TEM study of a special grain boundary in a synthetic K-feldspar bicrystal: Manebach Twin

 A monoclinic KAlSi₃O₈ feldspar Manebach twin boundary was synthesized by diffusion bonding and examined using high-resolution transmission electron microscopy. The sharp (001) twin boundary is straight and free of strain. The boundary width is smaller than d₀₀₁. There is no rigid body shift observed at the twin boundary, and the feldspar structure is arranged symmetrically across (001). The twin boundary structure consists of bridged tetrahedral crankshafts, which are characteristic of the feldspar lattice. The grain boundary structure is in good agreement with the geometrical model of Taylor et al. (1934). The grain boundary composition of K_1/2H_1/2AlSi₃O₈ differs from their model. Received: 13 February 2002 / Accepted: 24 December 2002 Acknowledgements We thank M. Rühle, S. Hutt, J. Mayer, A. Strecker and U. Salzberger at MPI, Stuttgart, for their support and valuable advice in preparing TEM sections of bicrystals.     

Water in minerals detectable by electron energy-loss spectroscopy EELS

Electron energy-loss spectroscopy EELS of the oxygen K edge of OH^– containing minerals and minerals with molecular water reveals a peak at about 528 eV prior to the onset of the O-K edge at 532 eV. This peak is never observed in minerals without water or OH^– groups. The intensity of the signal at 528 eV increases with increasing water content of the minerals. The peak at 528 eV is attributed to OH groups or water molecules. From the observations it is concluded that EELS provides a new method to determine the OH^– or water content of minerals with a spatial resolution far beyond that of optical spectroscopy. Received: 28 April 1997 / Revised, accepted: 25 July 1997     

Zircon M127 – A Homogeneous Reference Material for SIMS U–Pb Geochronology Combined with Hafnium,Oxygen and,Potentially, Lithium Isotope Analysis

In this article, we document a detailed analytical characterisation of zircon M127, a homogeneous 12.7 carat gemstone from Ratnapura, Sri Lanka. Zircon M127 has TIMS‐determined mean U–Pb radiogenic isotopic ratios of 0.084743 ± 0.000027 for ²⁰⁶Pb/²³⁸U and 0.67676 ± 0.00023 for ²⁰⁷Pb/²³⁵U (weighted means, 2s uncertainties). Its ²⁰⁶Pb/²³⁸U age of 524.36 ± 0.16 Ma (95% confidence uncertainty) is concordant within the uncertainties of decay constants. The δ¹⁸O value (determined by laser fluorination) is 8.26 ± 0.06‰ VSMOW (2s), and the mean ¹⁷⁶Hf/¹⁷⁷Hf ratio (determined by solution ICP‐MS) is 0.282396 ± 0.000004 (2s). The SIMS‐determined δ⁷Li value is ?0.6 ± 0.9‰ (2s), with a mean mass fraction of 1.0 ± 0.1 μg g^?1 Li (2s). Zircon M127 contains ~ 923 μg g^?1 U. The moderate degree of radiation damage corresponds well with the time‐integrated self‐irradiation dose of 1.82 × 10¹⁸ alpha events per gram. This observation, and the (U–Th)/He age of 426 ± 7 Ma (2s), which is typical of unheated Sri Lankan zircon, enable us to exclude any thermal treatment. Zircon M127 is proposed as a reference material for the determination of zircon U–Pb ages by means of SIMS in combination with hafnium and stable isotope (oxygen and potentially also lithium) determination.     

Microtexture,nanomineralogy, and local chemistry of cryptocrystalline cosmic spherules

The paper reports scanning electron microscopy (FEG-SEM) and transmission electron microscopy (TEM) data on three cryptocrystalline (CC) cosmic spherules of chondritic composition (Mg/Si ≈ 1) from two collections taken up at glaciers at the Novaya Zemlya and in the area of the Tunguska event. The spherules show “brickwork” microtextures formed by minute parallel olivine crystals set in glass of pyroxene–plagioclase composition. The bulk-rock silicate chemistry, microtexture, mineralogy, and the chemical composition of the olivine and the local chemistry of the glass in these spherules testify to a chondritic source of the spherules. The solidification of the spherules in the Earth’s atmosphere was proved to be a highly unequilibrated process. A metastable state of the material follows, for example, from the occurrence of numerous nanometer-sized SiO₂ globules in the interstitial glass. These globules were formed by liquid immiscibility in the pyroxene–SiO₂ system. Troilite FeS and schreibersite (Fe,Ni)₃P globules were found in the FeNi metal in one of the spherules, which suggests that the precursor was not chemically modified when melted in the Earth’s atmosphere. Our results allowed us to estimate the mineralogy of the precursor material and correlate the CC spherules with the chondrule material of chondrites. The bulk compositions of the spherules are closely similar to those of type-IIA chondrules.     

