The geochemistry of pyroxenes from the lower layered series of the Jimberlana intrusion,Western Australia     

I. H. Campbell  G. D. Borley 《Contributions to Mineralogy and Petrology》1974,47(4):281-297

Most of the Al³⁺ entering the pyroxenes does so by substituting for tetrahedral Si⁴⁺. This creates a charge imbalance that requires the simultaneous entry of Cr³⁺, Ti⁴⁺, Fe³⁺ or Al³⁺ into octahedral sites. Cr³⁺, because of its high crystal field stabilisation energy (CFSE), is the most important of these elements to enter the early-formed pyrosenes but it is replaced by Ti⁴⁺ later in fractionation when the Cr³⁺ content of the melt becomes depleted. The dependence of Cr³⁺ and Ti⁴⁺ on charge balance controls their partition between coexisting pyroxenes and olivines. Ca-rich pyroxene which contains more Al³⁺ than Ca-poor pyroxene also has more Ti⁴⁺ and Cr³⁺ whereas olivine, which contains negligible Al³⁺, has low Cr³⁺ and Ti⁴⁺. The Al³⁺ content of pyroxenes is influenced by changes in P, T, \(a_{{\text{SiO}}_{\text{2}} }\) and \(a_{{\text{Al}}_{\text{2}} {\text{O}}_{\text{3}} }\) of the magma and by the nature of the ion providing charge balance in the octahedral site. Of these \(a_{{\text{SiO}}_{\text{2}} }\) is dominant and variations in the Al³⁺ content of the Jimberlana pyroxenes correspond closely with the expected changes in the \(a_{{\text{SiO}}_{\text{2}} }\) of the melt. The substitution of divalent ions, such as Mn²⁺ and Ni²⁺, in the pyroxene lattice is by replacement of Fe²⁺ or Mg²⁺ in the octahedral M ₃ and M ₂ sites and is therefore independent of charge balance. If there are no size restrictions, the principal factor to be considered is the CFSE the ion receives in octahedral co-ordination. Ni²⁺, which receives a high CFSE, partitions strongly between the early-formed pyroxenes and olivines and therefore becomes depleted in the magma with fractionation. Conversely Mn²⁺, which receives zero CFSE, concentrates in the magma with fractionation and becomes a more important substitute in the later-formed pyroxenes. Its geochemical behaviour is controlled by its size. The narrow miscibility gap of the Jimberlana pyroxenes and the high En content of the Ca-poor pyroxenes at the bronzite pigeonite changeover suggest that these pyroxenes crystallised at a higher temperature than pyroxenes of comparable composition from other intrusions.  相似文献   

Electron spin resonance of trivalent chromium in forsterite,Mg2SiO4     

H. Rager 《Physics and Chemistry of Minerals》1977,1(4):371-378

The electron spin resonance (ESR) spectrum of Cr³⁺ in a synthetic single crystal of forsterite doped with Cr₂O₃ was studied at room temperature in the X-band frequency range. The dependence of the observed spectra on the crystal orientation with respect to the applied magnetic field was investigated. The ESR spectra are described by the spin Hamiltonian \(H = \beta HgS + D(S_Z^{\text{2}} - {\text{1/3}}S{\text{(}}S{\text{ + 1)) + }}E{\text{(}}S_x^{\text{2}} - S_y^{\text{2}} {\text{)}}\) with S=3/2. The spin resonance reveals that the chromium ions are located at both the M1 and M2 positions. Other possible substitutional or interstitial Cr³⁺ positions may be possible, but were not observed. The site occupancy numbers of Cr³⁺ at M1 and M2 are roughly 1.2×10^?4 and 0.8×10^?4, respectively, assuming that chromium is oxidized completely. The preference of the chromium ions for M1 was interpreted qualitatively in terms of crystal field criteria. The rhombic and axial spin Hamiltonian parameters, D and E, and the directions of the magnetic axes obtained for M1 and M2 are consistent with the respective oxygen coordination polyhedra.  相似文献   

