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1.
Solutions of H2O–NaCl–CH4 occur in fluid inclusions enclosed by quartz, apatite and feldspar from gabbroic pegmatitites, anorthositic structures and intercumulus minerals within the Skaergaard intrusion. The majority of the fluid inclusions resemble 10 m diameter sub-to euhedral negative crystals. A vapour phase and a liquid phase are visible at room temperature, solids are normally absent. The salinity of the fluids ranges from 17.5 to 22.8 wt.% NaCl. CH4, which comprises less than six mole percent of the solution, was detected in the vapour phase of the fluid inclusions with Raman microprobe analysis. Homogenization of the fluid inclusions occurred in the liquid phase in the majority of the fluid inclusions, though 10% of the inclusions homogenized in the gas phase. Thermodynamic consideration of the stability of feldspars + quartz, and the C–O–H system, indicates that the solutions were trapped at temperatures between 655 and 770°C, at oxygen fugacities between 1.5 and 2.0 log units below the QFM oxygen buffer. Textural evidence and the composition of the solutions suggest that the fluids coexisted with late-magmatic intercumulus melts and the melts which formed gabbroic pegmatites. These solutions are thought to have contributed to late-magmatic metasomatism of the primocryst assemblages of the Skaergaard intrusion.  相似文献   

2.
Conventional diamond exploration seldom searches directly for diamonds in rock and soil samples. Instead, it focuses on the search for indicator minerals like chrome spinel, which can be used to evaluate diamond potential. Chrome spinels are preserved as pristine minerals in the early Paleozoic (∼465 Ma), hydrothermally altered, Group I No. 30 pipe kimberlite that intruded the Neoproterozoic Qingbaikou strata in Wafangdian, North China Craton (NCC). The characteristics of the chrome spinels were investigated by petrographic observation (BSE imaging), quantitative chemical analysis (EPMA), and Raman spectral analysis. The results show that the chrome spinels are mostly sub-rounded with extremely few grains being subhedral, and these spinels are macrocrystic, more than 500 µm in size. The chrome spinels also have compositional zones: the cores are classified as magnesiochromite as they have distinctly chromium-rich (Cr2O3 up to 66.56 wt%) and titanium-poor (TiO2 < 1 wt%) compositions; and the rims are classified as magnetite as they have chromium-poor and iron-rich composition. In the cores of chrome spinels, compositional variations are controlled by Al3+-Cr3+ isomorphism, which results in a strong Raman spectra peak (A1g mode) varying from 690 cm−1 to 702.9 cm−1. In the rims of chrome spinel, compositional variations result in the A1g peak varying from 660 cm−1 to 672 cm−1. The morphology and chemical compositions indicate that the chrome spinels are mantle xenocrysts. The cores of the spinel are remnants of primary mantle xenocrysts that have been resorbed, and the rims were formed during kimberlite magmatism. The compositions of the cores are used to evaluate the diamond potential of this kimberlite through comparison with the compositions of chrome spinels from the Changmazhuang and No. 50 pipe kimberlites in the NCC. In MgO, Al2O3 and TiO2 versus Cr2O3 plots, the chrome spinels from the Changmazhuang and No. 50 pipe kimberlites are mostly located in the diamond stability field. However, only a small proportion of chrome spinels from No. 30 pipe kimberlite have same behavior, which indicates that the diamond potential of the former two kimberlites is greater than that of the No. 30 pipe kimberlite. This is also supported by compositional zones in the spinel grains: there is with an increase in Fe3+ in the rims, which suggests that the chrome spinels experienced highly oxidizing conditions. Oxidizing conditions may have been imparted by fluids/melts that have a great influence on diamond destruction. Here, we suggest that chrome spinel compositions can be a useful tool for identifying the target for diamond potential in the North China Craton.  相似文献   

