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1.
A number of mixed valence iron oxides and silicates (e.g., magnetite, ilvaite) exhibit thermally induced electron delocalization between adjacent Fe2+ and Fe3+ ions and optically induced electronic transitions which are assigned to Fe2+→Fe3+ intervalence charge transfer. In this paper, the mechanism of electron delocalization (i.e., polarons versus itinerant electrons) and the nature of optically induced intervalence charge-transfer in minerals are investigated using molecular orbital theory. SCF-Xα-SW molecular orbital calculations were done for several mixed-valence (Fe2O10)15? clusters corresponding to edgesharing Fe2+ and Fe3+ coordination polyhedra. A spinunrestricted formalism was used so that the effect of ferromagnetic versus antiferromagnetic coupling of adjacent Fe2+ and Fe3+ cations could be determined. The molecular orbital results can be related to the polaron theory of solid state physics and the perturbation theory formalism used by Robin and Day (1967) and others to describe electron transfer in mixed valence compounds. Intervalence charge-transfer results from the overlap of Fe(3d) orbitals across the shared edges of adjacent FeO6 polyhedra to give weak Fe-Fe bonds. Electron delocalization, however, requires that adjacent Fe cations be ferromagnetically coupled. Antiferromagnetic coupling results in distinguishable Fe2+ and Fe3+ cations. Electronic transitions between the Fe-Fe bonding and Fe-Fe antibonding orbitals results in the optically-induced intervalence charge transfer bands observed in the electronic spectra of mixed valence minerals. Such transitions are predicted to be polarized along the metal-metal bond direction, in agreement with experimental observations.  相似文献   

2.
In both nature and synthetic experiments, the common iron oxide haematite (α‐Fe2O3) can incorporate significant amounts of U into its crystal structure and retain radiogenic Pb over geological time. Haematite is a ubiquitous component of many ore deposit types and, therefore, represents a valuable hydrothermal mineral geochronometer, allowing direct constraints to be placed on the timing of ore formation and upgrading. However, to date, no suitable natural haematite reference material has been identified. Here, a synthetic haematite U‐Pb reference material (MR‐HFO) is characterised using LA‐ICP‐MS and ID‐TIMS. Centimetre‐scale ‘chips’ of synthesised α‐Fe2O3 were randomly microsampled via laser ablation‐extraction and analysed using ID‐TIMS. Reproducible U/Pb and Pb/Pb measurements were obtained across four separate chips (n = 13). Subsequently, an evaluation of the suitability MR‐HFO in constraining U‐Pb data via LA‐ICP‐MS is presented using a selection of natural samples ranging from Cenozoic to Proterozoic in age. The MR‐HFO normalised U‐Pb ratios are more concordant and ages more accurate versus the same LA‐ICP‐MS spot analyses normalised to zircon reference material, when compared with independently acquired ID‐TIMS data from the same natural haematite grains. Results establish MR‐HFO as a suitable reference material for LA‐ICP‐MS haematite U‐Pb geochronology.  相似文献   

3.
Wadi Sifein podiform chromite deposits, Central Eastern Desert of Egypt, are hosted by fully serpentinized peridotite that is a part of the dismembered Pan‐African ophiolite complexes. Relics of primary minerals and the chemical characters indicate that the ophiolitic rocks were derived from depleted mantle peridotite of harzburgite and subordinate dunite compositions. The mantle rocks were initially formed at a mid‐oceanic ridge and subsequently thrust at a supra‐subduction zone. The chromite mineralization at Wadi Sifein area displays either pod‐shaped bodies with massive and lumpy chromitite appearance or dissemination of chromian‐spinel in serpentinite matrix. The podiform chromitite exhibits a very limited compositional range in terms of Cr# [Cr/(Cr + Al) atomic ratio] and Mg# [Mg/(Mg + Fe) atomic ratio]. The chromian‐spinel, however, frequently displays optical and geochemical zoning. Four zones can be identified from core to edge: inner core representing the original composition of the chromian‐spinel; narrow Cr‐rich ferritchromit zone; wide ferritchromit zone; and outer Cr‐magnetite/magnetite zone. The zonation of chromian‐spinel is interpreted to be a result of serpentinization rather than magmatic or metamorphic processes. The geochemical data obtained from the chromitite and chromian‐spinel was statistically processed using discriminant and R‐mode factor analyses. Two trends, minor and major, were achieved considering the formation of ferritchromit. The minor trend is controlled by the redistribution of trivalent cations, where Cr2O3 increased on the expense mainly of Al2O3 and to less extent Fe2O3 to form zone II during the peak of serpentinization. The major trend of alteration, however, is explained by the exchange between Mg‐Fe2+ rather than Cr, Al, and Fe3+ to form zone III. Kammererite formation was accompanied the formation of zones III and IV at a 314°C temperature of formation.  相似文献   

