Sequential Chemical Separation of Cr and Ti from a Single Digest for High‐Precision Isotope Measurements of Planetary Materials

Combined determination of Cr and Ti isotopes of planetary materials offers a means with which to investigate their genetic relationship and the evolution of the protoplanetary disk. Here, we report the new sequential chemical separation procedure for combined Cr and Ti isotope ratio measurements. It comprises three steps: (a) Fe removal using AG1‐X8 anion exchange resin, (b) Ti separation using TODGA resin and (c) Cr separation using AG50W‐X8 cation exchange resin (with one additional step of Ti purification using AG1‐X8 anion exchange resin for samples having high Cr/Ti and Ca/Ti ratios). We applied the proposed procedure to terrestrial and meteorite samples with various compositions. Typical recovery rates of 90–100% were achieved with total procedural Cr and Ti blanks of 3–5 and 2–3 ng, respectively. We measured the Cr and Ti isotope compositions of the separated samples using thermal ionisation mass spectrometry and multiple collector‐inductively coupled plasma‐mass spectrometry, respectively. Our Cr and Ti isotope data were found to be consistent with those of previous studies of individual Cr and Ti isotopic compositions of the meteorites. These results demonstrate the capability of our separation method when applied to combined high‐precision Cr and Ti isotope analyses for single digests of planetary materials.     

High temperature infrared spectra of hydrous microcrystalline quartz

A series of in-situ high temperature infrared (IR) measurements of water in an agate sample and in a milky quartz has been conducted in order to understand the nature of water in silica at high temperatures (50–700?°C) and the dehydration behavior. IR absorption bands of water molecules trapped in the milky quartz showed a systematic decrease in intensities and a shift from 3425?cm^?1 at 50?°C toward 3590?cm^?1 at 700?°C without any loss of water. This indicates a change in IR absorption coefficients corresponding to different polymeric states of water at different temperatures. The broad 3430?cm^?1 band in the agate sample also showed a systematic decrease in IR intensity and a band shift toward higher frequency with increasing temperature (～700?°C). This indicates that the agate sample also contains fluid inclusion-like water. For this agate sample, a dehydration of loosely hydrogen-bonded molecular water occurred at lower temperatures (<200?°C). At higher temperatures (>400?°C), sharp bands around 3660 and 3725?cm^?1 (3740?cm^?1 at 50?°C) due to surface silanols, appeared. This indicates dehydration of H₂O molecules that are hydrogen bonded to surface silanols. SiOH species in the agate are divided into three groups, namely SiOH group located at structural defects, surface silanols hydrogen bonded to each other and free surface silanols. Former two dehydrate below 700?°C and the dehydration rate of the SiOH at structural defects is faster than the other. IR spectra show that SiOH species decrease continuously even after the dehydration of most of H₂O molecules. All these results provide realistic bases for the change in physicochemical states of different OH species in silica at high temperatures.     

Crustal structure, fault segmentation, and activity of the Median Tectonic Line in Shikoku, Japan

We conducted a seismic tomographic analysis to estimate the crustal structure beneath the Shikoku and Chugoku regions in Japan. The Philippine Sea slab (PHS slab) subducts continuously in a SE–NW direction beneath this region, and the crustal structure is complex. Furthermore, the Median Tectonic Line (MTL), one of the longest and most active arc-parallel fault systems in Japan (hereafter, the MTL active fault system), is located in this area, and the right-lateral strike–slip movement of this fault system is related to the oblique subduction of the PHS slab. The MTL active fault system has ruptured repeatedly during the last 10 000 years, and has high seismic potential. Our tomographic analysis clarified the heterogeneous crustal structure along the MTL active fault system. This fault system in Shikoku can be divided into two segments, an east segment and a west segment, on the basis of the velocity structure. This segmentation model is consistent with other such models that have been determined from geological and geomorphological data such as fault geometry, slip rate, and faulting history. This consistency suggests that the surface characteristics of the MTL active fault system are related to structural properties of the crust. In particular, a prominent low-velocity (low-V) zone is present in the lower crust beneath the east segment. Our tomographic images show that the lower crust structure beneath the east segment is obviously different from that of the other segment. Furthermore, this low-V zone may indicate the presence of fluid, possibly related to dehydration of the PHS slab. As the presence of fluid in the lower crust affects the activity of the fault, stress accumulation and the fault failure mechanism may differ between the two segments of the MTL active fault system.     

