Lamellar Intergrowths Research Articles

Coherent solvus of disordered alkali feldspar: experiment, atom probe tomography and thermodynamic model

At temperatures above about 600 °C, alkali feldspar forms a continuous solid solution between the Na and K end members. Towards lower temperatures a miscibility gap opens, and alkali feldspar of intermediate composition exsolves, forming an intergrowth of relatively more Na-rich and K-rich lamellae. During exsolution, the crystal structure usually remains coherent across the lamellar interfaces, a feature that may be preserved over geological times. Due to the compositional dependence of the lattice parameters, coherent intergrowth requires that the lamellae are elastically strained. The associated elastic strain energy counteracts exsolution, and the solvus delimiting the misciblity gap for coherent intergrowth lies below the solvus for strain free phase equilibria. To determine the coherent solvus, homogeneous gem quality alkali feldspar of intermediate composition was annealed at conditions falling into the two-phase region of the phase diagram. Thereby a coherent intergrowth of approximately 10–20 nanometers wide lamellae was produced. Lamellar compositions were determined with atom probe tomography defining points on the coherent solvus. In parallel, the coherent solvus was calculated using a thermodynamic mixing model calibrated on the same alkali feldspar as used for the exsolution experiments and accounting for the elastic strain energy associated with coherent lamellar intergrwoth. The experimentally determined and the calculated coherent solvus are in excellent agreement indicating that phase equilibria in coherent lamellar intergrowth of alkali feldspar are adequately described, providing a sound basis for the interpretation of phase relations in coherently exsolved alkali feldspar.

Coherent lamellar intergrowth in alkali feldspar

A thermodynamic analysis of coherent lamellar intergrowth resulting from the exsolution of initially homogeneous alkali feldspar is presented. In contrast to earlier treatments, where the simplifying assumption of zero strain in the lamellar interfaces was used, our treatment is more general. The elastic stresses and strains associated with coherent lamellar intergrowth of Na-rich and K-rich alkali feldspar are calculated by minimising the overall elastic energy of the lamellar microstructure. At given pressure and temperature, the elastic energy depends on the volume proportions of the two lamellar types, and thus on the composition of the homogeneous precursor feldspar. As a consequence, there is no single coherent solvus for alkali feldspar, but coherent solvi are different for different compositions of the homogeneous precursor phase. Experimentally observed lamellar orientations agree with those predicted by minimising the strain energy on a set of all possible lamellar orientations.

Microstructures in the Baima layered intrusion, SW China: Constraints on the late-stage magmatic processes during solidification of a crystal mush

Magmatic microstructures in layered intrusions record key petrographic evidence for the late-stage magmatic processes that took place during solidification of a crystal mush. Systematic examination of the magmatic microstructures can reveal dynamic evolution of interstitial liquid in crystal mush, which however has been only conducted in a few studies on layered intrusions by far. In order to constrain the late-stage magmatic processes related to the Fe-Ti oxide-bearing layered intrusions, we investigated the magmatic microstructures of the Baima intrusion in the Panxi region (SW China). The intrusion is divided into three major units from the base upwards, including the lower zone (LZ), middle zone (MZ) and upper zone (UZ). Through detailed examination of a series of drill core samples, we found several different types of reactive microstructures, such as replacive symplectites, fish-hook pyroxene/olivine/amphibole and amphibole rim. Replacive symplectites include fine-grained, lamellar intergrowths of An-rich plagioclase + olivine/clinopyroxene/amphibole/phlogopite/biotite that are rooted to Fe-Ti oxides and replacing plagioclase primocrysts (Type 1) and intergrowths of An-rich plagioclase + orthopyroxene/olivine/amphibole that are rooted to olivine and replacing plagioclase primocrysts (Type 2). These microstructures are particularly abundant in the LZ except for the Type 2 symplectites, which are rare throughout the intrusion. An-rich plagioclase in the replacive symplectites and fish-hook textures have An contents up to 96, much higher than those of plagioclase primocrysts. Overall, fish-hook amphibole and amphibole rims contain 0.19−4.24 wt.% TiO2, higher than those of amphibole lamellae in the replacive symplectites that varying from 2.38 wt.% TiO2 to below the detection limit. These microstructures were developed during solidification of the intrusion due to the reaction between plagioclase primocrysts and ambient Fe-rich liquid, accompanying with addition of Fe, Ti and Ca and removal of alkalis and silica in an open system. The abundance of such reactive microstructures in the LZ are therefore attributed to silicate liquid immiscibility within a crystal mush, in which the segregation of the buoyant Si-rich component left behind the dense Fe-rich liquid in the lower part of magma chamber. The common presence of amphibole and phlogopite/biotite in the replacive symplectites indicates that continuous fractionation of the Fe-rich liquid leads to hydration of interstitial liquid during the late-stage solidification.

