Teruyoshi Imaoka

Niobian and zincian ilmenites in syenites from Cape Ashizuri, Southwest Japan

SummaryIlmenite in alkali feldspar quartz syenite from Cape Ashizuri contains up to 4.4 wt.% Nb2O5. Niobium substitutes for Ti in the octahedral site of the ilmenite structure. Substitution of Nb for Ti may involve a coupled exchange to maintain charge balance, and an exchange of 2Nb + 2Fe3+ = 3Ti + 2Fe2+ is advocated. An Fe-Ti oxide geothermometer obtained from mineral pairs of granular and lamellar intergrowths indicates a subsolidus re-equilibration temperature of 510–640 °C andfO2 between the FMQ and MW-buffers, implying that it is very undersaturated with respect to water. On the other hand, Zn-ilmenite, containing up to 5.4 wt.% ZnO, occurs in miarolitic cavities in peralkaline rhyolite which cuts the quartz syenite. The Zn-ilmenite is one of the last crystalline phases of the Ashizuri magmatic activities under volatile-rich conditions. Nb-oxides, such as fergusonite, samarskite, columbite and a pyrochlore-like mineral, are Ta- and Mn-poor, which corresponds to those of less-fractionated rocks of anorogenic alkali granite and pegmatitic granite in the continental situation. Ta- and Mn-poor Nb-oxides in F- and Li-rich alkaline felsic magmas such as the Ashizuri syenites are unusual; this may be related to a rapid emplacement and cooling of mantle-derived small-volume magma in the island are situation.ZusammenfassungIlmenit in Alkalifeldspat-Quarz-Syenit von Cap Ashizuri enthält bis zu 4,4 Gew. % Nb2O5. Niob ersetzt Ti in der oktaedrischen Position der Ilmenit-Struktur. Substitution von Nb für Ti erfolgt über einen gekooppelten Austausch zum Erhalt der Ladungsgleichgewichte und hier wird der Austausch von 2Nb + 2Fe3+ = 3Ti + 2Fe2+ vorgeschlagen. Ein Fe-Ti-Oxid Geothermometer auf der Basis von Mineral-Paaren körniger und lamellarer Verwachsungen weist auf Subsolidus Re-Equilibrationstemperaturen von 510 bis 640 °C undfO2 zwischen den QFM und MW-Puffern hin. Dies bedeutet Wasser-Untersättigung. Andererseits kommt Zn-Ilmenit mit bis zu 5,4 Gew.% ZnO in miarolitischen Hohlräumen in peralkalinem Rhyolit vor, der den Quarzsyenit durchschlägt. Der Zn-Ilmenit ist einer der am spätesten gebildeten kristallinen Phasen der magmatischen Aktivitäten von Ashizuri, bei Bedingungen, die an volatilen Phasen reich sind. Nb-Oxide, wie zum Beispiel Fergusonit, Samarskit, Columbit und ein Pyrochlor-ähnliches Mineral sind Ta- und Mn-arm; dies entspricht weniger fraktionierten Gesteinen aus dem Bildungsberich anorogener Alkali-Granite und pegmatitischer Granite in einer kontinentalen Situation. Ta- und Mn-arme Nb-Oxide in F- und Li-reichen alkalischen felsischen Magmen, wie die Ashizuri Syenite, sind ungewöhnlich; dies mag mit rascher Platznahme und Abkühlung von kleinen Volumina von Magmen, die aus dem Mantel stammen, in einer Inselbogen-Situation zusammenhängen.

Crystal chemistry of Ti-rich ferriallanite-(Ce) from Cape Ashizuri, Shikoku Island, Japan

Abstract The crystal chemistry of Ti-rich ferriallanite-(Ce) in syenites from Cape Ashizuri, Shikoku Island, Japan, was studied using electron microprobe analysis (EMPA) and single-crystal X‑ray diffraction methods. Our specimens (AS001 and AS304) are characterized by high-Ti (-3.6 wt% TiO2) and Fe contents (-21.3 wt% FeO*; Fe2+/total Fe = 0.6-0.7). Structure refinements of two ferriallanite-(Ce) crystals converged to R1 = 1.50-1.57%. In both specimens, the dominant cations at A1, A2, and M3 are Ca, Ce, and Fe2+, respectively. However, depending on Ti assignment, two different schemes of the cation distributions at M1 and M2 can be considered: (1) (Fe0.72Ti0.23Al0.05)M1(Al0.82Fe3+0.18)M2 and (2) (Fe0.90Al0.10)M1(Al0.77Ti0.23)M2 for AS001, and (1) (Fe0.65Ti0.29Al0.06)M1(Al0.89Fe3+0.11)M2 and (2) (Fe0.76Ti0.13Al0.11)M1(Al0.84Ti0.16)M2 for AS304. The Si2O7 group is compressed along Sil-O9-Si2 direction because of the expansions of the M1O6 and M3O6 octahedra due to substitution of large octahedral cations for Al. This compression is monitored by the atom position of O9 that shifts away from the cation at A1 decreasing the Si1-O9-Si2 angle. In allanite-subgroup minerals, the A1-O9 distance is longer and the bridging angle is smaller than those of clinozoisite-subgroup minerals. Although the A1 polyhedron is generally described as a ninefold-coordinated site, it is appropriately described as sevenfold-coordinated in Ti-rich allanite-(Ce) because of the lengthened A1-O9 (×2) distance. The cation substitutions at M1 and M3 indirectly affect the topology of the A1 polyhedron.

