Phase relations in hydrous MORB at 18-28 GPa: implications for heterogeneity of the lower mantle

The phase relations in hydrous and anhydrous mid-ocean ridge basalt were determined at pressures of 18-28 GPa. Liquidus phase relations in hydrous and anhydrous MORB are different. Garnet is the liquidus phase at pressures below 21 GPa, Ca-Al (CAS) phase and stishovite are the liquidus phases at pressures of 22-27 GPa, and stishovite and Ca-perovskite are the liquidus phases above 27 GPa, whereas Ca-perovskite is a liquidus phase of anhydrous MORB at pressures above 23 GPa. Under subsolidus conditions, we have found that in the hydrous MORB system the stability fields of Al-bearing perovskite and Na-Al (NAL) phase might shift to lower pressure by about 1.5 GPa compared to the dry MORB system. This shift could be explained by oxidation of a garnet-bearing assemblage by hydrous fluid and formation of Fe³⁺-bearing aluminous perovskite at lower pressures relative to the anhydrous system and/or differences in water solubility of the phases existing in perovskite-bearing assemblages. Our data indicate that hydrous basaltic crust remains denser than peridotite along the geotherm of a subducting slab, i.e. there is no density crossover between peridotite and basalt. Therefore, in slabs going through the 660 km discontinuity, basalt would gravitationally sink into the lower mantle under relatively hydrous conditions. The delamination of former basaltic crust near the 660 km discontinuity might be possible under relatively dry conditions of subduction. There are no stable highly hydrous phases in MORB above 10 GPa even at lower temperatures corresponding to subducting slabs. Therefore, MORB cannot be an important carrier of water to the deep Earth interior. However, it can be constantly supplied by water-bearing fluid from the underlying peridotite part of the descending slab. Thus, it is plausible that water can control subduction of the oceanic crust into the lower mantle.     

Comparison of reductive accumulation of Re and Os in seawater-sediment systems

In order to understand the fractionation of Re and Os in marine environments, their removal from artificial seawater to Tokyo Bay sediments is studied using a multitracer technique. The chemical processes of the removal of Re and Os are also estimated based on their speciation analyses by X-ray absorption fine structure (XAFS) spectroscopy. The partitioning experiments, which use the multitracer technique, provide information on Re and Os regarding (i) their distributions between artificial seawater-sediment systems, (ii) their complexation with humic acid, and (iii) their carriers in sediments. In addition, XAFS spectroscopy provides direct information on the chemical states of Re and Os in the sediments.In an artificial seawater-sediment system containing a multitracer, Re is removed from the artificial seawater only under a reducing environment. The speciation of Re by X-ray absorption near-edge structure (XANES) suggests that the majority of Re remains as in the artificial seawater even under highly reducing conditions, during laboratory time scale (about 2 weeks). Moreover, XANES simulation shows that some Re exists at a lower oxidation state, such as ReO₂, in the reducing sediment. These results can be explained by the slow kinetics of the reaction which is similar to those suggested by previous geochemical studies.In contrast, Os is readily removed from the artificial seawater into sediments under various redox conditions. Even under oxic conditions, a large fraction of Os is removed from the artificial seawater to sediments without organic matter. Based on the Os XANES study, it is confirmed that the oxidation states of Os incorporated in the reducing sediment and oxic sediment are trivalent and tetravalent, respectively. Sequential extraction suggests that the main carrier of Os in the organic-rich sediment is either ferromanganese oxides or organic matter, and that the Os in these two fractions may correspond to hydrolyzed insoluble Os species and Os species interacting with organic matter, at lower valence, respectively. The results of distribution study of Os in the absence and presence of humic acid (HA) also imply that Os assumes more than one chemical species, and a small fraction of Os may interact with HA in the experimental system. Meanwhile, extended X-ray absorption fine structure (EXAFS) confirms that the first neighboring atom of Os in the reducing sediment is oxygen. If Os(VIII) is the main dissolved species in seawater, as is expected thermodynamically, reductive removal may control the enrichment of Os in the sediment. Osmium, which is removed as Os(IV), is reduced further to Os(III) by a diagenetic process and may be complexed with organic matter in the reducing sediment.The results of the removal behaviors of Re and Os obtained in the current study show that Re can be removed from the artificial seawater only under highly reducing conditions within 2 weeks, but Os removal from the artificial seawater can be found under various redox conditions. Thus, a high ¹⁸⁷Re/¹⁸⁸Os ratio can occur only in reducing sediments, such as black shales. The high¹⁸⁷Re/¹⁸⁸Os ratio, in turn, makes black shales suitable for Re-Os dating. In contrast, authigenic sediments (and minerals) under oxic environments can enrich Os, but since Re is not distributed to the sediments under oxic conditions, this will cause a much lower ¹⁸⁷Re/¹⁸⁸Os ratio than that of seawater. The Os isotope system of these materials can be used as a paleo-marine environmental tracer since the ¹⁸⁷Os/¹⁸⁸Os ratio cannot grow significantly due to its extremely low ¹⁸⁷Re/¹⁸⁸Os ratio.     