Composition of chromites from kimberlites of the Botuobinskaya pipe in Yakutia     

V. A. Minin  V. P. Prugov  N. M. Podgornykh  S. V. Kovyazin  L. D. Kholodova 《Geology of Ore Deposits》2011,53(7):626-638

A representative collection (138 analyses) of chromites from kimberlites of the Botuobinskaya pipe in Yakutia was studied. With allowance for the Cr, Ti, and Al contents, the chromites are subdivided into the low-Cr aluminous group A and the high-Cr and high-Ti group B. The chromites of group A with their compositional variations controlled by the Al³⁺-Cr³⁺ isomorphism are not related to kimberlite in composition and reveal attributes of restites. The chromites of group B with heterovalent Ti⁴⁺ + Fe²⁺ + Fe³⁺-3Cr³⁺ isomorphism vary in their composition in line with the compositional variations of kimberlites, thus demonstrating their primary magmatic origin. The chromites of the second group crystallized simultaneously with olivines from kimberlites, and both minerals could have formed nodules of spinel dunite.  相似文献   

Strong site preference of Co2+ in olivine,Co1.10Mg0.90SiO4     

Subrata Ghose  Che'ng Wan 《Contributions to Mineralogy and Petrology》1974,47(2):131-140

The crystal structure and site preference of Co²⁺ in a synthetic Co_1.10Mg_0.90SiO₄ olivine have been determined from single crystal X-ray diffraction data collected on an automatic diffractometer. The R factor is 0.044 for 612 reflections. The site occupancies are: Ml site: Co 0.730±0.006; Mg 0.270; M2 site: Co 0.370, Mg 0.630. The Gibbs free energy change, ΔG° for the ion-exchange reaction between M1 and M2 sites is ?4.06 kcals/mole, assuming ideal mixing at each set of sites. This energy may be called ‘site preference energy’ of Co²⁺ in olivine. The strong preference of Co²⁺ for the M1 site can be quantitatively explained by two competing forces: preference of ions larger than Mg²⁺ for the M2 site and stronger covalent bonding of transition metal ions at the M1 site. For Fe²⁺, Mg²⁺, these two effects nearly neutralize each other, explaining the lack of considerable cation-ordering in Fe-Mg olivines.  相似文献   

Optical spectroscopy study of variously colored gem-quality topazes from Ouro Preto,Minas Gerais,Brazil     

M. N.?TaranEmail author  A. N.?Tarashchan  H.?Rager  St.?Schott  K.?Schürmann  W.?Iwanuch 《Physics and Chemistry of Minerals》2003,30(9):546-555

Variously colored gem-quality topazes from Ouro Preto, Minas Gerais, Brazil, were studied by optical absorption spectroscopy and photoluminescence methods. In the near infrared range (750–2500 nm) the absorption spectra display an identical pattern of narrow intense absorption lines caused by overtones and combination vibrations of OH groups, which do not relate to the coloration of the topazes studied. Their colors were found to be caused by combination of three sets of absorption features, (1), (2), and (3) in the visible and near-UV range, which are due to different color center. (1) denotes a pair of broad split bands with maxima 18 000 and 25 000 cm^–1 caused by electronic spin-allowed dd transitions of Cr³⁺ ions. They cause a light rose to deep violet color and characteristic pleochroism of Cr³⁺-containing topazes. Photoluminescence evidences of at least three different types of Cr³⁺ complexes which, most probably, differ by ligand surroundings, O₄F₂, O₄F(OH) and O₄(OH) (2) Corresponds to the intense weakly polarized UV absorption edge. Two different parts, the thermally stable one, caused by ligand-to-metal charge transfer, and the thermally unstable one, caused by some defect center(s), contribute to the edge. (3) denotes a system of two broad unstructured bands with maxima around 19 000 cm^–1 (X>Y Z) and 24 000 cm^–1 (Y Z X). They cause the unique orange color and characteristic pleochroism of Brazilian Imperial topazes. Combinations of (1) and (3) absorption features cause various yellow-rose colors of the samples. Investigations of natural irradiated and thermally treated topazes show that the color centers (1) and (3) transform to each other at annealing and X- or gamma irradiation. The color of natural orange-red Imperial topazes is assumed to be caused by Cr⁴⁺, stabilized by other impurity ions and/or defect irradiation EPR centers. At T=300 °C Cr⁴⁺ reduces to Cr³⁺, the color of Imperial topazes changes to pale rose, caused by spin-allowed bands of Cr³⁺. In artificially irradiated crystals the (3)-center, Cr⁴⁺, may be induced according to the reaction 2Cr³⁺ Cr⁴⁺ + Cr²⁺, which involves chromium pairs in adjacent Al sites of the structure. Such artificially induced color is unstable at room temperature and in daylight. The process of the decay of (3)-centers may be described as a recombination Cr⁴⁺+Cr²⁺ 2Cr³⁺ that results in vanishing of the (3)-bands accompanied by the appearance or increase in Cr³⁺ dd bands, the original orange color turning to a pale rose.  相似文献   