(Cd,Mn)S in the Composite Photocatalyst: Zinc Blende and Wurtzite Particles or Integrowth of These Two Modifications?

In this study, the crystalline structure and particle shape of Cd1-xMnxS (x~0.3) in the composite photocatalysts prepared by hydrothermal synthesis at different temperatures (T = 80, 100, 120, and 140 °C) were analyzed. Along with mixed Cd-Mn sulfide, the catalysts contain a small amount of β-Mn3O4. XRD patterns of (Cd,Mn)S have features inherent to both cubic zinc blende and hexagonal wurtzite structure. Moreover, XRD peaks are anisotropically broadened. First, the heterogeneous (or two-phased) model was considered by the commonly used Rietveld method. Phase ratio, average crystallite sizes, and strains for both phases were formally determined. However, it was shown that this model is not correct because relatively narrow and broad peaks cannot be fitted simultaneously. Then, the homogeneous model was tested by Debye Function Analysis. This model assumes that particles are statistically homogeneous, but each particle contains lamellar intergrowth of zinc blende and wurtzite modifications. The probability of stacking faults, as well as the average radii of spherical and ellipsoidal particles, were varied. It was shown that nanocrystalline Cd0.7Mn0.3S particles have an ellipsoidal shape. Ellipsoids are elongated along the direction normal to the plane of defects. An increase in the hydrothermal synthesis temperature from 80 °C to 140 °C leads to an enlargement of particles and a gradual decrease in the probability of stacking faults in the wurtzite structure from 0.47 to 0.36. Therefore, with increasing temperature, the structure of (Cd,Mn)S nanoparticles transforms from almost random polytype cubic/hexagonal (ZB:WZ = 47:53) to a preferably hexagonal structure (ZB:WZ = 36:64). Mn2+ ions facilitate CdS phase transformation from zinc blende to wurtzite structure. There is no direct correlation between the structure and photocatalytic activity.

Three-Dimensional Distribution of Platinum Group Minerals in Natural MSS-ISS Ores From the Norilsk One Deposit, Russia

The Mt. Rudnaya MSS-ISS (monosulfide and intermediate solid solution) fine-grained ores from a NE termination of Norilsk 1 deposit were analyzed using a combination of X-ray computed micro tomography, spectral X-ray computed micro tomography and scanning electron microscopy to achieve both, 2D and 3D data. The ores consist of ISS composed of tiny lamellar intergrowths of cubanite and chalcopyrite solid solutions, which form up to 4-mm distinct globules surrounded by an ISS-MSS matrix. Our X-ray computed micro tomography results may provide 3D textural evidence of a possible natural sulfide-sulfide liquid immiscibility between Cu-rich and Cu-poor sulfide liquids that occurred before MSS and ISS were crystallized. The platinum group minerals (PGM) distribution shows that 20.6 vol% of all PGM occur in the ISS-MSS matrix and 79.4 vol% in the ISS globules. We suggest that this distributional behavior is due to the fact that the platinum group elements (PGE) cannot be dissolved in ISS, which led to the formation of the large PGM grains, which are up to 120 μm on their longest axis. The initial enrichment of ISS in PGE was controlled by differences in the partition coefficients of platinum and palladium between Cu-poor and Cu-rich liquids.

