Crystal chemistry of Fe3+-bearing (Mg,Fe)SiO3 perovskite: a single-crystal X-ray diffraction study

Magnesium silicate perovskite is the predominant phase in the Earth’s lower mantle, and it is well known that incorporation of iron has a strong effect on its crystal structure and physical properties. To constrain the crystal chemistry of (Mg, Fe)SiO₃ perovskite more accurately, we synthesized single crystals of Mg_0.946(17)Fe_0.056(12)Si_0.997(16)O₃ perovskite at 26 GPa and 2,073 K using a multianvil press and investigated its crystal structure, oxidation state and iron-site occupancy using single-crystal X-ray diffraction and energy-domain Synchrotron Mössbauer Source spectroscopy. Single-crystal refinements indicate that all iron (Fe²⁺ and Fe³⁺) substitutes on the A-site only, where \( {\text{Fe}}^{ 3+ } /\Upsigma {\text{Fe}}\sim 20\,\% \) based on Mössbauer spectroscopy. Charge balance likely occurs through a small number of cation vacancies on either the A- or the B-site. The octahedral tilt angle (Φ) calculated for our sample from the refined atomic coordinates is 20.3°, which is 2° higher than the value calculated from the unit-cell parameters (a = 4.7877 Å, b = 4.9480 Å, c = 6.915 Å) which assumes undistorted octahedra. A compilation of all available single-crystal data (atomic coordinates) for (Mg, Fe)(Si, Al)O₃ perovskite from the literature shows a smooth increase of Φ with composition that is independent of the nature of cation substitution (e.g., \( {\text{Mg}}^{ 2+ } - {\text{Fe}}^{ 2+ } \) or \( {\text{Mg}}^{ 2+ } {\text{Si}}^{ 4+ } - {\text{Fe}}^{ 3+ } {\text{Al}}^{ 3+ } \) substitution mechanism), contrary to previous observations based on unit-cell parameter calculations.     

Ferric/ferrous iron ratios in sodic amphiboles: Mössbauer analysis, stoichiometry-based model calculations and the high-resolution microanalytical flank method

Although the electron microprobe has become the standard microanalytical tool in modern geosciences, conventional electron microprobe analysis does not allow determination of the valence states of elements such as Fe. The correct classification of minerals and interpretation of reaction microfabrics and grain zonation require high-quality information on ferric/ferrous ratios on a scale of micrometers. The flank method developed by Höfer et?al. (1994, Eur J Mineral 6:407–418) has revived new interest in electron-induced X-ray-spectroscopy to resolve oxidation states in minerals with high spatial resolution. We have recharacterized well-documented sodic amphiboles of the glaucophane–ferroglaucophane–riebeckite–magnesioriebeckite series by electron probe microanalysis and combined the microanalytical data with ferric/ferrous ratios from Mössbauer spectroscopy, Li data from bulk ICP-AES analysis and H₂O data from bulk Karl–Fischer titration. The combination of microanalysis and high-quality analysis on the bulk materials results in a data set that allows comparison of model-based stoichiometric calculations and the calibration of the high-resolution flank method. The calibration obtained allows ferric/ferrous ratios to be determined within an error of ±5%. We have found it necessary to apply an empirical correction for absorption phenomena. The advantages of the method must be weighed against the complex calibration procedures necessary and thus the flank method will probably not find use as a routine method. However, in cases where high-resolution data in terms of valence state are needed, the flank method will provide useful data on ferric/ferrous ratios down to minimum FeO_total content of 6–8 wt%.     

The CaGeO3–Ca3Fe2Ge3O12 garnet join: an experimental study

Germanate garnets are often used as isostructural analogues of silicate garnets to provide insight into the crystal chemistry and symmetry of the less accessible natural garnet solid solutions. We synthesised two series of germanate garnets at 3 GPa along the join^VIIICa₃^VI(CaGe)^IVGe₃O₁₂–^VIIICa₃^VIFe₂^IVGe₃O₁₂ at 900 °C and 1,100 °C. Samples with compositions close to the CaGeO₃ end-member consist of tetragonal garnet with a small amount of triclinic CaGe₂O₅. Samples with nominal compositions between X_Fe=0.4 and 1.0 consist of a mixture of tetragonal and cubic garnets; whereas, single-phase cubic garnets were obtained for compositions with X_Fe>1.2 (X_Fe gives the iron content expressed in atoms per formula unit, and varies between 0 and 2 along the join). Run products which were primarily single-phase garnet were investigated using Mössbauer spectroscopy. Spectra from samples synthesised at 1,100°C consist of one well-resolved doublet that can be assigned to Fe³⁺ in the octahedral site of the garnet structure. A second doublet, present primarily in samples synthesised at 900°C, can be assigned to Fe²⁺ at the octahedral sites of the garnet structure. The relative abundance of Fe²⁺ decreases with increasing iron content. Transmission electron microscopy analyses confirm this tendency and show that the garnets are essentially defect-free. The unit-cell parameters of tetragonal ^VIIICa₃^VI(CaGe)^IVGe₃O₃ garnet decrease with increasing synthesis temperature, and the deviation from cubic symmetry becomes smaller. Cubic garnets show a linear decrease of unit-cell parameter with increasing iron content. The results are discussed in the context of iron incorporation into ^VIIIMg₃^VI(MgSi)^IVSi₃O₃ majorite.     

