Synthesis and optical absorption spectra of Cr2+-containing orthosilicates

By reacting chromium metal with appropriate oxides in a neutral atmosphere at high temperature it is possible to prepare Mg₂SiO₄ with the olivine structure containing Cr⁺⁺ and also Cr₂SiO₄. X-ray powder diffraction data for chromous orthosilicate may be indexed on an orthorhombic cell with a=5.690, b=11.262, and c=9.584 Å. The compound is not isotructural with olivine. Optical absorption spectra of Cr²⁺ in both hosts have been obtained and also indicate large differences between the two structures.     

The influence of crystal field stabilization energy on Fe2+ partitioning in paragenetic minerals

In order to explore possible quantitative relations between crystal field stabilization energy, CFSE, and partitioning behaviour of the 3d ⁶-configured Fe²⁺ ion, a suite of 29 paragenetic rock-forming minerals from 12 high-grade metamorphic rock samples of the Ukrainian shield, including the parageneses garnet/orthopyroxene/clinopyroxene (2x), orthopyroxene/clinopyroxene, garnet/clinopyroxene, garnet/orthopyroxene/biotite, garnet/biotite, garnet/cordierite, garnet/cordierite/biotite, garnet/orthopyroxene/clinopyroxene/Ca-amphibole, Ca-amphibole/biotite (retrograde), was studied by electron microprobe analysis to obtain the respective K _D Fe^{2+ (Ph1/Ph2)} values and by polarized single crystal electronic absorption spectroscopy to evaluate the respective CFSE_Fe2+ values. Other than in the case of Cr³⁺, a clear quantitative relation between K _D ^(Ph1/Ph2) and the ΔCFSE^(Ph1/Ph2) was only observed when geometrical factors, mainly the volume of crystallographic sites and ionic radii of ions competing in the partitioning process, are similar in the respective two paragenetic phases to within 15–20%. In such cases, the ΔCFSE_Fe2+ contribution to K _D ^(Ph1/Ph2) amounts to 0.1 to 0.2 log K _D per 100 cm⁻¹ΔCFSE. The conclusion is that ΔCFSE_Fe2+ plays only a secondary role after geometrical factors, in the partitioning behaviour of Fe²⁺. The reason for this is seen in the facts that, compared to the 3d ³-configured Cr³⁺ ion, CFSE of the 3d ⁶-configured Fe²⁺ amounts only to 20–25%, and that the former ion enters only octahedral sites with similar geometrical properties in the paragenetic mineral phases. Received: 17 November 1998 / Accepted: 28 June 1999     

Hydrogen and carbon in solid solution in oxides and silicates

The dissolution of H₂O and CO₂ in structurally dense, nominally anhydrous and non-carbonate oxide matrices such as MgO and CaO is reviewed. H₂O and CO₂ are treated as gaseous oxide components which enter into solid solution with the refractory oxide hosts. They form anion complexes associated with cation vacancy sites. Evidence is presented that OH^? pairs which derive from the dissolution of H₂O are subject to a charge transfer (CT) conversion into peroxy moieties and molecular hydrogen, O ₂ ^2? ... H₂. Because the O ₂ ^2? moiety is small (O^?-O^? distance ≈ 1.5 Å) high pressure probably favors the CT conversion. Mass spectroscopic studies show that molecular H₂ may be lost from the solid which retains excess oxygen in the form of O ₂ ^2? , leading to the release of atomic O. The dissociation of O ₂ ^2? moieties into a vacancy-bound O^? state and an unbound O^? state can be followed by measuring the internal redox reactions involving transition metal impurities, the transient paramagnetism of the O^? and their effect on the d.c. conductivity. Evidence is presented that CO₂ molecules dissolve dissociatively in the structurally dense oxide matrix, as if they were first to dissociate into CO+O and then to form separate solute moieties CO ₂ ^2? and O ₂ ^2? , both associated with cation vacancy sites. In the CO ₂ ^2? moiety (C-O^? distance 1.2–1.3 Å, OCO angle ≈ 130°) the C atom probably sits off center. The transition of the C atom into interstitial sites is accompanied by dissociation of the CO ₂ ^2? moiety into CO^? and O^?. This transition can be followed by infrared spectroscopy, using OH^? as local probes. Further support derives from magnetic susceptibility, thermal expansion, low frequency dielectric loss and low temperature deformation measurements. The recently observed emission of O and Mg atoms besides a variety of molecules such as CO, CO₂, CH₄, HCN and other hydrocarbons during impact fracture of MgO single crystals is presented and discussed in the light of the other experimental data.     

