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.     

Numerical simulation of migration–accumulation of oil resources

Numerical simulation of oil migration and accumulation is to describe the history of oil migration and accumulation in basin evolution. It is of great value to the evaluation of oil resources and to the determination of the location and amount of oil deposits. This thesis discusses the characteristics of petroleum geology and permeation fluid mechanics. For the three-dimensional problems of Dongying hollow of Shengli Petroleum Oil Field, it puts forward a new model and a kind of modified method of upwind finite difference fractional steps implicit interactive scheme. For the famous hydraulic experiment of secondary migration–accumulation, the numerical simulation test has been done, and both the computational and experimental results are basically identical. For the actual problem of Dongying hollow, the numerical simulation test and the actual conditions are basically coincident. Thus, the well-known problem has been solved.     

Scattering of Semidiurnal Internal Kelvin Wave at Step Bottom Topography

A three-dimensional, multi-level model was used to study the energy dissipation of semidiurnal internal Kelvin waves due to their interaction with bottom topography. A simplified topography consisting of a channel with an additional shallow bay was used to clarify the wave’s scattering process. When the first mode semidiurnal internal wave given at an open boundary arrives at the bay mouth, higher-mode internal waves are generated at a step bottom of the bay mouth. As a result, the energy of the first mode internal Kelvin wave is effectively decayed. The decay rate of the internal Kelvin wave depends on both the width and length of the additional bay. The maximum decay rate was found when a resonance condition occurs the bay, that is, the bay length is equal to a quarter of wave length of the first mode internal wave on the shallow region. The decay rate in the wide bay cases is higher than that in a narrow case, due to a contribution from the scattering due to the Poincare wave that emanates from the corners of the bay head. The decay rate with the additional bay is 1.1–1.8 times that of the case without the additional bay. The decay rate due to the scattering process is found to be of the same order as that of the internal and bottom friction.     

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.     

Possibility of recent changes in vertical distribution and size composition of chlorophyll-a in the western North Pacific region

Our analysis of the last three decades of retrospective data of vertical distributions and size composition of chlorophyll-a (Chl-a) over the western North Pacific has revealed significant changes of three indices related to Chl-a during summer season, as follows: (1) decreasing linear trend of the proportion of Chl-a in surface layer to that of the whole water column by 0.4 and 2.3% year⁻¹ in the subtropical area along 137°E (STA₁₃₇) during 1972 to 1997 and in the Kuroshio Extension area along 175°E (KEA₁₇₅) during 1990 to 2001; (2) increasing linear trend of the depth of subsurface Chl-a maximum (DCM) by 0.4 and 2.6 m year⁻¹ in STA₁₃₇ and KEA₁₇₅; and (3) decreasing linear trend of larger-size Chl-a (>3 μm) by 0.1 and 2.5% year⁻¹ in STA₁₃₇ and KEA₁₇₅, respectively. Water density (σ _θ ) at 75 m depth had also decreased by 0.006 and 0.05 year⁻¹ in STA₁₃₇ and KEA₁₇₅, respectively. The ratio of biogenic opal to biogenic CaCO₃ in the sinking flux decreased by 0.015 year⁻¹ in the subtropical region from 1997 to 2005. These findings may indicate that the subsurface chlorophyll maximum is deepening and larger phytoplankton such as diatoms has been decreasing during the past decade, associated with the decreasing density of surface water caused by warming in the western North Pacific, especially in the summer.