Atomic-scale structure and non-stoichiometry of meteoritic hibonite: A transmission electron microscope study

Abstract Hibonite (CaAl12O19) is a common refractory mineral in Ca-Al-rich inclusions (CAIs) in primitive meteorites. Transmission electron microscope (TEM) studies have identified enigmatic planar defects in different occurrences of hibonite in the Allende meteorite that give rise to strong streaking along c* in electron diffraction patterns. Atomic resolution high-angle annular dark-field (HAADF) imaging and energy-dispersive X-ray (EDX) analyses were used to determine the nature and origin of these planar features. HAADF images of hibonite grains reveal lamellar intergrowths of common 1.6 nm spacing, and less commonly 2.0 and 2.5 nm spacings, interspersed in stoichiometric hibonite showing 1.1 nm (002) spacing. Stoichiometric hibonite consists of alternating Ca-containing (“R”) and spinel-structured (“S”) blocks stacked in a sequence RS. In contrast, the 1.6 nm layers result from a doubled S block such that the stacking sequence is RSS, while in the widest defect observed, the stacking sequence is RSSSS. These intergrowths are epitaxial and have coherent, low-strain boundaries with the host hibonite Meteoritic hibonite shows common Ti and Mg substitution for Al in its structure. Atomic-resolution EDX maps of hibonite grains in the Allende CAI confirm the preferred site occupancy of Mg on tetragonal M3 sites in S blocks and of Ti on trigonal bipyramidal M2 and octahedral M4 sites in R blocks. Mg is highly concentrated, but Ti is absent in the planar defects where wider S blocks show Al-rich compositions compared to stoichiometric MgAl2O4 spinel. Therefore, Mg likely played the major role in the formation and metastability of planar defects in hibonite. Electron energy loss spectroscopy data from the Ti L2,3 edge show the presence of mixed Ti oxidation states with ~15–20% of Ti as Ti3+ in hibonite, suggesting a direct substitution of Ti3+ ↔ Al3+ in hibonite. The remaining ~80–85% of Ti is present as Ti4+ and corresponding EDX analyses are consistent with the well-known coupled substitution 2Al3+ ↔ Ti4+ + Mg2+ being the major mechanism for Ti and Mg substitution in hibonite. The formation of planar defects in hibonite occurred during high-temperature nebular condensation or melting/crystallization processes. The occurrence of non-stoichiometric hibonite in the Allende CAI deviates from the mineral formation sequence predicted from equilibrium condensation models. Overall, our atomic resolution TEM observations signify non-equilibrium, kinetic-controlled crystal growth during the high-temperature formation of refractory solids in the early solar nebula.

Platinum Group Element Enrichment of Natural Quenched Sulfide Solid Solutions, the Norilsk 1 Deposit, Russia

Abstract The deepest terminations of the Mount Rudnaya subvertical massive sulfide offshoots of the Norilsk 1 orebody are composed of exceptionally fine grained sulfides that are believed to be natural quenched sulfide solid solutions. Copper-rich intermediate solid solution (ISS) and Fe-rich monosulfide solid solution (MSS) form an equigranular and lamellar matrix hosting MSS- and ISS-dominant globules. The nonstoichiometric chemical compositions of the solid solutions plot within their high-temperature fields known from experiments. MSS contains 19 to 35 wt % Ni, 0.09 to 0.45 wt % Co, and up to 0.6 wt % Cu and is heterogeneously enriched in Rh (up to 32 ppm), Ir (up to 0.6 ppm), Pt (up to 65 ppm), and Pd (up to 168 ppm). ISS occurs as the lamellar intergrowths of the chalcopyrite (Ccpss) and cubanite (Cubss) solid solutions, which bear up to 4.74 wt % Ni and 0.2 wt % Co and are heterogeneously enriched in Zn, Ag, and In. The assemblage of platinum group minerals (PGMs) is hosted mostly in the ISS and is dominated by Pt-Fe alloys and minerals of the rustenburgite-atokite series, like the set of PGMs at the Norilsk 1 deposit. Similar Pt-Pd-Sn compounds in the laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) spectra of profiles through MSS and ISS are interpreted to be trapped microinclusions. The pentlandite contains up to 0.13 wt % Pt, up to 4.62 wt % Pd, <0.53 wt % Co, and <0.4 wt % Cu according to electron microprobe analysis. LA-ICP-MS data and mapping show that Pd content in the pentlandite increases toward contacts with ISS and decreases toward contacts with MSS, supporting a reaction origin of pentlandite. The wide variations of the concentrations of major and trace elements in the solid solutions, as well as the coexistence of Pd-poor (a few ppm Pd) and Pd-rich (over 4.62 wt % Pd) pentlandite within a single sample, seem to characterize the different generations of the MSS to MSS-ISS globules, antecrysts, and phenocrysts with the distinct histories of enrichment due to exchange with fractionated Cu-platinum group element-rich residue. The directional distribution of Pd of high-temperature primary magmatic origin is preserved due to rapid quenching of the sulfides from ~650°C.

