Silicon in magnetite: High resolution microanalysis of magnetite-ilmenite intergrowths

Magnetite-ilmenite oxidation-exsolution intergrowths from an original titanomagnetite microphenocryst from an ash flow tuff unit have been studied using conventional transmission electron microscopy and analytical electron microscopy. Silicon has been found to be in solid solution in all of the magnetite studied and in some of the coexisting ilmenite. The average value in magnetite is 1.2 wt.% Si, equivalent to solid solution of 9 mole % Fe₂SiO₄. Silicon is also present in very small silicate inclusions and as unusual Si-rich domains of uncertain origin in magnetite. The inclusions and domains may be irregularly distributed through the magnetite in sizes well below those resolvable with the electron microprobe. Microprobe analyses for Si in magnetite generally reflect these heterogeneities in addition to a component presumably in solid solution. The petrologic implications of the data can be assessed only when relevant thermochemical data become available and the distribution of Si in magnetite is better understood.Contribution No. 376 from the Mineralogical Laboratory, Department of Geological Sciences, The University of Michigan     

SEM/microprobe study of some symplectic intergrowths replacing cordierite

Scanning electron microscopy (SEM), involving images produced by back-scattered electrons, reveals the microstructures of symplectic intergrowths replacing cordierite, which generally are too fine-grained and/or intricately intergrown for investigation using an optical microscope. Microprobe analysis, combined with the SEM technique, enables accurate identification of the intergrown minerals, and permits inference of equations for the local chemical changes involved in the formation of the intergrowths. Generally, the local replacement appears to have involved partial reactions taking place in a larger reactive system. Intergrowths forming partial pseudomorphs of cordierite in three metamorphic complexes consists of up to three minerals, only two of which comprise the intergrowth in any one domain. The following intergrown pairs of minerals have been identified: quartz-Al₂SiO₃, quartz-biotite, biotite-oligoclase, biotite-K-feldspar, muscovite-oligoclase, oligoclase-andalusite, K-feldspar-andalusite, aluminous orthopyroxene-Al₂SiO₃, and aluminous anthophylite-Al₂SiO₃.     

Compositional limits and analogs of monoclinic triple-chain silicates

Growing recognition of triple-chain silicates in nature has prompted experimental research into the conditions under which they can form and the extent of solid solution that is feasible for some key chemical substitutions. Experiments were done primarily in the range of 0.1–0.5 GPa and 200–850 °C for durations of 18–1,034 h. A wide range of bulk compositions were explored in this study that can be classified broadly into two groups: those that are Na free and involve various possible chemical substitutions into jimthompsonite (Mg₁₀Si₁₂O₃₂(OH)₄), and those that are Na bearing and involve chemical substitutions into the ideal end-member Na₄Mg₈Si₁₂O₃₂(OH)₄. Numerous attempts to synthesize jimthompsonite or clinojimthompsonite were unsuccessful despite the type of starting material used (reagent oxides, magnesite + SiO₂, talc + enstatite, or anthophyllite). Similarly, the chemical substitutions of F⁻ for OH⁻, Mn²⁺, Ca²⁺, or Fe²⁺ for Mg²⁺, and 2Li⁺ for Mg²⁺ and a vacancy were unsuccessful at nucleating triple-chain silicates. Conversely, nearly pure yields of monoclinic triple-chain silicate could be made at temperatures of 440–630 °C and 0.2 GPa from the composition Na₄Mg₈Si₁₂O₃₂(OH)₄, as found in previous studies, though its composition is most likely depleted in Na as evidenced by electron microprobe and FTIR analysis. Pure yields of triple-chain silicate were also obtained for the F-analog composition Na₄Mg₈Si₁₂O₃₂F₄ at 550–750 °C and 0.2–0.5 GPa if a flux consisting of Na-halide salt and water in a 2:1 ratio by weight was used. In addition, limited chemical substitution could be documented for the substitutions of 2 Na⁺ for Na⁺ + H⁺ and of Mg²⁺ + vacancy for 2Na⁺. For the former, the Na content appears to be limited to 2.5 cations giving the ideal composition of Na_2.5Mg₈Si₁₂O_30.5(OH)_5.5, while for the latter substitution the Na content may go as low as 1.1 cations giving the composition Na_1.1Mg_9.4Si₁₂O_31.9(OH)_4.1 based on a fixed number of Si cations. Further investigation involving Mg for Na cation exchange may provide a pathway for the synthesis of Na-free clinojimthompsonite. Fairly extensive solid solution was also observed for triple-chain silicates made along the compositional join Na₄Mg₈Si₁₂O₃₂(OH)₄–Ca₂Mg₈Si₁₂O₃₂(OH)₄ where the limit of Ca substitution at 450 °C and 0.2 GPa corresponds to Na_0.7Ca_1.8Mg_7.8Si₁₂O_31.9(OH)_4.1 (with the OH content adjusted to achieve charge balance). Aside from the Na content, this composition is similar to that observed as wide-chain lamellae in host actinolite. The relative ease with which Na-rich triple chains can be made experimentally suggests that these phases might exist in nature; this study provides additional insights into the range of compositions and formation conditions at which they might occur.     

