Refinement of the Micro‐Distillation Technique for Isotopic Analysis of Geological Samples with pg‐Level Osmium Contents

In recent years, the ¹⁸⁷Re–¹⁸⁷Os isotope system has been increasingly used to study samples containing very small quantities of Os. For such samples, optimisation of measurement procedures is essential to minimise the loss of Os before mass spectrometric measurements. Micro‐distillation is a necessary purification step that is applied after the main Os chemical separation procedure, prior to Os isotope ratio measurements by negative‐thermal ionisation mass spectrometry (N‐TIMS). However, unlike the other separation steps, this procedure has not yet been optimised for small samples. In this study, we present a refined micro‐distillation method that achieved higher yields and allowed high‐precision R(¹⁸⁷Os/¹⁸⁸Os) expressed as ¹⁸⁷Os/¹⁸⁸Os measurements for small‐sized geological samples that contain only a few pg Os. The Os recovery in the micro‐distillation step was tested by changing the operating conditions including heating time and temperature, and amounts of oxidant and reductant. Recoveries were measured by the isotope dilution ICP‐MS method after the addition of ¹⁹⁰Os‐enriched spike solution. We found that the most critical factor controlling the chemical yield of Os during micro‐distillation is the extent of dilution of the reductant (HBr) by H₂O evaporated from the oxidant. A refined micro‐distillation method, in which the amount of oxidant solution is reduced from the conventional method, achieved an improved chemical yield of Os (~ 90%). This refined method was applied to the measurement of ¹⁸⁷Os/¹⁸⁸Os by N‐TIMS of varying test portions of the geological reference material BIR‐1a. The resulting ¹⁸⁷Os/¹⁸⁸Os ratios of BIR‐1a matched the literature data, with propagated uncertainties of 0.2, 1.1 and 11% digested sample quantities containing 150, 10 and 1 pg of Os, respectively.     

Timing of Himalayan ultrahigh-pressure metamorphism: sinking rate and subduction angle of the Indian continental crust beneath Asia

Coesite relics were discovered as inclusions in clinopyroxene in eclogite and as inclusions in zircon in felsic and pelitic gneisses from Higher Himalayan Crystalline rocks in the upper Kaghan Valley, north‐west Himalaya. The metamorphic peak conditions of the coesite‐bearing eclogites are estimated to be 27–32 kbar and 700–770 °C, using garnet–pyroxene–phengite geobarometry and garnet–pyroxene geothermometry, respectively. Cathodoluminescence (CL) and backscattered electron (BSE) imaging distinguished three different domains in zircon: inner detrital core, widely spaced euhedral oscillatory zones, and thin, broadly zoned outermost rims. Each zircon domain contains a characteristic suite of micrometre‐sized mineral inclusions which were identified by in situ laser Raman microspectroscopy. Core and mantle domains contain quartz, apatite, plagioclase, muscovite and rutile. In contrast, the rim domains contain coesite and minor muscovite. Quartz inclusions were identified in all coesite‐bearing zircon grains, but not coexisting with coesite in the same growth domain (rim domain). ²⁰⁶Pb/²³⁸U zircon ages reveal that the quartz‐bearing mantle domains and the coesite‐bearing rim were formed at c. 50 Ma and 46.2 ± 0.7 Ma, respectively. These facts demonstrate that the continental materials were buried to 100 km within 7–9 Myr after initiation of the India–Asia collision (palaeomagnetic data from the Indian oceanic floor supports an initial India‐Asia contact at 55–53 Ma). Combination of the sinking rate of 1.1–1.4 cm year^?1 with Indian plate velocity of 4.5 cm year^?1 suggests that the Indian continent subducted to about 100 km depth at an average subduction angle of 14–19°.     