Hydrothermal activity in the Obiro deposit embedded in the Tagawa acidic rocks,Uetsu region,NE Japan

The Obiro deposit is located in the Tagawa Acidic Rocks (AR), Uetsu region, NE Japan. The Tagawa AR is composed of a volcanic phase of dacitic welded tuff and a plutonic phase of porphyritic granodiorite. Drill core and ore samples were collected from the deposit and examined by XRD, EPMA, and microthermometry. The drill core samples have suffered pervasively from sericite (illite) alteration, whereas pinkish K‐feldspar alteration halo occur close to veins. The results of EPMA and microthermometry is interpreted as that the magnatic‐hydrothermal fluids has changed as follows; the granodioritic magma intruded at about 1.0 kb and 700°C near the water‐saturated granite solidus; after cooling to about 500°C the fluids boiled according to a change in the pressure regime from lithostatic to hydrostatic; mixing with meteoric water led to sulfide mineralization at around 400°C or less. The main reasons for the mineralization in the Obiro deposit are as follows; the oxidized magma intruded at a shallower level, and thereafter hydrothermal fluids were boiled, resulting in a saline fluid. The saline fluid then dissolved metals such as Pb, Zn, Cu, and Bi, and these metals precipitated during cooling accompanied by dilution of the meteoric water and increasing pH, resulting in decreasing solubility.     

Diffuse bifurcations engraving diverse shear bands in granular materials

Shear bands with characteristic spatial patterns observed in an experiment for a cubic or parallelepiped specimen of dry dense sand were simulated by numerical bifurcation analysis using the Cam‐clay plasticity model. By incorporating the subloading surface concept into the plasticity model, the model became capable of reproducing hardening/softening and contractive/dilative behavior observed in the experiment. The model was reformulated to be compatible with the multiplicative hyperelasto‐plasticity for finite strains. This enhanced constitutive model was implemented into a finite‐element code reinforced by a stress updating algorithm based on the return‐mapping scheme, and by an efficient numerical procedure to compute critical eigenvectors of elastoplastic tangent stiffness matrix at bifurcation points. The emergence of diamond‐ and column‐like diffuse bifurcation modes breaking uniformity of the materials, followed by the evolution of shear bands through strain localization, was observed in the analysis. In the bifurcation analysis of plane strain compression test, unexpected bifurcation modes, which broke out‐of‐plane uniformity and led to 3‐dimensional diamond‐like patterns, were detected. Diffuse bifurcations, which were difficult to observe by experiments, have thus been found as a catalyst creating diverse shear band patterns.     

Dark red debris from three short-period comets: 2P/Encke, 22P/Kopff, and 65P/Gunn

We present observations of the extended dust structures near the orbits of three short-period comets: 2P/Encke, 22P/Kopff, and 65P/Gunn. The dust trails were originally discovered by the Infrared Astronomical Satellite (IRAS). Our observations were made using wide-field optical CCD cameras on the University of Hawaii 2.24-m telescope, the Canada-France-Hawaii 3.6-m telescope, and the Kiso 1.05-m Schmidt telescope. We compared the observed images with models and found that the extended structures seen around 2P/Encke and 22P/Kopff before perihelion passage were most likely “dust trails,” whereas images taken after perihelion passage show a high contamination by recently released particles (i.e., particles in Neck-Line structures are visible). We could not confirm the existence of a dust trail from 65P/Gunn within the field of view of the camera used. The effective sizes of the particles responsible for the scattered light were estimated at 1-100 mm (2P/Encke), 1-10 mm (22P/Kopff), and 100 μm-1 mm (65P/Gunn), respectively, which is consistent with previous studies of dust trails made with infrared space telescopes and optical telescopes. We evaluated the mass loss rates of these comets, averaged over their orbits, as reaching (2P/Encke), (22P/Kopff), and (65P/Gunn). These values are consistent with previous work. Therefore, the total amount of material ejected from these three comets is , which would contribute a considerable fraction of the lost within 1 AU that needs to be replaced if the zodiacal cloud is to be maintained in a steady state. We also found that the particles in the dust structures are significantly redder than the Sun and the zodiacal light, and might be redder than the average short-period comet nuclei. Specifically, the reflectivity gradients of 2P/Encke, 22P/Kopff, and 65P/Gunn are 13±7 (% ¹⁰³ Å⁻¹), 20±5 (% ¹⁰³ Å⁻¹), and 15±4 (% ¹⁰³ Å⁻¹), respectively. We examined the change in color with distance from the nucleus. No clear correlation was detected for 2P/Encke or 22P/Kopff to an accuracy of 3-11%, while the 65P/Gunn tail did show color variation, becoming redder with increasing distance from the nucleus. This dark red material, consisting of particles of sand-cobble size, has marginally escaped from the nuclei and will evolve into finer-grained interplanetary dust particles after subsequent collisions.     

