Garnet-ilmenite-perovskite transitions in the system Mg4Si4O12-Mg3Al2Si3O12 at high pressures and high temperatures: phase equilibria, calorimetry and implications for mantle structure

Phase relations in the system Mg₄Si₄O₁₂-Mg₃Al₂Si₃O₁₂ were examined at pressures of 19-27 GPa and relatively low temperatures of 800-1000 °C using a multianvil apparatus to clarify phase transitions of pyroxene-garnet assemblages in the mantle. Both of glass and crystalline starting materials were used for the experiments. At 1000 °C, garnet solid solution (s.s.) transforms to aluminous ilmenite s.s. at 20-26 GPa which is stable in the whole compositional range in the system. In Mg₄Si₄O₁₂-rich composition, ilmenite s.s. transforms to a single-phase aluminous perovskite s.s., while Mg₃Al₂Si₃O₁₂-rich ilmenite s.s. dissociates into perovskite s.s. and corundum s.s. These newly determined phase relations at 1000 °C supersede preliminary phase relations determined at about 900 °C in the previous study. The phase relations at 1000 °C are quite different from those reported previously at 1600 °C where garnet s.s. transforms directly to perovskite s.s. and ilmenite is stable only very close to Mg₄Si₄O₁₂. The stability field of Mg₃Al₂Si₃O₁₂ ilmenite was determined at 800-1000 °C and 25-27 GPa by reversed phase boundaries. In ilmenite s.s., the a-axis slightly increases but the c-axis and molar volume decrease substantially with increasing Al₂O₃ content. Enthalpies of ilmenite s.s. were measured by differential drop-solution calorimetry method using a high-temperature calorimeter. The excess enthalpy of mixing of ilmenite s.s. was almost zero within the errors. The measured enthalpies of garnet-ilmenite and ilmenite-perovskite transitions at 298 K were 105.2±10.4 and 168.6±8.2 kJ/mol, respectively, for Mg₄Si₄O₁₂, and 150.2±15.9 and 98.7±27.3 kJ/mol, respectively, for Mg₃Al₂Si₃O₁₂. Thermodynamic calculations using these data give rise to phase relations in the system Mg₄Si₄O₁₂-Mg₃Al₂Si₃O₁₂ at 1000 and 1600 °C that are generally consistent with those determined experimentally, and confirm that the single-phase field of ilmenite expands from Mg₄Si₄O₁₂ to Mg₃Al₂Si₃O₁₂ with decreasing temperature. The earlier mentioned phase relations in the simplified system as well as those in the Mg₂SiO₄-Fe₂SiO₄ system are applied to estimate mineral proportions in pyrolite as a function of depth along two different geotherms: one is a horizontally-averaged temperature distribution in a normal mantle, and the other being 600 °C lower than the former as a possible representative geotherm in subducting slabs. Based on the previously described estimated mineral proportions versus depth along the two geotherms, density and compressional and shear wave velocities are calculated as functions of depth, using available mineral physics data. Along a normal mantle geotherm, jumps of density and velocities at about 660 km corresponding to the post-spinel transition are followed by steep gradients due to the garnet-perovskite transition between 660 and 710 km. In contrast, along a low-temperature geotherm, the first steep gradients of density and velocities are due to the garnet-ilmenite transition between 610 and 690 km. This is followed by abrupt jumps at about 690 km for the post-spinel transition, and steep gradients between 700 and 740 km that correspond to the ilmenite-perovskite transition. In the latter profile along the low-temperature geotherm, density and velocity increases for garnet-ilmenite and ilmenite-perovskite transitions are similar in magnitude to those for the post-spinel transition. The likely presence of ilmenite in cooler regions of subducting slabs is suggested by the fact that the calculated velocity profiles along the low-temperature geotherm are compatible with recent seismic observations indicating three discontinuities or steep velocity gradients at around 600-750 km depth in the regions of subducting slabs.     

