New W-isotope evidence for rapid terrestrial accretion and very early core formation

The short-lived ¹⁸²Hf-¹⁸²W-isotope system is an ideal clock to trace core formation and accretion processes of planets. Planetary accretion and metal/silicate fractionation chronologies are calculated relative to the chondritic ¹⁸²Hf-¹⁸²W-isotope evolution. Here, we report new high-precision W-isotope data for the carbonaceous chondrite Allende that are much less radiogenic than previously reported and are in good agreement with published internal Hf-W chronometry of enstatite chondrites. If the W-isotope composition of terrestrial rocks, representing the bulk silicate Earth, is homogeneous and 2.24 ε_182W units more radiogenic than that of the bulk Earth, metal/silicate differentiation of the Earth occurred very early. The new W-isotope data constrain the mean time of terrestrial core formation to 34 million years after the start of solar system accretion. Early terrestrial core formation implies rapid terrestrial accretion, thus permitting formation of the Moon by giant impact while ¹⁸²Hf was still alive. This could explain why lunar W-isotopes are more radiogenic than the terrestrial value.     

An X-ray absorption fine structure and nuclear magnetic resonance spectroscopy study of gallium-silica complexes in aqueous solution

The influence of aqueous silica on gallium(III) hydrolysis in dilute (2 × 10⁻⁴ ≤ m_Ga ≤ 5 × 10⁻³) and moderately concentrated (0.02 ≤ m_Ga ≤ 0.3) aqueous solutions was studied at ambient temperature, using high resolution X-ray absorption fine structure (XAFS) and nuclear magnetic resonance (NMR) spectroscopies, respectively. Results show that, in Si-free acidic solutions (pH < 3), Ga is hexa-coordinated with oxygens of H₂O molecules and/or OH groups in the first coordination sphere of the metal. With increasing pH, these hydroxyl groups are progressively replaced by bridging oxygens (-O-), and polymerized Ga-hydroxide complexes form via Ga-O-Ga chemical bonds. In the 2.5-3.5 pH range, both XAFS and NMR spectra are consistent with the dominant presence of the Ga₁₃ Keggin polycation, which has the same local structure as A1₁₃. Under basic pH (pH > 8), Ga exhibits a tetrahedral coordination, corresponding to Ga(OH)₄⁻ species, in agreement with previous NMR and potentiometric studies. Major changes in Ga hydrolysis have been detected in the presence of aqueous silica. Ga is tetra-coordinated, both in basic and acid (i.e., at pH > 2.7) Si-bearing solutions (0.01 ≤ m_Si ≤ 0.2), and forms stable gallium-silicate complexes. In these species, Ga binds via bridging oxygen to 2 ± 1 silicons, with an average Ga-Si distance of 3.16 ± 0.05 Å, and to 2 ± 1 silicons, with an average Ga-Si distance of 3.39 ± 0.03 Å. These two sets of Ga-Si distances imply the formation of two types of Ga-silicate aqueous complex, cyclic Ga-Si_2-3 species (formed by the substitution of Si in its tri-, tetra- or hexa-cyclic polymers by Ga atoms), and chainlike GaSi_2-4 species (similar to those found for A1), respectively. The increase in the number of Si neighbors (a measure of the complex concentration and stability), in alkaline media, with increasing SiO₂(aq) content and decreasing pH is similar to that for A1-Si complexes found in neutral to basic solutions. At very acid pH and moderate silica concentrations, the presence of another type of Ga-Si complex, in which Ga remains hexa-coordinated and binds to the silicon tetrahedra via the GaO₆ octahedron corners, has also been detected. These species are similar to those found for Al³⁺ in acid solutions. Thus, as for aluminum, silicic acid greatly hampers Ga hydrolysis and enhances Ga mobility in natural waters via the formation of gallium-silicate complexes.     

Rapid photo-oxidation of Mn(II) mediated by humic substances

The oxidation of Mn(II) by O₂ to Mn(III) or Mn(IV) is thermodynamically favored under the pH and pO₂ conditions present in most near surface waters, but the kinetics of this reaction are extremely slow. This work investigated whether reactive oxygen species, produced through illumination of humic substances, could oxidize Mn at an environmentally relavent rate. The simulated sunlight illumination of a solution containing 200 μM Mn(II) and 5 mg/L Aldrich humic acid buffered at pH 8.1 produced ∼19 μM of oxidized Mn (MnO_x where x is between one and two) after 45 minutes. The major oxidants reponsible for this reaction appear to be photoproduced superoxide radical anion, O₂⁻, and singlet molecular oxygen, ¹O₂. The dependencies of MnO_x formation on Mn(II), humic acid, and H⁺ concentration were characterized. A kinetic model based largely on published rate constants was established and fit to the experimental data. As expected, analysis of the model indicates that the key reaction rate controlling MnO_x production is the rate of decomposition of a MnO₂⁺ complex formed from the reaction of Mn(II) with O₂⁻. This rate is strongly dependent on the Mn(II) complexing ligands in solution. The MnO_x production in the seawater sample taken from Bodega Bay, USA and spiked with 200 μM Mn(II) was well reproduced by the model. Extrapolations from the model imply that Mn photo-oxidation should be a significant reaction in typical surface seawaters. Calculated rates, 5.8 to 55 pM h⁻¹, are comparable to reported rates of biological Mn oxidation, 0.07 to 89 pM h⁻¹. Four fresh water samples that were spiked with 200 μM Mn(II) also showed significant MnO_x production. Based on these results, it appears that Mn photo-oxidation could constitute a significant, and apparently unrecognized geochemical pathway in natural waters.     

