Formation of refractory inclusions by evaporation of condensate precursors

Berman’s (1983) activity-composition model for CaO-MgO-Al₂O₃-SiO₂ liquids is used to calculate the change in bulk chemical and isotopic composition during simultaneous cooling, evaporation, and crystallization of droplets having the compositions of reasonable condensate precursors of Types A and B refractory inclusions in CV3 chondrites. The degree of evaporation of MgO and SiO₂, calculated to be faithfully recorded in chemical and isotopic zoning of individual melilite crystals, is directly proportional to evaporation rate, which is a sensitive function of P_H2, and inversely proportional to the droplet radius and cooling rate. When the precursors are partially melted in pure hydrogen at peak temperatures in the vicinity of the initial crystallization temperature of melilite, their bulk chemical compositions evolve into the composition fields of refractory inclusions, mass-fractionated isotopic compositions of Mg, Si, and O are produced that are in the range of the isotopic compositions of natural inclusions, and melilite zoning profiles result that are similar to those observed in real inclusions. For droplets of radius 0.25 cm evaporating at P_H2 = 10⁻⁶ bar, precursors containing 8 to 13 wt.% MgO and 20 to 23% SiO₂ evolve into objects similar to compact Type A inclusions at cooling rates of 2 to 12 K/h, depending on the precise starting composition. Precursors containing 13 to 14 wt.% MgO and 23 to 26% SiO₂ evolve into objects with the characteristics of Type B1 inclusions at cooling rates of 1.5 to 3 K/h. The relatively SiO₂-poor members of the Type B2 group can be produced from precursors containing 14 to 16 wt.% MgO and 27 to 33% SiO₂ at cooling rates of <1 K/h. Type B2’s containing 27 to 35 wt.% SiO₂ and <12% MgO require precursors with higher SiO₂/MgO ratios at MgO > 15% than are found on any condensation curve. The characteristics of fluffy Type A inclusions, including their reversely zoned melilite, can only be understood in the context of this model if they contain relict melilite.     

Source and H2O content of high-MgO magmas in island arc settings: an experimental study of a primitive calc-alkaline basalt from St. Vincent, lesser antilles arc

Liquidus phase relationships have been determined for a high-MgO basalt (STV301: MgO=12.5 wt%, Ni=250 ppm, Cr=728 ppm) from Black Point, St Vincent (Lesser Antilles arc). Piston-cylinder experiments were conducted between 7.5 and 20 kbar under both hydrous and oxidizing conditions. AuPd capsules were used as containers. Compositions of supraliquidus glasses and mass-balance calculations show that Fe loss is < 10% in the majority of experiments. Two series of water concentrations in melt were investigated: (i) 1.5 wt% and (ii) 4.5 wt% H₂O, as determined by SIMS analyses on quenched glasses and with the by difference technique. The Fe³⁺/Fe²⁺ partitioning between Cr-Al spinel and melt and olivine-spinel equilibria show that oxidizing fO₂ were imposed (NNO + 1.5 for the 1.5 wt% H₂O series, NNO + 2.3 for the 4.5 wt% H₂O series). For both series of water concentrations, the liquid is multiply-saturated with a spinel lherzolite phase assemblage on its liquidus, at 1235°C, 11.5 kbar (1.5 wt% H₂O) and 1185°C, 16 kbar (4.5 wt% H₂O). Liquidus phases are homogeneous and comparable to typical mantle compositions. Mineral-melt partition coefficients are generally identical to values under anhydrous conditions. The modal proportion cpx/opx on the liquidus decreases from the 1.5 wt% to the 4.5 wt% H₂O series. The experimental data are consistent with STV301 being a product of partial melting of lherzolitic mantle. Conditions of multiple saturation progressively evolve toward lower temperatures and higher pressures with increasing melt H₂O concentration. Phase equilibria constraints, i.e., the necessity of preserving the mantle signature seen in high-MgO and picritic arc basalts, and glass inclusion data suggest that STV301 was extracted relatively dry (∼ 2 wt% H₂O) from its mantle source. However, not all primary arc basalts are extracted under similarly dry conditions because more hydrous melts will crystallize during ascent and will not be present unmodified at the surface. From degrees of melting calculated from experiments on KLB-1, extraction of a 12.5 wt% MgO melt with ∼ 2 wt% H₂O would require a H₂O concentration of 0.3 wt% in the sub-arc mantle. For mantle sources fluxed with a slab-derived hydrous component, extracted melts may contain up to ∼ 5.5 wt% H₂O.     

Thermal expansivities of supercooled haplobasaltic liquids

The thermal expansion of supercooled liquids in the haplobasaltic (anorthite-diopside) system have been determined via methods of container-based dilatometry. The expansivity data obtained in this study agree well with estimates provided by previous dilatometric determinations in the system that have relied on alternative experimental strategies. The data have been combined with high-temperature, superliquidus determinations of melt density to obtain expressions for the volume-temperature (V-T) relationships of liquids in the anorthite-diopside system. The V-T data clearly indicate a nonlinear temperature dependence of volume for all melts investigated. The variation is most striking for diopside, where the coefficient of volume thermal expansion decreases ∼56% from temperatures near the glass transition to superliquidus temperatures. With increasing anorthite content, the degree of variation appears to decrease. An₄₂Di₅₈ exhibits a decrease of 39% of its coefficient of thermal expansion and An₉₈Di₀₂ of 33%, respectively. The expansivities obtained in this study cannot be reproduced by means of published models that are based on linear V-T relationships. They require instead a reanalysis of existing pressure-V-T equations of state models for silicate melts.     

