A plagioclase-olivine-spinel-magnetite inclusion from Maralinga (CK): evidence for sequential condensation and solid-gas exchange

We report a detailed petrography, mineral chemistry, and trace element study of MaTroc, a large calcium-aluminum-rich inclusion (CAI) (5 × 2.5 mm) of irregular triangular shape. The inclusion has a zonal structure: The core consists of a porous plagioclase-olivine-Ca-rich pyroxene intergrowth with subordinate apatite. Its texture is meta-gabbro-like, similar to other plagioclase-olivine inclusions (POIs). The mantle has variable thickness (0.1-1.5 mm) and consists of a compact symplectitic intergrowth of spinel (hercynite) and plagioclase with abundant dispersed magnetite, subordinate Ca-rich pyroxene, and traces of sulfides. The thin (5-50 μm) discontinuous crust of MaTroc consists mainly of plagioclase with some olivine and magnetite.The Mg-Fe phases of MaTroc are Fe-rich: olivine has Fa33.2 and high NiO content, similar to that in the host rock, Ca-rich pyroxene has much lower TiO₂ and Cr₂O₃ contents than that of the host chondrite, and plagioclase is An55-An74. Magnetites have variable compositions, are poorer in Al₂O₃ and Cr₂O₃ and richer in NiO than those in the host. Spinels have also variable compositions, rich in FeO, NiO, and ZnO.Despite their different mineralogy, both core and mantle have bulk trace element abundances similar to those in average group II CAIs. However, the mantle is richer in Nb and U and poorer in Eu, Be, B, Sr, and Li than the core. All minerals have high trace element contents. Minerals in the core show signs of incomplete equilibration of trace elements within and between them. Mantle minerals are far from equilibrium with each other and the bulk system. Spinel and anorthite carry the trace element signature of their precursor melilite (or hibonite), and magnetite contains large amounts of a heterogeneously distributed remnant extremely rich in trace elements (“obscurite”), possibly of a former perovskite.Inclusion MaTroc has a complex history. The POI core probably formed by reaction of an unknown precursor(s) of condensation origin with a vapor to form olivine, plagioclase, clinopyroxene, apatite, and (an) unknown phase(s) that vanished, leaving abundant void space. The spinel-rich mantle is also a secondary mineral assemblage that formed by breakdown of and solid-vapor reactions with a precursor or precursors, possibly melilite (or hibonite). The abundant magnetite formed by reaction of perovskite with an oxidizing vapor and by precipitation from such a vapor. All phases of the inclusion experienced the metasomatic addition of Fe, Ni, and moderately volatile elements such as V, Be, Li, Cr, and Mn—similar to all other constituents of the Maralinga CK chondrite. Phases in MaTroc and in the host rock are close to equilibrium in the distribution of Fe, Mg, Ni, and Mn but far from equilibrium in the distribution of M⁺³ and M⁺⁴ ions. The minor and trace element abundances in the magnetite of the host rock and of MaTroc preclude an origin by oxidation of a metal precursor.     

Chemical fluid transport (CFT): A window into Earth and its development

Gas phase transport according to chemical fluid transport (CFT) in Earth's crust as well as in the solar nebula is characterized by very high transport efficiency. Systematic investigations of mobilization, transport and deposition of gaseous MeX (Me = metal, X = F or Cl) compounds by solid gas equilibrium reactions are suitable to explain numerous extensive accumulations of minerals and ores. More than 40 of the considered chemical elements form volatile MeX compounds. Some elements tend to form MeF compounds, whereas others are more likely to form MeCl compounds. Silicon reacts with HF to form SiF₄ and replaces other elements to form MeF compounds at low temperature ranges. Accumulations caused by SiF₄ transport explain the formation of numerous quartz varieties and silicate minerals in Earth's crust. Iron most likely reacts with HCl to form FeCl₂ as well as FeCl₃ and explain the formation of iron or iron compounds. Thermodynamically directed transport from cool to hot areas in connection with cyclic processes increases the transport efficiency of MeX-species. Such species are SiF₄, Al₂F₆, POF₃, Cu₃Cl₃, SnCl₄, BF₃, GeF₄, GeCl₄, Ga₂Cl₆, ZrF₄, NbF₅ and TiF₄. The transport gases SiF₄ and POF₃ often react with environmental compounds forming pneumatolytic and metasomatical mineral accumulations. CFT is the “motor” of pneumatolytic and metasomatical processes.     

