Hidemi Ishibashi

Retentivity of CO 2 in fluid inclusions in mantle minerals

To assess the capacity of fluid inclusions in mantle minerals for CO 2 retention, annealing experiments were conducted for two mantle xenoliths with CO 2 inclusions for 8 days at 1000 °C under atmospheric pressure and f O 2 of 10 −11 MPa. The results show no marked decrease in the CO 2 density of the CO 2 inclusions for any examined minerals – olivine, orthopyroxene, clinopyroxene, or spinel. The CO 2 density of CO 2 inclusions in olivine in the present mantle xenoliths is lower than that in pyroxenes or spinel. Results of previous studies indicate that the low CO 2 density in olivine is attributable to plastic deformation of olivine around CO 2 inclusions during annealing in ascending magma. Results of this study present fundamental implications for deformation mechanisms that arise from internal pressure of fluid inclusions in silicate minerals. We calculated the stress field in minerals having a CO 2 inclusion. Results show a steep stress gradient in the host around the inclusion. Such local stress in the mineral induces a local rise in the density of dislocations around the CO 2 inclusions. The orthopyroxene used for this study showed a sparse distribution of dislocations around a CO 2 inclusion, whereas olivine showed dense dislocations around CO 2 inclusions, implying that the low CO 2 density of the CO 2 inclusions in olivine results from volume expansion of the CO 2 inclusions through plastic deformation of the host mineral during annealing of the xenoliths in ascending magma. In this respect, constancy of CO 2 density during the annealing experiments for all minerals is an interesting finding. Regarding olivines, the reduction of internal pressure of the CO 2 inclusions or interaction of the dense dislocations possibly inhibits decrepitation or further volume expansion of the CO 2 inclusions during annealing experiments. However, pyroxenes and spinel show higher and similar CO 2 density, which reflects the resistance to plastic deformation and which indicates the effectiveness of CO 2 inclusions in these minerals as a depth probe for mantle xenoliths.

Micro- and nano-inclusions in a superdeep diamond from São Luiz, Brazil

We report cloudy micro- and nano-inclusions in a superdeep diamond from São-Luiz, Brazil which contains inclusions of ferropericlase (Mg, Fe)O and former bridgmanite (Mg, Fe)SiO3 and ringwoodite (Mg, Fe)2SiO4. Field emission-SEM and TEM observations showed that the cloudy inclusions were composed of euhedral micro-inclusions with grain sizes ranging from tens nanometers to submicrometers. Infrared absorption spectra of the cloudy inclusions showed that water, carbonate, and silicates were not major components of these micro- and nano-inclusions and suggested that the main constituent of the inclusions was infrared-inactive. Some inclusions were suggested to contain material with lower atomic numbers than that of carbon. Mineral phase of nano- and micro-inclusions is unclear at present. Microbeam X-ray fluorescence analysis clarified that the micro-inclusions contained transition metals (Cr, Mn, Fe, Co, Ni, Cu, Zn) possibly as metallic or sulfide phases. The cloudy inclusions provide an important information on the growth environment of superdeep diamonds in the transition zone or the lower mantle.

Hydrous fluid as the growth media of natural polycrystalline diamond, carbonado: Implication from IR spectra and microtextural observations

Abstract Carbonado, a variety of natural polycrystalline diamond whose origin remains unknown, differs notably in the properties from common diamonds of mantle origin. In this study, infrared spectroscopic and microscopic analyses were conducted on carbonado from the Central African Republic. Stepwise heating followed by infrared spectroscopic measurements indicated that liquid H2O is enclosed within diamond single crystals in carbonado. Transmission electron microscope observation revealed a negative crystal that is interpreted as a primary fluid inclusion in a diamond single crystal. Observations by field-emission scanning electron microscope and electron backscatter diffraction analysis show an absence of lattice preferred orientation of diamond crystals, {111} growth steps along grain boundaries, and the crystal-size distribution of diamond similar to those of crystals formed in liquid media. In addition, the redox conditions of carbonado formation is inferred to be ~3 log units below the quartz-magnetite-fayalite buffer, which is the prevailing condition in cratonic upper mantle. These lines of evidence suggest that the carbonado crystallized in C-O-H fluid, supporting the hypothesis of a mantle-depth origin of carbonado.

Rheological behavior of water-ash mixtures from Sakurajima and Ontake volcanoes: implications for lahar flow dynamics

Lahars represent one of the most serious volcanic hazards, potentially causing severe damage to the surrounding environment, not only immediately after eruption but also later due to rainfall or snowfall. The flow of a lahar is governed by volcanic topography and its rheological behavior, which is controlled by its volume, microscale properties, and the concentration of particles. However, the effects of particle properties on the rheology of lahars are poorly understood. In this study, viscosity measurements were performed on water-ash mixtures from Sakurajima and Ontake volcanoes. Samples from Sakurajima show strong and simple shear thinning, whereas those from Ontake show viscosity fluctuations and a transition between shear thinning and shear thickening. Particle analysis of the volcanic ash together with a theoretical analysis suggests that the rheological difference between the two types of suspension can be explained by variations in particle size distribution and shape. In particular, to induce the complex rheology of the Ontake samples, coexistence of two particle size groups may be required since two independent behaviors, one of which follows the streamline (Stokes number St << 1, inertial number I < 0.001) and the other shows a complicated motion (St ~ 1, I ~ 0.001), compete against each other. The variations in the spatial distribution of polydisperse particles, and the time dependence of this feature which generates apparent rheological changes, indicate that processes related to microscale particle heterogeneities are important in understanding the flow dynamics of lahars and natural polydisperse granular-fluid mixtures in general.

Relationships between textural and photoluminescence spectral features of carbonado (natural polycrystalline diamond) and implications for its origin

Field Emission SEM (FESEM) textural observations, crystal size distribution (CSD) analyses, UV-excited luminescence imaging, and photoluminescence (PL) microspectroscopy excited by 488 nm laser were conducted on two texturally contrasting samples of carbonado, a kind of natural polycrystalline diamond from the Central African Republic (CAR). The investigated carbonado samples A and B show extremely different textures: sample A is made up of faceted crystals accompanied by abundant, small rectangular pores, whereas sample B has a granular texture with coarser crystals and scarce, large pores. Diamond crystals smaller than 2–3 µm are enriched in sample A but depleted in sample B. These textural features indicate that sample B diamonds were annealed under thermodynamically stable P–T conditions. The pore characteristics indicate that fluid permeability was higher for sample A than sample B. Photoluminescence (PL) spectra indicate that samples A and B correspond to Group A and B carbonados in the classification of Kagi et al. (1994), respectively, so that sample A reveals emissions from the H3 center without any N–V0 derived emission at 575 nm, whereas sample B shows emissions from the 3H center and the N–V0 defect. In addition, UV-excited luminescence images and photoluminescence spectra for sample B indicate that the rims of diamond crystals within several microns of a pore show luminescence features similar to those of Group AB carbonados (Kagi et al., 1994), indicating that this Group AB material was formed from Group B by irradiation from pore-filling, radioactive-element-bearing materials at a low temperature. The extent of the low-temperature irradiation is considered to depend on fluid permeability, and the Group A material was strongly irradiated due to its permeable texture whereas the Group B material was not significantly irradiated due to its less permeable granular texture. These results indicate that Group B carbonados have retained their original PL spectral features produced under high pressures and temperatures at mantle depths.