Mechanical response of the south flank of kilauea volcano, hawaii, to intrusive events along the rift systems

Increased earthquake activity and compression of the south flank of Kilauea volcano, Hawaii, have been recognized by previous investigators to accompany rift intrusions. We further detail the temporal and spatial changes in earthquake rates and ground strain along the south flank induced by six major rift intrusions which occurred between December 1971 and January 1981. The seismic response of the south flank to individual rift intrusions is immediate; the increased rate of earthquake activity lasts from 1 to 4 weeks. Horizontal strain measurements indicate that compression of the south flank usually accompanies rift intrusions and eruptions. Emplacement of an intrusion at a depth greater than about 4 km, such as the June 1982 southwest rift intrusion, however, results in a slight extension of the subaerial portion of the south flank.Horizontal strain measurements along the south flank are used to locate the January 1983 east-rift intrusion, which resulted in eruptive activity. The intrusion is modeled as a vertical rectangular sheet with constant displacement perpendicular to the plane of the sheet. This model suggests that the intrusive body that compressed the south flank in January 1983 extended from the surface to about 2.4 km depth, and was aligned along a strike of N66°E. The intrusion is approximately 11 km in length, extended beyond the January 1983 eruptive fissures, which are 8 km in length and is contained within the 14-km-long region of shallow rift earthquakes.     

High-pressure phase transitions of CaRhO<Subscript>3</Subscript> perovskite

High-pressure phase transitions of CaRhO₃ perovskite were examined at pressures of 6–27 GPa and temperatures of 1,000–1,930°C, using a multi-anvil apparatus. The results indicate that CaRhO₃ perovskite successively transforms to two new high-pressure phases with increasing pressure. Rietveld analysis of powder X-ray diffraction data indicated that, in the two new phases, the phase stable at higher pressure possesses the CaIrO₃-type post-perovskite structure (space group Cmcm) with lattice parameters: a = 3.1013(1) Å, b = 9.8555(2) Å, c = 7.2643(1) Å, V _m  = 33.43(1) cm³/mol. The Rietveld analysis also indicated that CaRhO₃ perovskite has the GdFeO₃-type structure (space group Pnma) with lattice parameters: a = 5.5631(1) Å, b = 7.6308(1) Å, c = 5.3267(1) Å, V _m  = 34.04(1) cm³/mol. The third phase stable in the intermediate P, T conditions between perovskite and post-perovskite has monoclinic symmetry with the cell parameters: a = 12.490(3) Å, b = 3.1233(3) Å, c = 8.8630(7) Å, β = 103.96(1)°, V _m  = 33.66(1) cm³/mol (Z = 6). Molar volume changes from perovskite to the intermediate phase and from the intermediate phase to post-perovskite are –1.1 and –0.7%, respectively. The equilibrium phase relations determined indicate that the boundary slopes are large positive values: 29 ± 2 MPa/K for the perovskite—intermediate phase transition and 62 ± 6 MPa/K for the intermediate phase—post-perovskite transition. The structural features of the CaRhO₃ intermediate phase suggest that the phase has edge-sharing RhO₆ octahedra and may have an intermediate structure between perovskite and post-perovskite.     

Determination of the freshwater origin of Coastal Oyashio Water using humic-like fluorescence in dissolved organic matter

Coastal Oyashio Water (COW), defined as a water mass with a temperature lower than 2 °C and a salinity lower than 33.0, is distributed in the North Pacific Ocean off southeastern Hokkaido, Japan, from winter to spring. COW is rich in macronutrients and dissolved iron and is thus considered to affect the spring phytoplankton blooms in the Oyashio region. Although river water and sea-ice melt water have been considered freshwater end-members of COW, the contributions of these freshwater sources to COW have not been well described. In this study, the humic-like components in dissolved organic matter were first applied as a parameter to evaluate the freshwater end-members of COW in March 2015. Linear regressions with negative slopes were determined between the humic-like components and the salinity of COW. The intercepts of the regressions against the humic-like components were within the ranges of those observed for the local rivers of Hokkaido but were very different from those of sea ice. These findings suggest that river water contributed to the COW observed here as a freshwater end-member, although the contribution of sea-ice melt water to COW could not be evaluated. This novel approach also highlighted two different less-saline water masses in COW. The first was characterized by a lower temperature and relatively high levels of humic-like components, while the second was higher in temperature and had higher levels of humic-like components. It is suggested that these different characteristics are due to the contributions of water from different rivers and/or different effects of sea-ice melt water.     