Effect of adsorbed metal ions on the transport of Zn- and Ni-EDTA complexes in a sand and gravel aquifer

Adsorption, complexation, and dissolution reactions strongly influenced the transport of metal ions complexed with ethylenediaminetetraacetic acid (EDTA) in a predominantly quartz-sand aquifer during two tracer tests conducted under mildly reducing conditions at pH 5.8 to 6.1. In tracer test M89, EDTA complexes of zinc (Zn) and nickel (Ni), along with excess free EDTA, were injected such that the lower portion of the tracer cloud traveled through a region with adsorbed manganese (Mn) and the upper portion of the tracer cloud traveled through a region with adsorbed Zn. In tracer test S89, Ni- and Zn-EDTA complexes, along with excess EDTA complexed with calcium (Ca), were injected into a region with adsorbed Mn. The only discernable chemical reaction between Ni-EDTA and the sediments was a small degree of reversible adsorption leading to minor retardation. In the absence of adsorbed Zn, the injected Zn was displaced from EDTA complexes by iron(III) [Fe(III)] dissolved from the sediments. Displacement of Zn by Fe(III) on EDTA became increasingly thermodynamically favorable with decreasing total EDTA concentration. The reaction was slow compared to the time-scale of transport. Free EDTA rapidly dissolved aluminum (Al) from the sediments, which was subsequently displaced slowly by Fe. In the portion of tracer cloud M89 that traveled through the region contaminated with adsorbed Zn, little displacement of Zn complexed with EDTA was observed, and Al was rapidly displaced from EDTA by Zn desorbed from the sediments, in agreement with equilibrium calculations. In tracer test S89, desorption of Mn dominated over the more thermodynamically favorable dissolution of Al oxyhydroxides. Comparison with results from M89 suggests that dissolution of Al oxyhydroxides in coatings on these sediment grains by Ca-EDTA was rate-limited whereas that by free EDTA reached equilibrium on the time-scale of transport. Rates of desorption are much faster than rates of dissolution of Fe oxyhydroxides from sediment-grain surfaces and, therefore, adsorbed metal ions can strongly influence the speciation of ligands like EDTA in soils and sediments, especially over small temporal and spatial scales.     

Uranium co-precipitation with iron oxide minerals

In oxidizing environments, the toxic and radioactive element uranium (U) is most soluble and mobile in the hexavalent oxidation state. Sorption of U(VI) on Fe-oxides minerals (such as hematite [α-Fe₂O₃] and goethite [α-FeOOH]) and occlusion of U(VI) by Fe-oxide coatings are processes that can retard U transport in environments. In aged U-contaminated geologic materials, the transport and the biological availability of U toward reduction may be limited by coprecipitation with Fe-oxide minerals. These processes also affect the biological availability of U(VI) species toward reduction and precipitation as the less soluble U(IV) species by metal-reducing bacteria.To examine the dynamics of interactions between U(VI) and Fe oxides during crystallization, Fe-oxide phases (containing 0.5 to 5.4 mol% U/(U + Fe)) were synthesized by means of solutions of U(VI) and Fe(III). Wet chemical (digestions and chemical extractions) and spectroscopic techniques were used to characterize the synthesized Fe oxide coprecipitates after rinsing in deionized water. Leaching the high mol% U solids with concentrated carbonate solution (for sorbed and solid-phase U(VI) species) typically removed most of the U, leaving, on average, about 0.6 mol% U. Oxalate leaching of solids with low mol% U contents (about 1 mol% U or less) indicated that almost all of the Fe in these solids was crystalline and that most of the U was associated with these crystalline Fe oxides. X-ray diffraction and Fourier-transform infrared (FT-IR) spectroscopic studies indicate that hematite formation is preferred over that of goethite when the amount of U in the Fe-oxides exceeds 1 mol% U (∼4 wt% U). FT-IR and room temperature continuous wave luminescence spectroscopic studies with unleached U/Fe solids indicate a relationship between the mol% U in the Fe oxide and the intensity or existence of the spectra features that can be assigned to UO₂²⁺ species (such as the IR asymmetric υ₃ stretch for O = U = O for uranyl). These spectral features were undetectable in carbonate- or oxalate-leached solids, suggesting solid phase and sorbed U(VI)O₂²⁺ species are extracted by the leach solutions. Uranium L₃-edge x-ray absorption spectroscopic (XAFS) analyses of the unleached U-Fe oxide solids with less than 1 mol% U reveal that U(VI) exists with four O atoms at radial distances of 2.19 and 2.36 Å and second shell Fe at a radial distance at 3.19 Å.Because of the large ionic radius of UO₂²⁺ (∼1.8 Å) relative to that of Fe³⁺ (0.65 Å), the UO₂²⁺ ion is unlikely to be incorporated in the place of Fe in Fe(III)-oxide structures. Solid-phase U(VI) can exist as the uranyl [U(VI)O₂²⁺] species with two axial U-O double bonds and four or more equatorial U-O bonds or as the uranate species (such as γ-UO₃) without axial U-O bonds. Our findings indicate U⁶⁺ (with ionic radii of 0.72 to 0.8 Å, depending on the coordination environment) is incorporated in the Fe oxides as uranate (without axial O atoms) until a point of saturation is reached. Beyond this excess in U concentration, precipitating U(VI) forms discrete crystalline uranyl phases that resemble the uranyl oxide hydrate schoepite [UO₂(OH)₂·2H₂O]. Molecular modeling studies reveal that U⁶⁺ species could bond with O atoms from distorted Fe octahedra in the hematite structure with an environment that is consistent with the results of the XAFS. The results provide compelling evidence of U incorporation within the hematite structure.     