3.
The Oroscocha Quaternary volcano, in the Inner Arc Domain of the Andean Cordillera (southern Peru), emitted peraluminous rhyolites and trachydacites that entrained decimetric to millimetric lamprophyric blobs. These latter show kersantite modal compositions (equal proportion of groundmass plagioclase and K-feldspar) and potassic bulk-rock compositions (1<K2O/Na2O<2; 6.7–7.2 wt.% CaO). Kersantite blobs have shapes and microstructures consistent with an origin from a mixing process between mafic potassic melts and rhyolitic melts. Both melts did exchange their phenocrysts during the mixing process. In addition to index minerals of lamprophyres (Ba–Ti–phlogopite, F-rich apatite, andesine and Ca-rich sanidine), the groundmass of kersantite blobs displays essenite-rich diopside (up to 22 mol%), Ti-poor magnetite microlites, Ti-poor hematite microlites and a series of Ca–Ti–Zr- and REE-rich accessory minerals that have never been reported from lamprophyres. Titanite [up to 5.3 wt.% ZrO2 and 5.2 wt.% (Y2O3 + REE2O3)] and Zr- and Ca-rich perrierite (up to 7.2 wt.% ZrO2 and 10.8 wt.% CaO) predate LREE- and iron-rich zirconolite and Fe-, Ti-, Hf-, Nb- and Ce-rich baddeleyite (up to 5.3 wt.% Fe2O3, 3.2 wt.% TiO2, 1.5 wt.% HfO2, 1.2 wt.% Nb2O5, 0.25 wt.% CeO2) in the crystallization order of the groundmass. Isomorphic substitutions suggest iron to occur as Fe3+ in all the accessory phases. This feature, the essenitic substitution in the clinopyroxene and the occurrence of hematite microlites, all indicate a drastic increase of the oxygen fugacity (from FMQ − 1 to FMQ + 5 log units) well above the HM synthetic buffer within a narrow temperature range (1100–1000 °C). Such a late-magmatic oxidation is ascribed to assimilation of water from the felsic melts during magma mixing, followed by rapid degassing and water dissociation during eruption of host felsic lavas. Thus, magma mixing involving felsic melt end-members provides a mechanism for mafic potassic melts to be oxidized beyond the HM synthetic buffer curve.  相似文献   

4.
Hualalai Volcano, Hawaii, is best known for the abundant and varied xenoliths included in the historic 1800 Kaupulehu alkalic basalt flow. Xenoliths, which range in composition from dunite to anorthosite, are concentrated at 915-m elevation in the flow. Rare cumulate ultramafic xenoliths, which include websterite, olivine websterite, wehrlite, and clinopyroxenite, display complex pyroxene exsolution textures that indicate slow cooling. Websterite, olivine websterite, and one wehrlite are spinel-bearing orthopyroxene +olivine cumulates with intercumulus clinopyroxene +plagioclase. Two wehrlite samples and clinopyroxenite are spinel-bearing olivine cumulates with intercumulus clinopyroxene+orthopyroxene + plagioclase. Two-pyroxene geothermometry calculations, based on reconstructed pyroxene compositions, indicate that crystallization temperatures range from 1225° to 1350° C. Migration or unmixing of clinopyroxene and orthopyroxene stopped between 1045° and 1090° C. Comparisons of the abundance of K2O in plagioclase and the abundances of TiO2 and Fe2O3in spinel of xenoliths and mid-ocean ridge basalt, and a single 87Sr/ 86Sr determination, indicate that these Hualalai xenoliths are unrelated to mid-ocean ridge basalt. Similarity between the crystallization sequence of these xenoliths and the experimental crystallization sequence of a Hawaiian olivine tholeiite suggest that the parental magma of the xenoliths is Hualalai tholeiitic basalt. Xenoliths probably crystallized between about 4.5 and 9 kb. The 155°–230° C of cooling which took place over about 120 ka — the age of the youngest Hualalai tholeiitic basalt — yield maximum cooling rates of 1.3×10–3–1.91×10–3 °C/yr. Hualalai ultramafic xenoliths with exsolved pyroxenes crystallized from Hualalai tholeiitic basalt and accumulated in a magma reservoir located between 13 and 28 km below sealevel. We suspect that this reservoir occurs just below the base of the oceanic crust at about 19 km below sealevel.  相似文献   