Spinodal decomposition in alkali feldspar studied by atom probe tomography

We used atom probe tomography to complement electron microscopy for the investigation of spinodal decomposition in alkali feldspar. To this end, gem-quality alkali feldspar of intermediate composition with a mole fraction of a_{text {K}}=0.43 of the K end-member was prepared from Madagascar orthoclase by ion-exchange with (NaK)Cl molten salt. During subsequent annealing at 550,^circ hbox {C} and close to ambient pressure the ion-exchanged orthoclase unmixed producing a coherent lamellar intergrowth of Na-rich and K-rich lamellae. The chemical separation was completed, and equilibrium Na–K partitioning between the different lamellae was attained within four days, which was followed by microstructural coarsening. After annealing for 4 days, the wavelength of the lamellar microstructure was approx 17,hbox {nm} and it increased to approx 30,hbox {nm} after annealing for 16 days. The observed equilibrium compositions of the Na-rich and K-rich lamellae are in reasonable agreement with an earlier experimental determination of the coherent solvus. The excess energy associated with compositional gradients at the lamellar interfaces was quantified from the initial wavelength of the lamellar microstructure and the lamellar compositions as obtained from atom probe tomography using the Cahn–Hilliard theory. The capability of atom probe tomography to deliver quantitative chemical compositions at nm resolution opens new perspectives for studying the early stages of exsolution. In particular, it helps to shed light on the phase relations in nm scaled coherent intergrowth.

Magnetic Mineral Populations in Lower Oceanic Crustal Gabbros (Atlantis Bank, SW Indian Ridge): Implications for Marine Magnetic Anomalies

AbstractTo learn more about magnetic properties of the lower ocean crust and its contributions to marine magnetic anomalies, gabbro samples were collected from International Ocean Discovery Program Hole U1473A at Atlantis Bank on the Southwest Indian Ridge. Detailed magnetic property work links certain magnetic behaviors and domain states to specific magnetic mineral populations. Measurements on whole rocks and mineral separates included magnetic hysteresis, first‐order reversal curves, low‐temperature remanence measurements, thermomagnetic analysis, and magnetic force microscopy. Characteristics of the thermomagnetic data indicate that the upper ~500 m of the hole has undergone hydrothermal alteration. The thermomagnetic and natural remanent magnetization data are consistent with earlier observations from Hole 735B that show remanence arises from low‐Ti magnetite and that natural remanent magnetizations are up to 25 A m−1 in evolved Fe‐Ti oxide gabbros, but are mostly <1 A m−1. Magnetite is present in at least three forms. Primary magnetite is associated with coarse‐grained oxides that are more frequent in the upper part of the hole. This magnetic population is linked to dominantly “pseudo‐single‐domain” behavior that arises from fine‐scale lamellar intergrowths within the large oxides. Deeper in the hole the magnetic signal is more commonly dominated by an interacting single‐domain assemblage most likely found along crystal discontinuities in olivine and/or pyroxene. A third contribution is from noninteracting single‐domain inclusions within plagioclase. Because the concentration of the highly magnetic, oxide‐rich gabbros is greatest toward the surface, the signal from coarse oxides will likely dominate the near‐bottom magnetic anomaly signal at Atlantis Bank.