Experimental study on the phase equilibria in the join CaMgSi2O6-CaCrCrSiO6 with special reference to the blue diopside     

Ko Ikeda  Kenzo Yagi 《Contributions to Mineralogy and Petrology》1977,61(1):91-106

The behaviour of tetrahedrally coordinated and octahedrally coordinated Cr³⁺ ions in diopside is discussed from the study on the join CaMg-Si₂O₆-CaCrCrSiO₆. The molecule CaCrCrSiO₆ decomposes into uvarovite+eskolaite and its maximum solubility in diopside is 6.7 wt percent at 940 ° C. Crystalline phases are diopside ss (ss is abbreviation of solid solution), uvarovite ss, wollastonite ss, spinel and eskolaite. The diopside ss is blue in colour. Its optical spectra were measured in the wavelenght range of 325–2600 nm, and assigned after tetrahedral configuration Td and octahedral configuration Oh. It is estimated that octahedral Cr³⁺ ions are in high spin state, while tetrahedral Cr³⁺ ions may be probably in low spin state. The _t and B are 10,300–10,370 cm^–1 and 429–432 cm^–1. The CFSE for tetrahedral low spin Cr³⁺ ions is nearly the same as that for octahedral high spin Cr³⁺ ions. The ionic radii of tetrahedral low spin Cr³⁺ ions calculated are 0.47–0.53 Å, shrinked from the radius of octahedral high spin Cr³⁺ ion (0.615 Å) as much as 14–24 percent. Petrologic implications of the result are also discussed.The first half of the D. Sc. dissertation of K. Ikeda presented to Hokkaido University in June, 1976  相似文献   

Chromium-bearing olivine in the St. Mesmin chondrite     

R.T. Dodd  D.J. Morrison-Smith  J.V. Heyse 《Geochimica et cosmochimica acta》1975,39(12):1621-1627

Olivine phenocrysts in microporphyritic xenoliths in the St. Mesmin chondrite (LL-breccia) show parallel rimward variations of FeO (10 to > -30wt.%), CaO (0·1–0·4%), MnO (0·2–0·8%) and Cr₂O₃ (0·2–0·7%). Aluminum is near background levels and does not vary systematically with iron. Titanium, sodium and nickel are below the limit of detection. Covariation of Fe and Cr in this olivine distinguishes it from the olivines in lunar mare basalts, in which Cr varies inversely with Fe.Transmission electron microscopy of the St. Mesmin olivine suggests that it is free of submicroscopic inclusions and exsolution lamellae and that the chromium present occurs in solid solution in the olivine. Charge balance and ionic radius considerations suggest that it occurs as Cr²⁺, whose effective ionic radius is nearly identical to that of Mn²⁺.The different Fe-Cr relationships observed in the lunar basaltic and St. Mesmin olivines reflect different crystallization sequences. Chromian spinel coprecipitated with olivine in the lunar basalts, reducing the activity of chromium in the melt and leading to the observed anticorrelation of Fe and Cr in olivine (butler, 1972). By contrast, olivine precipitated first in the St. Mesmin microporphyry and was the only solid phase present until more than half of the rock had crystallized. Parallel variation of Fe and Cr reflects crystallization from a melt in which the activity of chromium was increasing.  相似文献   

Crystal-field spectra for blue and green diopsides synthesized in the join CaMgSi2O6-CaCrAlSiO6     

Ko Ikeda  Kenzo Yagi 《Contributions to Mineralogy and Petrology》1982,81(2):113-118