5.
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   

6.
Metasomatic oxidation of upper mantle periodotite   总被引：1，自引：0，他引：1  
Examination of Fe3+ in metasomatized spinel peridotite xenoliths reveals new information about metasomatic redox processes. Composite xenoliths from Dish Hill, California possess remnants of magmatic dikes which were the sources of the silicate fluids responsible for metasomatism of the peridotite part of the same xenoliths. Mössbauer spectra of mineral separates taken at several distances from the dike remnants provide data on Fe3+ contents of minerals in the metasomatized peridotite. Clinopyroxenes contain 33% of total iron (FeT) as Fe3+ (Fe3+/FeT=0.33); orthopyroxenes contain 0.06–0.09 Fe3+/FeT; spinels contain 0.30–0.40 Fe3+/FeT; olivines contain 0.01–0.06 Fe3+/FeT; and metasomatic amphibole in the peridotite contains 0.85–0.90 Fe3+/FeT. In each mineral, Fe3+ and Fe2+ cations per formula unit (p.f.u.) decrease with distance from the dike, but the Fe3+/FeT ratios of each mineral do not vary. Clinopyroxene, spinel, and olivine Fe3+/FeT ratios are significantly higher than in unmetasomatized spinel peridotites. Metasomatic changes in Fe3+/FeT ratios in each mineral are controlled by the oxygen fugacity of the system, but the mechanism by which each phase accommodates this ratio is affected by crystal chemistry, kinetics, rock mode, fluid composition, fluid/rock ratio, and fluid-mineral partition coefficients. Ratio increases in pyroxene and spinel occur by exchange reactions involving diffusion of Fe3+ into existing mineral grains rather than by oxidation of existing Fe2+ in peridotite mineral grains. The very high Fe3+/FeT ratio in the metasomatic amphibole may be a function of the high Fe3+/FeT of the metasomatic fluid, crystal chemical limitations on the amount of Fe3+ that could be accommodated by the pyroxene, spinel, and olivine of the peridotite, and the ability of the amphibole structure to accommodate large amounts of 3 + valence cations. In the samples studied, metasomatic amphibole accounts for half of the bulk-rock Fe2O3. This suggests that patent metasomatism may produce a greater change in the redox state of mantle peridotite than cryptic metasomatism. Comparison of the metasomatized samples with unmetasomatized peridotites reveals that both Fe2+ and Fe3+ cations p.f.u. were increased during metasomatism and 50% or more of iron added was Fe3+. With increasing distance from the dike, the ratio of added Fe3+ to added Fe2+ increases. The high Fe3+/FeT of amphibole and phlogopite in the dikes and in the peridotite, and the high ratios of added Fe3+/added Fe2+ in pyroxenes and spinel suggest that the Fe3+/FeT ratio of the metasomatic silicate fluid was high. As the fluid perolated through and reacted with the peridotite, Fe3+ and C–O–H volatile species were concentrated in the fluid, increasing the fluid Fe3+/FeT.  相似文献   

7.
The ophiolitic peridotites in the Wadi Arais area, south Eastern Desert of Egypt, represent a part of Neoproterozoic ophiolites of the Arabian-Nubian Shield (ANS). We found relics of fresh dunites enveloped by serpentinites that show abundances of bastite after orthopyroxene, reflecting harzburgite protoliths. The bulk-rock chemistry confirmed the harzburgites as the main protoliths. The primary mantle minerals such as orthopyroxene, olivine and chromian spinel in Arais serpentinites are still preserved. The orthopyroxene has high Mg# [=Mg/(Mg + Fe2+)], ~0.923 on average. It shows intra-grain chemical homogeneity and contains, on average, 2.28 wt.% A12O3, 0.88 wt.% Cr2O3 and 0.53 wt.% CaO, similar to primary orthopyroxenes in modern forearc peridotites. The olivine in harzburgites has lower Fo (93?94.5) than that in dunites (Fo94.3?Fo95.9). The Arais olivine is similar in NiO (0.47 wt.% on average) and MnO (0.08 wt.% on average) contents to the mantle olivine in primary peridotites. This olivine is high in Fo content, similar to Mg-rich olivines in ANS ophiolitic harzburgites, because of its residual origin. The chromian spinel, found in harzburgites, shows wide ranges of Cr#s [=Cr/(Cr + Al)], 0.46?0.81 and Mg#s, 0.34?0.67. The chromian spinel in dunites shows an intra-grain chemical homogeneity with high Cr#s (0.82?0.86). The chromian spinels in Arais peridotites are low in TiO2, 0.05 wt.% and YFe [= Fe3+/(Cr + Al + Fe3+)], ~0.06 on average. They are similar in chemistry to spinels in forearc peridotites. Their compositions associated with olivine’s Fo suggest that the harzburgites are refractory residues after high-degree partial melting (mainly ~25?30 % partial melting) and dunites are more depleted, similar to highly refractory peridotites recovered from forearcs. This is in accordance with the partial melting (>20 % melt) obtained by the whole-rock Al2O3 composition. The Arais peridotites have been possibly formed in a sub-arc setting (mantle wedge), where high degrees of partial melting were available during subduction and closing of the Mozambique Ocean, and emplaced in a forearc basin. Their equilibrium temperature based on olivine?spinel thermometry ranges from 650 to 780 °C, and their oxygen fugacity is high (Δlog ?O2?=?2.3 to 2.8), which is characteristic of mantle-wedge peridotites. The Arais peridotites are affected by secondary processes forming microinclusions inside the dunitic olivine, abundances of carbonates and talc flakes in serpentinites. These microinclusions have been formed by reaction between trapped fluids and host olivine in a closed system. Lizardite and chrysotile, based on Raman analyses, are the main serpentine minerals with lesser antigorite, indicating that serpentines were possibly formed under retrograde metamorphism during exhumation and near the surface at low T (<400 °C).  相似文献   