Apatite-hosted melt inclusions from the Panzhihua gabbroic-layered intrusion associated with a giant Fe–Ti oxide deposit in SW China: insights for magma unmixing within a crystal mush

The ∼ 2-km-thick Panzhihua gabbroic-layered intrusion in SW China is unusual because it hosts a giant Fe–Ti oxide deposit in its lower zone. The deposit consists of laterally extensive net-textured and massive Fe–Ti oxide ore layers, the thickest of which is ∼ 60 m. To examine the magmatic processes that resulted in the Fe enrichment of parental high-Ti basaltic magma and the formation of thick, Fe–Ti oxide ore layers, we carried out a detailed study of melt inclusions in apatite from a ∼ 500-m-thick profile of apatite-bearing leucogabbro in the middle zone of the intrusion. The apatite-hosted melt inclusions are light to dark brown in color and appear as polygonal, rounded, oval and negative crystal shapes, which range from ∼ 5 to ∼ 50 µm in width and from ∼ 5 to ∼ 100 µm in length. They have highly variable compositions and show a large and continuous range of SiO2 and FeOt with contrasting end-members; one end-member being Fe-rich and Si-poor (40.2 wt% FeOt and 17.7 wt% SiO2) and the other being Si-rich and Fe-poor (74.0 wt% SiO2 and 1.20 wt% FeOt). This range in composition may be attributed to entrapment of the melt inclusions over a range of temperature and may reflect the presence of µm-scale and immiscible Fe-rich and Si-rich components in different proportions. Simulating results for the motion of Si-rich droplets within a crystal mush indicate that Si-rich droplets would be separated from Fe-rich melt and migrate upward due to density differences in the interstitial liquid when the magma unmixed. Migration of the Si-rich, immiscible liquid component from the interstitial liquid caused the remaining Fe-rich melt in the lower part to react with plagioclase primocrysts (An59–60), as evidenced by fine-grained lamellar intergrowth of An-rich plagioclase (An79–84) + clinopyroxene in the oxide gabbro of the lower zone. Therefore, magma unmixing within a crystal mush, combined with gravitationally driven loss of the Si-rich component, resulted in the formation of Fe-rich, melagabbro and major Fe–Ti oxide ores in the lower part and Si-rich, leucogabbro in the upper part of the intrusion.

Graftonite-(Mn), ideallyM1MnM2,M3Fe2(PO4)2, and graftonite-(Ca), ideallyM1CaM2,M3Fe2(PO4)2, two new minerals of the graftonite group from Poland

AbstractTwo new minerals of the graftonite group, graftonite-(Mn), ideallyM(1)MnM(2),M(3)Fe2(PO4)2, and graftonite-(Ca), ideallyM(1)CaM(2),M(3)Fe2(PO4)2, were discovered in phosphate nodules of two beryl–columbite–phosphate pegmatites at Lutomia and Michałkowa, respectively, in the Góry Sowie Block, Lower Silesia, southwest Poland. Graftonite-(Mn) is pinkish brown, whereas graftonite-(Ca) shows more brownish colouration. Both minerals have a vitreous lustre, a good cleavage observed along (010) and irregular fracture; both are transparent and neither of them is fluorescent. They are brittle and have a Mohs hardness of ~5. The minerals are non-pleochroic, colourless in all orientations, biaxial (+), with mean refractive indices α = 1.710(2) and 1.690(2), β = 1.713(2) and 1.692(2), and γ = 1.725(2) and 1.710(5), respectively. With complete order of Ca at theM(1) site, the formulae of the holotype crystals areM(1)(Mn0.70Ca0.30)M(2),M(3)(Fe1.34Mn0.60Mg0.06Zn0.01)Σ3(PO4)2for graftonite-(Mn) andM(1)(Ca0.98Mn0.02)M(2),M(3)(Fe1.38Mn0.56Mg0.05)Σ3(PO4)2for graftonite-(Ca). Both crystal chemistry and crystal-structure refinement (R1= 2.34 and 1.63%, respectively) indicate that theM(1) site is occupied dominantly by Mn in graftonite-(Mn) and by Ca in graftonite-(Ca), and theM(2) andM(3) sites are occupied by Fe2+and Mn2+, with Fe2+dominant over Mn2+at the aggregateM(2) +M(3) sites. Graftonite-(Mn) and graftonite-(Ca) are isostructural with graftonite,M(1)FeM(2),M(3)Fe2(PO4)2(monoclinic system; space-group symmetryP21/c), with the unit-cell parametersa= 8.811(2) Å,b= 11.494(2) Å,c= 6.138(1) Å, β = 99.23(3)° and V = 613.5(4) Å3, anda= 8.792(2) Å,b= 11.743(2) Å,c= 6.169(1) Å, β = 99.35(3)° andV= 628.5(1) Å3, respectively. The densities calculated on the basis of molar weights and unit-cell volumes are 3.793 g/cm3for graftonite-(Mn) and 3.592 g/cm3for graftonite-(Ca). The eight strongest lines in powder X-ray diffraction patterns on the basis of single-crystal data are, respectively [d, Å,I(hkl)]: 2.874, 100, (230 + 040); 2.858, 79, (221); 3.506, 73, (130); 2.717, 79, ($\bar{3}$11); 2.952, 55, (131); 2.916, 53, ($\bar{1}$12); 2.899, 44, (300); 3.016, 35, ($\bar{1}$02); and 3.654, 100, (130); 2.979, 85, (221); 3.014, 77, (230); 3.042, 76, (040 +$\bar{1}$12); 2.834, 68, ($\bar{3}$11); 3.097, 57, (131); 3.133, 56, ($\bar{1}$02); 2.542, 30, (311). Both minerals are common primary phosphates in phosphate nodules, occurring as lamellar intergrowths with sarcopside ± triphylite/lithiophilite, products of exsolution from a (Li,Ca)-rich graftonite-like parent phase crystallized at high temperature from P-bearing hydrosaline melts.