Consequences of diffuse and channelled porous melt migration on uranium series disequilibria

Magmas erupted at mid-ocean ridges (MORB) result from decompression melting of upwelling mantle. However, the mechanism of melt transport from the source region to the surface is poorly understood. It is debated whether melt is transported through melt-filled conduits or cracks on short time scales (<∼ 10³ yrs), or whether there is a significant component of slow, equilibrium porous flow on much longer time scales (>∼ 10³-10⁴ yrs). Radiogenic excess ²²⁶Ra in MORB indicates that melt is transported from the melting region on time scales less than the half life of ²²⁶Ra (∼1600 yrs), and has been used to argue for fast melt transport from the base of the melting column. However, excess ²²⁶Ra can be generated at the bottom of the melt column, during the onset of melting, and at the top of the melt column by reactive porous flow. Determining the depth at which ²²⁶Ra is generated is critical to interpreting the rate and mechanism of magma migration. A recent compilation of high quality U-series isotope data show that in many young basalts, ²²⁶Ra excess in MORB is negatively correlated with ²³⁰Th excess. The data suggest that ²²⁶Ra excess is generated independently of ²³⁰Th excess, and cannot be explained by “dynamic” or fractional melting, where observed radiogenic excesses are all generated at the base of the melt column. One explanation is that the negative correlation of activity ratios is a result of mixing of slow moving melt that has travelled through reactive, low-porosity pathways and relatively fast moving melt that has been transported in unreactive high-porosity channels. We investigate this possibility by calculating U-series disequilibria in a melting column in which high-porosity, unreactive channels form within a low-porosity matrix that is undergoing melting. The results show that the negative correlation of ²²⁶Ra and ²³⁰Th excesses observed in MORB can be produced if ∼60% of the total melt flux travels through the low-porosity matrix. This melt maintains ²²⁶Ra excesses via chromatographic fractionation of Ra and Th during equilibrium transport. Melt that travels through the unreactive, high-porosity channels is not able to maintain significant ²²⁶Ra excesses because Ra and Th are not fractionated from each other during transport and the transport time for melt in the channels to reach the top of the melt column is longer than the time scale for ²²⁶Ra excesses to decay. Mixing of melt from the high porosity channels with melt from the low-porosity matrix at the top of the melting column can produce a negative correlation of ²²⁶Ra and ²³⁰Th excesses with the slope and magnitude observed in MORB. This transport process can also account for other aspects of the geochemistry of MORB, such as correlations between La/Yb, α_Sm/Nd, and Th/U and ²²⁶Ra and ²³⁰Th excess.     

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.     

井水位气压效率b值动态响应的断层-前兆场主应力组合模式

统计鲁03，04井流水作业闰的气压效率b值发现，在华北及其周缘绝大多数地震前两井前兆异常形态各异，经分析井孔定位断层走向与地震前兆场主应力的组合模式不同是产生上述现象的根本原因。     

1999年山西大同Ms 5.6地震的震源断层

大同震区先后在 1989、1991和 1999年发生MS >5地震 ,利用大同遥测地震台网的记录资料进行比较精确的地震序列震源定位 ,结合宏观烈度分布和震源机制解资料 ,详细地分析对比了 3次子序列的异同。结果显示 ,1999年MS5 .6地震的震源断层是走向NWW、长 16km、宽12km、埋深 5km以下、倾角近直立的左旋走滑断层。而前 2个子序列是NNE为主的右旋走滑断层活动所致 ,表明地震破裂方向发生了变化。这种 2个以上方向先后出现、并且强弱有别的地震破裂是普遍存在的 ,表明震源环境的复杂程度与地震序列的类型有关。虽然震区存在NE向的大王村断裂和NW向的团堡断裂 ,但目前没有证据说明震源断层和 2条构造断层连通。 3次子序列的震源断层都是走滑断层 ,也和 2条构造正断层有别。 1999年的子序列可能属于新破裂。