8.
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   

9.
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10.
Glasses have been analysed from six mantle-derived xenoliths (5 orthopyroxene and/or olivine-rich, 1 clinopyroxene-rich) from the Quaternary volcanics S.E. of Gees, West Eifel, Germany. The glasses in these xenoliths occur as pools surrounding and embaying spinels, as inclusions in spinels, as veins and stringers within phlogopiterich veins, and as jackets partially surrounding some of the xenoliths. Glasses analysed are felsic and characterised by low to intermediate SiO2 (40–62 wt.%), variable CaO (1–11 wt.%) and MgO (1–4 wt.%), high Al2O3 (14–21 wt.%), and up to 11 wt.% Na2O + K2O. The jacket glasses have the lowest SiO2, highest CaO and MgO. Variations in all of the glass compositions are similar and imply a unifying factor or process in their formation. Glass as pools and stringers within veins of phlogopite forms part of the same trends shown by all the glasses when plotted on bivariate (oxide vs SiO2) diagrams but can be distinguished from glass surrounding and enclosed by spinels. Glasses occurring as jackets are similar in composition to those in pools and veinlets associated with phlogopite but are of quite different composition to the glasses found within the xenoliths that they partially enclose. The occurrence and chemistry of the glasses do not support such glasses as representing original or differentiated magma trapped during formation of the xenolithic assemblages. The chemistry of the glasses also makes it unlikely that they were produced by dissociation of phlogopite during ascent of the xenoliths. The most likely origin for the glasses is that they represent volatile-rich melts which migrated through upper mantle material. These melts are likely to be responsible for the heterogeneous nature of the mantle underlying this part of the West Eifel region.  相似文献   

11.
Black sands rich in chromian spinel commonly occur in pockets along the eastern shoreline of Andaman Island where various types of peridotites and volcanics belonging to the Andaman ophiolite suite are exposed in close vicinity. The chemistry of these detrital chromian spinels has been extensively used here in identifying the source rocks vis-à-vis deciphering the source characteristics. The composition of the chromian spinels (Cr#: 0.20–0.88, Mg#: 0.26–0.77, Al 2 O 3: 5.04–48.21 wt.%, TiO 2: up to 1.39 wt.% and Fe 2+/Fe 3+: 1.73–9.12) varies widely signifying multiple sources, of which mantle peridotites and volcanic rocks are relevant in an ophiolitic terrain. The volcanic chromian spinels are relatively fresh, commonly euhedral, sometimes with compositional variations, and contain inclusions in contrast to the mantle peridotitic chromian spinels which are rounded, extensively fractured, and altered. We used a number of geochemical bivariate plots in order to know the provenance protoliths. The volcanic chromian spinels show geochemical characters of MORB, related to spreading centers (either MOR or back-arc) and also boninites/arc-tholeiites, related to active subduction. On the other hand, the peridotitic spinels indicate partially depleted lherzolite and depleted harzburgite source of the ophiolite suite.  相似文献   

