Neodymium isotopic variations in Northwest Pacific waters

Four vertical profiles of the concentration and isotopic composition of Nd in seawater were obtained in the western North Pacific. Two profiles from the Kuroshio Current regime showed congruently that although the Nd concentration increases gradually with depth, its isotopic composition varies significantly with depth depending upon the water mass occupying the water column. The high-salinity Kuroshio waters originating from the North Pacific Tropical Water (NPTW) carry the least radiogenic Nd (?_Nd = −7.4 to −8.7) to this region at ∼250 m from the western margin continental shelves, most likely from the East China Sea. The Nd isotopic compositions in the North Pacific Intermediate Water (NPIW) that occurs at 600 to 1000 m in the subtropical region are fairly uniform at ?_Nd = −3.7. The profile data from the ∼38° to 40°N Kuroshio/Oyashio mixed water region off Sanriku of Honshu, Japan, also suggest that the newest NPIW with ?_Nd = −3.2 is formed there by the mixing of various source waters, and the radiogenic component of Nd is derived mainly from the Oyashio waters.In the Pacific Deep Water (PDW) below ∼1000 m, the Nd isotopic composition is neither vertically nor horizontally homogeneous, suggesting that it serves as a useful tracer for sluggish deep water circulation as well. Two profiles from the Izu-Ogasawara Trench showed a minimum ?_Nd value at ∼2000 m, suggesting that there exists a horizontal advective flow in the vicinity of Honshu, Japan. There is some evidence from other chemical properties to support this observation. The waters below 4000 m including those within the trench in the subtropical region have ?_Nd values of around −5, suggesting that the deep waters are fed from the south along the western boundary, ultimately from the Antarctic Bottom Water (AABW) in the South Pacific. This extends up to ∼40°N along the Japanese Islands. In the subarctic region (>∼42°N), the waters have more radiogenic Nd with ?_Nd > −4.0 throughout the water column, presumably due to the supply of Nd by weathering in such igneous provinces as the Kuril-Kamchatska-Aleutian Island chain. The lateral inhomogeneity of the Nd isotopic composition in PDW suggests that there may be different circulation and mixing regimes in the North Pacific Basin.     

Partitioning of Ni2+, Co2+, Fe2+, Mn2+ and Mg2+ between olivine and silicate melts: compositional dependence of partition coefficient

Partitioning of Ni²⁺, Co²⁺, Fe²⁺, Mn²⁺ and Mg²⁺ between olivine and silicate melts has been determined near the join (Mg_0.5·-Fe_0.5)₂SiO₄-K₂O 4SiO₂ and for seven different basaltic compositions. The experiments were made at 1 atm total pressure, 1500-1100°C, and under moderate to reducing oxygen fugacities. The concentration factor, defined as K^MO = (MO)^ol/(MO)^liq (molar ratio), increases markedly for all the cations studied as the olivine component of the liquid decreases. Much of the increase in K^MO is considered as due to the compositional effect of the coexisting liquid: the temperature effect on K^MO is probably opposite to the compositional effect (K^MO decreases as temperature decreases).The partition coefficient K^MO-MgO = (MO/MgO)^ol/(MO/MgO)^liq for the reaction, M_ol²⁺ + Mg_liq²⁺ = M_liq²⁺ + Mg_ol²⁺. is relatively constant over a wide range of SiO₂ content of the liquid, except in the case of Ni²⁺. The partition coefficients have similar ranges both in synthetic and natural rock systems: K^NiO-MgO = 1.8–3.0, K^CoO-MgO = 0.6–0.8, K^FeO-MgO = 0.27–0.38, and K^MnO-MgO = 0.23–0.32. There is a systematic variation in the partition coefficient K^MO-MgO with the composition of liquid; K^MO-MgO increases with increasing SiO₂ content of melt. The partition coefficients for Co²⁺, Fe²⁺ and Mn²⁺ are useful to test the equilibration of olivine with magma of a wide compositional range.     