Synthetic diopsides in the join CaMgSi₂O₆ CaCrAlSiO₆ have been studied by means of crystal-field theory. These diopsides are either blue or pale green in colour. The former forms at lower temperatures and the latter at higher temperatures. The optical spectra and colours can be unequivocally explained based on the assumption that Cr³⁺ions occupy both tetrahedral and octahedral sites in the diopsides. In the blue diopsides Cr³⁺ions are present in two kinds of spin state, i.e., tetrahedrally coordinated low spin and octahedrally coordinated high spin. On heating the blue diopsides, tetrahedral occupancy of chromium decreases sharply due to spin transformation from tetrahedral low spin to octahedral high spin. Above 1,160° C nearly all chromium ions are present in octahedral sites with high spin state and the diopsides become pale green in colour. Some petrogenetic applications of the resultes are discussed.  相似文献   

Thermodynamics of water in cordierite and some petrologic consequences of cordierite as a hydrous phase     

R. C. Newton  B. J. Wood 《Contributions to Mineralogy and Petrology》1979,70(4):391-405

Olivine melilitites from Namaqualand, South Africa are characterized by a broad range in olivine compositions on the scale of individual hand specimens. It is possible to distinguish four petrographically and chemically distinct olivine populations in both the northern and southern pipe clusters studied: (a) Scarce anhedral or subhedral olivines that display marked disequilibrium features with the surrounding matrix, and which are characterized by having high iron and extremely low nickel contents (referred to as HILN olivines) relative to the other olivines in the same rock, (b) A dominant population of euhedral and often skeletal (hopper) olivines that are richer in Mg and Ni than the HILN olivines in the same rock. There are in addition unusual hopper olivines that are petrographically similar to the skeletal olivines, but show aberrant zonation patterns. Hopper and HILN type olivines contain fluid and carbonate inclusions which apparently record the loss of a vapour phase and an immiscible carbonate liquid during magma ascent, (c) A third population consists of large rounded olivines (megacrysts), up to 40 mm in greatest diameter. Individuals are chemically homogeneous, but megacrysts from the same pipe collectively define a trend of decreasing Mg and Ni (Fo₉₂, 0.36% Ni to Fo₇₅, 0.17% Ni). The most fayalitic megacrysts are depleted in Mg and Ni relative to the hopper olivines in the same rock, (d) Scarce magnesium-rich (Fo₉₁) anhedral olivines which show strained extinction are believed to be xenocrysts.It is suggested that the HILN-type olivines crystallized from primitive carbonate-rich magmas under conditions of low oxygen fugacity, intermediate between the Ni-NiO and Fe-FeO buffers. Mineral-melt partition coefficients for the transition elements determined in basaltic systems are considered to be inappropriate to such carbonate-rich melts. Loss of volatiles and an immiscible carbonate liquid during magma ascent resulted in an increase in oxygen activity, a decrease in the Fe-Mg distribution coefficient (K _D ) for olivine and liquid and an increase in liquidus temperatures. These effects led to the rapid crystallization of Mg- and Ni-enriched skeletal hopper olivines. The unusual hoppers crystallized later than the HILN olivines but prior to the normal hoppers, under conditions chracterized by rapid and independent changes in oxygen activity and partition coefficients associated with the loss of volatiles and an immiscible carbonate liquid. The range in chemistry which characterizes the megacryst-olivine suite is believed to record physico-chemical changes to the magmas subsequent to separation from a mantle source area, but prior to crystallization of the HILN olivines. Most important of these changes was an increasing degree of polymerization of the liquid structure and a progressive decrease in oxygen activity as the molar ratio (CO ₃ ^2- /(CO ₃ ^2- + CO₂)) in the magma increased with decreasing pressure. Increasing polymerization of the liquid resulted in an increase in olivine-liquid partition coefficients for transition elements.Olivines in kimberlites show compositional characteristics and zonation patterns similar to those recognized in the olivine melilitites which, coupled with ilmenite compositions, suggests that the two magma types initially evolved along similar physico-chemical paths.  相似文献   

