Structure and crystal chemistry of a dense polymorph of tricalcium phosphate Ca3 (PO4)2: A host to accommodate large lithophile elements in the earth's mantle

A phase of Ca₃ (PO₄)₂, synthesized at 12GPa and 2300° C, is structurally analyzed by the single crystal X-ray diffraction method. This Ca₃(PO₄)₂ is found to be a dense polymorph of tricalcium phosphate isostructural with Ba₃ (PO₄)₂ and named γ-Ca₃ (PO₄)₂. In the structure of Ca₃ (PO₄)₂, a phosphorus atom is tetrahedrally coordinated by oxygen atoms and calcium atoms occupy two types of large metal sites. The Ca(1) site has twelve oxygen neighbours with the mean bond length of 2.739 Å while the other Ca(2) site is coordinated by ten oxygen atoms with the mean Ca-O distance of 2.588Å. The structure is characterized by the translationally interconnected polyhedral sequence PO₄-Ca(2)O₁₀-Ca (1)O₁₂-Ca (2)O₁₀-PO₄ in the direction of the c axis. This dense phase of Ca₃(PO₄)₂ with two large metal sites may be an important host for very large lithophile elements in the deep upper mantle of the earth.     

A study of subsolidus relations of the Skaergaard pyroxenes by analytical electron microscopy

Within augite and pigeonite grains of the Skaergaard ferrogabbro 4430, the Ca-poor phases contain only three mole percent of CaSiO₃, and the Mg-Fe partition coefficients between the Ca-poor and Ca-rich phases are extremely small with 0.46 for augite and 0.51 for pigeonite grains. These values indicate existence of diffusion within each grain (intragranular diffusion) at considerably low temperatures.The compositions are slightly but definitely different between the Ca-rich phases in augite and pigeonite grains as well as between the Ca-poor phases in augite and pigeonite grains. This indicates that the diffusion among the grains (inter-granular diffusion) has not taken place under the subsolidus condition of the Skaergaard intrusion.     

Anomalous change in atmospheric radon concentration sourced from broad crustal deformation: A case study of the 1995 Kobe earthquake

Before the Kobe earthquake, an anomalous increase in atmospheric Rn concentration was observed. By separating the measured concentration of atmospheric Rn into three components according to the distance from the monitoring station, the variation of Rn exhalation rate can be estimated for the respective area using the daily minimum and maximum concentrations. The mean rate of Rn exhalation gradually increased in an area of 20 km around the monitoring station, becoming five times higher than normal in the period between October 1994 and the date of the earthquake. This area had a large co-seismic displacement of up to 30 cm, which roughly corresponds to the crustal strain of 10⁻⁶-order, and it is considered the main source for the atmospheric Rn prior to the Kobe earthquake. Analyses revealed that the pre-seismic change in the atmospheric Rn concentration exhibited an anomalous pattern which would yield information on the spatial distribution of the mechanical response of the ground.     

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.     

Barium Increasing Prior to Opal during the Last Termination of Glacial Ages in the Okhotsk Sea Sediments

Ba and Ti in a sediment core (10 m long) from the Okhotsk Sea, covering the last 120 kyrs, were measured. The authigenic Ba (Ba_ex) contents were calculated and compared with the opal. The correlation coefficient between Ba_ex and opal was quite small (r = 0.34), but it greatly grew larger (r = 0.90), if the Ba_ex contents were multiplied by a simple function increasing with depth, except for two intervals. This may be due to the gradual change in the sedimentation environment during the glacial ages. One of the exceptional interval is found at 60–170 cm in depth, corresponding to 10–17 calendar kyr ago, the last termination period of glacial ages, where the Ba_ex began to increase prior to opal. Since the calcium carbonate contents similarly increased prior to the opal increase, the Ba_ex may be also related to calcareous organisms besides siliceous ones. The other is the last interglacial period around 120 kyr ago when the opal contents were high, but those of the Ba_ex were not increased. This can be explained, if the Ba_ex was reduced to sulfide and dissolved away in a strongly anoxic environment during the biologically productive period. During the glacial ages, the mass accumulation rate (MAR) of lithogenic Ti was about twice the amount of that during the interglacial ages. For opal, however, the contrast between the glacial and interglacial ages was more remarkable in its MAR than in its concentration in sediments, due to the larger variation in the bulk sedimentation rates. This revised version was published online in July 2006 with corrections to the Cover Date.     