The replacement of anthophyllite by jimthompsonite: a model for hydration reactions in biopyriboles

Anthophyllite crystals found in ultramafic lenses of the Lepontine Alps (Switzerland) contain coherent, submicroscopic intergrowths of ordered and disordered biopyribole polysomes. The chain width distributions of disordered polysomes were analyzed using high resolution transmission electron microscopy (HRTEM). Chains wider than triple were interpreted as intermediate products in the transformation of anthophyllite to the triple chain silicate jimthompsonite. The concentration of individual chain types is strongly correlated with the reaction progress. Based on observed zipper terminations and the transformation rules given by Veblen and Buseck (1980) a scheme of possible reaction paths leading from anthophyllite to jimthomp sonite is proposed. The reaction scheme and a simple kinetic model for elementary reactions allow modeling of the observed chain width distributions. The model suggests that the complex reaction paths involving steps with increasing and decreasing chain width are more important in the formation of jimthompsonite than the direct transformation from anthophyllite. The wide chains (>triple) occurring as intermediate products of the multi-step paths are structurally closer to talc than jimthompsonite. The back-transformation of these wide chains to triple chains is, therefore, a strong argument that jimthompsonite is a stable phase and not only a metastable intermediate product in the transformation of anthophyllite to talc. Received: 8 July 1996 / Accepted: 13 December 1996     

Petrogenesis of orthopyroxene-magnetite-ilmenite intergrowths from an ultramafic layer

A new occurrence of myrmekitic orthopyroxene-magnetite-ilmenite intergrowth from a thin ultramafic layer within a heterogeneous noritic rock from the Frederiksdal area, South Greenland, was investigated chemically and texturally. Compositionally, the intergrown ilmenite and orthopyroxene show the lowest recorded MgO content from pyroxene-oxide mineral intergrowths. The magnetite-ilmenite intergrowth has skeletal morphology, consisting of sets of thinly tabular plates parallel to the (111) planes of the spinel structure. The orthopyroxene-oxide intergrowth is considered to be the result of a simultaneous magmatic crystallization, that of the oxide minerals being faster.     

Graphic intergrowths of feldspars and quartz in some Czechoslovak pegmatites

Graphic intergrowths of alkali feldspar+quartz, and plagioclase+quartz, occur together in pegmatites in the eastern part of the Czechoslovak Moldanubicum. They form zones between the finer-grained wall zone and the central blocky feldspar+quartz core. The normative Or-Pig-Q compositions of the graphic intergrowths and the Or-Ab-An contents of their feldspars show broad variations generally, but have a restricted range within individual pegmatites. At two localities studied in more detail, coexisting feldspars show gradual changes in composition, from the margins up to the innermost graphic pegmatite, compatible with fractional crystallization along the feldspar solidus-solvus intersection in the Or-Ab-An-Q-H₂O system, at different vapour pressures in different pegmatites. Two models are demonstrated for low and high pressure cases. The feldspar compositions from central blocky zones deviate from the magmatic fractional crystallizations paths; this corresponds with the general assumption that they crystallized from supercritical gaseous fluids.In these and in similar pegmatites, coexisting alkali feldspar+quartz and plagioclase + quartz intergrowths are interpreted as the last products of cotectic crystallization from an ultimately fractionated granitic magma. Positive correlation of Ab solid solution and quartz content in the potassic intergrowths suggests that these characteristics may be indicative of the relative pressure and temperature effective during their crystallization, when compared in pegmatites of the same bulk composition.     

