Systematics of the spinel structure type

Systematic trends in the geometry of 149 oxide and 80 sulfide binary and ternary spinels have been examined from the standpoint of ionic radius and electronegativity. The mean ionic radii of the octahedral and tetrahedral cations, taken together, account for 96.9 and 90.5% of the variation in the unit cell parameter, a, of the oxides and sulfides, respectively, with the octahedral cation exerting by far the dominant influence in sulfides. The mean electronegativity of the octahedral cation exerts an additional, but small, influence on the cell edge of the sulfides. The equation a=(8/3√d)d _tet+(8/3)d _oct, where d _tet and d _oct are the tetrahedral and octahedral bond lengths obained from the sum of the ionic radii, accounts for 96.7 and 83.2% of the variation in a in the oxides and sulfides, respectively, again testifying to the applicability of the hard-sphere ionic model in the case of the spinel structure. Comparison of observed and calculated u values for 94 spinels indicates that up to 40% of the experimentally measured anion coordinates may be significantly in error. In addition to these compounds, u values are given for 52 spinels for which no data have previously been determined. Diagrams are presented for the rapid interpretation of the internal consistency of published data and the prediction of the structural parameters of hypothetical or partially studied spinels.     

Centric or acentric crystal structure for natural schmitterite, UTeO5? New evidence from a crystal from the type locality

Summary Schmitterite, UTeO₅, was found in a sample of the mineralogical collection of the Natural History Museum of the University of Florence. The sample is from the Bambolla mine, Moctezuma, Sonora, Mexico and the mineral occurs as very rare crystals associated with emmonsite. Schmitterite is orthorhombic, space group Pca2₁, with the following unit-cell parameters: a = 10.163(1), b = 5.361(1), c = 7.865(1) ?, V = 428.5(1) ?³, and Z = 4. EDS chemical analyses showed only uranium and tellurium to be present. The crystal structure has been solved and refined to R = 2.28%. It consists of edge-sharing chains of UO₇ pentagonal bipyramids parallel to [001] linked into a framework by TeO₄ polyhedra. The crystal-chemical reasons for the choice of the non-centrosymmetric arrangement and the structural relationships with other natural tellurites are outlined.     

The crystal and melt structure of spinel and alumina at high temperature: An in-situ XANES study at the Al and Mg K-edge

We present structural information obtained on spinel and alumina at high temperature (298-2400 K) using in-situ XANES at the Mg and Al K-edges. For spinel, ^[4](Al_x,Mg_1−x)^[6](Al_2−x,Mg_x)O_4, with increasing temperature, a substitution of Mg by Al and Al by Mg in their respective sites is observed. This substitution corresponds to an inversion of the Mg and Al sites. There is a significant change in the Al K-edge spectra between crystal and liquid, which can be attributed to a change of the ^[6]Al normally observed in corundum at room temperature, to a mixture of ^[6]Al-^[4]Al in the liquid state. This conclusion is in good agreement with previous ²⁷Al NMR experiments. Furthermore, both experiments at the Al and Mg K-edges are in good agreement with XANES calculation made using FDMNES code.     

New data on the structure of diamond crystals of cubic habitus from the Lomonosov deposit

The data on the study of diamonds of cubic habitus from the Arkhangelsk diamondiferous province are presented. It is shown that the cubic crystals of diamonds that are visually similar in external morphology and color are different in their internal structures, defect-impurity compositions, and genesis.     