Microbial carbon cycling in oligotrophic regional aquifers near the Tono Uranium Mine, Japan as inferred from δC and ΔC values of in situ phospholipid fatty acids and carbon sources

Microorganisms are ubiquitous in deep subsurface environments, but their role in the global carbon cycle is not well-understood. The natural abundance δ¹³C and Δ¹⁴C values of microbial membrane phospholipid fatty acids (PLFAs) were measured and used to assess the carbon sources of bacteria in sedimentary and granitic groundwaters sampled from three boreholes in the vicinity of the Tono Uranium Mine, Gifu, Japan. Sample storage experiments were performed and drill waters analyzed to characterize potential sources of microbial contamination. The most abundant PLFA structures in all waters sampled were 16:0, 16:1ω7c, cy17:0, and 18:1ω7c. A PLFA biomarker for type II methanotrophs, 18:1ω8c, comprised 3% and 18% of total PLFAs in anoxic sedimentary and granitic waters, respectively, sampled from the KNA-6 borehole. The presence of this biomarker was unexpected given that type II methanotrophs are considered obligate aerobes. However, a bacterium that grows aerobically with CH₄ as the sole energy source and which also produces 56% of its total PLFAs as 18:1ω8c was isolated from both waters, providing additional evidence for the presence of type II methanotrophs. The Δ¹⁴C values determined for type II methanotroph PLFAs in the sedimentary (−861‰) and granite (−867‰) waters were very similar to the Δ¹⁴C values of dissolved inorganic carbon (DIC) in each water (∼−850‰). This suggests that type II methanotrophs ultimately derive all their carbon from inorganic sources, whether directly from DIC and/or from CH₄ produced by the reduction of DIC. In contrast, δ¹³C values of type II PLFAs in the sedimentary (−93‰) and granite (−60‰) waters indicate that these organisms use different carbon assimilation schemes in each environment despite very similar δ¹³C_CH4 values (∼−95‰) for each water. The δ¹³C_PLFA values (−28‰ to −45‰) of non-methanotrophic bacteria in the KNA-6 LTL water do not clearly distinguish between heterotrophic and autotrophic metabolisms, but Δ¹⁴C_PLFA values indicate that >65% of total bacteria filtered from the KNA-6 LTL water are heterotrophs. Ancient Δ¹⁴C values (∼−1000‰) of some PLFAs suggest that many heterotrophs utilize ancient organic matter, perhaps from lignite seams within the sedimentary rocks. The more negative range of δ¹³C_PLFA values determined for the KNA-6 granitic water (−42‰ to −66‰) are likely the result of a microbial ecosystem dominated by chemolithoautotrophy, perhaps fuelled by abiogenic H₂. Results of sample storage experiments showed substantial shifts in microbial community composition and δ¹³C_PLFA values (as much as 5‰) during 2-4 days of dark, refrigerated, aseptic storage. However, water samples collected and immediately filtered back in the lab from freshly drilled MSB-2 borehole appeared to maintain the same relative relationships between δ¹³C_PLFA values for sedimentary and granitic host rocks as observed for samples directly filtered under artesian flow from the KNA-6 borehole of the Tono Uranium Mine.     

Heterogeneous accretion,composition and core–mantle differentiation of the Earth

A model of core formation is presented that involves the Earth accreting heterogeneously through a series of impacts with smaller differentiated bodies. Each collision results in the impactor's metallic core reacting with a magma ocean before merging with the Earth's proto-core. The bulk compositions of accreting planetesimals are represented by average solar system abundances of non-volatile elements (i.e. CI-chondritic), with 22% enhancement of refractory elements and oxygen contents that are defined mainly by the Fe metal/FeO silicate ratio. Based on an anhydrous bulk chemistry, the compositions of coexisting core-forming metallic liquid and peridotitic silicate liquid are calculated by mass balance using experimentally-determined metal/silicate partition coefficients for the elements Fe, Si, O, Ni, Co, W, Nb, V, Ta and Cr. Oxygen fugacity is fixed by the partitioning of Fe between metal and silicate and depends on temperature, pressure and the oxygen content of the starting composition. Model parameters are determined by fitting the calculated mantle composition to the primitive mantle composition using least squares minimization. Models that involve homogeneous accretion or single-stage core formation do not provide acceptable fits. In the most successful models, involving 24 impacting bodies, the initial 60–70% (by mass) of the Earth accretes from highly-reduced material with the final 30–40% of accreted mass being more oxidised, which is consistent with results of dynamical accretion simulations. In order to obtain satisfactory fits for Ni, Co and W, it is required that the larger (and later) impactor cores fail to equilibrate completely before merging with the Earth's proto-core, as proposed previously on the basis of Hf-W isotopic studies. Estimated equilibration conditions may be consistent with magma oceans extending to the core–mantle boundary, thus making core formation extremely efficient. The model enables the compositional evolution of the Earth's mantle and core to be predicted throughout the course of accretion. The results are consistent with the late accretion of the Earth's water inventory, possibly with a late veneer after core formation was complete. Finally, the core is predicted to contain ~ 5 wt.% Ni, ~ 8 wt.% Si, ~ 2 wt.% S and ~ 0.5 wt.% O.     