Strontium isotopic and chemical variations of the granitic rocks in the Tsukuba district,Japan

Initial ⁸⁷Sr/⁸⁶Sr ratios, major and trace element compositions have been determined for the Paleogene granitic rocks in the Tsukuba district, Japan. Isotopic ages strongly suggest that the granitic rocks (seven units) were continuously emplaced and solidified during a short time interval. Initial ⁸⁷Sr/⁸⁶Sr ratios for seven granitic units vary from 0.7082 to 0.7132, while sedimentary and metasedimentary country rocks have ratios at the time of granitic magma emplacement ranging from 0.7149 to 0.7298. Continuous linear arrays for the granitic rocks in the diagrams of initial ⁸⁷Sr/⁸⁶Sr ratios versus some chemical parameters can be explained by either of following two processes. One is the assimilation — fractional crystallization (AFC) process between the parental magma (SiO₂ of 68% and initial ratio of 0.7078) and sedimentary country rocks, and the other is magma mixing process between above parental magma and sediment derived acidic magma (melt) (SiO₂ of 75%). The high initial ratios (0.7078–0.7098) for basic rocks such as gabbro or diorite in the Tsukuba district and the similar characteristics observed in the rocks of Ryoke belt (SW Japan) suggest that the parental magma had the same source region as the basic rocks, probably the lower crustal source.     

Molecular-scale mechanisms of distribution and isotopic fractionation of molybdenum between seawater and ferromanganese oxides

The distribution of Mo between seawater and marine ferromanganese oxides has great impacts on concentration and isotopic composition of Mo in modern oxic seawater. To reveal the adsorption chemistry of Mo to ferromanganese oxides, we performed (i) detailed structural analyses of Mo surface complexes on δ-MnO₂, ferrihydrite, and hydrogenetic ferromanganese oxides by L₃- and K-edge XAFS, and (ii) adsorption experiments of Mo to δ-MnO₂ and ferrihydrite over a wide range of pHs, ionic strengths, and Mo concentrations. XAFS analyses revealed that Mo forms distorted octahedral (Oh) inner-sphere complexes on δ-MnO₂ whereas it forms a tetrahedral (Td) outer-sphere complex on ferrihydrite. In the hydrogenetic ferromanganese oxides, the dominant host phase of Mo was revealed to be δ-MnO₂. These structural information are consistent with the macroscopic behaviors of Mo in adsorption experiments, and Mo concentration in modern oxic seawater can be explained by the equilibrium adsorption reaction on δ-MnO₂. In addition, the large isotopic fractionation of Mo between seawater and ferromanganese oxides detected in previous studies can be explained by the structural difference between and adsorbed species on the δ-MnO₂ phase in ferromanganese oxides. In contrast, smaller fractionation of Mo isotopes on ferrihydrite is due to little change in the Mo local structures during its adsorption to ferrihydrite.The structures of Mo species adsorbed on crystalline Fe (oxyhydr)oxides, goethite, and hematite were also investigated at pH 8 and I = 0.70 M (NaNO₃). Our XAFS analyses revealed that Mo forms inner-sphere complexes on both minerals: Td edge-sharing (46%) and Oh double corner-sharing (54%) for goethite, and Td double corner-sharing (14%) and Oh edge-sharing (86%) for hematite. These structural information, combined with those for amorphous ferrihydrite and δ-MnO₂, show the excellent correlation with the magnitude of adsorptive isotopic fractionation of Mo reported in previous studies: the proportion of Oh species or their magnitude of distortion in Mo surface complexes become larger in the order of ferrihydrite < goethite < hematite < δ-MnO₂, a trend identical to the magnitude of isotopic fractionation.Based on the comparison with previous reports for Mo surface species on various oxides, the chemical factors that affect Mo surface complex structures were also discussed. The hydrolysis constant of cation in oxides, log K_OH (or the acidity of the oxide surfaces, PZC) is well correlated with the mode of attachment (inner- or outer-sphere) of Mo surface complexes. Furthermore, the symmetric change in Mo species from Td to Oh is suggested to be driven by the formation of inner-sphere complexes on specific sites of the oxide surfaces.     

Alkaline leaching characteristics of biogenic opal in Eocene sediments from the central Arctic Ocean: a case study in the ACEX cores

Accurate knowledge of the extent of biogenic opal preservation in marine sediment cores is important for paleoceanographic reconstructions. The alkaline leaching method is widely employed for %biogenic opal analysis due to its ease and speed. In this study, a revised method for measuring %biogenic opal in sediment from arctic coring expedition samples was suggested. The studied middle Eocene sediments from the central Arctic Ocean presented a problem in insufficiently leaching biogenic opal with a Na₂CO₃ solution. Based on XRD analysis, it was suggested that such an alkaline resistance results from slight diagenesis of biogenic opal. In order to solve this problem, an alkaline leaching method utilizing a 2 M NaOH solution was suggested for the accurate measurement of %biogenic opal in the Eocene sediments from the central Arctic. Furthermore, dissolution rates from lithogenic matter by NaOH solution were measured in order to correct the %biogenic opal values.     