Measurements of carbon dioxide in the Seto Inland Sea of Japan

The carbon dioxide in seawater (pCO₂) was measured in the Seto Inland Sea of Japan using newly developed equilibrator instrument designed to be free from the correction for addition or extraction of the carbon dioxide from carrier gas. The temperature dependence of pCO₂ was about 4.5%pCO₂/°C for a single seawater sample which was processed as free from biological activity and change in total carbon dioxide content during an experiment. The decrease in pCO₂ during daylight hours due to the photosynthetic fixation was about 30% of the daily mean of pCO₂ during warm months and about 15% during cold months. The effect of carbon dioxide exchange between air and seawater on pCO₂ was about 0.6 ppm in August and about 0.1 ppm in March. This is negligible small compared with the daily oscillation of carbon dioxide in seawater.     

Vertical and horizontal distribution of fluorescent dissolved organic matter in the Southern Ocean

The vertical and horizontal distribution of fluorescent dissolved organic matter (FDOM), determined by fluorescence intensity at 320 nm excitation and 420 nm emission, were clarified in nine stations on two transects at the Southern Ocean, including a subtropical, subantarctic, polar frontal and Antarctic zone. All vertical profiles of fluorescence intensity showed that levels were lowest in the surface waters, increased with increasing the depth in mid-depth waters ( 2000 m), and then stayed within a relatively narrow range from there to the bottom. Such vertical profiles of FDOM were similar to those of nutrients, but were adverse to dissolved oxygen. In water columns below the temperature-minimum subsurface water (dichothermal waters) in the Antarctic zone and below the winter mixed layer in the other zones, we determined the relationships of fluorescence intensity to concentrations of nutrients and apparent oxygen utilization (AOU) over the entire area of the present study, and found significant linear correlations between the levels of fluorescence intensity and nutrient concentrations (r =  0.70 and 0.71 for phosphate and nitrate + nitrite, respectively) and AOU (r = 0.91). From the strong correlation coefficient between fluorescence intensity and AOU, we concluded that FDOM in the Southern Ocean is formed in situ via the biological oxidation of organic matter. The regeneration of the nutrients/consumption of the oxygen/formation of FDOM was active in mid-depth waters. However, the correlations between fluorescence intensities and nutrients and AOU were different in the mid-depth water masses, Subantarctic Mode Water (SAMW), and Antarctic Intermediate Water (AAIW), indicating that the sources of organic matter responsible for FDOM formation were different. A considerable amount of FDOM in the SAMW is thought to be produced by the remineralization of DOM in addition to sinking particulate organic matter, while DOM is less responsible for FDOM formation in the AAIW.     

Intrusion of less saline shelf water into the Kuroshio subsurface layer in the East China Sea

The possible origin and cause of the less saline shelf water detected in the Kuroshio subsurface layer around the shelf edge of the East China Sea are investigated using observational results obtained in May 1998–2001 in conjunction with a dataset archived by Japan Oceanographic Data Center and a numerical model. The observations show that subsurface intrusions of less saline water are always detected in May in layers above 24.5σθ isopycnal surface, and that salinity inversions (i.e., areas in which the less saline water lies beneath the saline water) are detected around the trough of the Kuroshio frontal eddy (or wave). Analyses of the archived dataset reveal that the isopycnal surface of 24.5σθ is the deepest layer of the Kuroshio pycnocline outcropping to the sea surface on the shallow shelf in early spring. Outcropping isopycnals above 24.5σθ encounter a less saline water plume originating from the Changjiang, especially in the western East China Sea. Thereafter, the less saline water moves along isopycnal layers and reaches the Kuroshio front around the shelf edge. Numerical models demonstrate that, when the frontal wave captures the less saline water, the shelf water takes the form of a salinity inversion in the trough because isohalines in the frontal wave have a phase lag between the upper and lower layers in consequence of the baroclinic instability.