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1.
An unusual association of chromite and hornblende was found in the spessartites of andesite composition, occurring as a dike swarm associated with a Cretaceous granite batholith. The spessartites are largely porphyritic with phenocrysts of either hornblende or augite. One dike, comprising a finegrained spessartite, exhibits distinct chilled selvages of aphanitic facies. The chromites in the fine-grained and augite-spessartites are significantly higher in Cr/ (Cr+Al) than those occurring rarely as inclusions in the phenocrystic hornblendes in the hornblende spessartite, although both are similar in Mg/ (Mg+Fe), Fe2O3, and TiO2. The phenocrystic hornblendes are titaniferous pargasite with high Mg/ (Mg+Fe), and differ in their higher octahedral Al from the groundmass hornblendes including those in the fine-grained spessartite. The crystallization sequence in the phenocrystic hornblende-bearing spessartites is Al-rich chromite, phenocrystic hornblende, and plagioclase without pyroxene, suggesting a high water content in the magma and the start of the crystallization at relatively high pressures. The finegrained spessartite from which the porphyritic spessartites have been derived by fractionation of dominant mafic minerals, has the high Mg-value and Cr content equivalent to those in primitive, undifferentiated basalts, although still andesitic in SiO2 content. Chemically similar magnesian andesites, although uncommon, found in some orogenic calc-alkalic suites may represent a magma composition in equilibrium with mantle peridotite under the condition of high water pressures.  相似文献   

2.
Composition of chromiferous spinel included in olivines of Mg-rich basalts and gabbros of the Deccan Traps (Gujarat and Western Ghats) are reported here. They vary from Al-rich compositions [Al2O3 = 53wt.%; Cr#, 100Cr/(Cr + Al) = 12] to Cr-rich compositions [Cr2O3 = 51wt.%; Cr# = 84], and from Cr-Al rich compositions towards Cr-rich Ti-magnetite (TiO2 up to 23 wt.%, ulvöspinel up to 67mol.%). The Mg# [100Mg/(Mg + Fe2+)] of spinel decreases from 81 to nearly zero. The highest Cr# has been found in the Bushe Fm., Thakurvadi Fm., and some high-Ti basalts of the Pavagadh section, whereas some of the low-Ti basalts of Saurashtra have Al-rich compositions typical of spinels found in mid-ocean ridge basalts. The chemical composition of the Deccan Trap spinels is completely different compared to that observed in mantle spinel suites, with very few exceptions. The decreasing Al and increasing Fe and Ti of spinel seems to be mainly the result of decrease of Mg in the locally coexisting melts and favourable cationic substitutions in the lattice. There is barely any evidence of general relationships between the composition of the Deccan spinels and inferred mantle sources of the host magmas. Pyroxene inclusions in spinels may witness a high-pressure stage of crystallization, but the possibility of non-equilibrium crystallization, or even magma mixing, cannot be ruled out. Overall, the compositional ranges of chromiferous spinel in the Deccan Traps closely match those observed in the other Large Igneous Provinces having mafic/ultramafic intrusions and mafic magma compositions (e.g., Siberian Traps, Karoo, Emeishan).  相似文献   

3.
Orthorhombic magnesium-iron ludwigite-vonsenite forms a continuous isomorphic series Mg2Fe3+[BO3]O2-Fe 2 2+ Fe[BO3]O2; its composition at the magnesioskarn and other deposits varies from magnesian to ferriferous members. In addition, they demonstrate isovalent substitution of Mn for Mg (in pinakiolite, blatterite, and others) and practically complete substitution of Ni for Mg (in bonaccordite). Ferric iron in the borates is substituted by isovalent Al and Cr. The incorporation of Ti, Sn, Sb, and V via heterovalent substitution has been studied in less detail. Our research revealed new manifestations of Ti-and Sn-bearing borates. They are magnesioludwigite and azoproite with variable Ti content, as well as by Sn-bearing aluminian borates formed via the 2Fe3+ → (Ti4+ + Mg)6+ and/or (Sn4+ + Mg)6+ substitution. The incorporation of pentavalent elements according to the scheme 3Fe3+ → (Sb5+ + 2Mg)9+ or (V5+ + 2Mg)9+ is not excluded. The highest Ti borates were found in the marbles and calciphyres of the Tazheran deposit in the Baikal region and Nalednoe, Dokuchan, and Titovskoe deposits in Yakutia, where azoproites contain more than 50 and even higher 75 mol % of the Mg2(TiMg)0.5[BO3]O2 end member. Aluminum magnesioludwigites from Yakutia and Chukotka simultaneously contain tin and titanium. Mount Brooks, Alaska, contains tin-bearing azoproite or its tin-bearing varieties. New data are reported on Sb-and V-bearing orthoborates. Calciphyres of Alaska contain monoclinic magnesiohulsite (Mg,Fe)2(SnMg) 0.5 6+ [BO3]O2, which is replaced by schoenfliesite MgSn(OH)6. The studied borate occurrences belong to hypabyssal magnesian skarns of the periclase and monticellite metasomatic PT facies at contacts of dolomites with granitoid intrusions of increasing alkalinity or leucocratic granites. Their formation was related to interaction between disequilibrium kotoite and early oxides and spinellides of various compositions, on the one hand, and, on the other hand, to the influx of Ti-and Sn-bearing hydrothermal solutions.  相似文献   