4.
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   

5.
Titanomagnetite–melt partitioning of Mg, Mn, Al, Ti, Sc, V, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Hf and Ta was investigated experimentally as a function of oxygen fugacity (fO2) and temperature (T) in an andesitic–dacitic bulk-chemical compositional range. In these bulk systems, at constant T, there are strong increases in the titanomagnetite–melt partitioning of the divalent cations (Mg2+, Mn2+, Co2+, Ni2+, Zn2+) and Cu2+/Cu+ with increasing fO2 between 0.2 and 3.7 log units above the fayalite–magnetite–quartz buffer. This is attributed to a coupling between magnetite crystallisation and melt composition. Although melt structure has been invoked to explain the patterns of mineral–melt partitioning of divalent cations, a more rigorous justification of magnetite–melt partitioning can be derived from thermodynamic principles, which accounts for much of the supposed influence ascribed to melt structure. The presence of magnetite-rich spinel in equilibrium with melt over a range of fO2 implies a reciprocal relationship between a(Fe2+O) and a(Fe3+O1.5) in the melt. We show that this relationship accounts for the observed dependence of titanomagnetite–melt partitioning of divalent cations with fO2 in magnetite-rich spinel. As a result of this, titanomagnetite–melt partitioning of divalent cations is indirectly sensitive to changes in fO2 in silicic, but less so in mafic bulk systems.  相似文献   

6.
Exsolution microstructures in olivine grains from dunite units in a few selected tectonic environments are reported here. They include lamellae of clinopyroxene and clinopyroxene-magnetite intergrowth in the Gaositai and Yellow Hill Alaskan-type complexes, clinopyroxene-magnetite intergrowth in the K?z?lda? ophiolite, and chromite lamellae in the Hongshishan mafic-ultramafic intrusive complex. These lamellae commonly occur as needle-or rod-like features and are oriented in olivine grains. The host olivine grains have Fo contents of 92.5–92.6 in the Gaositai complex, 86.5–90.1 in the Yellow Hill complex, 93.2–93.4 in the K?z?lda? ophiolite and 86.9–88.3 in the Hongshishan complex. Clinopyroxene in the rod-like intergrowth exsolved in olivine grains in the Gaositai and Yellow Hill is diopside with similar major element compositions of Ca O(23.6–24.3 wt%), SiO_2(52.2–54.0 wt%), Al_2O_3(0.67–2.15 wt%), Cr_2O_3(0.10–0.42 wt%) and Na_2O(0.14–0.26 wt%). It falls into the compositional field of hydrothermal clinopyroxene and its origin is thus probably related to reaction between dunite and fluids. The enrichment of the fluids in Ca~(2+), Fe~(3+), Cr~(3+) and Na+, resulted in elevated concentrations of these cations in olivine solid solutions via the reaction. With decreasing temperature, the olivine solid solutions altered to an intergrowth of magnetite and clinopyroxene. The Fe~(3+) and Cr~(3+) preferentially partitioned into magnetite, while Ca~(2+) and Na+ entered clinopyroxene. Since the studied Alaskan-type complexes and ophiolite formed in a subduction environment, the fluids were probably released from the subducted slab. In contrast, the exsolved chromite in olivine grains from the Hongshishan complex that formed in post-orogenic extension setting can be related to olivine equilibrated with Cr-bearing liquid. Similarly, these lamellae have all been observed in serpentine surrounding olivine grains, indicating genetic relations with serpentinization.  相似文献   

7.
The Adamello gabbro exposed on the summit of Cornone di Blumone, Western Alps, Italy, has been fused by lightning strikes to form magnetite-rich fulgurites produced by melting of magnetite, hornblende, calcic plagioclase and minor clinopyroxene. The composition of quench magnetite in the fulgurite is 44.4 Fe3O4; 27.5 MgFe2O4; 15.1 FeAl2O4; 7.9 Fe2TiO4; 2.5 Fe2SiO4; 1.9 CaFe2O4; 0.8 MnFe2O4 and is inferred to have crystallized from a low-Si, Fe-rich melt under high oxidation conditions of about 1 log unit below the log10?O2 of hematite–magnetite. The low Si, Fe-rich melt is considered to have been produced from fusion of magnetite + hornblende-rich areas of the host gabbro and/or possible separation of an immiscible high Fe2O3/FeO Fe-rich, low-Si melt from a more siliceous glass during superheating. Skeletal-dendritic morphologies of magnetite in the fulgurite indicate crystallization under conditions of extreme supercooling. Juxtaposition of areas exhibiting different growth habits and crystal sizes of magnetite may reflect compositionally different local melt domains and/or small differences in the delicate balance between nucleation and growth in domains that had slightly different, although ultrafast, cooling rates.  相似文献   