Local relaxations around Fe3+ and Cr3+ in Al sites in minerals

Second-order zero-field splitting (ZFS) parameters from the literature for Fe³⁺ in twelve and for Cr³⁺ in seven minerals substituting for Al were evaluated by application of the superposition model. For Fe³⁺ in monoclinic site symmetries a fair agreement of the observed splitting patterns with those calculated from the crystal structure data was observed in most cases, but the distortions for Fe³⁺ appear to be usually larger than those of the unrelaxed Al sites. In cases of not too large local relaxation the unknown sign of the axialZFS parameterb ₀ ² could be predicted, in two cases a different sign than that reported was postulated. In cordierite and scolecite the reportedEPR spectra could thus be assigned to the sites with larger average bond distances. For Fe³⁺ in beryl the relaxation of the axial site can be deduced within narrow limits. For Cr³⁺ significantly larger differences between observed and calculatedZFS patterns are found suggesting additional relaxations due to the non-spherical electron distribution in the ground state of this ion.     

Fe2+ -F avoidance in silicates

Fe²⁺-F avoidance, reported in the literature in micas and amphiboles, can be accounted for by crystal field theory. The crystal field splitting parameter, Δ_O, of Fe²⁺ octahedrally coordinated to F^? is significantly smaller than its value when (OH)^? is the coordinating anion. Thus, the presence of Fe²⁺ is not favored at sites where F^? substitutes for (OH)^? due to smaller crystal field stabilization energy.     

Kinetics of dissolution of mechanically comminuted rock-forming oxides and silicates—II. Deformation and dissolution of oxides and silicates in the laboratory and at the Earth's surface

Comparison of the patterns of fracture under tensile stress, indentation, and scratching of periclase. quartz, and corundum indicates that the properties relevant to dissolution of rock-forming oxides and of rock-forming non-layer silicates should be changed by mechanical comminution in essentially the same way as those of quartz. The changes are accomplished by brittle fracture under the tensile component of the stress field, which does not generate subsurface damage, and by microplastic behavior under local stresses with high net compressive and shear components, which does.Mechanical comminution should therefore affect the apparent rates of dissolution (rates calculated with respect to the initial interface area) of rock-forming oxides and of rock-forming non-layer silicates in essentially the same way in which it affects the apparent rate of dissolution of quartz. This is supported by the available evidence on the effect of dry grinding on the kinetics of dissolution of feldspars, pyroxenes, and olivines in aqueous solutions.Different effects of mechanical comminution on solubilities and dissolution rate constants can be related to certain measured or calculated properties of the considered minerals. Notably, the effect of grain size on the dissolution rate constant can be rigorously related to the Kelvin effect.The available evidence on the mechanical comminution at the bases of dry-based glaciers in highgradient segments of streams, in certain high-energy coastal and epeiric environments, and in sandy deserts indicates that such mechanical comminution should significantly affect the simultaneous or subsequent dissolution of the comminuted material.     

Reactivity and point defects of double oxides with emphasis on simple silicates

Heterogeneous solid-state reactions in quasibinary oxide systems are analyzed. As long as local thermodynamic equilibrium prevails, diffusion processes through the reaction product are rate-controlling. The diffusion coefficients are governed by point-defect concentrations. Point-defect thermodynamics allow calculation of relative point-defect concentrations as a function of the relevant thermodynamic variables, if the disorder type of the crystalline product is known. Disorder types in ternary ionic crystals are introduced. On this basis, several reactions leading to simple silicates of the form A ₂ BO ₄ are discussed in terms of ion mobilities and Gibbs energies of formation, and the possible reaction mechanisms are analyzed. Finally some remarks are included on the influence of the gas atmosphere on the reaction rate, on powder reactions and on phase boundary-controlled reaction rates.     