Naturally occurring radionuclides and rare earth elements in weathered Japanese soil samples

The activity concentrations of ²²⁶Ra and ²²⁸Ac in weathered Japanese soils from two selected prefectures have been measured using a γ-ray spectroscopy system with high purity germanium detector. The uranium, thorium, and rare earth elements (REEs) concentrations were determined from the same soil samples using inductively coupled plasma mass spectrometry (ICP-MS). For example, granitic rocks contain higher amounts of U, Th, and light REEs compared to other igneous rocks such as basalt and andesites. Therefore, it is necessary to understand the interaction between REEs and nature of soils since soils are complex heterogeneous mixture of organic and inorganic solids, water, and gases. In this paper, we will discuss about distribution pattern of ²³⁸U and ²³²Th along with REEs in soil samples of weathered acid rock (granite) collected from two prefectures of Japan: Hiroshima and Miyagi.     

High temperature X-ray study of single crystal stishovite synthesized with Li2WO4 as flux

Single crystal stishovite with a square prismatic habit and maximum length 0.8 mm was grown from α-quartz at 120 kbar and ～1,300° C. Li₂WO₄, chosen as a result of a previous experiment in growing coesite, was also successful as flux for stishovite. Single crystal X-ray structure analysis of the crystals thus obtained has been carried out at high temperatures under ambient pressure. Lattice constant measurements give a larger thermal expansion coefficient along the a-axis than along the c-axis. The bond distances and bond angles show a decreasing distortion of the SiO₆ octahedron with increasing temperature. The increasing amplitude of thermal vibrations of oxygen atoms with increasing temperature results in increasing O-O repulsion in the basal plane, which explains the observed crystallographic changes.     

Natural radionuclide analysis in chattarpur area of southeastern coastal area of Odisha, India

The energy released in a spontaneous decay process of natural radionuclides is the main source of the total radiation dose to human beings. Natural radionuclides are widely distributed in soil, rocks, air, and groundwater. In present investigation, the analysis of terrestrial radionuclides such as ²²⁶Ra, ²³²Th, and ⁴⁰K in soil and sand of Chattarpur area of southeastern coast of Odisha has been carried out using NaI(Tl) gamma ray detector. The higher activity concentrations of naturally occurring radionuclides have been reported from the study area. The gamma radiationdose originating from the terrestrial radionuclides was found to vary from 95 to 1813 nGy/h with an average of 700 nGy/h. This study is important to generate a baseline data of radiation exposure in the area. Health hazard effects due to natural radiation exposure are discussed in details.     

Temperature dependence of intersite distribution of Mg and Fe in olivine and the associated change of lattice parameters

The cation distribution of natural and heated ferromagnesian olivine with chemical composition, Fo₆₇Fa₃₃, from metagabbro was examined by X-ray diffraction. Heating and quenching experiments were made by a newly devised apparatus which enables us to obtain very fast quenching speed in comparison with the usual technique. The distribution constants, K _D=(Fe⁺²/Mg) _M1/(Fe⁺²/Mg) _M2, of the natural samples were less than 1.07, and those of heat-treated samples were more than 1.15, indicating that cation ordering takes place with temperature. The distribution of Fe⁺² and Mg is nearly random at low temperatures, whereas Fe⁺² shows a slight but significant preference for a smaller M1 site at high temperatures. The change of the distribution constant was observed on specimens which were heated for a short period of time (6–1,060 s) and quenched within 10 ms. Thus the rate of the cation reordering reaction is a very fast process. The lattice parameters b and c decrease whereas a increases with the increase of distribution constant. The overall effect on unit cell volume is a decrease with the increasing distribution constant, suggesting the presence of significant pressure dependence of the cation distribution towards the ordering of Fe at M1 site in ferromagnesian olivine.     

Distribution of titanium atoms in oxy-kaersutite

The distribution of Ti atoms in oxy-kaersutite has been studied by the neutron diffraction method. The cation distribution over the three octahedral sites determined by the x-ray method (Kitamura and Tokonami, 1971) is as follows; M1∶0.40MG+0.60 FE, M2∶0.75 MG+0.25 FE, M3∶0.50 MG+0.50 FE, where MG and FE represent (Mg+Al) and (Fe+Ti), respectively. The neutron diffraction study indicates that Ti atoms are enriched in the M1 site more than M2 and M3 sites as follows; M1∶0.40 MG+0.33 Fe+0.27 Ti, M2∶ 0.75 MG+0.23 Fe+0.02 Ti, M3∶0.50 MG+0.46 Fe+0.04 Ti. This distribution agrees with the result based on the Madelung energy of oxy-kaersutite by Whittaker (1972).