calcic than the plagioclase in equilibrium with the surrounding melt, and the interface remained smooth if the crystal is more calcic than the equilibrium plagioclase. From these results the following two types of dissolution have been recognized; (1) a crystal simply dissolves in the melt which is undersaturated with respect to the phase (simple dissolution), and a crystal is partially dissolved to form mantled plagioclase by reaction between sodic plagioclase and calcic melt (partial dissolution). The amount of a crystal dissolved and reacted increased proportional to the square root of time. This suggests that these processes are controlled by diffusion, probably in the crystal.Mantled plagioclase produced in the experiments were very similar both texturally and chemically to some of the so-called resorbed plagioclase in igneous rocks. Chemical compositions and textures of plagioclase phenocrysts in island-arc andesites of magma mixing origin have been examined. Cores of clear and dusty plagioclase were clacic (about An₉₀) and sodic (about An₅₀), respectively. This result indicates that dusty plagioclases were formed by the partial melting due to reaction between sodic plagioclase already precipitated in a dacitic magma and a melt of intermediate composition in a mixed magma during the magma mixing.