Diverse Range of Mineralization Induced by Phase Separation of Hydrothermal Fluid: Case Study of the Yonaguni Knoll IV Hydrothermal Field in the Okinawa Trough Back-Arc Basin

The Yonaguni Knoll IV hydrothermal vent field (24°51′N, 122°42′E) is located at water depths of 1370–1385 m near the western edge of the southern Okinawa Trough. During the YK03–05 and YK04–05 expeditions using the submersible Shinkai 6500, both hydrothermal precipitates (sulfide/sulfate/carbonate) and high temperature fluids (Tmax = 328°C) presently venting from chimney‐mound structures were extensively sampled. The collected venting fluids had a wide range of chemistry (Cl concentration 376–635 mmol kg^?1), which is considered as evidence for sub‐seafloor phase separation. While the Cl‐enriched smoky black fluids were venting from two adjacent chimney‐mound structures in the hydrothermal center, the clear transparent fluids sometimes containing CO₂ droplet were found in the peripheral area of the field. This distribution pattern could be explained by migration of the vapor‐rich hydrothermal fluid within a porous sediment layer after the sub‐seafloor phase separation. The collected hydrothermal precipitates demonstrated a diverse range of mineralization, which can be classified into five groups: (i) anhydrite‐rich chimneys, immature precipitates including sulfide disseminations in anhydrite; (ii) massive Zn‐Pb‐Cu sulfides, consisting of sphalerite, wurtzite, galena, chalcopyrite, pyrite, and marcasite; (iii) Ba‐As chimneys, composed of barite with sulfide disseminations, sometimes associated with realgar and orpiment overgrowth; (iv) Mn‐rich chimneys, consisting of carbonates (calcite and magnesite) and sulfides (sphalerite, galena, chalcopyrite, alabandite, and minor amount of tennantite and enargite); and (v) pavement, silicified sediment including abundant native sulfur or barite. Sulfide/sulfate mineralization (groups i–iii) was found in the chimney–mound structure associated with vapor‐loss (Cl‐enriched) fluid venting. In contrast, the sulfide/carbonate mineralization (group iv) was specifically found in the chimneys where vapor‐rich (Cl‐depleted) fluid venting is expected, and the pavement (group v) was associated with diffusive venting from the seafloor sediment. This correspondence strongly suggests that the subseafloor phase separation plays an important role in the diverse range of mineralization in the Yonaguni IV field. The observed sulfide mineral assemblage was consistent with the sulfur fugacity calculated from the FeS content in sphalerite/wurtzite and the fluid temperature for each site, which suggests that the shift of the sulfur fugacity due to participation of volatile species during phase separation is an important factor to induce diverse mineralization. In contrast, carbonate mineralization is attributed to the significant mixing of vapor‐rich hydrothermal fluid and seawater. A submarine hydrothermal system within a back‐arc basin in the continental margin may be considered as developed in a geologic setting favorable to a diverse range of mineralization, where relatively shallow water depth induces sub‐seafloor phase separation of hydrothermal fluid, and sediment accumulation could enhance migration of the vapor‐rich hydrothermal fluid.     

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.     

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.     

Hydrothermal plumes in the eastern Manus Basin, Bismarck Sea: CH4, Mn, Al and pH anomalies