Evolution of spinel–pyroxene symplectite in spinel–lherzolites from the Horoman Complex,Japan

We examined the textural and geochemical characteristics of spinel-pyroxene symplectites in spinel-lherzolites collected from the lowest, middle, and upper parts (LZ1, MZ, and UZ1, respectively) of the Horoman Peridotite Complex, Japan. The modal proportion of the minerals within symplectite is almost the same, i.e., orthopyroxene:clinopyroxene:spinel = 2:1:1. The size of the symplectite minerals increases from the lowest through to the middle to the upper parts in the complex. The reconstructed major element composition of the bulk symplectites is intermediate between pyrope-rich garnet and olivine. The model garnet compositions of the LZ1satisfies garnet stoichiometry and those of the MZ and UZ1 are not consistent with garnet stoichiometry. The primitive mantle-normalized pattern in trace elements for the LZ1 symplectite is similar to that of pyrope-rich garnet from fertile peridotites, particularly in its enrichment of HREE and a positive Zr anomaly. Thus, the LZ1 symplectite has inherited both major and trace element signatures from pre-existing garnet whereas the compositions of the MZ and UZ1 symplectites were modified during and/or after breakdown of pre-existing garnet. Geochemical and textural variations of symplectites might basically correspond to temperature differences within the complex during upwelling of the Horoman Complex. The basal part of the complex (LZ1) experienced the lowest temperature decompression path in the complex, which resulted in less textural and chemical modification. On the other hand, the higher part of the complex (UZ1) experienced a relatively higher temperature decompression path than other parts of the complex, resulting in chemical equilibration among the constituent minerals and coarsening of the symplectite minerals. Selective enrichment of Sr and LREE in the symplectite may indicate that the metasomatism by a Sr- and LREE-rich melt/fluid occurred during and/or after the formation of symplectite.     

IIb trioctahedral chlorite from the Barberton greenstone belt: crystal structure and rock composition constraints with implications to geothermometry

IIb trioctahedral chlorite in the Barberton greenstone belt (BGB) metavolcanic rocks was formed during pervasive greenschist metamorphism. The chem‐ical composition of the chlorite is highly variable, with the Fe/(Fe+Mg) ratio ranging from 0.12 to 0.8 among 53 samples. The chemical variation of the chlorite results from the chemical diversity of the host rock, especially the MgO content of the rock, but major details of the variation pattern of the chlorite are due to the crystal structure of the chlorite. All major cation abundances in the chlorite are strongly correlated with each other. Sil‐icon increases with Mg and decreases with Fe, while Al^IV and Al^VI decrease with Mg and increase with Fe²⁺. A complex exchange vector explains over 90% of the chlorite compositional variation: Mg₄SiFe²⁺ ₋₃Al^VI ₋₁ Al^IV ₋₁, which has 3 parts Fe-Mg substitution coupled with one part tschermakite substitution. This ratio is required to maintain the charge and site balances and the dimensional fit between the tetrahedral and octahedral sheets. The subtle change in Al substitution in chlorite implies that Al^VI is preferentially ordered in the M(4) site, and about 84% of the Al^VI present is in the M(4) sites when they are nearly filled with Al^VI. Based on 47 analyzed chlorite-bearing rock samples, chlorite (Chl) composition is strongly correlated with the MgO content of the host rock. Calculated correlation coefficients are +0.91 for SiO_2Chl-MgO_Rock, −0.87 for Al₂O_3Chl-MgO_Rock, +0.89 for MgO_Chl-MgO_Rock, and −0.85 for FeO_Chl-MgO_Rock. Only weak correlations have been found between chlorite oxides and other oxides of rock (between same oxides in chlorite and rock: SiO₂−0.67, Al₂O₃ + 0.59, FeO −0.41). However, MgO_Chl is saturated at about 36 wt% in rocks that have MgO above 22 wt%.The MgO_Chl is about 5 wt% when the host rock approaches 0 wt% of MgO. This implies that Mg substituting into the chlorite is approximately limited to 1.5–9.2 Mg atoms per formula unit and 1.0–3.2 Al^IV. Chlorite geothermometers can not be applied to all BGB samples. However, the empirical chlorite geothermometer based on Al^IV of chlorite may be applicable to chlorites formed under metamorphic conditions because it can predict the chemical composition of the chlorite from basaltic and dacitic samples in this study. An estimated temperature of about 320°C for the greenschist metamorphism of the greenstone belt through this geothermometer is consistent with that obtained by other geothermometers. Received: 22 January 1996 / Accepted: 15 August 1996     

Rare minerals of the spinel group in ultrabasites from Bulgaria

Summary Chromite mineralization was found during a detailed geological mapping, carried out in 1962, in the region of the Seven Lakes, Northern Rila Mountain. Mineralogical studies showed that the ore minerals of this mineralization are of a great variety, and are members of the little known group of ferrospinels with varying chromium-, aluminium- and magnesium-content. Only three minerals are described in the present paper. They are well defined varieties, differing from one another by their chemical composition and physical properties.