Decompressional microstructure from garnet-bearing mafic granulite in Yanai district, Ryoke belt, Southwest Japan

Newly found garnet-bearing mafic granulite in Yanai district, Ryoke belt occurs as blocks in gneissose tonalite. This granulite consists mainly of brown hornblende, orthopyroxene and plagioclase, with trace amounts of garnet, biotite and quartz. Garnet porphyroblast up to 3 cm in diameter is locally contained, and is surrounded by orthopyroxene and plagioclase symplectites that coexist with quartz. On the basis of microstructure and mineral assemblage in the garnet-bearing mafic granulite, it reveals that the reaction of garnet + quartz→orthopyroxene + plagioclase occurred at a decompressional process under the granulite facies condition.

The Cretaceous Ofuku Pluton and Its Relation to Mineralization in the Western Akiyoshi Plateau, Yamaguchi Prefecture, Japan

The relationship between the magmatism of the Cretaceous Ofuku pluton and mineralization in and around the Akiyoshi Plateau, Yamaguchi Prefecture, Japan was investigated using a combination of field observation, petrographic and geochemical analyses, K–Ar geochronology, and fluid inclusion data. The Ofuku pluton has a surface area of 1.5 × 1.0 km, and was intruded into the Paleozoic accretionary complexes of the Akiyoshi Limestone, Ota Group and Tsunemori Formation in the western part of the Akiyoshi Plateau. The pluton belongs to the ilmenite-series and is zoned, consisting mainly of early tonalite and granodiorite that share a gradational contact, and later granite and aplite that intruded the tonalite and granodiorite. Harker diagrams show that the Ofuku pluton has intermediate to silicic compositions ranging from 60.4 to 77.9 wt.% SiO2, but a compositional gap exists between 70.5 to 73.4 wt.% SiO2 (anhydrous basis). Modal and chemical variations indicate that the assumed parental magma is tonalitic. Quantitative models of fractional crystallization based on mass balance calculations and the Rayleigh fractionation model using major and trace element data for all crystalline phases indicate that magmatic fractionation was controlled mainly by crystal fractionation of plagioclase, hornblende, clinopyroxene and orthopyroxene at the early stage, and quartz, plagioclase, biotite, hornblende, apatite, ilmenite and zircon at the later stage. The residual melt extracted from the granodiorite mush was subsequently intruded into the northern and western parts of the Ofuku pluton as melt lens to form the granite and aplite. The age of the pluton was estimated at 99–97 Ma and 101–98 Ma based on K–Ar dating of hornblende and biotite, respectively. Both ages are consistent within analytical error, indicating that the Ofuku pluton and the associated Yamato mine belong to the Tungsten Province of the San-yo Belt, which is genetically related to the ilmenite-series granitoids of the Kanmon to Shunan stages. The aplite contains Cl-rich apatite and REE-rich monazite-(Ce), allanite-(Ce), xenotime and bastnasite-(Ce), indicating that the residual melt was rich in halogens and REEs. The tonalite–granodiorite of the Ofuku pluton contains many three-phase fluid inclusions, along with daughter minerals such as NaCl and KCl, and vapor/liquid (V/L) volume ratios range from 0.2 to 0.9, suggesting that the fluid was boiling. In contrast, the granite and aplite contain low salinity two-phase inclusions with low V/L ratios. The granodiorite occupies a large part of the pluton, and the inclusions with various V/L ratios with chloride daughter minerals suggest the boiling fluids might be related to the mineralization. This fluid could have carried base metals such as Cu and Zn, forming Cu ore deposits in and around the Ofuku pluton. The occurrence and composition of fluid inclusions in the igneous rocks from the Akiyoshi Plateau are directly linked to Cu mineralization in the area, demonstrating that fluid inclusions are useful indicators of mineralization.