Variation in calcite dissolution rates:: A fundamental problem?

A comparison of published calcite dissolution rates measured far from equilibrium at a pH of ∼ 6 and above shows well over an order of magnitude in variation. Recently published AFM step velocities extend this range further still. In an effort to understand the source of this variation, and to provide additional constraint from a new analytical approach, we have measured dissolution rates by vertical scanning interferometry. In areas of the calcite cleavage surface dominated by etch pits, our measured dissolution rate is 10^−10.95 mol/cm²/s (PCO₂ 10^−3.41 atm, pH 8.82), 5 to ∼100 times slower than published rates derived from bulk powder experiments, although similar to rates derived from AFM step velocities. On cleavage surfaces free of local etch pit development, dissolution is limited by a slow, “global” rate (10^−11.68 mol/cm²/s). Although these differences confirm the importance of etch pit (defect) distribution as a controlling mechanism in calcite dissolution, they also suggest that “bulk” calcite dissolution rates observed in powder experiments may derive substantial enhancement from grain boundaries having high step and kink density. We also observed significant rate inhibition by introduction of dissolved manganese. At 2.0 μM Mn, the rate diminished to 10^−12.4 mol/cm²/s, and the well formed rhombic etch pits that characterized dissolution in pure solution were absent. These results are in good agreement with the pattern of manganese inhibition in published AFM step velocities, assuming a step density on smooth terraces of ∼9 μm⁻¹.     

Water dissolution in albite melts:: Constraints from ab initio NMR calculations

Hartree-Fock and B3LYP NMR calculations were performed at the 6-311+G(2df,p) level on cluster models representing albite glasses using B3LYP/6 to 31G* optimized geometries. Calculation results on several well-known crystalline materials, such as low albite and KHSi₂O_5, were used to check the accuracy of the calculation methods.Calculated ²⁹Si-NMR results on clusters that model protonation of Al-O-Si linkages and the replacement of Na⁺ by H⁺ indicate a major increase in Si-O(H) bond length and a 5 ppm difference in δ_iso for ²⁹Si compared to that for anhydrous albite glass. The calculated δ_iso of ²⁷Al in such linkages agrees with the experimental data, but shows an increase in C_q that cannot be fully diminished by H-bonding to additional water molecules. This protonation model is consistent with both experimental ¹⁷O NMR data and the major peak of ¹H-NMR spectra. It cannot readily explain the existence of the small peak in the experimental ¹H spectra around 1.5 ppm. Production of the depolymerized units Al [Q³]-O-H upon the dissolution of water is not consistent with ²⁷Al, ¹H, or ¹⁷O NMR experimental results. Production of Si [Q³]-O-H is consistent with all of the experimental ¹⁷O and ¹H-NMR data; such units can produce both the major peak at 3.5 ppm and the small peak at 1.5 ppm in ¹H spectra, either with or without hydrogen bonding. This species, however, cannot produce the main features of ²⁹Si spectra.It is concluded that although neither protonation nor the production of Si [Q³]-O-H alone is consistent with the available experimental data, the combination of these two processes is consistent with available experimental NMR data.     

Proximity effects on semiconducting mineral surfaces II:: Distance dependence of indirect interactions