12.
Summary Chromian spinel occurs in feldspathic metaperidotites and feldspathic metaharzburgites, respectively, at Mangabal I and II mafic-ultramafic layered complexes, Brazil. Both complexes were metamorphosed (700-750°C and 6-7 Kbars) under variable PH 2O conditions. Wherever PH 2O = Ptot an almost complete metamorphic recrystallization occurred, but where PH 2O < Ptot relict igneous cumulate textures are well preserved. Chromian spinel occurs as opaque grains included in cumulus olivine and as brown translucent crystals enclosed by intercumulus orthopyroxene, clinopyroxene, and plagioclase. Subsolidus reactions resulted in exsolution of opaque spinel into two phases: a Fe+2Fe 2 +3 -rich and a MgAl2-rich one. Fe2TiO4-rich lamellae and patches may also occur. Coronas developed between olivine and plagioclase including orthopyroxene, pargasite and MgAl2-rich green spinel. Whenever complete metamorphic reequilibration occurred (PH 2O = Ptot) the brown and green spinels reacted with silicate phase to form clinochlore, leaving the Fe+2Fe 2 +3 -rich spinel phase, magnetite.
Chromspinelle in metamorphen, ultramafischen Gesteinen der Mangabal I und II Komplexe, Goiás, Brasilien
Zusammenfassung Chromspinell kommt in feldspatführenden Metaperidotiten und Metaharzburgiten in den geschichteten mafisch-ultramafischen Komplexen in Mangabal I and II, Brasilien, vor. Beide Komplexe wurden unter variablem PH 2O metamorphisiert (700–750°C, 6–7 Kbar). Während unter fluidreichen Bedingungen (PH 2(O = Ptot) eine beinahe vollständige metamorphe Rekristallisation erfolgte, bleiben unter PH 2O < Ptot reliktische magmatische Kumulustexturen erhalten. Chromspinell tritt in opaken körnern in Kumulus-Olivin und als braune, durchscheinende Körner, eingeschlossen in den Interkumulusmineralen Orthopyroxen, Klinopyroxen und Plagioklas, auf. Subsolidusreaktionen resultierten in der Entmischung von opakem Spinell in eine Fe2+ Fe 2 3+ -und eine MgAl2-reiche Phase. Fe2TiO4-reiche Lamellen und Nester treten außerdem auf. Koronas zwischen Olivin und Plagioklas bestehen aus Orthopyroxen, Pargasit und grünem MgAl2-reichem Spinell. Dort wo ein vollständige metamorphe Reequilibration (PH 2O = Ptot) erfolgte, reagierte brauner und grüner Spinell mit Silikaten und bildete clinochlor, unter Zurücklassung von Fe2+Fe 2 3+ -reichem Spinell, dem Magnetit.

With 8 Figures  相似文献   

13.
The Zambales ophiolite is the major source of chromite ore in the Philippines. The chromitites are concordant cumulates and are associated with distinct chromitite-bearing sequences within the mantle peridotites. Refractory and metallurgical chromite deposits are spatially separated and related to different lithologic associations, which crystallized from different parental magmas. — Refractory chromite ores (30–44 wt% Cr2O3; 20–30 wt% Al2O3) are linked with the peridotite-troctolite-olivine gabbro lineage. Two main types were found: (1) Al-rich refractory ores associated with harzburgites and feldspathic periodotites and (2) more Cr-rich varieties associated with lherzolites. — Metallurgical chromite ores (45–53 wt% Cr2O3; 12–18 wt% Al2O3) are linked with the peridotite-pyroxenite-norite lineage. Two main types were also found: (1) Cr-rich metallurgical ores associated with orthopyroxenites and (2) more Al-rich varieties related to clinopyroxenites. — The chemical composition of chromite within the deposits varies depending on the chromite/silicate ratios of the ore types and grades continuously into accessory chrome spinels in the wall-rock peridotites. — The geochemistry of accessory chrome spinels in various peridotites and mafic cumulates depends on the mineralogical composition and the stratigraphic position of their host rocks.New address: BEB Erdgas und Erdöl GmbH, Riethorst 12, D-3000 Hannover 51The terms chrome-spinels and chromite are used as follows: 1. Chrome-spinel is only used for those occuring as accessory minerals in various ultramafic and mafic rocks (= accessory chrome-spinels). Their chemical composition has been determined only by microprobe analysis. — 2. Chromite is used for ore and ore deposits (=chromitites); the chemical composition has been determined by wet chemistry (AAS) or by microprobe analysis  相似文献   