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Seltene Vertreter der Spinell-Gruppe in Ultrabasiten von Bulgarien

Zusammenfassung Bei einer detaillierten geologischen Kartierung im Gebiet der Sieben Seen, nördliches Rila-Gebirge, wurden im Jahre 1962 Chromit-Mineralisationen gefunden. Die mineralogische Bearbeitung zeigte, daß die Erzminerale dieser Mineralisation stark variieren und daß sie zu der noch wenig bekannten Gruppe der Ferrospinelle mit wechselndem Chrom-, Aluminium- und Magnesiumgehalt gehören. In der vorliegenden Arbeit werden nur drei Glieder beschrieben. Es handelt sich um gut definierte Varietäten, die sich in der chemischen Zusammensetzung und in den physikalischen Eigenschaften unterscheiden.

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With 6 Figures     

Erratum to: Iron isotope variations in spinel peridotite xenoliths from North China Craton: implications for mantle metasomatism

Iron isotopes, together with mineral elemental compositions of spinel peridotite xenoliths and clinopyroxenites from Hannuoba and Hebi Cenozoic alkaline basalts, were analyzed to investigate iron isotopic features of the lithospheric mantle beneath the North China Craton. The results show that the Hannuoba spinel peridotite xenoliths have small but distinguishable Fe isotopic variations. Overall variations in δ⁵⁷Fe are in a range of −0.25 to 0.14‰ for olivine, −0.17 to 0.17‰ for orthopyroxene, −0.21 to 0.27‰ for clinopyroxene, and −0.16 to 0.26‰ for spinel, respectively. Clinopyroxene has the heaviest iron isotopic ratio and olivine the lightest within individual sample. No clear linear relationships between the mineral pairs on “δ-δ” plot suggest that iron isotopes of mineral separates analyzed have been affected largely by some open system processes. The broadly negative correlations between mineral iron isotopes and metasomatic indexes such as spinel Cr#, (La/Yb)_N ratios of clinopyroxenes suggest that iron isotopic variations in different minerals and peridotites were probably produced by mantle metasomatism. The Hebi phlogopite-bearing lherzolite, which is significantly modified by metasomatic events, appears to be much heavier isotopically than clinopyroxene-poor lherzolite. This study further confirms previous conclusions that the lithospheric mantle has distinguishable and heterogeneous iron isotopic variations at the xenoliths scale. Mantle metasomatism is the most likely cause for the iron isotope variations in mantle peridotites.     

Lamellar nigerite in Zn-rich spinel from the Falun deposit,Sweden

Lamellar nigerite is found in Zn-rich spinel from a sample that contains chiefly anthophyllite + spinel + cordierite, lesser amounts of quartz and chlorite, as well as sphalerite, pyrite, pyrrhotite, and galena, and rare cassiterite and rutile. Nigerite can be described as interlayering of spinel-like (R²⁺Al₂O₄) and nolanite-like ((Sn, Ti)Al₄O₈) structures. In nigerite, the spinel-like part is also compositionally related to spinel, but in the nolanite-like part only the structural analogy exists. Stoichiometric assumptions that relate the anhydrous cation sum to the amount of R⁴⁺ cations present, allow Fe³⁺ estimates from microprobe analyses, and a representative analysis gives the following anhydrous formula: Mg_1.30Fe _0.65 ²⁺ Zn_3.03Mn_0.03Al_11.65Fe _0.35 ³⁺ Sn_0.32Ti_0.18O₂₄.The nigerite is Zn-rich with a Zn ratio (Zn/(Zn+Mg+ Fe²⁺)) of about 0.59, and the Sn ratio (Sn/(Sn+Ti)) that ranges from about 0.63 to 0.41. The Fe³⁺ content in these samples ranges from 0.35 to 0.52 (24 oxygen basis).Textures suggest that the nigerite could have formed by the breakdown of R ₂ ²⁺ (Sn, Ti)O₄ and R²⁺Al₂O₄ spinel components during more complex reactions. An experimental investigation of the MgAl₂O₄-Mg₂SnO₄ join indicates that the solubility of Mg₂SnO₄ component in spinel over the T interval 500 to 900° C is about 0.5 to 3.0 mole %. This, coupled with the increased solubility expected from the presence of Ti, gives good agreement with the 2.4 to 2.6 mole % R ₂ ²⁺ (Sn, Ti)O₄ component in spinel that is estimated to be the maximum necessary to form the compositions and amounts of observed nigerite.     