4.
Based on modal and chemical composition, the rocks of the Prairie Creek diatreme situated 4 km SSE of Murfreesboro, Pike County, Arkansas, are classified as micaceous kimberlite. The K-Ar isotopic analysis of phlogopite from this diatreme yielded an age of 106 ± 3 m.y. (Albian) which is in agreement with stratigraphic relations. Electron beam probe data on minerals from kimberlite breccia, one of the three textural types, are presented. The breccia is considered as the potential source of the diamonds that have been mined at the diatreme. It contains phenocrysts of olivine (Fo90–92) and serpentine pseudomorphs after olivine embedded in a groundmass of serpentine, minor calcite, chrome-diopside, phlogopite (Mg/Mg+Fe = 84.15%), perovskite, spinels, and pentlandite. Xenoliths of shales, sandstones, and mantle-derived ultramafic material are also present. Spinels are rich in Cr, Ti, and Fe and generally low in Al. Zoned spinels show enrichments in Ti and Fe towards their rims. A positive correlation between 100(Fe3++Ti)/(Cr+Al+Fe3++Ti) and 100 Mg/(Mg+Fe2+) ratios exists in these spinels and probably reflects an oxygen fugacity increase during magma crystallization. Occluded gases in diamonds and kimberlites corroborate the hypothesis that the parent magma of the Prairie Creek kimberlite was derived by partial melting of upper-mantle garnet lherzolite under volatile-rich conditions, primarily enriched in H2O and CO2.  相似文献   

5.
The field setting, petrography, mineralogy, and geochemistry of a suite of picrite basalts and related magnesian olivine tholeiites (New Georgia arc picrites) from the New Georgia Volcanics, Kolo caldera in the active ensimatic Solomon Islands arc are presented. These lavas, with an areal extent in the order of 1002 km and almost 1 km thick in places, are located close to the intersection of the Woodlark spreading zone with the Pacific plate margin. They contain abundant olivine (Fo94-75) and diopside (Cr2O3 1.1-0.4%, Al2O3 1–3%), and spinels characterised by a large range in Cr/(Cr+Al) (0.85–0.46) and Mg/(Mg+ Fe++) (0.65–0.1). The spinels are Fe+++ rich, with Fe+++/ (Fe++++Cr+Al) varying from 0.06 to 1.0. A discrete group of spinels with the highest Cr/(Cr+Al) (0.83–0.86) and lowest Fe+++ contents are included in the most Mg-rich olivine (Fo91–94) and both may be xenocrystal in origin.The lavas, which range between 10–28% MgO, define linear trends on oxide (element) — MgO diagrams and these trends are interpreted as olivine (0.9) clinopyroxene (0.1) control lines. For the reconstructed parent magma composition of these arc picrites, ratios involving CaO, Al2O3, TiO2, Zr, V and Sc are very close to chondritic. REE patterns are slightly LREE — enriched ((La/Sm)N 1.3–1.43) and HREE are flat. All lavas show marked enrichments in K, Rb, Sr, Ba, and LREE relative to MORB with similar MgO contents, but the TiO2 content of the proposed parent magma is close to those of postulated primary MORB liquids. It is proposed that the arc parent magma was produced by partial melting of sub-oceanic upper mantle induced by the introduction of LILE — enriched hydrous fluids derived by dehydration and/or partial melting of subducted ocean crust and possibly minor sediments.  相似文献   