The crystal structure of CaFe3+SiAlO6 and the crystal chemistry of Fe3+—Al3+ substitution in calcium Tschermak's pyroxene

The crystal structure of a synthetic CaFe³⁺Al-SiO₆ pyroxene (20 kb, 1,375° C) with unit cell dimensions a=9.7797(16), b=8.7819(14), c=5.3685(5) Å, =105.78(1), space group C2/c has been refined by the method of least squares to an R-factor of 0.025 based on 812 reflections measured on an automatic single crystal diffractometer. The octahedral M1 site is occupied by 0.82 Fe³⁺ and 0.18 Al³⁺. Within the tetrahedral T site, Si⁴⁺ (0.50), Al³⁺ (0.41) and Fe³⁺ (0.09) ions are completely disordered, although submicroscopic domains with short-range order are very likely. The octahedral site preference energy of the Fe³⁺ ions with respect to Al³⁺ ions in CaFe³⁺AlSiO₆ is about 10 kcal/mole, which is much higher than that found in Y₃Al _x Fe_5–2O₁₂ garnets. Topologically the structure of CaFe³⁺AlSiO₆ is intermediate between that of diopside and calcium Tschermak's pyroxene, CaAlAlSiO₆. For CaM³⁺ AlSiO₆ clinopyroxenes an increase in the size of the M1 octahedron is accompanied by an increase in the average M2-0, bridging T-0 and 03-03 distances and kinking of the tetrahedral chain.     

The iron-titanium oxides of salic volcanic rocks and their associated ferromagnesian silicates

The co-existing microphenocrysts of magnetite and ilmenite together with the ferromagnesian silicates in salic volcanic rocks have been analysed with the electron microprobe. The temperatures and oxygen fugacities of the oxide equilibration have been estimated from the curves of Buddington and Lindsley (1965). The co-existing ferromagnesian silicate phenocrysts are either iron-rich olivine, or orthopyroxene or biotite and amphibole; for each of these groups of phenocrysts, the oxide equilibration data are specific and fall on three distinct curves, parallel to experimental oxygen buffer curves. Many of the investigated rhyolites were quenched at temperatures near 900°C, which may represent liquidus temperatures for those with sparse phenocrysts, and also the intrusion temperature of water-undersaturated granites. The composition of the biotite phenocrysts, which are Al-poor and Ti-rich, taken in conjunction with the oxide data, suggest that two Lassen dacites precipitated biotite at a water fugacity of approximately 400 bars. The composition of the later crystallizing ferromagnesian silicates, particularly the pyroxenes which show a wide range in Fe/Mg ratio, is strongly influenced by the prior crystallization of the oxide phases. If the biotite phenocrysts are typical of acid liquids, then they are incapable of generating by fractionation a peraluminous residual liquid; rather they would tend to make a liquid peralkaline.     

Stability and crystal chemistry of iron-bearing dense hydrous magnesium silicates

Dense hydrous magnesium silicates (DHMS) are supposed to be key phases in planetary water cycles because of their ability to carry water to deep mantle regions in subduction slab environments. In order to understand water cycles in iron-enriched planetary systems such as Mars knowledge of the water content and stability of iron-bearing DHMS is required. Iron-bearing DHMS were synthesized based on two starting compositions, MgFeSiO₄ + 9.5 wt% H₂O system and a simple hydrous Martian mantle composition containing Fe, Mg, Al and Si + 12.35 wt% H₂O (hydrous FMAS system). Compared to literature data on phase D, iron-bearing phase D shows analogous variations in water contents as Mg-phase D but appears to be stable at higher temperatures than Mg-phase D for both starting compositions used in this study. Iron-bearing superhydrous phase B contains up to 7 wt% H₂O and shows an extended thermal stability in the hydrous FMAS system. The high-temperature stability of iron-bearing DHMS with a Mars-like bulk composition indicates that these hydrous phases could host significant amounts of water at core-mantle boundary conditions (1500 °C and 23 GPa) in a hydrous Martian mantle.     