贺根山豆荚状铬铁矿中硅酸盐包体及其地质意义

贺根山豆荚状铬铁矿是典型的高Al型铬铁矿(Cr#=47.8～54.9,Mg#=64.1～73.7),其中的包体以硅酸盐矿物为主(包括橄榄石、斜方辉石、单斜辉石、韭闪石、钠长石).根据包体形状、矿物组合及分布特征可将其划分为三类.第一类包体呈孤立单矿物相,主要包括橄榄石和单斜辉石,第二类包体由平衡共生的单斜辉石和斜方辉石构成,上述两类包体均具有被熔蚀的边,且零星分布在尖晶石中,属于捕虏晶成因.第三类包体属于熔融包体,具有多边形外形,包含复杂的矿物相并密集分布于尖晶石核部.利用尖晶石颗粒内部保存完好的单斜辉石以及单斜辉石和斜方辉石包体估算的温度(1148～1254℃)与压力(490～1290 MPa)表明,贺根山豆荚状铬铁矿矿床的形成深度为16～43 km.熔融包体中含大量钠长石和韭闪石,指示铬铁矿母熔体富集H2 O、Na和Si.与铬铁矿平衡母熔体的Al2 O3含量(15.4％～16.3％)、TiO2含量(0.3％～0.9％)和FeO/MgO比值(0.6～1.1)与低Ti拉斑玄武质熔体的类似.利用尖晶石和橄榄石包体计算获得铬铁矿原始熔体的Mg O含量为～19.8％.贺根山豆荚状铬铁矿经历了深部预富集和浅部成矿两个阶段,其中浅部成矿作用涉及熔体与方辉橄榄岩反应以及演化的熔体与原始熔体混合等过程.     

High-temperature X-ray diffraction study of Co3O4: Transition from normal to disordered spinel

A high-temperature x-ray powder diffraction structural refinement indicates that the room-temperature normal spinel, Co²⁺[Co ₂ ³⁺ ]O₄, transforms to a disordered spinel at temperatures above 1150±30 K, as shown by the decrease of the oxygen u parameter. It is also shown that this transition between normal and disordered spinel is a high order one, where the degree of disordering increases with increasing temperature up to the highest temperature of this study, 1201 K.     

Garnet and spinel in fertile and depleted mantle: insights from thermodynamic modelling