Boundaries of intergrowths between mineral individuals: A zone of secondary mineral formation in aggregates

Intergrowth boundaries between mineral individuals in dunite of the Gal’moenan massif in Koryakia was studied in terms of crystal morphology, crystal optics, and ontogenesis. The results obtained allowed us to trace the staged formation of olivine and chromite and four generations of these minerals. Micro-and nanotopography of boundary surfaces between intergrown mineral individuals of different generations was examined with optic, electron, and atomic force microscopes. The boundaries between mineral individuals of different generations are distinguished by their microsculpture for both olivine and chromite grains. Both minerals demonstrate a compositional trend toward refinement from older to younger generations. The decrease in the iron mole fraction in olivine and chromite is accompanied by the crystallization of magnetite along weakened zones in olivine of the first generation and as outer rims around the chromite grains of the second generation observable under optic and electronic microscopes. The subsequent refinement of chromite results in the release of PGE from its lattice, as established by atomic power microscopy. The newly formed PGM are localized at the boundaries between mineral individuals and, thus, mark a special stage in the ontogenetic evolution of mineral aggregates. Further recrystallization is expressed in the spatial redistribution of grain boundaries and the formation of monomineralic intergrowth boundaries, i.e., the glomerogranular structure of rock and substructures of PGM, chromite, and olivine grains as intermediate types of organization of the granular assemblies in the form of reticulate, chain, and cellular structures and substructures of aggregates.     

Coherent elastic energies of exsolution boundaries in peristerite and böggild intergrowths

Elastic energy calculations based upon the coherent model of Willaime and Brown [Acta Cryst. A30, 316–331 (1974)] have been carried out for some exsolution textures in peristerite and Böggild intergrowths. For peristerites it is demonstrated that substitution of K for Na moves the orientation of the exsolution lamellae from (08 \(\overline {\text{1}} \) ) to about ( \(\overline {\text{1}} \) , 21, \(\overline {\text{2}} \) ) in agreement with observations. An electron microscope study of exsolution textures in labradorite and andesine plagioclases has been carried out and information about small structural differences in these lamellar structures has been obtained from elastic energy calculations.     

Regular intergrowths of minerals in pegmatites from the Il’meny mountains

This paper summarizes the data on oriented intergrowths of minerals in pegmatites of the Il’meny Mountains. Two-feldspar, two-mica, biotite-amphibole, biotite-pyroxene, and pyroxene-amphibole intergrowths have been revealed in syenitic and miaskitic pegmatites. The orientation of exsolution products has been studied in sunstone (aventurine) and moonstone feldspars, nepheline, and cancrinite. Corundum-biotite-feldspar and two-mica intergrowths and exsolution lamellae occur in stellate corundum from corundum-feldspar veins. Syntactic intergrowths of various amphiboles and chlorites have been detected in pegmatoid ultramafic rocks. Regular quartz-feldspar (graphic) and two-feldspar intergrowths are typical of granitic pegmatites. Two-mica, columbite-samarskite, columbite-ilmenorutile, zircon-xenotime, cassiterite-ilmenorutile, cassiterite-ixiolite, cassiterite-tantalite, tantalite-stibiotantalite, fergusonite-columbite, pyrochlore-fergusonite, and beryl-cordierite intergrowths have been found in granitic pegmatites as well. New intergrowth laws have been established for many pairs of minerals.     

Electron-probe investigation of some intergrowths in iron-titanium minerals from Rosetta black sands

The nature of exsolution of ilmenite in titanomagnetite and of the alteration of ilmenite in Rosetta black sands was investigated by the electron micro-probe analyzer. The mode of formation of such micro-intergrowths has been explained and mainly attributed to oxidation processes.

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Zusammenfassung Die Entmischungen von Ilmenit und Titanomagnetit und die Umwandlungen von Ilmenit des Schwarz-Sandes aus Rosetta wurden mit Hilfe der Elektronen-Mikrosonde qualitativ untersucht. Die Art von solchen Verwachsungen und deren Entwicklungsablauf wurden diskutiert.