Southward intrusion of the intermediate Oyashio water along the east coast of the Boso Peninsula I. Coastal salinity-minimum-layer water off the Boso Peninsula

Index species of zooplankton of the Oyashio water are found in and beneath the salinity minimum layer in Sagami Bay. In order to clarify the intrusion path of the intermediate Oyashio Water (or the water of the Mixed Water Region), the oceanographic conditions off the Boso Peninsula are studied by using available hydrographic data obtained mainly by Japan Meteorological Agency. The cross-sectional salinity distribution along KJ line which extends southeastward from off the tip of the peninsula always indicates the existence of a low salinity patch just off the coast in the salinity minimum layer. This water is well separated from the offshore low salinity water which is considered as the water in the western margin of the so-called North Pacific Intermediate Water. We refer to the former water as the coastal salinity-minimum-layer (SML) water and to the latter as the offshore SML water. The coastal SML water is usually bounded by the current zone of the Kuroshio. The existence of the coastal SML water seems to indicate the possible pathway of the intermediate Oyashio water along the Boso Peninsula into Sagami Bay. The detailed water type analysis is made in T-S plane, S-_st plane, and O₂-_st plane. There is no significant difference in distribution ranges of the water types between the coastal SML water and the offshore SML water. However, the water types of the coastal SML water is not uniformly distributed, and the water can be classified into two groups: group A with relatively high oxygen content and relatively low salinity value and group B with relatively low oxygen content and relatively high salinity value. Group A is thought to be associated with strong event-like intrusions, the details of which will be discussed in Part II.     

Transition processes between the three typical paths of the Kuroshio

Transitions between the three typical paths of the Kuroshio south of Japan (the nearshore and offshore non-large-meander paths and the large-meander path) are described using sea level data at Miyake-jima and HachijÔ-jima in the Izu Islands and temperature data at a depth of 200 m observed from 1964 to 1975 and in 1980.In transitions between the nearshore and offshore non-large-meander paths the variation of the Kuroshio path occurs first in the region off Enshû-nada between the Kii Peninsula and the Izu Ridge and subsequently over the ridge. In the nearshore to offshore transition the offshore displacement of the path occurs first off Enshû-nada and then develops southeastwardly in the direction of HachijÔ-jima. In the reverse transition shoreward displacement occurs first off Enshû-nada and then throughout the region west and east of the Izu Ridge. The position of the Kuroshio south of Cape Shiono-misaki (the southernmost tip of the Kii Peninsula) is almost fixed near the coast throughout these transition periods, and significant variations of the Kuroshio path only occur east of the cape. The nearshore to offshore and offshore to nearshore transitions can be estimated to take about 25 and 35 days, respectively, during which the variation of the Kuroshio path over the Izu Ridge occurs for the last 11 and 25 days.The transitions between the non-large-meander and large-meander paths show that the large-meander path is mostly formed from the nearshore non-large-meander path and always changes to the offshore non-large-meander path.     

Pacific ocean circulation based on observation

A thorough understanding of the Pacific Ocean circulation is a necessity to solve global climate and environmental problems. Here we present a new picture of the circulation by integrating observational results. Lower and Upper Circumpolar Deep Waters (LCDW, UCDW) and Antarctic Intermediate Water (AAIW) of 12, 7, and 5 Sv (10⁶ m³s⁻¹) in the lower and upper deep layers and the surface/intermediate layer, respectively, are transported to the North Pacific from the Antarctic Circumpolar Current (ACC). The flow of LCDW separates in the Central Pacific Basin into the western (4 Sv) and eastern (8 Sv) branches, and nearly half of the latter branch is further separated to flow eastward south of the Hawaiian Ridge into the Northeast Pacific Basin (NEPB). A large portion of LCDW on this southern route (4 Sv) upwells in the southern and mid-latitude eastern regions of the NEPB. The remaining eastern branch joins nearly half of the western branch; the confluence flows northward and enters the NEPB along the Aleutian Trench. Most of the LCDW on this northern route (5 Sv) upwells to the upper deep layer in the northern (in particular northeastern) region of the NEPB and is transformed into North Pacific Deep Water (NPDW). NPDW shifts southward in the upper deep layer and is modified by mixing with UCDW around the Hawaiian Islands. The modified NPDW of 13 Sv returns to the ACC. The remaining volume in the North Pacific (11 Sv) flows out to the Indian and Arctic Oceans in the surface/intermediate layer.     

Water masses and currents of deep circulation southwest of the Shatsky Rise in the western North Pacific