6.
Summary Chrome-bearing spinels in 21 ultramafic nodules contained in a basanite from San Giovanni Ilarione (SGI), Veneto Region, Italy, have been grouped from a textural and chemical standpoint into five types: (1) Interstitial, surrounded by silicates, homogeneous, with a Cr/(Cr + Al) ratio averaging 0.11; (2) Within alteration pods and veinlets, in contact with either silicates or alteration products, showing zonation with Mg/(Mg + Fe2+), Cr, and Ti increasing and Al decreasing from core to rim; (3) In contact with the basalt or surrounded by basalt but distinct from ground-mass grains. The former are strongly zoned while the latter, referred to as xenocrysts, are relatively homogeneous. Both belong to a trend distinct from that of (2); (4) Symplectic, intergrown with pyroxenes and homogeneous, or in contact with plagioclase and/or reaction products and showing more variable composition than the former. Both are generally richer in Cr than all other spinet types and define a trend parallel to and with higher Cr/(Cr + Al) and Cr values than that of (3); and (5) groundmass grains within the host basalt, showing lower Mg/(Mg + Fe2+) and Cr/(Cr + Al), and higher Fe values than for all other, types.Group 1 spinels and the cores of group 2 and group 3 spinets display very similar compositions, suggesting a common origin, modified by later events such as partial melting, solid-liquid reactions, and subsolidus reactions which occurred prior to, during, and subsequent to interaction with the host basalt. Group 2 and 3 spinels define trends diverging from a common composition—i.e., the same origin. Group 4 spinels are probably due to exsolution which occurred after formation of the original spinels, while group 5 spinels are not directly related to types 1–4.
Spinelle in Harzbugit- und Lherzolitheinschlüssen vom Steinbruch San Giovanni Ilarione, Lessini-Berge, Region Veneto, Italien
Zusammenfassung Chromhaltige Spinelle 21 ultramafischer Knollen aus einem Basanit von San Giovanni Ilarione (SGI), Region Veneto, Italien, wurden nach texturellen und chemischen Gesichtspunkten in fünf Gruppen eingeteilt: 1. Interstitiell, von Silikaten umgeben, mit einem durchschnittlichen Cr/(Cr + Al)-Verhältnis von 0,11.2. In Umwandlungstaschen und -gängchen, in Kontakt entweder mit Silikaten oder mit Umwandlungsprodukten, zoniert mit Mg/(Mg + Fe2+), Cr und Ti vom Kern zum Rand zunehmend, Al aber abnehmend. 3. Im Kontakt zum Basalt oder vom Basalt umgeben, aber von den Körnern der Grundmasse verschieden. Die ersteren sind stark zonar, während die Letzteren, die als Xenokrysten angesehen werden, relativ homogen sind. Beide gehören zu einem Trend, welcher von jenem der Gruppe 2 verschieden ist. 4. Simplektitisch, mit Pyroxenen verwachen und homogen, oder im Kontakt zu Plagioklas und/oder Reaktionsprodukten und von variablerer Zusammensetzung ab die ersteren. Beide sind allgemein reicher an Cr als alle anderen Spinelltypen und sie definieren einen Trend parallel zu und mit höheren Cr/(Cr + Al)- und Cr- Werten als jene von Gruppe 3. 5. Körner der Grundmasse des Wirtsbasaltes, die niedrigere Mg/(Mg + Fe2+)- und Cr/(Cr + Al)- Werte und höhere Fe-Werte zeigen als alle anderen Typen.Die Spinelle der Gruppe 1 und die Kerne der Spinelle der Gruppen 2 und 3 zeigen sehr ähnliche Zusammensetzungen, die auf einen gemeinsamen Ursprung hinweisen, der später modifiziert wurde durch Ereignisse wie partielles Schmelzen, fest-flüssig-Reaktionen und subsolidus-Reaktionen, die vor, wärend und nach der Wechselwirkung mit dem Wirtsbasalt stattfanden. Die Spinelle der Gruppen 2 und 3 definieren Trends, die von einer gemeinsamen Zusammensetzung und damit von einem gemeinsamen Ursprung her auseinanderlaufen Spinelle der Gruppe 4 entstanden wahrscheinlich durch Entmischung, die nach Bildung der Ursprungsspinele eintrat, während die Spinelle der Gruppe 5 zu denen der Gruppen 1 bis 4 in keiner direkten Beziehung stehen.
  相似文献   