Short-Range Stacking Disorder in Mixed-Layer Compounds: A HAADF STEM Study of Bastnäsite-Parisite Intergrowths

Atomic-scale high angle annular dark field scanning transmission electron microscopy (HAADF STEM) imaging and electron diffractions are used to address the complexity of lattice-scale intergrowths of REE-fluorocarbonates from an occurrence adjacent to the Olympic Dam deposit, South Australia. The aims are to define the species present within the intergrowths and also assess the value of the HAADF STEM technique in resolving stacking sequences within mixed-layer compounds. Results provide insights into the definition of species and crystal-structural modularity. Lattice-scale intergrowths account for the compositional range between bastnäsite and parasite, as measured by electron probe microanalysis (at the µm-scale throughout the entire area of the intergrowths). These comprise rhythmic intervals of parisite and bastnäsite, or stacking sequences with gradational changes in the slab stacking between B, BBS and BS types (B—bastnäsite, S—synchysite). An additional occurrence of an unnamed B2S phase [CaCe3(CO3)4F3], up to 11 unit cells in width, is identified among sequences of parisite and bastnäsite within the studied lamellar intergrowths. Both B2S and associated parisite show hexagonal lattices, interpreted as 2H polytypes with c = 28 and 38 Å, respectively. 2H parisite is a new, short hexagonal polytype that can be added to the 14 previously reported polytypes (both hexagonal and rhombohedral) for this mineral. The correlation between satellite reflections and the number of layers along the stacking direction (c*) can be written empirically as: Nsat = [(m × 2) + (n × 4)] − 1 for all BmSn compounds with S ≠ 0. The present study shows intergrowths characterised by short-range stacking disorder and coherent changes in stacking along perpendicular directions. Knowing that the same compositional range can be expressed as long-period stacking compounds in the group, the present intergrowths are interpreted as being related to disequilibrium crystallisation followed by replacement. HAADF STEM imaging is found to be efficient for depiction of stacking sequences and their changes in mixed-layer compounds, particularly those in which heavy atoms, such as rare-earth elements, are essential components.

Majorite-indicative ultradeep (>300 km) xenoliths with spinel associations from the Jagersfontein kimberlite, South Africa.