We present evidence for strong hydrothermal activity in the eastern Manus Basin (depth: 1700–2100 m), the existence of large scale triple-layered buoyant plumes at depths of 1100 m (“shallow plume”), 1700 m (“deep plume”), and 1400 m (“middle plume” with less extent than the other two plumes) that were revealed from water column anomalies of CH₄, Mn, Al and pH observed in November to December 1990. Judging from the horizontal distribution of these parameters, the deep plume seems to originate from two distinct hydrothermal sites (eastern and western sites) in the research area, the eastern site being visually ascertained with deep-tow observations at the same time. The CH₄/Mn ratio (mol mol⁻¹) of the deep plume (0.02–0.05) is the lowest yet observed in hydrothermal plumes. The order of magnitude difference of CH₄/Mn ratios between the shallow plume and the deep plume suggests that different kinds of fluid-rock interaction occurred to make the hydrothermal end members for the deep and shallow plumes. The shallow plume, which had an areal extent of more than 50 km, may be an episodic “megaplume”, because it was not recognized in the previous CH₄ profiles in 1986, and because it has a similar CH₄/Mn ratio as the megaplume observed in the North Fiji Basin. We found that the eastern deep plume is characterized by enormously high aluminium concentrations (0.6– 1.5 μmol kg⁻¹), pH anomalies (0.1) and high Al/Mn ratios (10–17). The endmember fluid for the eastern deep plume may have an unusually low pH value to dissolve this much aluminum during fluid-rock interaction, or this plume may originate from an eruption-influenced fluid.     

The chemical composition and the cadmium,chromium and vanadium contents of shall-water deposits in Tokyo Bay

The major elements and the minor elements cadmium, chromium and vanadium in 12 samples of shallow-water deposits collected in Tokyo Bay were studied. Average silica content of the deposits is 53.93%, which is approximate to the average of 54.15% of red clay. Iron (av. 5.67% Fe₂O₃), titanium (av. 0.71% TiO₂), especially manganese (av. 0.87% MnO), are more abundant in the deposits than in the deposits along the entire sea-coasts of Honshu and of Nanao Bay, Japan. The deposits show higher contents of cadmium (av. 0.61 ppm), the chromium (av. 86 ppm) and vanadium (av. 79ppm). About 3 to 17 times cadmium and manganese contents compared with those in the deposits along the sea-coasts of Honshu and of Nanao Bay, Japan was found. Such accumulation, of cadmium and manganese in the deposits is probably caused by artificial contamination rather than of natural origin. No relation was found between the contents of cadmium, chromium and vanadium and those of major elements.     

Chemical and mineralogical compositions of two grains recovered from asteroid Itokawa

Two silicate grains (RB‐QD04‐0049 and RA‐QD02‐0064, whose estimated masses are 0.050 μg and 0.048 μg, respectively) recovered from the asteroid Itokawa by the Hayabusa spacecraft were studied for their mineralogical characteristics by synchrotron X‐ray diffraction and synchrotron X‐ray microtomography and further analyzed for their bulk chemical compositions by instrumental neutron activation analysis (INAA). According to X‐ray tomography, RB‐QD004‐0049 is composed of olivine, high‐Ca pyroxene, plagioclase, Ca‐phosphate, and troilite, whereas RA‐QD002‐0064 entirely consists of olivine. INAA data are consistent with these mineral compositions except for rare earth elements (REEs). Although the grain RB‐QD004‐0049 contains measurable REEs, which seems to be consistent with the presence of Ca‐phosphate, their abundances are anomalously high. Very low abundance of Co implies less than 0.1 mass% of metals in these two grains by calculation, which is in contrast to the result for the previously analyzed grain RA‐QD02‐0049 (Ebihara et al., 2011). FeO/Sc ratios of the grains fall within the range of those for ordinary chondrite olivines, implying that these grains are extraterrestrial in origin. FeO/MnO ratios also confirm this conclusion and further suggest that the Hayabusa grains analyzed in this study are similar to material found in LL chondrites rather than CK chondrites although olivines from LL and CK chondrites have similar Fa# (molar% of Fe relative to [Fe+Mg] in olivine) (~30) to those of the Hayabusa grains including the two grains analyzed in this study.     