Numerical forecasting of the time interval between successive M8 earthquakes along the Nankai Trough,southwest Japan,using ocean bottom cable network data

One possible approach to estimating the time interval between large-scale Tōnankai (Tōkai) and Nankai earthquakes on the Japan arc is sequential assimilation of crustal deformation data. We conducted numerical modeling of sequential assimilation using surface deformation calculated from earthquake generation cycle simulations along the Nankai Trough. To account for observation noise, we used measured ocean bottom pressure gauge data, excluding tidal modulation, from a station on the ocean bottom cable network Dense Oceanfloor Network System for Earthquakes and Tsunamis in the Kumano basin. We used sequential importance sampling as our data assimilation method. We found that as the amount of data increased, the estimated time interval between the Tōnankai and Nankai earthquakes approached the “true” observed interval. In addition, the noise in the pressure gauge data was sufficiently small that simulated crustal deformation patterns could be distinguished for different time intervals.     

New record of occurrence ofSergia lncens (Hansen) (crustacea,sergestidae) off Tung-kang,Taiwan, with special reference to phylogeny and distribution of the species

The commercially important sergestid shrimp,Sergia lucens (Hansen), has long been considered an endemic species of Japan because it had been found only in Suruga Bay and neighbouring waters. Recently, however, a considerable amount of a similar shrimp was caught by trawl nets off Tung-kang, southwestern Taiwan. This shrimp is distributed at depths of 100–300 m on the continental slope, around a deep submarine canyon adjacent to the mouth of the Kao-ping River. A morphological comparison with specimens from Suruga Bay reveals that the shrimp is identical toS. lucens. However, a slight difference in the patterns of water-soluble proteins was observed in a thin layer isoelectrophoretic examination. A difference was also observed in the spawning season of the two populations, indicating sexual and geographic isolation. Considering the distribution and phylogeny of the family Sergestidae, based on a possible evolutionary development from a benthic neritic organism to a pelagic oceanic one along the generaSicyonella-Sergestes-Sergia, it is assumed thatS. lucens entered a lower epipelagic habitat in the coastal waters from the warm oceanic mesopelagic habitat of the original stock. A hypothesis is proposed that speciation ofS. lucens from the original stock occurred when it was trapped in a semi-enclosed inlet (the paleo-East China Sea Gulf) that existed at the present Okinawa Trough during the late Pliocene to early Pleistocene. The inlet was deep, but had a neritic environment due to drainage from ancient large river systems, including the paleo-Yangtze River. The species expanded its distribution to the neighbouring waters during the warm interglacial period. However, a rapid rise in sea level after 14,000 years significantly changed the environmental conditions in the distributional area and the species could not expand into a neritic environment, which was too shallow for survival. Accordingly,S. lucens populations remained only in Suruga Bay and Tung-kang waters, where the environment has remained stable for the last 17,000 years or more. The two areas have the following common characteristics:

1. A large amount of fresh water is discharged into the deep submarine canyon adjacent to the river mouth.
2. The northeastern part is surrounded by land so that a direct inflow of boreal water into the environment is blocked.
3. Warm Kuroshio extension water intrudes and mixes with water from the rivers, and for Suruga Bay there is a current system that keeps distribution of the eggs and larvae restricted to the local habitats.

Taiwan annually exported some tens of metric tons of the driedS. lucens to Japan for the last few years, but the standing stock of Tung-kang waters is probably not as large as that in Suruga Bay.     

Raman spectroscopic and calorimetric observations on natural gas hydrates with cubic structures I and II obtained from Lake Baikal

This study reports measurements of the Raman spectra of Lake Baikal gas hydrates and estimations of the hydration number of methane-rich samples. The hydration number of gas hydrates retrieved from the southern Baikal Basin (crystallographic structure I) was approx. 6.1. Consistent with previous results, the Raman spectra of gas hydrates retrieved from the Kukuy K-2 mud volcano in the central Baikal Basin indicated the existence of crystallographic structures I and II. Measurements of the dissociation heat of Lake Baikal gas hydrates by calorimetry (from the decomposition of gas hydrates to gas and water), employing the hydration number, revealed values of 53.7–55.5?kJ?mol^–1 for the southern basin samples (structure I), and of 54.3–55.5?kJ?mol^–1 for the structure I hydrates and 62.8–64.2?kJ?mol^–1 for the structure II hydrates from the Kukuy K-2 mud volcano.