7.
Al-containing MgSiO3 perovskites of four different compositions were synthesized at 27 GPa and 1,873 K using a Kawai-type high-pressure apparatus: stoichiometric compositions of Mg0.975Si0.975Al0.05O3 and Mg0.95Si0.95Al0.10O3 considering only coupled substitution Mg2+ + Si4+ = 2Al3+, and nonstoichiometric compositions of Mg0.99Si0.96Al0.05O2.985 and Mg0.97Si0.93Al0.10O2.98 taking account of not only the coupled substitution but also oxygen vacancy substitution 2Si4+ = 2Al3+ + VO¨. Using the X-ray diffraction profiles, Rietveld analyses were performed, and the results were compared between the stoichiometric and nonstoichiometric perovskites. Lattice parameter–composition relations, in space group Pbnm, were obtained as follows. The a parameters of both of the stoichiometric and nonstoichiometric perovskites are almost constant in the X Al range of 0–0.05, where X Al is Al number on the basis of total cation of two (X Al = 2Al/(Mg + Si + Al)), and decrease with further increasing X Al. The b and c parameters of the stoichiometric perovskites increase linearly with increasing Al content. The change in the b parameter of the nonstoichiometric perovskites with Al content is the same as that of the stoichiometric perovskites within the uncertainties. The c parameter of the nonstoichiometric perovskites is slightly smaller than that of the stoichiometric perovskites at X Al of 0.10, though they are the same as each other at X Al of 0.05. The Si(Al)–O1 distance, Si(Al)–O1–Si(Al) angle and minimum Mg(Al)–O distance of the nonstoichiometric perovskites keep almost constant up to X Al of 0.05, and then the Si(Al)–O1 increases and both of the Si(Al)–O1–Si(Al) angle and minimum Mg(Al)–O decrease with further Al substitution. These results suggest that the oxygen vacancy substitution may be superior to the coupled substitution up to X Al of about 0.05 and that more Al could be substituted only by the coupled substitution at 27 GPa. The Si(Al)–O1 distance and one of two independent Si(Al)–O2 distances in Si(Al)O6 octahedra in the nonstoichiometric perovskites are always shorter than those in the stoichiometric perovskite at the same Al content. These results imply that oxygen defects may exist in the nonstoichiometric perovskites and distribute randomly.  相似文献   

8.
We present results from low-temperature heat capacity measurements of spinels along the solid solution between MgAl2O4 and MgCr2O4. The data also include new low-temperature heat capacity measurements for MgAl2O4 spinel. Heat capacities were measured between 1.5 and 300 K, and thermochemical functions were derived from the results. No heat capacity anomaly was observed for MgAl2O4 spinel; however, we observe a low-temperature heat capacity anomaly for Cr-bearing spinels at temperatures below 15 K. From our data we calculate standard entropies (298.15 K) for Mg(Cr,Al)2O4 spinels. We suggest a standard entropy for MgAl2O4 of 80.9 ± 0.6 J mol−1 K−1. For the solid solution between MgAl2O4 and MgCr2O4, we observe a linear increase of the standard entropies from 80.9 J mol−1 K−1 for MgAl2O4 to 118.3 J mol−1 K−1 for MgCr2O4.  相似文献   

9.
The model for the thermodynamic properties of multicomponent pyroxenes (Part I) is calibrated for ortho- and clinopyroxenes in the quadrilateral subsystem defined by the end-member components Mg2Si2O6, CaMgSi2O6, CaFeSi2O6, and Fe2Si2O6. This calibration accounts for: (1) Fe-Mg partitioning relations between orthopyroxenes and augites, and between pigeonites and augites, (2) miscibility gap features along the constituent binary joins CaMgSi2O6-Mg2Si2O6 and CaFeSi2O6-Fe2Si2O6, (3) calorimetric data for CaMgSi2O6-Mg2Si2O6 pyroxenes, and (4) the P-T-X systematics of both the reaction pigeonite=orthopyroxene+augite, and miscibility gap featurs, over the temperature and pressure ranges 800–1500°C and 0–30 kbar. The calibration is achieved with the simplifying assumption that all regular-solution-type parameters are constants independent of temperature. It is predicated on the assumptions that: (1) the Ca-Mg substitution is more nonideal in Pbca pyroxenes than in C2/c pyroxenes, and (2) entropies of about 3 and 6.5 J/K-mol are associated with the change of Ca from 6- to 8-fold coordination in the M2 site in magnesian and iron C2/c pyroxenes, respectively. The model predicts that Fe2+-Mg2+ M1-M2 site preferences in C2/c pyroxenes are highly dependent on Ca and Mg contents, with Fe2+ more strongly preferring M2 sites both in Ca-rich C2/c pyroxenes with a given Fe/(Fe+Mg) ratio, and in magnesian C2/c pyroxenes with intermediate Ca/(Ca+Fe+Mg) ratios.The proposed model is internally consistent with our previous analyses of the solution properties of spinels, rhombohedral oxides, and Fe-Mg olivines and orthpyroxenes. Results of our calibration extend an existing database to include estimates for the thermodynamic properties of the C2/c and Pbca pyroxene end-members clinoenstatite, clinoferrosilite, hedenbergite, orthodiopside, and orthohedenbergite. Phase relations within the quadrilateral and its constitutent subsystems are calculated for temperatures and pressures over the range 800–1700°C and 0–50 kbar and compare favorably with experimental constraints.  相似文献   