Electron paramagnetic resonance and ENDOR studies of Cr3+ - Al3+ pairs in forsterite

The electron paramagnetic resonance (EPR) spectrum of Cr³⁺ in synthetic crystals of forsterite consists primarily of lines of Cr³⁺ “isolated” at the M1 and M2 positions in a “perfect” crystal environment without local charge compensation. In addition it shows two nonequivalent superhyperfine-split sextets with different intensities which are due to strong interaction of the Cr³⁺ electron spin S (S=3/2) with an adjacent nuclear spin I(I=5/2). Electron nuclear double resonance (ENDOR) experiments revealed that the sextets result from Cr³⁺ (M1) - Al³⁺ and Cr³⁺ (M2) - Al³⁺ pairs, Al being located at adjacent tetrahedral Si sites. The g, D, A, and A′ tensor components of the Cr³⁺ - Al³⁺ pairs have been determined at room temperature. The values of the pairs are distinct although they are not very different from the corresponding data of “isolated” Cr³⁺. From the intensities of the EPR spectra the relative concentration of the Cr³⁺ - Al³⁺ pairs with respect to “isolated” Cr³⁺ has been estimated.     

SCF-Xα-SW MO Study of Fe-O and Fe-OH chemical bonds; applications to the mössbauer spectra and magnetochemistry of hydroxyl-bearing Fe3+ oxides and silicates

Results of SCF-Xα-SW molecular orbital calculations on (FeO₄(OH)₂)^7? and (FeO₆)^9? clusters are used to investigate the differences between Fe-O and Fe-OH bonding in hydroxyl-bearing iron oxides and silicates. The Fe³⁺-OH^? bond is more ionic, and has a smaller spinpolarization, then the Fe³⁺-O^2? bond. The smaller spinpolarizability of OH^? ligands explains why superexchange interactions between hydroxo-bridged Fe³⁺ cations are much weaker than those between oxo-bridged Fe³⁺ cations. Replacement of oxygens in the Fe³⁺ coordination environment by OH^? ligands appears to promote the covalency between Fe³⁺ centers and O^2? oxygens. The increased covalency lowers the effective spin of the Fe atom. This, in turn, explains the decreased magnetic hyperfine fields at the Fe nucleus in FeOOH polymorphs relative to those found in Fe³⁺ oxides.     

Structural and other contributions to the third-law entropies of silicates

The true third-law entropies of many minerals are frequently quite different from those values derived from calorimetric measurements. The discrepancy can usually be attributed to neglected residual or unextracted entropies related either to site-mixing and molecular disorders or to the lack of significant magnetic ordering at those temperatures reached by the heat capacity measurements. A literature review indicates that many silicates present site-mixing and vacancies in one or several of their crystallographic sites. The effect on entropy is well known in feldspars, but residual entropies of similar or greater magnitudes are also present in many amphiboles, micas, chlorites, zeolites, scapolites, feldspathoids, and other silicates. Less conspicuously, disorder in water molecules or hydrogen bonding may be responsible for yet another frequently overlooked entropy contribution. Unextracted entropy results from limited heat capacity measurements so that magnetic ordering effects to be expected in minerals with transition metals are either not registered or only incompletely recorded. In some cases, significant magnetic ordering probably only takes place at temperatures well below 15 K.The discussion in this paper centers on the causes resulting in discrepancies between calorimetric and third-law entropies. A set of tables reproduces the crystallographic information for most important rock-forming silicates and indicates the entropy contribution arising from site-mixing and vacancies, and possible magnetic ordering in those substances with transition metals. In addition, most elements appear in several isotopic forms, and it is this effect that gives rise to isotopic site-mixing and thus to another configurational entropy. It can on the whole be neglected. A discussion centered on the system fayalite-iron oxides (wüstite, hematite, magnetite) indicates the uncertainties involved in deriving third-law entropies from either equilibrium data or calorimetric investigations, which is especially relevant when dealing with substances presenting vacancies (wüstite), transition metals, and the possibility of magnetic ordering. The published entropies of many minerals are probably only approximations to true third-law values and should be checked against structural and magnetic information.     