High-Reflectivity Coatings for a Vacuum Ultraviolet Spectropolarimeter

Precise polarization measurements in the vacuum ultraviolet (VUV) region are expected to be a new tool for inferring the magnetic fields in the upper atmosphere of the Sun. High-reflectivity coatings are key elements to achieving high-throughput optics for precise polarization measurements. We fabricated three types of high-reflectivity coatings for a solar spectropolarimeter in the hydrogen Lyman-\(\upalpha \) (Ly\(\upalpha \); 121.567 nm) region and evaluated their performance. The first high-reflectivity mirror coating offers a reflectivity of more than 80 % in Ly\(\upalpha \) optics. The second is a reflective narrow-band filter coating that has a peak reflectivity of 57 % in Ly\(\upalpha \), whereas its reflectivity in the visible light range is lower than 1/10 of the peak reflectivity (\(\sim 5~\%\) on average). This coating can be used to easily realize a visible light rejection system, which is indispensable for a solar telescope, while maintaining high throughput in the Ly\(\upalpha \) line. The third is a high-efficiency reflective polarizing coating that almost exclusively reflects an s-polarized beam at its Brewster angle of 68° with a reflectivity of 55 %. This coating achieves both high polarizing power and high throughput. These coatings contributed to the high-throughput solar VUV spectropolarimeter called the Chromospheric Lyman-Alpha SpectroPolarimeter (CLASP), which was launched on 3 September, 2015.     

Meteorological features in Adélie Land during the austral summer season

Intensive meteorological observations were carried out at three sites along the slope of Adélie Land, Antarctica, with the goal of documenting summertime meteorological features of the katabatic zone. Three observational sites were placed at 5 km (D10), 110 km (D47), and 210 km (D57) from the coast, and frequency distributions of meteorological parameters were obtained at each site. Some meteorological features at D47 and D57 (interior sites) were different than at D10 (the coastal site); namely, mean air temperatures averaged for the whole observational period showed more pronounced diurnal variations at the interior sites than at the coastal site. These variations could be represented by sinusoidal curves. Wind speeds also showed diurnal variations, whose extremes appeared several hours later than the temperature extremes. The prevailing wind direction for all sites was southerly, about 30° east of the fall line, with small variations in wind direction. The strength and the height of temperature inversions were examined in two different layers (0 to 50 m, 50 to 300 m) at D47. A strong, shallow inversion layer formed at night, however, completely vanished during the day. On the other hand, an upper level inversion whose strength was weak persisted. The katabatic characteristics of the surface wind found at D47 in summer could be due to this upper level temperature inversion.A contribution to I.A.G.O. (Interaction-Atmosphere-Glace-Ocean).     

Blended-acquisition design of irregular geometries towards faster,cheaper, safer and better seismic surveying

The application of blended acquisition has drawn considerable attention owing to its ability to improve the operational efficiency as well as the data quality and health, safety and environment performance. Furthermore, the acquisition of less data contributes to the business aspect, while the desired data density is still realizable via subsequent data reconstruction. The use of fewer detectors and sources also minimizes operational risks in the field. Therefore, a combined implementation of these technologies potentially enhances the value of a seismic survey further. One way to encourage this is to minimize any imperfection in deblending and data reconstruction during processing. In addition, one may derive survey parameters that enable a further improvement in these processes as introduced in this study. The proposed survey design workflow iteratively performs the following steps to derive the survey parameters responsible for source blending as well as the spatial sampling of detectors and sources. The first step is the application of blending and sampling operators to unblended and well-sampled data. We then apply closed-loop deblending and data reconstruction. The residue for a given design from this step is evaluated and subsequently used by genetic algorithms to simultaneously update the survey parameters related to both blending and spatial sampling. The updated parameters are fed into the next iteration until they satisfy the given termination criteria. We also propose a repeated encoding sequence to form a parameter sequence in genetic algorithms, making the size of problem space manageable. The results of the proposed workflow are outlined using blended dispersed source array data incorporating different scenarios that represent acquisition in marine, transition zone and land environments. Clear differences attributed solely to the parameter design are easily recognizable. Additionally, a comparison among different optimization schemes illustrates the ability of genetic algorithms along with a repeated encoding sequence to find better solutions within a computationally affordable time. The optimized parameters yield a notable enhancement in the deblending and data reconstruction quality and consequently provide optimal acquisition scenarios.     

Evolution of the composition of seawater through geologic time, and its influence on the evolution of life