Mineralogical studies of pyropes in kimberlites from China     

董振信 《中国地球化学学报》1998,17(1):29-43

Based on the measurements of refractive index,specific gravity,unit cell parameter,and mineral chemistry and infrared absorption spectrum analyses of pyropes in kimberlites from China,systematic studies of the Physical properties and compositional variations of pyropes of different colors and diverse paragenetic types,within and between kimberlite provinces have been undertaken,The origin of pyropes in the Kimberlites and the depth of their formation have been discussed.Pyropes of the purple series are different from those of the orange series in physical and chemical properties,for exaple,pyropes of the puple series are higher in α0,RI,SG,Cr2O3,MgO,Cr/(Cr Al),Mg/(Mg Fe),and Mg/(Mg Ca),and lower in Al2O3,Fe2O3 FeO than those of the orange series.The classification of garnets in kimberlites from china by the Dawson and Stephens‘ method(1975) has been undertaken and clearly demonstrates that pyropes of diamond-rich kimberlites contain much more groups than those of diamond-poor,especially diamond-free kimberlites.The higher in α0,RI,SG,Cr2O(3.Cr/(Cr Al),knorringite and Cr-component the pyropes are ,the richer in diamond the kimberlites will be.The infrared absorption spectrum patterns of pyropes change with their chemical composition regularly,as reflected in the shape and position of infrared absorption peaks.Two absortpion bands at 862-901 cm^-1 will grade into degeneration from splitting and the absorption band positions of pyropes shift toward lower frequency with increasing Cr2O3 content and Cr/(Cr Al) ratio of pyropes,LREE contents of orange pyrope megacrysts are similar to those of porple pyrope macrocrysts,but the former is higher in HREE than the latter,showing their different chondrite-normalized patterns.The formation pressures of pyropes calculated by Cr-component,Ca-component,knorringite molecules of pyropes show that some pyropes of the purple series in diamondiferous kimberlites fall into the diamond stability field.but all pyropes of diamond-free kimberlites lie outside the diamond stability field.The megacrysts were formed through early crystallization of kimberlites magma at high pressure condition,the majority of the purple pyrope macrocrysts have been derived from disaggregated xenoliths but the minoirty of them appear to be fragments of the discrete megacryst pyropes,or phenocrysts.  相似文献   

Exsolutions of Diopside and Magnetite in Olivine from Mantle Dunite, Luobusa Ophiolite, Tibet, China   总被引：1，自引：0，他引：1  

REN Yufeng  CHEN Fangyuan  YANG Jingsui  GAO Yuanhong 《《地质学报》英文版》2008,82(2):377-384

The exsolutious of diopside and magnetite occur as intergrowth and orient within olivine from the mantle dunite, Luobusa ophiolite, Tibet. The dunite is very fresh with a mineral assemblage of olivine （〉95%） ＋ chromite （1%-4%） ＋ diopside （〈1%）. Two types of olivine are found in thin sections： one （Fo = 94） is coarse-grained, elongated with development of kink bands, wavy extinction and irregular margins; and the other （Fo = 96） is fine-grained and poly-angied. Some of the olivine grains contain minor Ca, Cr and Ni. Besides the exsolutions in olivine, three micron-size inclusions are also discovered. Analyzed through energy dispersive system （EDS） with unitary analytical method, the average compositions of the inclusions are： Na20, 3.12%-3.84%; MgO, 19.51%-23.79%; Al2O3, 9.33%-11.31%; SiO2, 44.89%-46.29%; CaO, 11.46%-12.90%; Cr2O3, 0.74%-2.29%; FeO, 4.26%- 5.27%, which is quite similar to those of amphibole. Diopside is anhedral f＇dling between olivines, or as micro-inclusions oriented in olivines. Chromite appears euhedral distributed between olivines, sometimes with apparent compositional zone. From core to rim of the chromite, Fe content increases and Cr decreases; and A! and Mg drop greatly on the rim. There is always incomplete magnetite zone around the chromite. Compared with the nodular chromite in the same section, the euhedral chromite has higher Fe3O4 and lower MgCr2O4 and MgAI2O4 end member contents, which means it formed under higher oxygen fugacity environment. With a geothermometer estimation, the equilibrium crystalline temperature is 820℃-960℃ for olivine and nodular chromite, 630℃-770℃ for olivine and euhedral chromite, and 350℃-550℃ for olivine and exsoluted magnetite, showing that the exsolutions occurred late at low temperature. Thus we propose that previously depleted mantle harzburgite reacted with the melt containing Na, Al and Ca, and produced an olivine solid solution added with Na^＋, Al^3＋, Ca^2＋, Fe^3＋, Cr^3＋. With temperature d  相似文献   

Luminescence and other spectroscopic properties of purple and green Cr-clinochlore     