     

Statistical analysis of granophyric intergrowths in the Main Hill Arkasani Granophyre Pluton, eastern India

The Main Hill Arkasani Granophyre Pluton (MAG), a product of Proterozoic intraplate acid magmatic activity, represents an anatectic melt of the enveloping rocks of dominantly pelitic composition with subordinate trondhjemitic gneiss and basic rocks. Petrography, chemistry, correlation between compositional attributes, areal variation of volume percent granophyric intergrowth, and varimax rotated factor analysis of compositional attributes of these rocks suggest that in the MAG pluton, plagioclase phenocrysts and biotite crystallized first, followed by change of level of emplacement of the magma when the groundmass started crystallizing at a rapid rate. The rapid growth of quartz and alkali feldspar crystallizing from the residual melt gave rise to the ubiquitous granophyric intergrowth in the late stage of crystallization. The alkali-rich residual liquid tended to concentrate toward the margin of the pluton where there is a profusion of granophyric intergrowths.     

Bulk compositions of intimate intergrowths of chalcopyrite and sphalerite and their genetic implications

To determine the bulk chemical compositions of chalcopyrite containing starlike sphalerite and sphalerite including dotlike chalcopyrite, specimens from various types of ore deposits in Japan were used for modal and electron microprobe analyses. According to the analytical results, most of the measured zinc contents in chalcopyrite containing starlike sphalerite are less than 0.8 at%, corresponding to the maximum solubility of zinc in chalcopyrite as determined experimentally at 400°C. However, specimens from the Maruyama deposit in the Tsumo mine contain 1.2–1.4 at% Zn, which are within the solubility limit of an intermediate solid solution (ISS) above 400°C. It is therefore concluded that starlike sphalerite in chalcopyrite are exsolution products derived from primary chalcopyrite solid solution and/or zincic ISS. Measured copper contents in sphalerite including dotlike chalcopyrite yield considerably higher values, i.e., 1.5–6.0 at%, which exceed the solubility limits of copper in sphalerite solid solution as determined experimentally. This result suggests that not all the chalcopyrite dots were exsolved from sphalerite, but that most of them are the product of some other mechanisms.     

层状出溶结构导致拉长石晕彩形成——来自透射电镜的证据

从拉长石出溶结构的形态特征、成分差异和出溶结构的取向研究出发,采用TEM、STEM 以及SAED等手段对其进行测试,发现拉长石出溶结构层的厚度符合理论计算值,结构层的成分由富钙和贫钙两相长石组成,具备了产生干涉作用的必要条件.研究结果表明,拉长石的晕彩色是因其内部的层状出溶结构对光的干涉所致,结构层的厚度主要受富钙相长石的控制.随着钙(An)含量的增加,结构层相应地增厚,且富钙层的增大幅度大于贫钙层,从而导致晕彩色波长也随之增大.出溶结构层的取向为(153),近于平行晶体的(010)面,但不同产地的拉长石,尽管晕彩色相同,其出溶条纹中的钙含量和条纹的具体取向也不尽相同.     

Chalcopyrite Intergrowths in sphalerite in the Meixian Lead—Zine Deposit,Fujian Province and their Metallogenic Significance

Ore textures and electron microprobe analyses show that in addition to highly scattered blebs in sphalerite grains,intergrown chalcopyrite also occurs as rods,myrmekites and lamellae aligned along cleavages and twin boundaries of the host sphalerite.The majority of the intergrowths could have been formed by replacement of sphalerite by chalcopyrite,albeit part of them may have resulted from exsolution,Not only copper,but also iron were introduced into the sphalerite by replacive fluids.While the front of the replacing fluid was moving forward through a sulphide orebody,Zn and Pb were dissolved and Cu was precipitated,resulting in zonal refining of the sulphide ores,The remobilized zinc and lead were precipitated at favourable sites with changed physico-chemical conditions .This is a possible mechanism for the formation of copper-poor zinc and lead ores above or lateral to the copper orebodies in some of the massive sulphide deposits reworked and overprinted by late-stage granites and their hydrothermal fluids.     

Exsolution intergrowths of titanian ferrocolumbite and niobian rutile from the Weinebene Spodumene Pegmatites,Carinthia, Austria

Summary Titanian ferrocolumbite is a rare accessory mineral in the spodumene-bearing pegmatites at Weinebene, Carinthia, Austria. It contains abundant exsolved niobian rutile and scarce inclusions of cassiterite that may be primary. The titanian ferrocolumbite is relatively homogeneous with Mn/(Mn + Fe) 0.24–0.33, Ta/(Ta + Nb) 0.09–0.13 (atomic ratios) and 0.47–0.88 Ti per 12 cations (2.7–5.0 wt.% TiO₂). Natural specimens are considerably disordered but become more ordered on heating. Niobian rutile has Mn/(Mn + Fe) 0.00–0.04 and Ta/(Ta + Nb) 0.26–0.38; it concentrates Fe, Ta, Ti and Sn relative to the Mn- and Nb-enriched ferrocolumbite. The overall scarcity of Nb, Ta-oxide minerals in the spodumene-bearing pegmatites of southern Ostalpen conforms to their general features ranking them with the albite-spodumene type of rare-element pegmatites.With 4 Figures     