A Comparison of Two-Phase Dynamic Upscaling Methods Based on Fluid Potentials

Although a number of methods for calculating dynamic pseudo-functions have been developed over the years, there is still a lack of understanding as to why a certain method will succeed in some cases but fail in others. In this paper, we describe the results of an assessment of several upscaling methods, namely the Kyte and Berry (KB) method, the Stone method, the Hewett and Archer (HA) method and the Transmissibility-Weighted (TW) method. We have analyzed the equations for deriving the methods and investigated the results of numerical simulations of gas displacing oil, in a variety of models to enable us to gain new insights into these, and related, upscaling methods. In particular, some novel observations on methods based on fluid potential are presented and the issue of using predicted fluid mobilities as a criterion of accuracy of an upscaling method is clarified.     

Momentum transport of wave zero during March: A possible predictor for the Indian summer monsoon

Analysis of monthly momentum transport of zonal waves at 850 hPa for the period 1979 to 1993, between ‡S and ‡N for January to April, using zonal (u) and meridional (v) components of wind taken from the ECMWF reanalysis field, shows a positive correlation (.1% level of significance) between the Indian summer monsoon rainfall (June through September) and the momentum transport of wave zero TM(0) over latitudinal belt between 25‡S and 5‡N (LB) during March. Northward (Southward) TM(0) observed in March over LB subsequently leads to a good (drought) monsoon season over India which is found to be true even when the year is marked with the El-Nino event. Similarly a strong westerly zone in the Indian Ocean during March, indicates a good monsoon season for the country, even if the year is marked with El-Nino. The study thus suggests two predictors, TM(0) over LB and the strength of westerly zone in the Indian Ocean during March.     

Phytoplankton, nutrients, and transparency in Danish coastal waters

We present a comparative analysis of 1400 data series of water chemistry (particularly nitrogen and phosphorus concentrations), phytoplankton biomass as chlorophylla (chla) concentrations, concentrations of suspended matter and Secchi depth transparency collected from the mid-1980s to the mid-1990s from 162 stations in 27 Danish fjords and coastal waters. The results demonstrate that Danish coastal waters were heavily eutrophied and had high particle concentrations and turbid waters. Median values were 5.1 μg chla 1⁻¹, 10.0 mg DW 1⁻¹ of suspended particles, and Secchi depth of 3.6 m. Chlorophyll concentration was strongly linked to the total-nitrogen concentration. The strength of this relationship increased from spring to summer as the concentration of total nitrogen declined. During summer, total nitrogen concentrations accounted for about 60% of the variability in chlorophyll concentrations among the different coastal systems. The relationship between chlorophyll and total phosphorus was more consistant over the year and correlations were much weaker than encountered for total nitrogen. Secchi depth could be predicted with good precision from measurements of chlorophyll and suspended matter. In a multiple stepwise regression model with In-transformed values the two variables accounted for most of the variability in water transparency for the different seasons and the period March–October as a whole (c. 80%). We were able to demonstrate a significant relationship between total nitrogen and Secchi depth, with important implications for management purposes.     

Integrated Two-Dimensional Modeling of Fluid Flow and Compaction in a Sedimentary Basin

In this paper we employ mixed finite elements and numerically study an integrated two-dimensional model of fluid flow and compaction in a sedimentary basin. This model describes a single phase incompressible flow in a two-dimensional section of a sedimentary basin with vertical compaction. At each time step, an iterative algorithm is used to solve this model. The determination of the grid movement is based on the mass conservation and movement of sediments in the basin, while the mixed method is utilized to solve the fluid flow over the moving grid. Numerical experiments are presented to verify this iterative algorithm and show representative solutions for the model under consideration.     

藏南地壳速度结构与地壳物质东西向“逃逸”──以佩枯错-普莫雍错宽角反射剖面为例

根据佩枯错-普莫雍错480余公里长地震剖面上纵、横波波场特征识别的来自Moho界面反射及壳内界面反射震相, 通过正演拟合解释藏南地区近东西向剖面地壳纵、横波速度与泊松比结构. 结果显示: 该区地壳厚度东西向变化显著, 分别以定日西、定结东为界呈现“块体三分”格局, 西段Moho界面埋深为71 km, 中段约76 km, 东段约74 km; 上地壳底部深度20~30 km左右处存在一低速层, 其厚度沿东西向急剧变化, 即从西段的20 km减薄至东段的6 km左右; 地壳内纵、横波速度变化剧烈, 在东西方向上呈现出跳跃式周期性变化. 下地壳物质低波速与3条近南北向活动正断层的存在可能是伴随印度与欧亚板块碰撞、下地壳物质“拆沉”、地壳增厚与物质东西向“逃逸”耦合作用的结果.