Maria Czaja  Mariola Kądziołka-Gaweł  Radosław Lisiecki  Sabina Bodył-Gajowska  Zbigniew Mazurak 《Physics and Chemistry of Minerals》2014,41(2):115-126

For the first time ever, the luminescence spectra of Cr³⁺ centers in two chlorite crystals are presented. Chromium ions occupy the strong crystal-field site M4 in the brucite sheet and the intermediate crystal-field site in the inner octahedral sheet for purple and green chlorite, respectively. We discuss the influence of an effective positive charge on the Cr³⁺ ion and an effective negative charge of ligands on the differences in the values of the Dq and B parameters. It is concluded that the presence of Fe²⁺ ions and other point defects, as well as concentration quenching, causes the very short luminescence lifetimes of chromium ions.  相似文献   

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

L. V. Bershov  J.-M. Gaite  S. S. Hafner  H. Rager 《Physics and Chemistry of Minerals》1983,9(3-4):95-101

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.  相似文献   

The Cr<Superscript>6+</Superscript> impurity in supergene oxosalts in chromate mineralization occurrences of the Urals     

D. A. Khanin  I. V. Pekov  A. V. Pakunova  I. A. Ekimenkova  V. O. Yapaskurt 《Moscow University Geology Bulletin》2016,71(5):330-336

Based on the results of more than 600 electron microprobe analyses of 25 minerals the distribution pattern of the Cr⁶⁺ impurity in vanadates, phosphates, and arsenates collected in oxidation zones of six ore deposits of the Urals was studied. Among them are Pb minerals of the brackebuschite, apatite, adelite, and tsumcorite groups and alunite supergroup, as well as carminite, cornwallite, and bayidonite. Vanadates and arsenates with brackebuschite-type structures show a high affinity to Cr⁶⁺. The maximum content of the Cr⁶⁺ impurity is characteristic of minerals with specified Fe³⁺ trivalent cations (ferribushmakinite, arsenbrackebuschite, and gartrellite) or Al³⁺ (plumbogummite and bushmakinite). The prevailing scheme of isomorphous substitution, according to which chromium enters into the compositions of these minerals, is heterovalent: Cr⁶⁺ + M ²⁺ → Т ⁵⁺ + M ³⁺ (where Т = V, As, P; M ³⁺ = Fe, Al; M ²⁺ = Сu, Zn), whereas the role of isovalent substitutions Cr⁶⁺ → S⁶⁺ and Cr⁶⁺ → Mo⁶⁺ in oxosalts that formed in mineral occurrences of the Urals is insignificant.  相似文献   

Polarized electronic absorption spectra of Cr2SiO4 single crystals     

A. Furche  K. Langer 《Physics and Chemistry of Minerals》1998,25(5):393-400

Polarized electronic absorption spectra, E∥a(∥X), E∥b(∥Y) and E∥c(∥Z), in the energy range 3000–5000?cm^–1 were obtained for the orthorhombic thenardite-type phase Cr₂SiO₄, unique in its Cr²⁺-allocation suggesting some metal-metal bonding in Cr²⁺Cr²⁺ pairs with Cr-Cr distance 2.75?Å along [001]. The spectra were scanned at 273 and 120?K on single crystal platelets ∥(100), containing optical Y and Z, and ∥(010), containing optical X and Z, with thicknesses 12.3 and 15.6?μm, respectively. Microscope-spectrometric techniques with a spatial resolution of 20?μm and 1?nm spectral resolution were used. The orientations were obtained by means of X-ray precession photographs. The xenomorphic, strongly pleochroic crystal fragments (X deeply greenish-blue, Y faint blue almost colourless, Z deeply purple almost opaque) were extracted from polycrystalline Cr₂SiO₄, synthesized at 35?kbar, above 1440?°C from high purity Cr₂O₃, Cr (10% excess) and SiO₂ in chromium capsules. The Cr₂SiO₄-phase was identified by X-ray diffraction (XRD). Four strongly polarized bands, at about 13500 (I), 15700 (II), 18700 (III) and 19700 (IV) cm^–1, in the absorption spectra of Cr₂SiO₄ single crystals show properties (temperature behaviour of linear and integral absorption coefficients, polarization behaviour, molar absorptivities) which are compatible with an assignment to localized spin-allowed transitions of Cr²⁺ in a distorted square planar coordination of point symmetry C₂. The crystal field parameter of Cr²⁺ is estimated to be 10?Dq?10700?cm^–1. A relatively intense, sharp band at 18400?cm^–1 and three other minor features can, from their small half widths, be assigned to spin-forbidden dd-transitions of Cr²⁺. The intensity of such bands strongly decreases on decreasing temperature. The large half widths, near 5000?cm^–1 of band III are indicative of some Cr-Cr interactions, i.e. δ-δ* transitions of Cr₂ ⁴⁺, whereas the latter alone would be in conflict with the strong polarization of bands I and II parallel [100]. Therefore, it is concluded that the spectra obtained can best be interpreted assuming both dd-transitions of localized d-electrons at Cr²⁺ as well as δ-δ* transitions of Cr₂ ⁴⁺ pairs with metal-metal interaction. To explain this, a dynamic exchange process 2 Cr_loc ²⁺?Cr_{2, cpl} ⁴⁺ is suggested wherein the half life times of the ground states of both exchanging species are significantly longer than those of the respective optically excited states, such that the spectra show both dd- and δ-δ*-transitions.  相似文献   