In a previous study, we described proximity effects on surfaces of the semiconducting minerals galena and pyrite, whereby a chemical reaction at one surface site modifies the reactivity of a remote surface site several Ångstroms or even nanometers away (Becker et al., 2001). The modification of interest does not arise because of a direct “through space” interaction between the two sites, but rather an indirect interaction via the electronic structure of the substrate. Here we investigate the distance and direction dependence of proximity effects using quantum mechanical modeling. The direct and indirect interactions between co-adsorbed oxygen atoms and between adsorbed oxygen atoms and point defects on vacuum-terminated galena (100) surfaces were modeled. Density functional theory cluster and plane wave pseudopotential calculations were used to calculate the modifications to the adsorption energy as a function of separation. Energy-distance plots indicate that the proximity effect energy can become very strong at separations decreasing below about 5 to 6 Å, and persist at increasing separations up to 12 Å in a slowly decaying form. A strong attractive indirect interaction out-competes direct electrostatic repulsion for O-vacancy interactions. An oscillatory asymptotic behavior is found for co-adsorbed O-O indirect interactions, which indicates that the proximity effect energy can vary with surface crystallographic direction. It implies the presence of a strong organizing force on like adatoms that may explain the progressive oxidation of certain sulfide minerals by patchwork growth. These findings begin to pave the way for improved adsorption isotherms and extended surface complexation models that will include the specific influence of semiconductor-type proximity effects.     

An anisotropic Model for Structured Soils: Part I: Theory

The paper presents an incremental plasticity constitutive Model for Structured Soils (MSS–2) to describe the effects of structure (stress history and bonding) on the mechanical behaviour of cohesive soils. Such effects are high initial stiffness, dilatancy and peak strength, their appreciable reduction upon strain-induced de-structuring and the evolution of material anisotropy. The proposed model advances present practice in incremental elasto-plasticity for structured soils by incorporating: (a) distorted ellipsoids, rotated with respect to the isotropic axis, for the Structure Strength Envelope (bounding surface) and the Plastic Yield Envelope (yield surface) to describe the evolution of structure and anisotropy, (b) an Intrinsic Compressibility Framework and a corresponding Intrinsic Strength Envelope which represents a lower bound of the Structure Strength Envelope and is used as reference locus for the structureless material, (c) an improved damage mechanism to model structure degradation by plastic strains and (d) a non-associated flow rule controlled by structure. The proposed model is modular, its features can be activated simultaneously or selectively, and the 3-D tensorial formulation facilitates direct implementation in finite elements codes.     

Microscopic reversibility of Sm and Yb sorption onto smectite and kaolinite: Experimental evidence

The microscopic reversibility of the sorption of Sm and Yb onto kaolinite and smectite is investigated by introducing an isotopic disequilibrium between the clay and the solution. The experiments are performed at 25°C, in 0.025 or 0.5 M NaClO₄ and from pH 4 up to pH 7. The isotopic exchange is monitored as a function of time over a duration of 355 hours. The first stage of the experiment consists of equilibrating the clays with a natural or spiked lanthanide solution. The second stage consists of interchanging the solutions between twin phials (same clay, pH and ionic strength, but with different lanthanide isotopic compositions). The isotopic composition and concentration of aqueous lanthanides are analysed by ICP-MS. The results are as follows: (1) the lanthanide isotopic composition of the solution is rapidly modified and stabilised within 24 h; (2) the isotopic exchange between the solid and the solution is not always complete; (3) the degree of microscopic reversibility (isotopic exchange) decreases with increasing pH. These results are explained by the fact that exchange is easier for lanthanides linked to the surface as outer-sphere complexes (physical sorption), which predominate at low pH, than for atoms sorbed as inner-sphere complexes (chemical sorption) which predominate at high pH. The contrasted kinetics observed for the different kind of sites provide additional constraints for the modeling of migration processes in natural systems.     

Experimental study of the stability of aluminate-borate complexes in hydrothermal solutions