14.
A solution model is developed for rhombohedral oxide solid solutions having compositions within the ternary system ilmenite [(Fe 2+ s Ti 4+ 1–s ) A (Fe 2+ 1–s Ti 4+ s ) B O3]-geikielite [(Mg 2+ t Ti 4+ 1–t ) A (Mg 2+ 1–t Ti 4+ t ) B O3]-hematite [(Fe3+) A (Fe3+) B O3]. The model incorporates an expression for the configurational entropy of solution, which accounts for varying degrees of structural long-range order (0s, t1) and utilizes simple regular solution theory to characterize the excess Gibbs free energy of mixing within the five-dimensional composition-ordering space. The 13 model parameters are calibrated from available data on: (1) the degree of long-range order and the composition-temperature dependence of the transition along the ilmenite-hematite binary join; (2) the compositions of coexisting olivine and rhombohedral oxide solid solutions close to the Mg–Fe2+ join; (3) the shape of the miscibility gap along the ilmenite-hematite join; (4) the compositions of coexisting spinel and rhombohedral oxide solid solutions along the Fe2+–Fe3+ join. In the course of calibration, estimates are obtained for the reference state enthalpy of formation of ulvöspinel and stoichiometric hematite (–1488.5 and –822.0 kJ/mol at 298 K and 1 bar, respectively). The model involves no excess entropies of mixing nor does it incorporate ternary interaction parameters. The formulation fits the available data and represents an internally consistent energetic model when used in conjuction with the standard state thermodynamic data set of Berman (1988) and the solution theory for orthopyroxenes, olivines and Fe–Mg titanomagnetite-aluminate-chromate spinels developed by Sack and Ghiorso (1989, 1990a, b). Calculated activity-composition relations for the end-members of the series, demonstrate the substantial degree of nonideality associated with interactions between the ordered and disordered structures and the dominant influence of the miscibility gap across much of the ternary system. The predicted shape of the miscibility gap, and the orientation of tie-lines relating the compositions of coexisting phases, display the effects of coupling between the excess enthalpy of solution and the degree of long-range order. One limb of the miscibility gap follows the composititiontemperature surface corresponding to the ternary second-order transition.  相似文献   

15.
A model is developed for the thermodynamic properties of Fe2+–Mg2+-aluminate-titanate-ferrite spinels of space group Fd3m. The model incorporates an expression for the configurational entropy of mixing which accounts for long-range order over tetrahedral and octahedral sites. Short-range order or departures from cubic symmetry are not considered. The non-configurational Gibbs energy is formulated as a second degree Taylor expansion in six linearly independent composition and ordering variables. The model parameters are calibrated to reproduce miscibility gap constraints, order-disorder phenomena in MgAl2O4 and MgFe2O4, and Fe2+–Mg2+ partitioning data between olivine and: (1) aluminate spinels; (2) ferrite spinels; (3) titanate spinels; (4) mixed aluminate-ferrite spinels. This calibration is achieved without invoking non-configurational excess entropies of mixing. The model predicts that the ordering state of FeAl2O4 is more normal than that of MgAl2O4. It also successfully accounts for heat of solution measurements and activity-composition relations in the constituent binaries. Phase equilibrium constraints require that the structure of Fe3O4 is more inverse than random at all temperatures and that Mg2+ has a strong tetrahedral site preference with respect to that of Fe2+. The analysis suggests that in the titanates short range order on octahedral sites may be significant at temperatures as high as 1300° C. Constraints developed from calibrating the thermodynamic properties of Fe2+–Mg2+-aluminatetitanate-ferrite spinel solid solutions permit extension of the database of Berman (1988) to include estimates of the end-member properties of hercynite (FeAl2O4), ulvöspinel (Fe2TiO4), MgFe2O4 and cubic Mg2TiO4. In constructing these estimates, provision is made for low-temperature magnetic entropy contributions and the energetic consequences of disordering the aluminates and the ferrites. These estimates are consistent with all of the available low-temperature adiabatic calorimetry, high-temperature heat content, and heat of solution measurements on the end-members. The analysis implies that there is a substantial heat capacity anomaly in the range 300°–900° C associated with disordering of the MgAl2O4 structure while that in FeAl2O4 becomes significant at temperatures above 700° C. The same heat capacity response in the ferrites indicates that the order/disorder transformation is coupled to the antiferromagnetic-paramagnetic transition in MgFe2O4 but takes place well above the ferrimagnetic-paramagnetic transition in magnetite. The proposed model is internally consistent with solution theory reported elsewhere for Fe2+–Mg2+ olivines and orthopyroxenes (Sack and Ghiorso 1989), rhombohedral oxides (Ghiorso 1990a) and the remaining end-member properties of Berman (1988).  相似文献   