10.
The formation of phosphoran olivine by crystallization from a melt was investigated experimentally using a one atmosphere furnace, using San Carlos olivine [(Mg,Fe)2SiO4] mixed with either iron phosphide (FeP) or magnesium pyrophosphate (Mg2P2O7). Both dynamic crystallization and isothermal experiments produced phosphoran olivine as zoned single crystals and as overgrowths surrounding normal, phosphorus-free olivine grains. The crystallization pathways that form phosphoran olivine were traced and confirm that it is a metastable phase that can crystallize from a phosphorus-rich melt over timescales of hours to days. Removal of the P and equilibration of the olivine however requires weeks to months in the presence of silicate melt. Phosphoran olivine with up to 27 wt% P2O5 was generated and up to 69% of the Si tetrahedral sites were replaced by P. The substitution of Si by P into olivine was confirmed as 4VIM+2 + 2IVSi+4 ↔ 3VIM+2 + 2IVP+5 + VI[]. Phosphoran olivine compositions that vary from (Mg,Fe)2SiO4 to (Mg,Fe)1.65[]0.35Si0.3P0.7O4 have been produced in these experiments.Phosphoran pyroxene was also generated in a few experiments and forms when phosphoran olivine reacts with either tridymite or melt. It has compositions compatible with protopyroxene, orthopyroxene, pigeonite and sub-calcic augite, and can contain up to 31.5 wt% P2O5. Like phosphoran olivine, it is also a metastable phase. Phosphorus replaces Si in pyroxene by the following substitution methods: 8IVSi+4 ↔ 3IVSi+4 + 4IVP+5 + IV[] with Al entering the structure by the exchange 2IVSi+4 ↔ IVAl+3 + IVP+5. Phosphoran pyroxene compositions vary from (Mg,Fe)8Si8O24 to (Mg,Fe)8Si3P4[]O24.  相似文献   

11.
Summary Elevated P contents of up to 0.086 apfu (1.21 wt.% P2O5) were found in garnet from leucocratic granitic rocks (orthogneisses, granites, barren to highly evolved pegmatites) in the Moldanubicum and Silesicum, Czech Republic, and in complex granitic pegmatites from southern California, USA, and Australia. Minor concentrations (0.15–0.55 wt.% P2O5) appear ubiquitous in garnet from leucocratic granitic rocks of different origins and degrees of fractionation. Concentrations of P are not related to Mn/(Mn + Fe) that vary from 0.12–0.86 and to textural types of garnet (i.e., isolated anhedral to euhedral grains and nodules, graphic and random garnet–quartz aggregates, subsolidus veins of fine-grained garnet). Garnet compositions exhibit negative correlations for P/Si and P/R2+ where R2+ = Fe + Mn + Mg + Ca, while Al is constant at ∼2.05 apfu. Concentrations of Na are largely below 0.02 apfu but positively correlate with P. The main substitution may involve A-site vacancy and/or the presence of some light element(s) in the crystal structure. The substitution □P2 R2+ −1Si−2 and/or alluaudite-type Na□P3 R2+ −1Si−3 seem the most likely P-incorporating mechanisms. The partitioning of P among garnet and associated minerals in granitic systems remains unclear; however, it directly affects the distribution of Y and REEs.  相似文献   

12.
Glaucophane-lawsonite facies blueschists representing a metamorphosed sequence of basic igneous rocks, cherts and shales have been investigated northeast of the district of Tav?anli in Northwest Turkey. Sodic amphiboles are rich in magnesium reflecting the generally high oxidation states of the blueschists. Lawsonite has a very uniform composition with up to 2.5 wt.% Fe2O3. Sodic pyroxenes show an extensive range of compositions with all the end-members represented. Chlorites are uniform in their Al/(Al+Fe+Mg) ratio but show variable Fe/ (Fe+Mg) ratios. Garnets from metacherts are rich in spessartine (>50%) whereas those from metabasites are largely almandine. Pistacite rich epidote is found in metacherts coexisting with lawsonite. Phengites are distinctly higher in their Fe, Mg and Si contents than those from greenschist facies. Hematites with low TiO2 are ubiquitous in metacherts. Fe2+/Mg partitioning between chlorite and sodic amphibole is strongly controlled by the calcium content of the sodic amphibole and ranges from 1.1 for low calcium substitution to 0.8 for higher calcium substitution. The Al/Fe3+ partition coefficient between sodic amphibole and sodic pyroxene is 2.1. A model system has been constructed involving projections from lawsonite, iron-oxide and quartz onto a tetrahedron with Na, Al, Fe2+ and Mg at its apices. Calcite is treated as an indifferent phase. The model system illustrates the incompatibility of the sodic pyroxene with chlorite in the glaucophanelawsonite facies; this assemblage is represented by sodic amphibole. Sodic amphibole compositions are plotted in terms of coexisting ferromagnesian minerals. Five major areas on the sodic amphibole compositional field are delineated, each associated with one of the following minerals: chlorite, stilpnomelane, talc, almandine, deerite.  相似文献   