Our earlier studies continued in a diligent search for rare ultradeep xenoliths in the kimberlite diatreme at Jagersfontein. The search has met with moderate success insofar as 20 majorite-bearing (decomposed to *gt + lamellar px) xenoliths are identified. Discrete gts (1 to 2 cm), gt-rich layers (2 to 3 cm) in lherzolites, and rare megacrystic gts (>3 cm) from xenoliths characterize the ultradeep suite. Pyroxene lamellae are crystallographically controlled along {111} gt planes, but px may also be prismatic, lensoidal, coarsely graphic, or annular to gt; jigsaw, rather than 120° dihedral textures, are typical. Gt ranges from Pyr 68-74 mole% and CaO - Cr 2 O 3 relations, with two exceptions, are distinctly lherzolitic. Cpx 37-46 = Wo mole%, Jd 3-19 mole%, with 0.4 to 2.4 wt% Cr 2 O 3 ; opx = 92 to 95 mole% en, and ol averages 92.5 mole% with maximum wt% 0.1 CaO, 0.4 NiO, and 0.1 Cr 2 O 3 . A new class of 10 ultradeep xenoliths has lamellar spinel (Cr/Cr + Al = 0.74; Mg/Mg + Fe = 0.58) in addition to cpx with gt >3wt% Cr 2 O 3 (c.f. 0.5 to 1.5 for sp-free types). Five samples are texturally linked but are compositional outliers to the central body of data: two are sp hosts (Cr# 0.69, Mg# 0.76) and (Cr# 0.74, Mg# 0.57) to gt (Pyr 72 ) + cpx (Jd 14 ); one is a gt megacryst (Pyr 80 ) with sp (Cr# 57, Mg# 69); and the remaining two are unusually rich in chromium with gt = 7.3 to 8.2 wt% Cr 2 O 3 , rimmed by cpx (2.3 to 3.3 wt% Cr 2 O 3 ). In addition, there are 17 xenoliths with compositional affinities to the ultradeep suite but lacking the texturally diagnostic lamellar intergrowths of cpx in gt are possibly completely equilibrated to gt + irregular cpx. Results from the new collection substantiate our earlier conclusions that the mantle was sampled by the Jagersfontein kimberlite from the lower lithosphere (250 to 350 km) and the transition zone (435 km) with diagnostic high P-T majorite in lherzolite that decomposed to gt + px at one or more interruptive stations (e.g. lithosphere-asthenosphere boundary), and at one or another time, en route to the surface. Homogeneous majorite occurs as diamond inclusions at Jagersfontein but these are eclogitic, leading to the proposition that the source region in the asthenosphere was an unassimilated mixture of lherzolite and eclogite in the Mid-Cretaceous at the time of kimberlite sampling. Important questions arise: Is majorite primordial; did majorite form exclusively from the transition of pyroxene; or did subsequent dissolution into coexisting garnet take place? Why has majorite not been identified in eclogite, nor diamonds of lherzolitic affinity? Does the formation of majorite and the crystallization of encapsulating diamond imply distinct high P-T events?

Microstructures, mineral chemistry, noble gases and nitrogen in the recent fall, Bhuka iron (IAB) meteorite

We report some chemical, petrological and isotopic studies of the Bhuka iron meteorite that fell in Rajasthan, India in 2005. Numerous silicate and graphite inclusions are visible on the surface of the hand specimen. In the polished and etched surface studied, irregular patches of graphite are found as the most dominant inclusion and commonly associated with pure corundum (95wt% Al2O3), spinel, feldspar and Si-rich phases. Apart from typical lamellar intergrowth with kamacite (i.e. the Widmänstatten pattern), taenites are also commonly found to occur as a rim of the graphite inclusions. P-rich (up to 10wt%) taenites are also found locally within the recrystallised kamacite matrix. Based on mineralogy, texture and bulk composition, Bhuka resembles the low-Ni IAB subgroup (ungrouped). Noble gas isotope studies suggest He, Ne and Ar are mostly of cosmogenic origin, while Kr and Xe are a mixture of cosmogenic, radiogenic and trapped components. A pre-atmospheric radius of 10±1cm and a cosmic ray exposure age of 346±52Ma are derived based on depth dependant (3He/4He)c and 38Arc respectively, as per the production systematics of cosmogenic noble gas isotopes (Ammon et al., 2009). Cosmogenic 83Kr and 126Xe yield production rates of 12 and 0.335 ( in 10−15ccSTP/g Ma) for 83Kr and 126Xe respectively. Presence of trapped Kr and Xe, with (84Kr/132Xe)t=2 and radiogenic 129Xe=120×10−12 ccSTP/g are due to presence of graphite/silicate inclusions in the analysed sample. Over ~150% excess 131Xec than expected from spallation suggests contribution from (n,ɤ) reactions from Ba from inclusions and suggests irradiation of pre-atmospheric object in a larger body, indicative of complex irradiation. Trapped N of 24ppm, with δ15N=−10.7±0.8‰ observed in Bhuka, is heavier than the range observed hither to in IAB irons.