Crystal chemistry of wadsleyite II and water in the Earth’s interior

Wadsleyite II is a variably hydrous magnesium-iron silicate phase similar to spinelloid IV and a potential host for H in the Transition Zone of the Earths mantle. Two separate samples of wadsleyite II synthesized at 17.5 GPa and 1400°C and at 18 GPa and 1350°C have been characterized by electron microprobe, single-crystal X-ray diffraction, visible, IR, Raman, and Mössbauer spectroscopies, and transmission electron microscopy including electron energy-loss spectroscopy. The two samples have the following chemical formulae: Mg_1.71Fe_0.18Al_0.01H_0.33Si_0.96O₄ and Mg_1.60Fe_0.22Al_0.01 H_0.44Si_0.97O₄. Mössbauer spectroscopy and electron energy loss spectroscopy (EELS) indicate that about half of the iron present is ferric. Refinement of the structures shows them to be essentially the same as spinelloid IV. Calculated X-ray powder diffraction patterns show only subtle differences between wadsleyite and wadsleyite II. The hydration mechanism appears to be protonation of the non-silicate oxygen (O2) and possibly the oxygens surrounding the partially vacant tetrahedral site Si2, charge-balanced by cation vacancies in Si2, M5 and M6. The unit cell volume of this phase and its synthesis conditions indicate that it may be an intermediate phase occurring between the fields of wadsleyite and ringwoodite, if sufficient trivalent cations are available. The unit cell parameters have been refined at pressures up to 10.6 GPa by single-crystal X-ray diffraction in the diamond anvil cell. The refined bulk modulus for the sample containing 2.8 wt% H₂O is 145.6 ± 2.8 GPa with a K of 6.1 ± 0.7. Similar to wadsleyite and ringwoodite, hydration has a large effect on the bulk modulus. The presence of this phase in the mantle could serve to obscure the seismic expression of the phase boundary between wadsleyite and ringwoodite near 525 km. The large apparent effect of hydration on bulk modulus is consistent with hydration having a larger effect on seismic velocities than temperature in the Transition Zone.     

Pitfalls in geothermobarometry of eclogites: Fe<Superscript>3+</Superscript> and changes in the mineral chemistry of omphacite at ultrahigh pressures

The relatively low-variance mineral assemblage of a talc-kyanite eclogite from Dabie Shan enabled application of both conventional geothermobarometers (garnet-clinopyroxene geothermometer and the garnet-omphacite-phengite geobarometer) and a multi-equilibrium method to determine peak P-T conditions (THERMOCALC, average PT). The results were highly discrepant: 840 °C / 31.1 kbar vs. 590 °C / 29.8 kbar. Mössbauer spectroscopy showed that Fe³⁺/Fe_total in omphacite was significantly higher than the value obtained from standard formula recalculation. When the activities were corrected for Fe endmembers, geothermobarometry gave consistent results (606 °C / 31.3 kbar vs. 585 °C / 30.8 kbar). These are close to those obtained earlier by average PT, confirming the robustness of the multi-equilibrium approach. The high Fe³⁺ concentration in omphacite is best explained using a Ca-eskola endmember Ca_0.5[]_0.5AlSi₂O₆ and allowing corresponding vacancies in the omphacite structure.Editorial responsibility: W. Schreyer     

Estimates of Number of Undiscovered Deposits of Gold,Silver, Copper,Lead, and Zinc in the United States

Estimates of the number of undiscovered deposits offer a unique perspective on the nation's undiscovered mineral resources. As part of the 1998 assessment of undiscovered deposits of gold, silver, copper, lead, and zinc, estimates of the number of deposits were made for 305 of the 447 permissive tracts delineated in 19 assessment regions of the country. By aggregating number of undiscovered deposits by deposit type and by assessment region, a picture of the nation's undiscovered resources has emerged. For the nation as a whole, the mean estimate for the number of undiscovered deposits is 950. There is a 90% chance there are at least 747 undiscovered deposits and a 10% chance there are as many as 1,160 undiscovered deposits. For Alaska, the mean estimate for the number of undiscovered deposits is 281. There is a 90% chance there are at least 168 undiscovered deposits and a 10% chance there are as many as 402 undiscovered deposits. Assuming that the majority of deposits used to create the grade and tonnage models that formed the basis for estimating the number of undiscovered deposits are significant deposits, there remain about as many undiscovered deposits as have already been discovered. Consideration of the number of undiscovered deposits as part of national assessments carried out on a recurring basis serves as a leading indicator of the nation's total mineral resources.     

Ferric iron content of mineral inclusions in diamonds from George Creek, Colorado determined using Mössbauer spectroscopy

The Mössbauer milliprobe allows the determination of Fe³⁺/ΣFe in samples as small as 50?μm. For the first time this technique is applied to a suite of diamonds of eclogitic paragenesis, where three garnet and five clinopyroxene inclusions in diamonds from George Creek, Colorado have been analysed. For garnet Fe³⁺/ΣFe ranges from 0–7%, while values for clinopyroxene range from 8–14%. These results are consistent with the low oxygen fugacity conditions implied by the presence of the inclusions in diamond.