13.
Four samples of synthetic chromium-bearing spinels of (Mg, Fe2+)(Cr, Fe3+)2O4 composition and four samples of natural spinels of predominantly (Mg, Fe2+)(Al, Cr)2O4 composition were studied at ambient conditions by means of optical absorption spectroscopy. Synthetic end-member MgCr2O4 spinel was also studied at pressures up to ca. 10 GPa. In both synthetic and natural samples, chromium is present predominantly as octahedral Cr3+ seen in the spectra as two broad intense absorption bands in the visible range caused by the electronic spin-allowed 4 A 2g  → 4 T 2g and 4 A 2g  → 4 T 1g transitions (U- and Y-band, respectively). A distinct doublet structure of the Y-band in both synthetic and natural spinels is related to trigonal distortion of the octahedral site in the spinel structure. A small, if any, splitting of the U-band can only be resolved at curve-fitting analysis. In all synthetic high-chromium spinels, a couple of relatively narrow and weak bands of the spin-allowed transitions 4 A 2g  → 2 E g and 4 A 2g  → 2 T 1g of Cr3+, intensified by exchange-coupled interaction between Cr3+ and Fe3+ at neighboring octahedral sites of the structure, appear at ~14,400 and ~15,100 cm?1. A vague broad band in the range from ca. 15,000 to 12,000 cm?1 in synthetic spinels is tentatively attributed to IVCr2+ + VICr3+ → IVCr3+ + VICr2+ intervalence charge-transfer transition. Iron, mainly as octahedral Fe3+, causes intense high-energy absorption edge in near UV-range (ligand–metal charge-transfer O2? → Fe3+, Fe2+ transitions). As tetrahedral Fe2+, it appears as a strong infrared absorption band at around 4,850 cm?1 caused by electronic spin-allowed 5 E → 5 T 2 transitions of IVFe2+. From the composition shift of the U-band in natural and synthetic MgCr2O4 spinels, the coefficient of local structural relaxation around Cr3+ in spinel MgAl2O4–MgCr2O4 system was evaluated as ~0.56(4), one of the lowest among (Al, Cr)O6 polyhedra known so far. The octahedral modulus of Cr3+ in MgCr2O4, derived from pressure-induced shift of the U-band of Cr3+, is ~313 (50) GPa, which is nearly the same as in natural low-chromium Mg, Al-spinel reported by Langer et al. (1997). Calculated from the results of the curve-fitting analysis, the Racah parameter B of Cr3+ in natural and synthetic MgCr2O4 spinels indicates that Cr–O-bonding in octahedral sites of MgCr2O4 has more covalent character than in the diluted natural samples. Within the uncertainty of determination in synthetic MgAl2O4 spinel, B does not much depend on pressure.  相似文献   

14.
This paper presents new data on chromium mineralization in a fenitized xenolith in Mt. Kaskasnyunchorr in the Khibiny alkaline massif (Kola Peninsula, Russia) and summarizes data on Cr mineralogy in the Khibiny Mountains. Protolith silicates that contained Cr3+ admixture are believed to be the source of this element in the fenite. Cr-bearing (maximum Cr2O3 concentrations, wt %, are in parentheses) aegirine (5.8), crichtonite-group minerals (2.1), muscovite (1.3), zirconolite (1.1), titanite (1.0), fluorine-magnesioarfvedsonite (0.8), biotite (0.8), ilmenite (0.6), and aenigmatite (0.6) occur in the fenite. The late-stage spinellides of the FeTi-chromite-CrTi-magnetite series, which are very poor in Mg and Al and which formed after Crrich aegirine and ilmenite, are the richest in Cr (up to 42% Ct2O3). Cr concentrations grew with time during the fenitization process. Unlike minerals in the Khibiny ultramafic rocks where Cr is associated with Mg, Al (it is isomorphic with Cr), and with Ca, chromium in the fenites is associated with Fe, Ti, and V (with which Cr3+ is isomorphic) and with Na in silicate minerals. Cr3+ Mobility of Cr3+ and the unique character of chromium mineralization in the examined fenites were caused by high alkalinity of the fluid.  相似文献   