40Ar/39Ar age of material returned from asteroid 25143 Itokawa

The Hayabusa mission to asteroid 25143, Itokawa, brought back 2000 small particles, which most closely resemble material found in LL4‐6 chondrites. We report an ⁴⁰Ar/³⁹Ar age of 1.3 ± 0.3 Ga for a sample of Itokawa consisting of three grains with a total mass of ~2 μg. This age is lower than the >4.0 Ga ages measured for 75% of LL chondrites but close to one for Y‐790964 and its pairs. The flat ⁴⁰Ar/³⁹Ar release spectrum of the sample suggests complete degassing 1.3 Ga ago. Recent solar heating in Itokawa's current orbit does not appear likely to have reset that age. Solar or impact heating 1.3 Ga ago could have done so. If impact heating was responsible, then the 1.3 Ga age sets an upper bound on the time at which the Itokawa rubble pile was assembled and suggests that rubble pile creation was an ongoing process in the inner solar system for at least the first 3 billion years of solar system history.     

Two categories of earthquake precursors,physical and tectonic,and their roles in intermediate-term earthquake prediction

I suggest that earthquake precursors can be divided into two major categories, physical and tectonic. I define physical precursor to be a direct or indirect indication of initiation or progression of an irreversible rupture-generating physical process within the preparation zone of a forthcoming earthquake. Tectonic precursor is defined as a manifestation of tectonic movement which takes place outside the preparation zone of an impending earthquake as a link in a chain of particular local tectonism in each individual area preceding the earthquake.Most intermediate-term, short-term and immediate precursors of various disciplines within the source regions of main shocks are considered physical ones. Some precursory crustal deformations around the source regions are, however, possibly tectonic precursors, because they may be caused by episodic plate motions or resultant block movements in the neighboring regions of the fault segments that will break. A possible example of this phenomena is the anomalous crustal uplift in the Izu Peninsula, Japan, before the 1978 Izu-Oshima earthquake ofM _s 6.8. Some precursory changes in seismicity patterns in wide areas surrounding source regions also seem to be tectonic precursors, because they were probably caused by the particular tectonic setting of each region. A typical example is a so-called doughnut pattern before the 1923 Kanto, Japan, earthquake ofM _s 8.2.Although most studies on earthquake precursors so far seem to regard implicitly all precursory phenomena observed as physical ones, the two categories should be distinguished carefully when statistical analysis or physical modeling is carried out based on reported precursory phenomena. In active plate boundary zones, where a practical strategy for earthquake prediction may well be different from that in intraplate regions, tectonic precursors can be powerful additional tools for intermediate-term earthquake prediction.     

Investigation of cutting methods for small samples of Hayabusa and future sample return missions

We report the investigation of cutting methods for Hayabusa samples. The purpose of our study is to explore the possibility of applying multiple analyses to a single particle effectively. We investigated the cutting performance of a blade dicing saw, laser, focused ion beam (FIB), and physical breaking by microindenter. Cutting performance was examined by estimating the aspect ratio of the cut slit, i.e., depth over width of the slit. We also investigated the possible contamination and sample damage by cutting. The result of the investigation shows that we can cut the samples from <50 μm to 500 μm using those methods with aspect ratios from 10 to 20, although they would introduce some contamination or damage to the samples. Our investigations also provide an important basis for the analysis of samples obtained by future sample return missions.     

Crystallization temperature determination of Itokawa particles by plagioclase thermometry with X‐ray diffraction data obtained by a high‐resolution synchrotron Gandolfi camera

The crystallization temperatures of Itokawa surface particles recovered by the space probe Hayabusa were estimated by a plagioclase geothermometer using sodic plagioclase triclinicity. The Δ131‐index required for the thermometer, which is the difference in X‐ray diffraction peak positions between the 131 and 11 reflections of plagioclase, was obtained by a high‐resolution synchrotron Gandolfi camera developed for the third generation synchrotron radiation beamline, BL15XU at SPring‐8. Crystallization temperatures were successfully determined from the Δ131‐indices for four particles. The observed plagioclase crystallization temperatures were in a range from 655 to 660 °C. The temperatures indicate crystallization temperatures of plagioclases in the process of prograde metamorphism before the peak metamorphic stage.