Epithermal Gold Mineralization in the Trenggalek District,East Java,Indonesia

Gold‐mineralized quartz veins at the Trenggalek district of the Southern Mountains Range in East Java, Indonesia, are hosted by Oligo‐Miocene volcaniclastic and volcanic rocks, and are distributed close to andesitic plugs in the northern prospects (Dalangturu, Suruh, Jati, Gregah, Jombok, Salak, and Kojan) and the southern prospects (Sentul and Buluroto). The plugs are subalkaline tholeiitic basaltic‐andesite to calc‐alkaline andesite in composition. ⁴⁰Ar–³⁹Ar dating of a quartz‐adularia vein at the Dalangturu prospect yielded an age of 16.29 ± 0.56 Ma (2σ), and a crystal tuff of a limestone‐pyroclastic rock sequence at the southwest of the Dalangturu prospect was determined as 15.6 ± 0.5 Ma (2σ). Statistic overlap of ages suggests that the gold mineralization in the northern prospects took place in a shallow marine to subaerial transitional environment. Hydrothermal alteration of the host rocks is characterized by the replacement of quartz, illite and adularia. Quartz veins in surface outcrops are up to 50 cm wide in the northern prospects and up to 3 m wide in the southern prospects, showing a banded or brecciated texture, and are composed of quartz, adularia, carbonates with pyrite, electrum, sphalerite, galena, and polybasite. Gold contents of quartz veins are positively correlated with Ag, Zn, Pb, and Cu contents in both the northern and southern prospects. The quartz veins at the Jati, Gregah, and Sentul prospects have relatively lower gold‐silver ratios (Ag/Au = 23.2) compared to those at the Kojan, Dalangturu, Salak, and Suruh prospects (Ag/Au = 66.8). The quartz veins at the Dalangturu prospect are relatively rich in base metal sulfides. Ag/(Au+Ag) ratios of electrum in the Dalangturu prospect range from 45.2 to 65.0 at%, and FeS contents of sphalerite range from 1.2 to 6.4 mol%. Fluid inclusion microthermometry indicates ore‐forming temperatures of 190–200°C and 220–230°C at the Sentul and Kojan prospects, respectively. Widely variable vapor/liquid ratio of fluid inclusions indicates that fluid boiling took place within the hydrothermal system at the Sentul prospect. Salinities of ore‐fluids range from 0 to 0.7 wt% (av. 0.4 wt% NaCl equiv.) and from 0.5 to 1.4 wt% (av. 0.9 wt%) for the Sentul and Kojan prospects, respectively. The boiling of hydrothermal fluid was one of the gold deposition mechanisms in the Sentul prospect.     

Direct ascent to the surface of asthenospheric magma in a region of convex lithospheric flexure

The stress field of oceanic lithosphere controls the distribution of submarine petit-spot volcanoes. However, the eruption sites of these petit-spot volcanoes are considered to be limited to concavely flexed regions of lithosphere off the outer rise. Here, we present new data for a recently identified petit-spot lava field on a convexly flexed section of the lithosphere adjacent to the subduction zone offshore of northeast Japan in an area containing more than 80 volcanoes. This area is marked by strongly alkaline lavas that were erupted on the convexly flexed region. As for the concavely flexed region where the petit-spots previously reported, the base of the lithosphere beneath the eruption sites is under extension, whereas the upper part of the lithosphere is under compression. This change in the stress field, from the lower to upper lithosphere, causes ascending dikes to stall in the mid-lithosphere, leading to metasomatic interaction with the surrounding peridotite. The new geochemical data of rocks and xenocrysts presented in this study indicate that strongly alkaline magmas erupted on the convexly flexed region would have ascended more rapidly through the mid-depth of lithosphere because of the extensional regime of the upper lithosphere and decreasing the degree of metasomatic reaction with the surrounding mantle peridotite. The results indicate that the degree of metasomatism and the compositional variations of petit-spot magmas are controlled mainly by the stress field of the lithosphere.