The natural occurrence of hydroxide in olivine   总被引：1，自引：0，他引：1  

Gregory H. Miller  George R. Rossman  George E. Harlow 《Physics and Chemistry of Minerals》1987,14(5):461-472

Polarized infrared (IR) spectra of olivine single crystals from 17 different localities show a tremendous variability in both mode and abundance of hydroxide (OH) incorporation. Kimberlitic olivines contain the most total OH at an estimated concentration level of 976 H/10⁶Si, whereas olivines from basalts contain the least at 3 H/10⁶Si. Olivines of metamorphic and hydrothermal origin have widely varying concentration levels intermediate between those of basalts and kimberlites. Over 30 distinct OH absorption bands have been identified. Most of these bands are not unique to individual localities but may be found in samples from several different localities. Pleochroism is consistent among localities, but relative band intensities vary. No evidence is found for molecular H₂ in olivine. Hydrous minerals have been identified in olivine by their characteristic OH absorption bands. Serpentine is commonly found and is clearly distinguishable from intrinsic OH. Talc is present in one sample. Prominent OH bands at 3572 and 3525 cm^?1 are attributed to humite group minerals. San Carlos, Arizona, olivines annealed in the presence of H₂O develop absorption bands which are found in natural samples, however the OH absorption spectra of these annealed olivines are not identical to those of any single natural crystal. Sharp-band OH abundances in annealed samples are an order of magnitude lower than the maximum measured in natural specimens. The mechanical properties determined from these annealed olivines may not be directly applicable to mantle olivine because both the OH sites and concentrations are different.  相似文献   

The alleged kimberlite-carbonatite relationship: evidence from ilmenite and spinel from Premier and Wesselton mines and the Benfontein sill,South Africa     

Gaspar  Jose C.  Wyllie  Peter J. 《Contributions to Mineralogy and Petrology》1984,85(2):133-140

Carbonate-rich, SiO₂-poor residua are developed in some kimberlites solidifying as ocelli, layers, or discrete dikes which satisfy petrographic definitions of carbonatite. Arguments that these rocks have mineralogies, antecedents, and comagmatic rocks differing from those of the carbonatites in alkaline rock complexes, including the specific observation that kimberlites and carbonatites contain ilmenites and spinels of different composition, have been used to refute the alleged kimberlite-carbonatite relationship. New microprobe analyses of ilmenites and spinels from carbonate-rich rocks associated with kimberlites in three South African localities correspond to spinels and ilmenites of carbonatites from alkalic complexes, or have characteristics intermediate between those of carbonatites and kimberlites. The ilmenites are distinguished from kimberlite ilmenites by higher MnO, FeTiO₃, and Nb₂O₅, and by negligible Cr₂O₃. The spinels are distinguished from kimberlite spinels by their Al₂O₃ and Cr₂O₃ contents. There is clearly a genetic relationship between the kimberlites and the carbonate-rich rocks, despite the observation that their ilmenites and spinels are distinctly different, which indicates that the same observation is not a valid argument against a petrogenetic relationship between kimberlites and carbonatites. These rocks are among the diverse products from mantle processes influenced by CO₂, and we believe that the petrogenetic links among them are forged in the upper mantle. We see insufficient justification to deny the name carbonatite to carbonate-rich rocks associated with kimberlites if they satisfy the petrographic definition in terms of major mineralogy.  相似文献   