Synthesis of monticellite–forsterite and merwinite–forsterite symplectites in the CaO–MgO–SiO<Subscript>2</Subscript> model system: influence of temperature and water content on microstructure evolution

Homogeneous single crystals of synthetic monticellite with the composition \({\text{Ca}}_{0.88}{\text{Mg}}_{1.12}{\text{SiO}}_4\) (Mtc I) were annealed in a piston-cylinder apparatus at temperatures between 1000 and \(1200\,^{\circ }\hbox {C}\), pressures of 1.0–1.4 GPa, for run durations from 10 min to 24 h and applying bulk water contents ranging from 0.0 to 0.5 wt% of the total charge. At these conditions, Mtc I breaks down to a fine-grained, symplectic intergrowth. Thereby, two types of symplectites are produced: a first symplectite type (Sy I) is represented by an aggregate of rod-shaped forsterite immersed in a matrix of monticellite with end-member composition (Mtc II), and a second symplectite type (Sy II) takes the form of a lamellar merwinite–forsterite intergrowth. Both symplectites may form simultaneously, where the formation of Sy I is favoured by the presence of water. Sy I is metastable with respect to Sy II and is successively replaced by the latter. For both symplectite types, the characteristic spacing of the symplectite phases is independent of run duration and is only weeakly influenced by the water content, but it is strongly temperature dependent. It varies from about 400 nm at \(1000\,^{\circ }\hbox {C}\) to 1200 nm at \(1100\,^{\circ }\hbox {C}\) in Sy I, and from 300 nm at \(1000\,^{\circ }\hbox {C}\) to 700 nm at \(1200\,^{\circ }\hbox {C}\) in Sy II. A thermodynamic analysis reveals that the temperature dependence of the characteristic spacing of the symplectite phases is due to a relatively high activation energy for chemical segregation by diffusion within the reaction front as compared to the activation energy for interface reactions at the reaction front. The temperature dependence of the characteristic lamellar spacing and the temperature-time dependence of overall reaction progress have potential for applications in geo-thermometry and geo-speedometry.     

Mullite in Libyan Desert Glass: Evidence for high-temperature/low-pressure formation

Libyan Desert Glass (LDG) is a SiO₂-rich natural glass whose origin, formation mechanism, and target material are highly debated. We here report on the finding of a lens-shaped whitish inclusion within LDG. The object is dominantly composed of siliceous glass and separated from the surrounding LDG by numerous cristobalite grains. Within cristobalite, several regions rich in mullite often associated with ilmenite were detected. Mineral assemblage, chemical composition, and grain morphologies suggest that mullite was formed by thermal decomposition of kaolinitic clay at atmospheric pressure and T ≥ 1600 °C and also attested to high cooling rates under nonequilibrium conditions. Cristobalite contains concentric and irregular internal cracks and is intensely twinned, indicating that first crystallized β-cristobalite inverted to α-cristobalite during cooling of the SiO₂-rich melt. The accompanied volume reduction of 4% induced the high density of defects. The whitish inclusion also contains several partly molten rutile grains evidencing that at least locally the LDG melt was at T ≥ 1800 °C. Based on these observations, it is concluded that LDG was formed by high-temperature melting of kaolinitic clay-, rutile-, and ilmenite-bearing Cenozoic sandstone or sand very likely during an asteroid or comet impact onto Earth. While melting and ejection occurred at high pressures, the melt solidified quickly at atmospheric pressure.     