The redox state of the surface environment of the early Earth is still controversial, and a detailed and quantitative estimate is still lacking. We carried out in-situ analyses of major, trace, and rare-earth elements of carbonate minerals in rocks with primary sedimentary structures in shallow and deep sea-deposits, in order to eliminate secondary carbonate and contamination of detrital materials, and to estimate the redox condition of seawater through time. Based on the Ce content and anomalies of the carbonate minerals at given parameters of atmospheric CO₂ content (pCO₂) and Ca content of seawater, we calculated the oxygen contents of shallow and deep seawater, respectively. The results show that the oxygen content of the deep sea was low and constant until at least 1.9 Ga. The oxygen content of shallow seawater increased after 2.7 Ga, but fluctuated. It became quite high at 2.5 and 2.3 Ga, but eventually increased after the Phanerozoic. In addition, the calculation of a high pCO₂ condition shows that seawater was more oxic even in the Archean than at present, suggesting a relatively low pCO₂ through geologic time.Our detailed calculations from compositions of carbonate minerals in Three Gorge area, south China show a low oxygen content of seawater after the Snowball Earth until the late Ediacaran, an increase in the late Ediacaran, and a significant decrease around the Precambrian–Cambrian and Nemakit/Daldynian–Tommotian boundaries. These variations were possibly caused by global regression and dissolution of methane hydrates.     

Feldspar dissolution rates measured using phase-shift interferometry: Implications to CO2 underground sequestration

To assess CO₂ underground sequestration from a geochemical viewpoint, the anorthite dissolution rate, which is an important parameter of risk analysis, was measured in a CO₂–water system. The authors sought to obtain precise dissolution rate data in a short time observing a crystal surface on a nanoscale. For this purpose, phase-shift interferometry was applied. Using this method, uncertainty of the reactive surface area that is imparted on calculation of the dissolution rate constant can also be avoided. The time-course profile of vertical retreat of the surface revealed that the anorthite dissolution process changes from the initial transient state to a later steady state, which is consistent with results of numerous precedent studies. The transient dissolution rate depends strongly on local features (e.g., density of defects, variation of chemical compositions) of the crystal surface, rather than on temperature. Therefore, it is very important to determine the original properties of the anorthite surface for the examination of subsequent dissolution process. Contrary to general expectations, the anorthite dissolution can alter the physical properties of reservoir rock immediately after CO₂ injection. The simple estimation using the anorthite dissolution rate obtained in this study, which was done as a test case for the CO₂ underground sequestration project conducted by RITE, revealed that porosity of reservoir rock increased about 2% (23–23.4%) of initial values during 60 a. That change in physical property in such a short time might enhance the diffusion of injected CO₂ and formation water, and therefore accelerate further geochemical reactions. Results of this study demonstrate that the geochemical water–rock interaction, which is generally regarded as a longer-term phenomenon than various physical processes, can also affect the reservoir system from the initial stage.     

Lattice preferred orientation in CaIrO<Subscript>3</Subscript> perovskite and post-perovskite formed by plastic deformation under pressure

Lattice preferred orientations (LPO) developed in perovskite and post-perovskite structured CaIrO₃ were studied using the radial X-ray diffraction technique combined with a diamond anvil cell. Starting materials of each phase were deformed from 0.1 MPa to 6 GPa at room temperature. Only weak LPO was formed in the perovskite phase, whereas strong LPO was formed in the post-perovskite phase with an alignment of the (010) plane perpendicular to the compression axis. The present result suggests that the (010) is a dominant slip plane in the post-perovskite phase and it is in good agreement with the crystallographic prediction, dislocation observations via transmission electron microscopy, and a recent result of simple shear deformation experiment at 1 GPa–1,173 K. However, the present result contrasts markedly from the results on MgGeO₃ and (Mg,Fe)SiO₃, which suggested that the (100) or (110) is a dominant slip plane with respect to the post-perovskite structure. Therefore it is difficult to discuss the behavior of the post-perovskite phase in the Earth’s deep interior based on existing data of MgGeO₃, (Mg,Fe)SiO₃ and CaIrO₃. The possible sources of the differences between MgGeO₃, (Mg,Fe)SiO₃ and CaIrO₃ are discussed.     

Transfer coefficients of sensible heat on a snowmelt surface

Summary Field observations were carried out in order to determine the transfer coefficeient of sensible heat flux above a melting snow surface at the Moshiri experimental site. The coefficient is calculated as the ratio of the sensible heat flux determined by the eddy correlation method using a sonic anemometer to the product of the wind speed and the temperature difference between the air and snow surface. The sensible heat fluxes are also compared with the result of the precise heat balance observations. The nondimensional transfer coefficienth shows a good correlation with the atmospheric stability,Ri. The value ofh=2.3×10^–3 is obtained in the range of 0<Ri<0.1, however, it is smaller and scattered under stronger stable condition (Ri>0.1). The dimensional transfer coefficent for sensible heat flux is calculated, and a linear relationship is obtained as a function of the logarithm of atmospheric stability.With 11 Figures