Liquid bridge contribution to shear behavior of unsaturated soil: modeling and application to a micromechanics model

Acta Geotechnica - Liquid bridges in unsaturated soils attach to grain contacts and contribute to strengthening microscopic bonding forces, which leads to macroscopic high strength and stiffness...     

Raman spectra of methane hydrate up to 86 GPa

High-pressure Raman studies of methane hydrate were performed using a diamond anvil cell in the pressure range of 0.1–86 GPa at room temperature. Raman spectra of the methane molecules revealed that new softened intramolecular vibration mode of ν ₁ appeared at 17 GPa and that the splitting of vibration mode of ν ₃ occurred at 15 GPa. The appearance of these two modes indicates that an intermolecular attractive interaction increases between the methane molecules and the host water molecules and between the neighboring methane molecules. These interactions might result in the exceptional stability of a high-pressure structure, a filled ice Ih structure (FIIhS) for methane hydrate, up to 40 GPa. At 40 GPa, a clear change in the slope of the Raman shift versus pressure occurred, and above 40 GPa the Raman shift of the vibration modes increased monotonously up to 86 GPa. A previous XRD study showed that the FIIhS transformed into another new high-pressure structure at 40 GPa. The change in the Raman spectra at 40 GPa may be induced by the transition of the structure.     

The use of sintered diamond anvils in the MA8 type high-pressure apparatus

A new multi-anvil type high-presure apparatus has been developed using sintered diamond anvils to generate pressures over 30 GPa and temperatures up to about 2000°C. A maximum sample volume of about 1 mm³ is available in this system. The pressure was confirmed by dissociation of forsterite into Mg-perovskite and periclase. The basic techniques and problems in utilizing sintered diamond in the MA8 type high-pressure apparatus are discussed with an emphasis on the future prospect of incorporating simultancous X-ray diffraction observation.     

Equilibrium interface segregation in the diopside-forsterite system I: Analytical techniques, thermodynamics, and segregation characteristics

After syntheses of partially molten diopside-forsterite polycrystalline aggregates doped with various solutes, we analyzed the equilibrium segregation of Ni, Mn, Sr, Al, Yb, Y, Nd, La, and Ti at interfaces between diopside/diopside, diopside/forsterite and, forsterite/forsterite grains based on STEM/EDX (scanning transmission electron microscopy/energy dispersive X-ray spectrometry) to examine the effects of ionic size, valence state, co-segregation, and interface type on interface chemistry. We derive relationships between two quantities describing interface segregation and X-ray intensities acquired both from areas that include an interface and from areas that do not. These segregation quantities are (i) interface excess density and (ii) interface enrichment factor, which rely on Gibbsian thermodynamics and the Langmuir-McLean segregation model, respectively. Interface excess densities, which vary from −0.5 to 10 atoms/nm², indicate that the level of interface excess density depends on solutes and sample assemblage. Interface enrichment factors, which range from almost 1 to 130, reveal that the ionic size of the solutes affects their segregation via production of misfit lattice strain due to the difference between the size of a solute ion and that of the ideal strain-free lattice site. The ionic sizes of Yb and Y are almost identical to the size of the strain-free site; however, their segregation is significant indicating that a difference in valence state between the host elements (i.e., Ca and Mg) and the solutes also drives segregation. In contrast to other solutes, segregation characteristics of Al differ from these simple segregation rules. Segregation quantities do not change with interface type, indicating that the number of sites available for segregants and the driving force for segregation are similar among type of interfaces. We compare the element partitioning between diopside-melt and diopside-interfaces within the same sample assemblages. These two partition coefficients coincide if we approximate the number of segregation sites at interfaces as equivalent to 2 mono-atomic layers. Examination of the energetics in crystal-melt partitioning reveals that the interface segregation energy is essentially equal to the solute solution energy in a crystal.     

Equilibrium interface segregation in the diopside-forsterite system II: Applications of interface enrichment to mantle geochemistry

Segregation of incompatible elements at grain interfaces may have considerable influence on the physical and chemical properties of mantle rocks. Using a recently developed predictive model to estimate the interface enrichment of elements based on their mineral/melt partitioning (Hiraga and Kohlstedt, companion paper), we consider interface enrichment for a simplified model peridotite consisting of olivine, orthopyroxene, and clinopyroxene. Our calculated results reveal the following: (1) Significant amounts of heavy alkali elements and rare gases likely reside at grain-grain interfaces, whereas interface concentrations of less incompatible are less pronounced. (2) The contribution of the chemical components stored at interfaces to whole-rock chemistry strongly depends on mineral mode and, most importantly, on grain size. (3) Grain size reduction resulting from dynamic recrystallization can increase the total storage of highly incompatible elements on grain interfaces and thereby will diminish their concentration in mineral grains. (4) Analysis of Cs concentrations in mantle clinopyroxenes potentially provides estimates of the grain size of mantle rocks. (5) Transport through peridotite will be dominated by diffusion along interfaces rather than through grain interiors for elements less compatible than Lu.     