An experimental study of the effect of iron on magnesiochloritoid-talc-clinochlore-kyanite stability

The influence of Fe on the reaction clinochlore+kyanite&ding3F;magnesiochloritoid+talc (1) was determined experimentally as a function of pressure (1.6-2.6 GPa) and composition at 600 and 540 °C. Analytical electron microscopy (AEM) was used to determine the compositions of the coexisting phases in these complex multiphase run products. Within the compositional range studied (x_Fe^bulk=0.12-0.34), chlorite solid solutions were always richer in magnesium than the coexisting chloritoid solid solutions. Fractionation of Fe into the chloritoid extends the stability field of the assemblage chloritoid plus talc towards lower pressures. However, the extent of the stability field for increasing x_Fe is less than one would expect for ideal mixing behaviour in chloritoid and chlorite, and indicates a moderate positive deviation from ideality for chloritoid solid solutions. The thermodynamic data for magnesiochloritoid given in two earlier studies are in good agreement with the present experiments, those of a third study yield pressures which are much too high, at least compared with the experiments at 600 °C.     

TiO2 exsolution from garnet by open-system precipitation: evidence from crystallographic and shape preferred orientation of rutile inclusions

We investigated rutile needles with a clear shape preferred orientation in garnet from (ultra) high-pressure metapelites from the Kimi Complex of the Greek Rhodope by electron microprobe, electron backscatter diffraction and TEM techniques. A definite though complex crystallographic orientation relationship between the garnet host and rutile was identified in that Rt[001] is either parallel to Grt<111> or describes cones with opening angle 27.6° around Grt<111>. Each Rt[001] small circle representing a cone on the pole figure displays six maxima in the density plots. This evidence together with microchemical observations in TEM, when compared to various possible mechanisms of formation, corroborates a precipitate origin. A review of exchange vectors for Ti substitution in garnet indicates that rutile formation from garnet cannot occur in a closed system. It requires that components are exchanged between the garnet interior and the rock matrix by solid-state diffusion, a process we refer to as “open-system precipitation” (OSP). The kinetically most feasible reaction of this type will dominate the overall process. The perhaps most efficient reaction involves internal oxidation of Fe²⁺ to Fe³⁺ and transfer from the dodecahedral to the octahedral site just vacated by $ {\text{Ti}}^{ 4+ }: 6\,{\text{M}}^{ 2+ }_{ 3} {\text{TiAl}}\left[ {{\text{AlSi}}_{ 2} } \right]{\text{O}}_{ 1 2} + 6\,{\text{M}}^{ 2+ }_{ 2, 5} {\text{TiAlSi}}_{ 3} {\text{O}}_{ 1 2} = 10\,{\text{M}}^{ 2+ }_{ 3.0} {\text{Al}}_{ 1. 8} {\text{Fe}}_{0. 2} {\text{Si}}_{ 3} {\text{O}}_{ 1 2} + {\text{M}}^{2+} + 2 {\text{e}}^{-} + 1 2\,{\text{TiO}}_{ 2} . $ OSP is likely to occur at conditions where the transition of natural systems to open-system behaviour becomes apparent, as in the granulite and high-temperature eclogite facies.     

Volume diffusion of Ytterbium in YAG: thin-film experiments and combined TEM–RBS analysis

In this study, we address volume diffusion of ytterbium in yttrium aluminum garnet (YAG) using thin-film single crystal diffusion couples. We employ analytical transmission electron microscopy (ATEM) as a tool for combined microstructural and microchemical analysis and compare the results to Rutherford backscattering (RBS) analysis. Given the high spatial resolution of the method, we focus on microstructural changes of the thin-film diffusant source during the diffusion anneal. We evaluate the potential influence of the associated changes in its transport properties on the evolution of concentration profiles in the single crystal substrate. This approach allows us to test the reliability of determination of volume diffusion coefficients from thin-film diffusion experiments. We found that for the chosen experimental setting, the influence of thin-film re-crystallization is small when compared with the experimental uncertainty and good estimates for the volume diffusion coefficients of Yb in YAG can be obtained using standard assumptions. Both Yb-concentration profiles analyzed with ATEM and with RBS give similar results. At 1,450°C and 1 bar, we infer log D _Yb (m²/s) values of −19.37 ± 0.07 (TEM) and −19.84 ± 0.02 (RBS). Although the change in thin-film transport properties associated with successive crystallization during the diffusion anneal does not play a major role for our experimental setup, this effect cannot generally be ignored.