Distinct ruby suite at Sardapur, Orissa: A spectroscopic investigation     

Alik Sundar Majumdar  George Mathew 《Journal of the Geological Society of India》2012,80(5):715-722

Orissa is an important area for gem variety of corundum deposits in India. Spectroscopic studies, such as ESR, OAS on samples from Sardapur, Orissa, were carried out to ascertain the colour cause of corundum. Electron spin resonance (ESR) spectroscopic study was carried out on the samples to detect the presence of paramagnetic ions i.e. Fe²⁺, Fe³⁺, Ti⁴⁺, Cr³⁺ and V³⁺ etc. The variable temperature experiment carried out to observe the effect of heating on peak valence state change in paramagnetic ions. Samples were cut and polished to obtain the optical absorption spectrum (OAS) to detect the colour causing transition ions/defect centres. The samples of gem variety were step heated up to 300°C for colour enhancement studies. EPMA analysis has revealed the low chromium concentration in the rubies. The varying hues of red in the corundum are due to the presence of bivalent and trivalent iron and charge transfer process along with Cr³⁺ absorption in the 550 nm region.  相似文献   

Study of structural and valence state of Cr and Fe in chrysoberyl and alexandrite with EPR and M?ssbauer spectroscopy     

V. S. Urusov  N. A. Gromalova  S. V. Vyatkin  V. S. Rusakov  V. V. Maltsev  N. N. Eremin 《Moscow University Geology Bulletin》2011,66(2):102-107

Data on the structural and valence distribution of Cr and Fe in chrysoberyl and in alexandrite, its gem variety, are given. It is shown that the Cr³⁺ line in the natural Ural and Tanzania samples is the strongest in the M1 site and for the synthetic stones, in the M2 site. During the annealing of the alexandrite crystals, Cr³⁺ passes from the smaller M1 site into the larger M2 site. The M?ssbauer spectroscopy quantitatively determined the distribution of different valence Fe ions. The various proportions of both Fe²⁺ and Fe³⁺ ions isomorphically entering the octahedral sites in the BeAl₂O₄ crystal structure were established.  相似文献   

Chromium solubility in anhydrous Phase B     

Luca Bindi  Ekaterina A. Sirotkina  Andrey V. Bobrov  Fabrizio Nestola  Tetsuo Irifune 《Physics and Chemistry of Minerals》2016,43(2):103-110

The crystal structure and chemical composition of a crystal of (Mg_14?x Cr _x )(Si_5?x Cr _x )O₂₄ (x ≈ 0.30) anhydrous Phase B (Anh-B) synthesized in the model system MgCr₂O₄–Mg₂SiO₄ at 12 GPa and 1600 °C have been investigated. The compound was found to be orthorhombic, space group Pmcb, with lattice parameters a = 5.900(1), b = 14.218(2), c = 10.029(2) Å, V = 841.3(2) Å³ and Z = 2. The structure was refined to R ₁ = 0.065 using 1492 independent reflections. Chromium was found to substitute for both Mg at the M3 site (with a mean bond distance of 2.145 Å) and Si at the octahedral Si1 site (mean bond distance: 1.856 Å), according to the reaction Mg²⁺ + Si⁴⁺ = 2Cr³⁺. Such substitutions cause a reduction in the volume of the M3 site and an increase in the volume of the Si-dominant octahedron with respect to the values typically observed for pure Anh-B and Fe²⁺-bearing Anh-B. Taking into account that Cr³⁺ is not expected to be Jahn–Teller active, it appears that both the Cr³⁺–for–Mg and Cr³⁺–for–Si substitutions in the Anh-B structure decrease the distortion of the octahedra. Electron microprobe analysis gave the Mg_13.66(8)Si_4.70(6)Cr_0.62(4)O₂₄ stoichiometry for the studied phase. The successful synthesis of this phase provides new information for the possible mineral assemblages occurring in the Earth’s deep upper mantle and shed new light on the so-called X discontinuity that has been observed at 275–345 km depth in several subcontinental and subduction zone environments.  相似文献