We conducted full-depth hydrographic observations in the southwestern region of the Northwest Pacific Basin in September 2004 and November 2005. Deep-circulation currents crossed the observation line between the East Mariana Ridge and the Shatsky Rise, carrying Lower Circumpolar Deep Water westward in the lower deep layer (θ<1.2 °C) and Upper Circumpolar Deep Water (UCDW) and North Pacific Deep Water (NPDW) eastward in the upper deep layer (1.3–2.2 °C). In the lower deep layer at depths greater than approximately 3500 m, the eastern branch current of the deep circulation was located south of the Shatsky Rise at 30°24′–30°59′N with volume transport of 3.9 Sv (1 Sv=10⁶ m³ s⁻¹) in 2004 and at 30°06′–31°15′N with 1.6 Sv in 2005. The western branch current of the deep circulation was located north of the Ogasawara Plateau at 26°27′–27°03′N with almost 2.1 Sv in 2004 and at 26°27′–26°45′N with 2.7 Sv in 2005. Integrating past and present results, volume transport southwest of the Shatsky Rise is concluded to be a little less than 4 Sv for the eastern branch current and a little more than 2 Sv for the western branch current. In the upper deep layer at depths of approximately 2000–3500 m, UCDW and NPDW, characterized by high and low dissolved oxygen, respectively, were carried eastward at the observation line by the return flow of the deep circulation composing meridional overturning circulation. UCDW was confined between the East Mariana Ridge and the Ogasawara Plateau (22°03′–25°33′N) in 2004, whereas it extended to 26°45′N north of the Ogasawara Plateau in 2005. NPDW existed over the foot and slope of the Shatsky Rise from 29°48′N in 2004 and 30°06′N in 2005 to at least 32°30′N at the top of the Shatsky Rise. Volume transport of UCDW was estimated to be 4.6 Sv in 2004, whereas that of NPDW was 1.4 Sv in 2004 and 2.6 Sv in 2005, although the values for NPDW may be slightly underestimated, because they do not include the component north of the top of the Shatsky Rise. Volume transport of UCDW and NPDW southwest of the Shatsky Rise is concluded to be approximately 5 and 3 Sv, respectively. The pathways of UCDW and NPDW are new findings and suggest a correction for the past view of the deep circulation in the Pacific Ocean.     

Water and flow variations in Sagami Bay under the influence of the Kuroshio path

Variations of water and flow in Sagami Bay in relation to the Kuroshio path variations are examined by using 100m-depth temperature and salinity data from 25 stations as well as sea level data from five stations (Minami-Izu, ItÔ, Ôshima, Aburatsubo, Mera). In regard to temperature, anomalies from the mean seasonal variations are used. Results show that water properties are clearly different between the three typical paths of the Kuroshio. The difference is more remarkable in temperature than in salinity; temperature is higher during the typical large-eander (LM) path, and lower during the offshore non-large-meander (NLM) path, compared with the nearshore NLM path. Temperature anomaly and salinity distributions, as well as the Ôshima minus Minami-Izu and Ôshima minus Mera sea-level differences strongly suggest that the flows during the typical LM path are distributed as hitherto described in past studies, that is, water in the mouth region of the bay flows clockwise around Ôshima from the west channel to the east channel, and a counterclockwise eddy exists in the interior. On the other hand, flows during the nearshore and offshore NLM paths seem to be quite different from those during the typical LM path; velocities are very weak, and the directions of circulation is frequently reversed. This tendency also can be seen during parts of LM period in which the Kuroshio takes a non-typical LM path.Water properties in Sagami Bay are most characteristic during transitions between nearshore and offshore NLM paths. During transitions from nearshore to offshore NLM paths, temperatures are extremely high as a whole in the bay, while during reverse transitions, both temperatures and salinities are very low in the entire region.     

Computational model of the structural and elastic properties of the ilmenite and perovskite phases of MgSiO3

The structural and elastic properties of the ilmenite and perovskite phases of MgSiO₃ are investigated with a computational model based on energy minimization. The potential energies of these two crystals are approximated by the sum of Coulomb, van der Waals, and repulsion terms between atoms. Required energy parameters are derived by fitting the parameters to the observed crystal structures of these two phases as well as to the measured elastic constants of the ilmenite phase. The resulting potential model is applied to predicting the elastic constants of the perovskite phase. The calculated bulk modulus of the perovskite phase compares favorably with the data obtained from volume-compression experiments as well as the values estimated from empirical elasticity systematics of perovskite type compounds. The predicted shear modulus of the perovskite phase is also in reasonable agreement with the values proposed from similar empirical elasticity systematics. Subsequently, the model is used to simulate the high pressure behaviors of the crystal structures and elastic constants of these two phases.     