Formation of aqueous aluminate-borate complexes was characterized at 25°C using ²⁷Al NMR spectroscopy, and at 50-200°C via measurements of gibbsite and boehmite solubility in the presence of boric acid. ²⁷Al spectra performed at pH = 9 in Al-B solution with m(B) = 0.02 show the presence of two peaks at 80.5 and 74.5 ppm which correspond to Al(OH)₄⁻ and a single Al-substituted Q¹_Al dimer, Al(OH)₃OB(OH)₂⁻, respectively. In 0.08 m and 0.2 m borate solution, a third peak appears at 68.5 ppm which can be assigned to the Q²_Al trimer Al(OH)₂O₂(B(OH)₂)₂⁻. These chemical shifts are close to those measured for Al(OH)₃OSi(OH)₃⁻ and Al(OH)₂O₂(Si(OH)₃)₂⁻ (74 and 69.5 ppm, respectively; Pokrovski et al., Min. Mag.62a (1998), 1194) which demonstrates the similar structure of Al-B and Al-Si complexes formed in alkaline solutions. Gibbsite and boehmite solubility were measured in weakly basic solutions as a function of boric acid concentration at 50°C and 78 to 200°C, respectively. Equilibrium was reached within several days at m(B) = 0.01-0.1, but more slowly at higher boron concentrations, and at 50°C and m(B) = 0.2, Al concentration increased continuously during at least 3 months as a result of the sluggish formation of Al-polyborates. The equilibrium constant of the reaction Al(OH)₄⁻ + B(OH)₃⁰_(aq) = Al(OH)₃OB(OH)₂⁻ + H₂O decreases very slowly with increasing temperature to 200°C. The log K values are 1.58 ± 0.10, 1.46 ± 0.10, 1.52 ± 0.15, and 1.25 ± 0.15 at 50, 78, 150 and 200°C, respectively, which result in the following values of the standard thermodynamic properties for this reaction: Δ_rG⁰ = −9.22 ± 3.25 kJ/mol, Δ_rH⁰ = −4.6 ± 2.5 kJ/mol, Δ_rS⁰ = 15.5 ± 6.9 J/mol K. The thermodynamic data generated in this study indicate that Al-B complexes can dominate aqueous aluminum speciation in solutions containing ≥0.7 g/L of boron at temperature to at least 400°C.     

Major element chemistry of surface- and ground waters in basaltic terrain, N-Iceland.: I. primary mineral saturation

This contribution describes primary basalt mineral saturation in surface- and up to 90°C ground waters in a tholeiite flood basalt region in northern Iceland. It is based on data on 253 water samples and the mineralogical composition of the associated basalts. Surface waters are significantly under-saturated with plagioclase and olivine of the compositions occurring in the study area, saturation index (SI) values ranging from −1 to −10 and −5 to −20, respectively. With few exceptions these waters are also significantly under-saturated with pigeonite and augite of all compositions (SI = −1 to −7) and with ilmenite (SI = −0.5 to −6). The surface waters are generally over-saturated with respect to the titano-magnetite of the compositions occurring in the basalts of the study area, the range in SI being from −2 to +10. For crystalline OH-apatite, SI values in surface waters range from strong under-saturation (−10) to strong over-saturation (+5) but for crystalline F-apatite they lie in the range 0 to 15. Systematic under-saturation is, on the other hand, observed for “amorphous apatite,” i.e. an apatite of the kind Clark (1955) prepared by mixing Ca(OH)₂ and H₃PO₄ solutions. Like surface waters, ground waters are under-saturated with plagioclase and olivine, its degree increasing with increasing Ca content of the plagioclase and increasing Fe content of the olivine, the SI values being −2 to −7 and 0 to −4 for the Ca-richest and Ca-poorest plagioclase, respectively, and about −3 to −18 and 0 to −15 for forsterite and fayalite, respectively. Ground waters are generally close to saturation with pigeonite and augite of all compositions. However, some non-thermal ground waters in highland areas are strongly under-saturated. Above 25°C the ground waters are ilmenite under-saturated but generally over-saturated at lower temperatures. These waters are titano-magnetite over-saturated at temperatures below 70°C, the SI values decreasing with increasing temperature from about 6 to 8 at 10°C to 0 at 70°C. The ground waters are highly over-saturated with both crystalline OH- and F-apatite, or by approximately 10 to 15 SI units but close to saturation with “amorphous apatite” containing about equal amounts of F and OH. The results presented here for the pyroxenes carry an unknown error because available thermodynamic data do not permit but a simple solid solution model for the calculation of their solubility. Published values on the dissociation constants for ferrous iron hydroxide complexes are very variable and those for ferric iron are limited. This casts an error of an unknown magnitude on the calculated SI values for all iron bearing minerals. This error may not be large for waters with a pH of less than 9 but it is apparently high for waters with a higher pH. Improved experimental data on the stability of ferrous and ferric hydrolysis constants are needed to improve the accuracy by which Fe-mineral saturation can be calculated in natural waters.