Effect of hydrostatic pressure on the lattice parameters of Fe2SiO4 olivine up to 70 kbar

The pressure dependence of the three lattice parameters and unit cell volume of fayalite (Fe₂SiO₄ olivine) was determined by X-ray diffraction under hydrostatic pressures up to 70 kbar. In order to eliminate stress inhomogeneity within a composite material consisting of a specimen mixed with an internal-pressure standard, a liquid (1 : 1 mixture of ethanol and methanol) was used as a pressure-transmitting medium. The isothermal bulk modulus calculated on the basis of the second-order Birch-Murnaghan equation of state gives the values K₀ = 1.19 ± 0.10 Mbar and K₀′ = 7 ± 4, and if we assume K₀′ = 5: K₀ = 1.24 ± 0.02 Mbar. Three axes of fayalite were found to be compressible in the following order, b >c >a. Comparisons with the results obtained under non-hydrostatic compression are made.     

Synthesis of highly dense and fine-grained aggregates of mantle composites by vacuum sintering of nano-sized mineral powders

Synthesized mineral powders with particle size of <100 nm are vacuum sintered to obtain highly dense and fine-grained polycrystalline mantle composites: single phase aggregates of forsterite (iron-free), olivine (iron containing), enstatite and diopside; two-phase composites of forsterite + spinel and forsterite + periclase; and, three-phase composites of forsterite + enstatite + diopside. Nano-sized powders of colloidal SiO₂ and highly dispersed Mg(OH)₂ with particle size of ≤50 nm are used as chemical sources for MgO and SiO₂, which are common components for all of the aggregates. These powders are mixed with powders of CaCO₃, MgAl₂O_4, and Fe(CO₂CH₃)₂ to introduce mineral phases of diopside, spinel, and olivine to the aggregates, respectively. To synthesize highly dense composites through pressureless sintering, we find that calcined powders should be composed of particles that have: (1) fully or partially reacted to the desired minerals, (2) a size of <100 nm and (3) less propensity to coalesce. Such calcined powders are cold isostatically pressed and then vacuum sintered. The temperature and duration of the sintering process are tuned to achieve a balance between high density and fine grain size. Highly dense (i.e., porosity ≤1 vol%) polycrystalline mantle mineral composites with grain size of 0.3–1.1 μm are successfully synthesized with this method.     

Geochemical study of arsenic and other trace elements in groundwater and sediments of the Old Brahmaputra River Plain,Bangladesh

The geochemical study of groundwaters and core sediments from the Old Brahmaputra plain of Bangladesh was conducted to investigate the distribution of arsenic and related trace elements. Groundwaters from tube wells are characterized by pH of 6.4–7.4, dissolved oxygen (DO) of 0.8–1.8 mg/l, Ca contents of 5–50 mg/l, and Fe contents of 0.2–12.9 mg/l. Arsenic concentrations ranged from 8 to 251 μg/l, with an average value of 63 μg/l. A strong positive correlation exists between As and Fe (r ² = 0.802; p = 0.001) concentrations in groundwater. The stratigraphic sequences in the cores consist of yellowish silty clays at top, passing downward into grayish to yellowish clays and sands. The uppermost 3 m and lower parts (from 13 to 31 m) of the core sediments are oxidized (average oxidation reduction potential (ORP) +170 and +220 mV, respectively), and the ORP values gradually become negative from 3 to 13 m depths (−35 to −180 mV), indicating that anoxic conditions prevail in the shallow aquifers of the Brahmaputra plain. Age determinations suggest that clay horizons at ~10 m depth were deposited at around 2,000 and 5,000 years BP (¹⁴C ages) during the transgressive phase of sea-level change. Elevated concentrations of As, Pb, Zn, Cu, Ni, Cr, and V are present in the silts and clays, probably due to adsorption onto clay particles. Significant concentrations of As occur in black peat and peaty sediments at depths between 9 and 13 m. A strong positive correlation between As and Fe was found in the sediments, indicating As may be adsorbed onto Fe oxides in aquifer sediments.     

An anomalous eucrite,Dhofar 007, and a possible genetic relationship with mesosiderites

Abstract— We studied the texture, mineralogy, and bulk chemical composition of Dhofar 007, a basaltic achondrite. Dhofar 007 is a polymict breccia that is mostly composed of coarse‐grained granular (CG) clasts with a minor amount of xenolithic components, such as a fragment of Mg‐rich pyroxene. The coarse‐grained, relict gabbroic texture, mineral chemistry, and bulk chemical data of the coarse‐grained clast indicate that the CG clasts were originally a cumulate rock crystallized in a crust of the parent body. However, in contrast to monomict eucrites, the siderophile elements are highly enriched and could have been introduced by impact events. Dhofar 007 appears to have experienced a two‐stage postcrystallization thermal history: rapid cooling at high temperatures and slow cooling at lower temperatures. The presence of pigeonite with closely spaced, fine augite lamellae suggests that this rock was cooled rapidly from higher temperatures (>0.5 °C/yr at ˜1000 °C) than typical cumulate eucrites. However, the presence of the cloudy zone in taenite and the Ni profile across the kamacite‐taenite boundaries indicates that the cooling rate was very slow at lower temperatures (˜1–10 °C/Myr at <600–700 °C). The slow cooling rate is comparable to those in mesosiderites and pallasites. The two‐stage thermal history and the relative abundance of siderophile elements similar to those for metallic portions in mesosiderites suggest that Dhofar 007 is a large inclusion of mesosiderite. However, we cannot rule out a possibility that Dhofar 007 is an anomalous eucrite.