16.
Silicate-oxide symplectites in complex mineral intergrowths are relatively common in upper mantle xenoliths and in xenoliths in the Jagersfontein Kimberlite, South Africa.Harzburgites of olivine and high-Al (1.9–3.6 wt%), Ca (0.6–0.9 wt%) and Cr (0.3–0.9 wt%) enstatite contain symplectites of spinel and diopside, or spinel, diopside and lower-Al (0.8–2.2 wt%), Ca (0.1–0.4 wt%) and Cr (0.02–0.8 wt%) enstatite. From textures and mineral chemistries these symplectites are interpreted to have formed by mineral unmixing and migration from Al–Ca–Cr discrete enstatite to adjoining mineral interfaces.Garnet harzburgites are composed of large (0.5–1 cm) olivine, equally large discrete low-Al (0.6–1.1 wt%), Ca (0.1–0.5 wt%), and Cr (0.1–0.3 wt%) enstatite and smaller interstitial garnet, diopside, and high-Cr and low-Al spinel. Symplectites are composed of either spinel+diopside+garnet, or garnet+spinel. Spinel diopside garnet symplectites have cores of spinel+diopside, resembling symplectites inharzburgites, but surrounded by rims of garnet or garnet+undigested globular spinel. From textures and chemistries we suggest that the spinel+diopside cores formed from Ca-Al-Cr-rich orthopyroxene initially as a nonstoichiometric homogeneous single phase clinopyroxene enriched in Fe, Cr and Al. This was followed by decomposition of the clinopyroxene to diopside+spinel, and subsequent garnet formation in a prograde reaction with olivine or enstatite. In bothharzburgites andgarnet harzburgites the metastable cellular structures may also have formed by the simultaneous precipitation of pyroxene and spinel. In all cases there is a strongly preferred embayment of symplectite bodies into olivine. Olivine appears to have activated adjacent  相似文献   

17.
Uralian-Alaskan-type mafic–ultramafic complexes are recognized as a distinct class of intrusions regarding lithologic assemblage, mineral chemistry and petrogenetic setting. In the present study, we discuss new data on the distribution of major elements in minerals of the spinel group in rocks from Uralian-Alaskan-type complexes in the Ural Mountains, Russia. Cr-rich spinel (Cr2O3 = 20–53 wt%) in dunite with interstitial clinopyroxene and in wehrlite cumulates indicate that it reacted with interstitial liquid resulting in the progressive substitution of Al2O2 and Cr2O3 by Fe2O3 and TiO2. A distinct change in the spinel chemistry in dunite (Cr2O3 = 47–53 wt%), towards Al2O3- and Cr2O3-poor but Fe2O3-rich compositions monitors the onset of clinopyroxene fractionation in wehrlite (Cr2O3 = 15–35 wt%, Al2O3 = 1–8 wt%, Fe2O3 = 25–55 wt%). In more fractionated mafic rocks, the calculated initial composition of exsolved spinel traces the sustained crystallization of clinopyroxene by decreasing Cr2O3 and increasing FeO, Fe2O3 and fO2. Finally, the initiation of feldspar crystallization buffers the Al2O3 content in most of the spinels in mafic rocks at very low Cr2O3 contents (<5 wt%). The fractionation path all along and the reaction with interstitial liquid are accompanied by increasing Fe2O3 contents in the spinel. This likely is caused by a significant increase in the oxygen fugacity, which suggests closed system fractionation processes. Spinel with Cr2O3 < 27 wt% is exsolved into a Fe2O3-rich and an Al2O3-rich phase forming a variety of textures. Remarkably, exsolved spinel in different lithologies from complexes 200 km apart follows one distinct solvus line defining a temperature of ca. 600°C. This indicates that the parental magmas were emplaced and eventually cooled at similar levels in the lithosphere, likely near the crust–mantle boundary. Eventually, these 600°C hot bodies were rapidly transported into colder regions of the upper crust during a regional tectonic event, probably during the major active phase of the Main Uralian Fault.  相似文献   