15.
Subsolidus phase relations have been determined in the systems SiO2-Cr-O and MgO-SiO2-Cr-O in equilibrium with metallic Cr, at 1100 to 1500℃ and 0 to 2.88 GPa. The results show that there are no ternary phases in the SiO2-Cr-O system at these conditions, i.e., only the assemblage eskolaite-Cr-metal-quartz (or tridymite) is found. In the MgO-containing system, however, extensive substitution of Cr2+ for Mg is observed in (Mg, Cr2+)2SiO4 olivine, (Mg, Cr2+)2Si2O6 pyroxene, and (Mg, Cr2+)Cr2O4 spinel. Cr3+ levels in olivine and pyroxene are below detection limits. The pyroxene is orthohombic at XCrPx2+ < 0.2, monoclinic at higher XCrPx2+ . Thestructure of the spinels becomes tetragonally distorted at XCr2+Sp >0.2. The experimental datahave been fitted to a thermodynamic model, and the authors obtained the mixing parameter (W) of Mg-Cr2+ in olivine, pyroxene and spinel, and the relation between temperatures and free energies of formation for the end-members: Cr2+-olivine (Cr2SiO4), Cr2+-pyroxene (Cr2Si2O6)  相似文献   

16.
Fifteen samples of (Mg,Fe)SiO3 majorite with varying Fe/Mg composition and one sample of (Mg,Fe)(Si,Al)O3 majorite were synthesized at high pressure and temperature under different conditions of oxygen fugacity using a multianvil press, and examined ex situ using X-ray diffraction and Mössbauer and optical absorption spectroscopy. The relative concentration of Fe3+ increases both with total iron content and increasing oxygen fugacity, but not with Al concentration. Optical absorption spectra indicate the presence of Fe2+–Fe3+ charge transfer, where band intensity increases with increasing Fe3+ concentration. Mössbauer data were used in conjunction with electron microprobe analyses to determine the site distribution of all cations. Both Al and Fe3+ substitute on the octahedral site, and charge balance occurs through the removal of Si. The degree of Mg/Si ordering on the octahedral sites in (Mg,Fe)SiO3 majorite, which affects both the c/a ratio and the unit cell volume, is influenced by the thermal history of the sample. The Fe3+ concentration of (Mg,Fe)(Si,Al)O3 majorite in the mantle will reflect prevailing redox conditions, which are believed to be relatively reducing in the transition zone. Exchange of material across the transition boundary to (Mg,Fe) (Si,Al)O3 perovskite would then require a mechanism to oxidize sufficient iron to satisfy crystal-chemical requirements of the lower-mantle perovskite phase.  相似文献   

17.
(Mg,Fe)(Si,Al)O3 perovskite samples with varying Fe and Al concentration were synthesised at high pressure and temperature at varying conditions of oxygen fugacity using a multianvil press, and were characterised using ex?situ X-ray diffraction, electron microprobe, Mössbauer spectroscopy and analytical transmission electron microscopy. The Fe3+/ΣFe ratio was determined from Mössbauer spectra recorded at 293 and 80?K, and shows a nearly linear dependence of Fe3+/ΣFe with Al composition of (Mg,Fe)(Si,Al)O3 perovskite. The Fe3+/ΣFe values were obtained for selected samples of (Mg,Fe)(Si,Al)O3 perovskite using electron energy-loss near-edge structure (ELNES) spectroscopy, and are in excellent agreement with Mössbauer data, demonstrating that Fe3+/ΣFe can be determined with a spatial resolution on the order of nm. Oxygen concentrations were determined by combining bulk chemical data with Fe3+/ΣFe data determined by Mössbauer spectroscopy, and show a significant concentration of oxygen vacancies in (Mg,Fe)(Si,Al)O3 perovskite.  相似文献   