We performed thermodynamic calculations based on model and natural peridotitic compositions at pressure and temperature conditions relevant to the Earth’s upper mantle, using well-established free energy minimization techniques. The model is consistent with the available experimental data in Cr-bearing peridotitic systems and can therefore be used to predict phase relations and mineral compositions in a wide range of realistic mantle compositions. The generated phase diagrams for six different bulk compositions, representative of fertile, depleted and ultra-depleted peridotitic mantle, shown that the garnet + spinel stability field is always broad at low temperatures and progressively narrows with increasing temperatures. In lithospheric sections with hot geotherms (ca. 60 mW/m²), garnet coexists with spinel across an interval of 10–15 km, at ca. 50–70 km depths. In colder, cratonic, lithospheric sections (e.g. along a 40 mW/m² geotherm), the width of the garnet–spinel transition strongly depends on bulk composition: In fertile mantle, spinel can coexist with garnet to about 120 km depth, while in an ultra-depleted harzburgitic mantle, it can be stable to over 180 km depth. The formation of chromian spinel inclusions in diamonds is restricted to pressures between 4.0 and 6.0 GPa. The modes of spinel decrease rapidly to less than 1 vol % when it coexists with garnet; hence, spinel grains can be easily overlooked during the petrographical characterization of small mantle xenoliths. The very Cr-rich nature of many spinels from xenoliths and diamonds from cratonic settings may be simply a consequence of their low modes in high-pressure assemblages; thus, their composition does not necessarily imply an extremely refractory composition of the source rock. The model also shows that large Ca and Cr variations in lherzolitic garnets in equilibrium with spinel can be explained by variations of pressure and temperature along a continental geotherm and do not necessarily imply variations of bulk composition. The slope of the Cr# [i.e. Cr/(Cr + Al)mol] isopleths in garnet in equilibrium with spinel changes significantly at high temperatures, posing serious limitations to the applicability of empirical geobarometric methods calibrated on cratonic mantle xenoliths in hotter, off-craton, lithospheric mantle sections.     

Formation of clinopyroxene + spinel and amphibole + spinel symplectites in coronitic gabbros from the Sierra de San Luis (Argentina): a key to post-magmatic evolution

The El Arenal metagabbros preserve coronitic shells of orthopyroxene ± Fe‐oxide around olivine, as well as three different types of symplectite consisting of amphibole + spinel, clinopyroxene + spinel and, more rarely, orthopyroxene + spinel. The textural features of the metagabbros can be explained by the breakdown of the olivine + plagioclase pair, producing orthopyroxene coronas and clinopyroxene + spinel symplectites, followed by the formation of amphibole + spinel symplectites, reflecting a decrease in temperature and, possibly, an increase in water activity with respect to the previous stage. The metagabbros underwent a complex P–T history consisting of an igneous stage followed by cooling in granulite, amphibolite and greenschist facies conditions. Although the P–T conditions of emplacement of the igneous protolith are still doubtful, the magmatic assemblage suggests that igneous crystallization occurred at a pressure lower than 6 kbar and at 900–1100 °C. Granulitic P–T conditions have been estimated at about 900 °C and 7–8 kbar combining conventional thermobarometry and pseudosection analysis. Pseudosection calculation has also shown that the formation of the amphibole + spinel symplectite could have been favoured by an increase in water activity during the amphibolite stage, as the temperature of formation of this symplectite strongly depends on aH₂O (<740 °C for aH₂O = 0.5; <790 °C for aH₂O = 1). Furthermore, but not pervasive, re‐equilibration under greenschist facies P–T conditions is documented by retrograde epidote and chlorite. The resulting counterclockwise P–T path consists of progressive, nearly isobaric cooling from the igneous stage down to the granulite, amphibolite and greenschist stage.     

Modification to the crystal structure of chlorite during early stages of its dissolution

Early stage processes of Mg-rich chlorite (clinochlore) dissolution were examined, focusing especially on the structural modification at grain edges during dissolution. Focused ion beam transmission electron microscopy sample preparation was applied to crystals dissolved in a flow-through reaction system at pH 3.0 and 25°C for 31 days. The obtained Si and Mg dissolution rates are −11.49 and −11.14 (logR, mol/(m²/s)), respectively, implying dissolution is non-stoichiometric. TEM-EDX analyses of dissolved samples reveal the development of 20–50-nm thick amorphous zone at an outermost rim with a chemical gradient of Mg, lower towards the solid surface, and Si enrichment in this amorphous zone. Crystalline material is partially interwoven with amorphous one at the interface between the amorphous and crystalline regions. These results indicate that the amorphous zone was produced by selective leaching of cations except for Si. Chlorite dissolution may proceed via the formation and thickening of leached layer as a by-product of release to solution of Si at slightly slower rate than Mg.