18.
Disseminated cumulus chrome spinel in the lower-most olivine orthocumulates from the Western Laouni intrusion (Southern Hoggar, Algeria) contains inclusions of silicates enriched in Mg-Ti-Na and H2O, and Fe-Ti (Zr) rich oxides, occurring either as numerous micro-inclusions or as large solitary cavities. Regardless of the inclusion type, titanian pargasite (or kaersutite) and the sodium analog of phlogopite predominate over orthopyroxene (En86 to En92) and Na-rich plagioclase (An50Ab50 to An7Ab93). Oxide inclusions are magnesian ilmenite (up to 37 mol% MgTiO3), rutile, loveringite (Ca,REE-(Ti,Fe,Cr,Mg,Zr)21O38) and accessory magnesian pseudo-brookite (kennedyite); apatite, Fe-Ni-Cu sulfides and alteration products (saussurite, bastite) are also present. Apart from kennedyite, all minerals included in chrome spinel form larger intercumulus crystals in the host rock as well. The micro-inclusions were trapped as the consequence of chrome spinel dissolving against the intercumulus liquid, 150 to 300° C below its liquidus temperature. The solitary cavities are attributed to fluid-assisted solid-state recrystallization of chains of spinel crystals; the role of capillary fluids is demonstrated by both the hydrous nature of solid inclusions and a strong positive correlation between the amphibole content and the abundance of solid inclusions in the rock. Phlogopite locally showing similar optical orientation within and outside the inclusions indicates that spinel was still recrystallizing down to 950° C. In the temperature range 1100-900° C determined for the formation of inclusions, chrome spinel probably trapped various combinations of crystals, liquids and fluids, the respective quantities of which varied greatly over distances of few tens of micrometres in a single spinel. The volume ratio of solids to liquids or to fluids must have been low enough to permit magmatic or hydrothermal reactions, which are otherwise never possible for the larger intercumulus crystals. Hence, the lack of olivine and clinopyroxene as inclusions in spinel while abundant in the host rock suggests that, as trapped, they completely reacted with the residual liquid to form phlogopite and pargasite respectively. Likewise, plagioclase and phlogopite have been enriched in Na against hydrothermal fluids to form albite and Na-phlogopite in the mineral inclusions.  相似文献   

19.
A new thermodynamic model for multi-component spinel solid solutions has been developed which takes into account thermodynamic consequences of cation mixing in spinel sublattices. It has been applied to the evaluation of thermodynamic functions of cation mixing and thermodynamic properties of Fe3O4–FeCr2O4 spinels using intracrystalline cation distribution in magnetite, lattice parameters and activity-composition relations of magnetite–chromite solid solutions. According to the model, cation distribution in binary spinels, (Fe1-x2+ Fex3+)[Fex2+Fe2-2y-x3+Cr2y]O4, and their thermodynamic properties depend strongly on Fe2+–Cr3+ cation mixing. Mixing of Fe2+–Fe3+ and Fe3+–Cr3+ can be accepted as ideal. If Fe2+, Fe3+ and Cr are denoted as 1, 3 and 4 respectively, the equation of cation distribution is –RT ln(x2/((1–x)(2–2y–x)))= G13* + (1–2x)W13+y(W14–W13–W34) where G13* is the difference between the Gibbs energy of inverse and normal magnetite, Wij is a Margules parameter of cation mixing and G13*, J/mol =–23,000+13.4 T, W14=36 kJ/mol, W13=W34=0. The positive nonconfigurational Gibbs energy of mixing is the main reason for changing activity–composition relations with temperature. According to the model, the solvus in Fe3O4–FeCr2O4 spinel has a critical temperature close to 500°C, which is consistent with mineralogical data.  相似文献   

20.
High-Cr podiform chromitites hosted by upper mantle depleted harzburgite were investigated for PGM and other solid inclusions from Faryab ophiolitic complex, southern Iran. Chemical composition of the chromian spinels, Cr#[100*Cr/(Cr+Al) = 77–85], Mg# [100*Mg/(Mg+Fe2+) = 56–73], TiO2≤0.25wt%, and the presence of abundant primary hydrosilicates included in the chromian spinels indicate that the deposits were formed from aqueous melt generated by high degree of partial melting in a suprasubduction zone setting. Solid phases hosted by chromian spinel grains from the Faryab ophiolitic chromitites can be divided into three categories: PGM, base-metal minerals and silicates. Most of the studied PGM occurred as very small (generally less than 20 μm in size) primary single or composite inclusions of IPGE-bearing phases with or without silicates and base metal minerals. The PGM were divided into the three subgroups: sulfides, alloys and sulfarsenides. Spinel-olivine geothermometry gives the temperatures 1,131–1,177 °C for the formation of the studied chromitites. At those temperatures, fS2 values ranged from 10?3 to 10?1 and provided a suitable condition for Ru-rich laurite formation in equilibrium with Os-Ir alloys. Progressive crystallization of chromian spinel was accompanied by increase of fS2 in the melt. The formation of Os-rich laurite, erlichmanite and then sulfarsenides occurred by increase of fS2 and slight decrease in temperature of the milieu. The compositional and mineralogical determinations of PGM inclusions respect to their spatial distribution in chromian spinels show that the minerals regularly distributed within the chromitites, reflecting cryptic variation consistent with magmatic evolution during host chromian spinel crystallization.  相似文献   

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