18.
Multiphase solid inclusions in minerals formed at ultra-high-pressure (UHP) provide evidence for the presence of fluids during deep subduction. This study focuses on barian mica, which is a common phase in multiphase solid inclusions enclosed in garnet from mantle-derived UHP garnet peridotites in the Saxothuringian basement of the northern Bohemian Massif. The documented compositional variability and substitution trends provide constraints on crystallization medium of the barian mica and allow making inferences on its source. Barian mica in the multiphase solid inclusions belongs to trioctahedral micas and represents a solid solution of phlogopite KMg3(Si3Al)O10(OH)2, kinoshitalite BaMg3(Al2Si2)O10(OH)2 and ferrokinoshitalite BaFe3(Al2Si2)O10(OH)2. In addition to Ba (0.24–0.67 apfu), mica is significantly enriched in Mg (XMg ~ 0.85 to 0.95), Cr (0.03–0.43 apfu) and Cl (0.04–0.34 apfu). The substitution vector involving Ba in the I-site which describes the observed chemical variability can be expressed as BaFeIVAlClK?1Mg?1Si?1(OH)?1. A minor amount of Cr and VIAl enters octahedral sites following a substitution vector VI(Cr,Al)2VI(Mg,Fe)?3 towards chromphyllite and muscovite. As demonstrated by variable Ba and Cl contents positively correlating with Fe, barian mica composition is partly controlled by its crystal structure. Textural evidence shows that barian mica, together with other minerals in multiphase solid inclusions, crystallized from fluids trapped during garnet growth. The unusual chemical composition of mica reflects the mixing of two distinct sources: (1) an internal source, i.e. the host peridotite and its garnet, providing Mg, Fe, Al, Cr, and (2) an external source, represented by crustal-derived subduction-zone fluids supplying Ba, K and Cl. At UHP–UHT conditions recorded by the associated diamond-bearing metasediments (c. 1100 °C and 4.5 GPa) located above the second critical point in the pelitic system, the produced subduction-zone fluids transporting the elements into the overlying mantle wedge had a solute-rich composition with properties of a hydrous melt. The occurrence of barian mica with a specific chemistry in barium-poor mantle rocks demonstrates the importance of its thorough chemical characterization.  相似文献   

19.
Chrome-spinels from the layered Peridotilte Series of the unmetamorphosed, anorogenic 60 Ma Cuillin Igneous Complex, Isle of Skye, display a wide variety of compositions. Cumulus (within seams) chrome-spinels from the lowest exposed portion of the Peridotite Series exhibit features indicative of textural equilibrium, are rich in Al and Mg, and have low values of the ratio Cr/(Cr+Al). Cumulus chrome-spinels from higher up in the series are different from these: particularly, textural disequilibrium is evident, intercumulus plagioclase and olivine are present, and the chrome-spinels are rich in Cr, Fe and Ti, with high values of the ratio Cr/(Cr+Al). Intercumulus (dispersed) chrome-spinels tend towards anhedral forms and define enrichment trends towards Fe (both Fe2+ and Fe3+) with decreasing Mg, Cr and Al, and towards Al, with decreasing Fe2+ and Cr (and increasing Mg). Individual crystals are completely homogeneous and are devoid of reaction rims. The observed textural characteristics and compositional data of the chrome-spinels documented here suggest that the semi-quantitative peritectic reaction: aluminous chrome-spinel + meltplagioclase + olivine + chromian chrome-spinel, is responsible for the observed parageneses, and that both the environment of crystallization (eumulus or intercumulus) and the role of plagioclase ±olivine crystallization are critical parameters for this geochemical trend in spinels within upper crustal magmatic systems. The effects of pyroxene crystallization on the development of this geochemical trend are also considered. This investigation highlights the need to consider the role of post-cumulus mineral-melt reactions and their influences upon the final compositions of major oxide and silicate phases within layered intrusions.  相似文献   

20.
We determined activity-composition relationships in Pt-Cr and Pt-Fe-Cr alloys at 1300°C experimentally and used the results to constrain the thermodynamic properties of chromite-picrochromite spinels. The Pt-Cr binary is characterized by strong negative deviations from ideality throughout the investigated composition range and the activity-composition relationship can be fit by a four-suffix asymmetric regular solution with three binary interaction parameters. The ternary alloy was modeled as a four-suffix asymmetric regular solution; the three ternary interaction parameters in this model were constrained by combining interaction parameters for the three bounding binaries taken from this and previous work with results for a set of experiments in which the activity of Cr in Pt-Fe-Cr-alloys was fixed by coexisting Cr2O3 at known fO2.The free energy of formation of FeCr2O4 at 1300°C was determined using the activities of Fe and Cr in Pt-alloys in equilibrium with oxide mixes of FeCr2O4 and Cr2O3. The free energy of formation of chromite from Fe+Cr2O3+O2 is −202.7 ± 0.4 kJ/mol (1σ), indistinguishable from literature values. The corresponding free energy of formation of FeCr2O4 from the elements is −923.5 ± 2.1 kJ/mol (1σ), and the enthalpy of formation at 298 K is −1438 kJ/mol. The activity-composition relationship for the chromite component in (Fe,Mg)Cr2O4 solid solutions was determined from a set of experiments in which Pt-alloys were equilibrated with spinel + Cr2O3. (Fe,Mg)Cr2O4 spinels are nearly ideal at 1300°C; modeling our data with a one-site symmetric regular solution yields an interaction parameter of +2.14 ± 0.62 kJ/mol (1σ), similar to values based on data from the literature.  相似文献   

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