Cellular plagioclase intergrowths as a result of crystal-magma mixing in the Proterozoic Åland rapakivi batholith,SW Finland

Finely cellular plagioclase intergrowths have been studied in xenocrystic andesine (An₃₂) and andesine mantled K-feldspars within mafic magmatic enclaves in a quartz-feldspar porphyry from the Proterozoic subvolcanic Hammarudda complex, Åland rapakivi batholith, SW Finland. The cellular intergrowths usually occur as 0.2–2.0 mm mantles around xenocrysts but also as entirely cellular grains, and are built up of a network of two distinct phases: one relatively Na-rich (An₃₁) and one relatively Ca-rich (An₅₀). The grains are also covered by a thin (0.08–0.12 mm), continuous, normally zoned rim outside the cellular mantle. Small inclusions (0.01–0.05 mm) of Fe–Mg minerals are concentrated in the Ca-rich part of the network. Compositionally, the Na-rich phase of the network is close to the inner non-cellular andesine of the xenocrysts. However, it has a lower Or- and a slightly lower An-content. The Ca-rich phase has the same composition as the inner part of the normally zoned rim, which outwards grades into lower An-contents that overlap the An-content of the matrix plagioclases. The cellular network was developed after the andesine xenocrysts (or andesine mantled K-feldspars) were engulfed in mafic magmatic enclaves during a mixing event. The xenocrysts became heated to a temperature just below the liquidus of the mafic magma. Dissolution of the xenocrysts developed a spongy cellular texture which was penetrated by enclave magma. Ca-rich plagioclase crystallized in the cells in equilibrium with the enclave magma, trapping Fe–Mg-rich melt. As the enclaves cooled the outermost thin rim and matrix plagioclases crystallized from the mafic melt. These processes operated in fairly large enclaves, as the one studied here, which has a diameter of 70cm. Smaller enclaves, on the other hand, were cooled more rapidly to temperatures close to the solidus of the enclave magma, and consequently had no time to dissolve the xenoxrysts.     

Plagioclase-spinel intergrowths in alkali basaltic rocks from the Southern Highlands,N.S.W.

Dominant plagioclase (An₅₉) and minor spinel form possible cumulates in alkali basaltic flows from the Southern Highlands, N.S.W. The mode of occurrence of the spinel, and the chemical composition of both the spinel and the plagioclase suggest the spinel originated by exsolution from plagioclase formed at high pressure.     

The lamellar structure in moonstone and anorthoclase from Korea

Moonstone and anorthoclase from Korea were investigated using electron microscope. Lamellae of moonstone were in the range of 1,200 to 3,000 Å, and anorthoclase have fine lamellae ranging from 20 to 900 Å. The outer part of every specimen has exsolved more perfectly, and the lamellae are coarse. The inner part is in the process of exsolution, and the lamellae are extremely fine. The lamellae are parallel to (¯801), and the streations on diffraction spots are oriented normal to the lamellae.     

Characterization of Dichotomoceras in the Oxfordian of Kachchh

We report here the first Dichotomoceras of the Indian subcontinent at Kantkote (Wagad) in the proximal most exposed part of the Kachchh Basin. This is further addition to the significant enlargement of the Oxfordian ammonoid record made earlier (Krishna et al. 1994, 1995, 1998, 2000). Near continuous presence of ammonoids has been recorded in ca 55 m thick succession, almost immediately above the Schilli Subzone, that was considered ammonoid devoid earlier. The ammonoid density, diversity and frequency in this just discovered ca 55 m thick column are much scarcer in comparison to the underlying 10 m thick ammonoid abundant Schilli Subzone. Examples of Dichotomoceras are determined almost throughout the said interval which in our preliminary taxonomic evaluation appear identical or close to D. rotoides (Ronch.), D. stenocycloides (Siem.), D. bifurcatus (Quenst.) and D. crassus Enay. It thus suggests the characterization of the Rotoides Subzone of the Transversarium Zone and the superjacent Bifurcatus Zone of the column at least up to the early Late Oxfordian.