Hyperfine interactions and spin transfer between Cr3+ and Al3+ in a synthetic single crystal of Mg2SiO4. A theoretical approach to the interpretation of EPR data

The occurrence of Cr-Al pairs in Mg₂SiO₄ has been detected by EPR spectroscopy. In the case where Cr³⁺ replaces Mg at the M2 position three different neighboring Si sites may be substituted by Al³⁺, which should yield different superhyperfine interactions. A new spectrum is presented which shows the presence of two of these possible pair configurations. An assignment of the spectral features to a specific Cr-Al pair with Cr at M2 from the experimental data alone was not possible, therefore, MSX _α cluster calculations have been performed from which the differences in the superhyperfine interaction for the various pair configurations could be obtained. Best agreement with the data of the Cr³⁺(M2)-Al pair exhibiting the most intense group of lines in the EPR spectrum was obtained for the situation where Al³⁺ is at the Si position with the shortest distance to M2. The second observed Cr³⁺(M2)-Al pair, which is significantly weaker in intensity, could not yet be assigned.     

Electronic absorption spectra of Cr3+ ions in natural clinopyroxenes

The polarized (E‖a′, E‖b and E‖c) electronic absorption spectra of five natural chromium-containing clinopyroxenes with compositions close to chromdiopside, omphacite, ureyite-jadeite (12.8% Cr₂O₃), jadeite, and spodumene (hiddenite) were studied. The polarization dependence of the intensities of the Cr³⁺ bands in the clinopyroxene spectra cannot be explained by the selection rules for the point groups C ₂ or C _2v but can be accounted for satisfactorily with the help of the higher order pseudosymmetry model, i.e. with selection rules for the point symmetry group C _3v. The trigonal axis of the pseudosymmetry crystal field forms an angle of 20.5° with the crystallographic direction c in the (010) plane. D _q increases from diopside (1542 cm^?1) through omphacite (1552 cm^?1), jadeite (1574 cm^?1) to spodumene (1592 cm^?1). The parameter B which is a measure of covalency for Cr³⁺-O bonds at M1 sites in clinopyroxene depends on the Cr³⁺ concentration and the cations at M2 sites.     

The A and B mica layers and the crystal structure of sheet silicates

A discussion of the transition from the ideal hexagonal mica structure to the ideal ditrigonal one, leads to the conclusion that the single mica layer may have two different structures (labelled A and B). The recent literature data show that both the A and B structures have been detected in some triocahedral layer lattice silicates found in nature. An examination of the structural stability of the A and B structures suggests that the last one may not be realized by dioctahedral layer lattice silicates. The concept of two structurally different mica layers, which however have the same lattice constants, greatly improves the understanding of polymorphism and twin laws in layer lattice silicates.The structural features of the tetrahedral sheet, octahedral sheet and interlayer region are carefully examined. Thus we can reach the following conclusions: the tetrahedal sheet is not entirely free to reduce its lateral dimensions by the mechanism of tetrahedal rotation owing to the repulsion among O_bas atoms; the octahedral sheet in layer lattice silicates, may increase or reduce its lateral dimensions as compared to the lateral dimensions it has in the hydroxide minerals; the interlayer region is characterized by a regular octahedral coordination of the O_bas around the interlayer cation. On the ground of these conclusions, new structural models for some selected layer lattice silicates are proposed.Notations O_bas basal oxygen atoms of the (Al, Si)O₄ tetrahedra - O_ap apical oxygen atoms of the (Al, Si)O₄ tetrahedra - b _tetr b dimension which the tetrahedral sheet would assume if unconstrained - b _oct b dimension which the octahedral sheet has in the hydroxide minerals - b _obs observed value of b - c _oct ^* thickness of the octahedral sheet - d _o distance between an octahedral cation and an O_ap atom - d _int distance between an interlayer cation and an O_bas atom - average tetrahedral rotation from ideal hexagonal symmetry     