8.
Textural and mineral–chemical characteristics in the Bangriposi wehrlites (Eastern India) provide insight into metamorphic processes that morphologically and chemically modified magmatic spinel during serpentinization of wehrlite. Aluminous chromite included in unaltered magmatic olivine is chemically homogenous. In sub-cm to 10s-of-micron-wide veins, magnetite associated with antigorite and clinochlore comprising the serpentine matrix is near-stoichiometric. But Al–Cr–Fe3+ spinels in the chlorite–magnetite veins are invariably zoned, e.g., chemically homogenous Al-rich chromite interior successively mantled by ferritchromite/Cr-rich magnetite zone and magnetite continuous with vein magnetite in the serpentine matrix. In aluminous chromite, ferritchromite/Cr-rich magnetite zones are symmetrically disposed adjacent to fracture-controlled magnetite veins that are physically continuous with magnetite rim. The morphology of ferritchromite–Cr-rich magnetite mimics the morphology of aluminous chromite interior but is incongruous with the exterior margin of magnetite mantle. Micropores are abundant in magnetite veins, but are fewer in and do not appear to be integral to the adjacent ferritchromite–Cr-rich magnetite zones. Sandwiched between chemically homogenous aluminous chromite interior and magnetite mantle, ferritchromite–Cr-rich magnetite zones show rim-ward decrease in Cr2O3, Al2O3 and MgO and complementary increase in Fe2O3 at constant FeO. In diffusion profiles, Fe2O3–Cr2O3 crossover coincides with Al2O3 decrease to values <0.5 wt% in ferritchromite zone, with Cr2O3 continuing to decrease within magnetite mantle. Following fluid-mediated (hydrous) dissolution of magmatic olivine and olivine + Al–chromite aggregates, antigorite + magnetite and chlorite + magnetite were transported in 10s-of-microns to sub-cm-wide veins and precipitated along porosity networks during serpentinization (T: 550–600 °C, f(O2): ?19 to ?22 log units). These veins acted as conduits for precipitation of magnetite as mantles and veins apophytic in chemically/morphologically modified magmatic Al-rich chromite. Inter-crystalline diffusion induced by chemical gradient at interfaces separating aluminous chromite interiors and magnetite mantles/veins led to the growth of ferritchromite/Cr-rich magnetite zones, mimicking the morphology of chemically modified Al–Cr–Fe–Mg spinel interiors. Inter-crystalline diffusion outlasted fluid-mediated aluminous chromite dissolution, mass transfer and magnetite precipitation.  相似文献   

9.
A two-stage model of oxidation was devised to explain the observed variations in crystallographic parameters in two artificially oxidized natural spinels. In the first stage, oxygen is added to the crystal boundary as cations are preserved, with Fe rising in total valence and vacant sites being formed. In the second stage, oxygen is preserved and α−Fe2O3 intergrowth occurs, at the expense of the oxygen of the parent spinel structure. On the basis of this model, crystallochemical formulae were calculated and cations partitioned in the various conditions. It was found that, both before and after oxidation, the spinel site population varies continuously in the direction of an increase in random charge distribution, depending on the increase of heat to the crystals. This trend was found to be reversible. Cation vacancies produced during oxidation are distributed between tetrahedral site T and octahedral site M. Received: 12 June 1997 / Revised, accepted: 17 February 1998  相似文献   

10.
Geochemical and mineralogical investigations have been carried out on laterite profiles developed in the Lake Sonfon Au district of northern Sierra Leone. The area is underlain by Archean metavolcanics and constitutes part of the Sula Mountains greenstone belt, which is mineralized in Au. Extensive lateritization has affected the rocks of this region, resulting in a profile which from bottom to top consists typically of a decomposed bedrock zone, a pisolitic laterite layer and a duricrust layer. Both the pisolitic and duricrust layers of the laterite are sometimes punctuated by lenses of ironstones containing high amounts of Cu, Zn, Ni, Co and Ce. Gold occurs as small grains within the heavy mineral fraction recovered from the decomposed rock zones and pisolitic layers of the profiles and also in gravels of streams draining the area. The mineralogy of the duricrust and pisolitic layers is dominated by goethite, gibbsite and quartz, with minor amounts (<5% by volume) of ilmenite, magnetite, haematite, rutile and kaolinite. The kaolinite content increases towards the decomposed rock zone, where talc, vermiculite and other layer lattice silicates become abundant. The heavy-mineral fraction of stream sediments is composed essentially of ilmenite, magnetite, haematite, and traces of rutile, zircon, tourmaline and Au. The Au grains are often characterized by a 10–200-μm-wide rim having a much lower content of Ag (0.3 wt.% or lower) than the grain interior (about 5 wt.% on average). Dissolution effects are also observed on the grain surfaces. It is considered that Au derived from the amphibolite parent rock is dissolved, transported, and redeposited during laterization.The duricrust cover of the laterite profiles is characterized by high contents of Fe2O3 (ca. 60 wt.%) and Al2O3 (ca. 32wt.%) and low content of SiO2 (ca. 9 wt.%). In comparison, the pisolitic layer is higher in SiO2 (ca. 18 wt.%) as well as a slightly higher in Al2O3 (ca. 34 wt.%). Lateritic weathering has resulted in the removal of CaO, Na2O, MgO and SiO2, with relative enrichment of Fe2O3 and Al2O3. The geochemical distribution of the trace elements in the laterite profiles can be related to the occurrence of the auriferous mineralization. The significance of these observations is discussed in relation to the origin of the lateritic Au and the role of the associated trace elements as indicators of the mineralization.  相似文献   

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