Coexisting sodic augite and omphacite in a Sanbagawa metamorphic rock,Japan

Coexisting sodic augite and omphacite were found in a zoisite amphibolite from the Iratsu epidote amphibolite mass in the Sanbagawa metamorphic terrain of central Shikoku, Japan. The occurrences of the sodic augite-omphacite pairs are classified into four types by texture: independent, composite, intergrowth and exsolution types. Sodic augite and omphacite of the independent and composite types (pair A) have X _Na (=Na/(Na + Ca)) = 0.15 and 0.35, respectively, and were stable in the epidote amphibolite facies during the Sanbagawa progressive metamorphism. On the other hand, X ^Na values of sodic augite and omphacite of the intergrowth and exsolution types (pair B) are 0.10 and 0.44, respectively. The Na-poor augite and Na-rich omphacite of the pair B were formed by re-equilibration of the pair A at lower temperature. The pair A of the Iratsu sample suggests that a compositional gap lies between sodic augite and C2/c omphacite under epidote amphibolite facies conditions, and is in marked contrast to the coexistence of sodic augite and P2/n omphacite reported from some low-grade, high-pressure metamorphic terrains. A possible phase diagram to explain the chemistry and mode of occurrence of the coexisting sodic pyroxenes is proposed.     

Voyage of the Indian subcontinent since Pangea breakup and driving force of supercontinent cycles: Insights on dynamics from numerical modeling

Recent advances in three-dimensional numerical simulations of mantle convection have aided in approximately reproducing continental movement since the Pangea breakup at 200 Ma. These have also led to a better understanding of the thermal and mechanical coupling between mantle convection and surface plate motion and predictions of the configuration of the next supercontinent. The simulations of mantle convection from 200 Ma to the present reveals that the development of large-scale cold mantle downwellings in the North Tethys Ocean at the earlier stage of the Pangea breakup triggered the northward movement of the Indian subcontinent. The model of high temperature anomaly region beneath Pangea resulting from the thermal insulation effect support the breakup of Pangea in the real Earth time scale, as also suggested in previous geological and geodynamic models. However, considering the low radioactive heat generation rate of the depleted upper mantle, the high temperature anomaly region might have been generated by upwelling plumes with contribution of deep subducted TTG(tonalite-trondhjemite-granite) materials enriched in radiogenic elements. Integrating the numerical results of mantle convection from 200 Ma to the present, and from the present to the future, it is considered that the mantle drag force acting on the base of continents may be comparable to the slab pull force, which implies that convection in the shallower part of the mantle is strongly coupled with surface plate motion.     

Factors affecting preservation of coesite in ultrahigh‐pressure metamorphic rocks: Insights from TEM observations of dislocations within kyanite

To understand the preservation of coesite inclusions in ultrahigh‐pressure (UHP) metamorphic rocks, an integrated petrological, Raman spectroscopic and focussed ion beam (FIB) system–transmission electron microscope (TEM) study was performed on a UHP kyanite eclogite from the Sulu belt in eastern China. Coesite grains have been observed only as rare inclusions in kyanite from the outer segment of garnet and in the matrix. Raman mapping analysis shows that a coesite inclusion in kyanite from the garnet rim records an anisotropic residual stress and retains a maximum residual pressure of ~0.35 GPa. TEM observations show quartz is absent from the coesite inclusion–host kyanite grain boundaries. Numerous dislocations and sub‐grain boundaries are present in the kyanite, but dislocations are not confirmed in the coesite. In particular, dislocations concentrate in the kyanite adjacent to the boundary with the coesite inclusion, and they form a dislocation concentration zone with a dislocation density of ~10⁹ cm^?2. A high‐resolution TEM image and a fast Fourier transform‐filtered image reveal that a tiny dislocation in the dislocation concentration zone is composed of multiple edge dislocations. The estimated dislocation density in most of the kyanite away from the coesite inclusion–host kyanite grain boundaries is ~10⁸ cm^?2, being lower than that in kyanite adjacent to the coesite. In the case of a coesite inclusion in a matrix kyanite, using Raman and TEM analyses, we could not identify any quartz at the grain boundaries. Dislocations are not observed in the coesite, but numerous dislocations and stacking faults are developed in the kyanite. The estimated overall dislocation density in the coesite‐bearing matrix kyanite is ~10⁸ cm^?2, but a high dislocation density region of ~10⁹ cm^?2 is also present near the coesite inclusion–host kyanite grain boundaries. Inclusion and matrix kyanite grains with no coesite have dislocation densities of ≤10⁸ cm^?2. Dislocation density is generally reduced during an annealing process, but our results show that not all dislocations in the kyanite have recovered uniformly during exhumation of the UHP rocks. Hence, one of the key factors acting as a buffer to inhibit the coesite to quartz transformation is the mechanical interaction between the host and the inclusion that lead to the formation of dislocations in the kyanite. The kyanite acts as an excellent pressure container that can preserve coesite during the decompression of rocks from UHP conditions. The search for and study of inclusions in kyanite may be a more suitable approach for tracing the spatial distribution of UHP metamorphic rocks.