Mechanism of the water and carbon dioxide solubility in oxides and silicates and the role of O−

The dissolution of water does not stop at the OH^– stage but may proceed further towards H₂ plus O^– formation. The discovery of atomic carbon dissolved in minerals suggests that, if CO₂ enters oxides and silicates at high pressures and temperatures, not only [CO₃]^2– ions but also [CO ₄ ^. ]^4– complexes are formed via a charge transfer which produces O^– and essentially zero-valent, atomic carbon. Under P —T-conditions of the mantle, where the solubility for water and CO₂ is high, the silicate phases formed may therefore consist to a large volume fraction of O^– ions which are much smaller than O^2–ions and strongly cova-lently bonding. The implications for the crystal chemistry of high pressure phases, for the petrology of mantle rocks are outlined.     

The crystal chemistry of lithium and Fe3+ in synthetic orthopyroxene

Lithian ferrian enstatite with Li₂O = 1.39 wt% and Fe₂O₃ 7.54 wt% was synthesised in the (MgO–Li₂O–FeO–SiO₂–H₂O) system at P = 0.3 GPa, T = 1,000°C, fO₂ = +2 Pbca, and a = 18.2113(7), b = 8.8172(3), c = 5.2050(2) Å, V = 835.79(9) Å³. The composition of the orthopyroxene was determined combining EMP, LA-ICP-MS and single-crystal XRD analysis, yielding the unit formula ^M2(Mg_0.59Fe _0.21 ²⁺ Li_0.20) ^M1(Mg_0.74Fe _0.20 ³⁺ Fe _0.06 ²⁺ ) Si₂O₆. Structure refinements done on crystals obtained from synthesis runs with variable Mg-content show that the orthopyroxene is virtually constant in composition and hence in structure, whereas coexisting clinopyroxenes occurring both as individual grains or thin rims around the orthopyroxene crystals have variable amounts of Li, Fe³⁺ and Mg contents. Structure refinement shows that Li is ordered at the M2 site and Fe³⁺ is ordered at the M1 site of the orthopyroxene, whereas Mg (and Fe²⁺) distributes over both octahedral sites. The main geometrical variations observed for Li-rich samples are actually due to the presence of Fe³⁺, which affects significantly the geometry of the M1 site; changes in the geometry of the M2 site due to the lower coordination of Li are likely to affect both the degree and the kinetics of the non-convergent Fe²⁺-Mg ordering process in octahedral sites.     

Sorptive stabilization of organic matter in soils by hydrous iron oxides

Strong correlations between iron oxides (FeOx) and organic matter (OM) in soils have implied the importance of the former in stabilizing the latter. One mechanism thought to be important in this stabilization is sorption. We tested this possibility by reductively dissolving FeOx in a wide variety of soils and measuring the organic carbon (OC) that was solubilized. The OC dissolved from non-FeOx phases via anion exchange was corrected for by parallel control extractions. The resultant pool, reductively soluble OC, made up a minor amount of total soil OC in all but one of these soils, indicating that simple sorption reactions do not stabilize the bulk of soil OC in most mineral soils. OC:Fe ratios in the extracts from 2/3 of these soils were less than 0.22 (wt/wt), consistent with a sorbed state for this OC and showing that OC sorption by FeOx in these soils is limited by the amount of FeOx. The remaining soils had low pH and high OM concentrations; their higher OC:Fe ratios indicate inclusion of precipitated organo-Fe complexes in the extracts, which are likely only partially extracted by our method. The high volumetric ratios of OM to FeOx found in correlations between them from the literature are inconsistent with a dominant sorption control and point instead to stabilization to other mechanisms such as organo-Fe complexes or ternary associations among FeOx, OM and other minerals.