Flamite, (Ca,Na,K)2(Si,P)O4, a new mineral from ultrahightemperature combustion metamorphic rocks, Hatrurim Basin, Negev Desert, Israel

AbstractFlamite (Ca,Na,K)2(Si,P)O4 (P63; a = 43.3726(18), c = 6.8270(4) Å; V = 11122.2(9) Å3), a natural analogue of the P,Na,K-doped high-temperature α-Ca2SiO4 modification, is a new mineral from Ca- and Al-rich paralava, an ultrahigh-temperature combustion metamorphic melt rock. The type locality is situated in the southern Hatrurim Basin, the Negev Desert, Israel. Flamite occurs as regular lamellar intergrowths with partially hydrated larnite, together with rock-forming gehlenite, rankinite and Ti-rich andradite, minor ferrian perovskite, magnesioferrite, hematite, and retrograde ettringite and calcium silicate hydrates. The mineral is greyish to yellowish, transparent with a vitreous lustre, non-fluorescent under ultraviolet light and shows no parting or cleavage; Mohs hardness is 5–5½; calculated density is 3.264 g cm–3. The empirical formula of holotype flamite (mean of 21 analyses) is (Ca1.82Na0.09K0.06(Mg,Fe,Sr,Ba)0.02)Σ1.99(Si0.82P0.18)Σ1.00O4. The strongest lines in the powder X-ray diffraction pattern are [d, Å (Iobs)]: 2.713(100), 2.765(44), 2.759(42), 1.762(32), 2.518(29), 2.402(23), 2.897(19), 1.967(18), 2.220(15), 1.813(15). The strongest bands in the Raman spectrum are 170, 260, 520, 538, 850, 863, 885, 952 and 1003 cm–1.

Nanoscale records of ancient shock deformation: Reidite (ZrSiO4) in sandstone at the Ordovician Rock Elm impact crater

Research Article| April 01, 2015 Nanoscale records of ancient shock deformation: Reidite (ZrSiO4) in sandstone at the Ordovician Rock Elm impact crater Aaron J. Cavosie; Aaron J. Cavosie 1Department of Applied Geology, Curtin University, Perth, WA 6102, Australia2Department of Geoscience, University of Wisconsin–Madison, Madison, Wisconsin 53706, USA3Department of Geology, University of Puerto Rico–Mayagüez, Mayagüez, Puerto Rico 00681, USA Search for other works by this author on: GSW Google Scholar Timmons M. Erickson; Timmons M. Erickson 1Department of Applied Geology, Curtin University, Perth, WA 6102, Australia Search for other works by this author on: GSW Google Scholar Nicholas E. Timms Nicholas E. Timms 1Department of Applied Geology, Curtin University, Perth, WA 6102, Australia Search for other works by this author on: GSW Google Scholar Author and Article Information Aaron J. Cavosie 1Department of Applied Geology, Curtin University, Perth, WA 6102, Australia2Department of Geoscience, University of Wisconsin–Madison, Madison, Wisconsin 53706, USA3Department of Geology, University of Puerto Rico–Mayagüez, Mayagüez, Puerto Rico 00681, USA Timmons M. Erickson 1Department of Applied Geology, Curtin University, Perth, WA 6102, Australia Nicholas E. Timms 1Department of Applied Geology, Curtin University, Perth, WA 6102, Australia Publisher: Geological Society of America Received: 28 Nov 2014 Revision Received: 22 Jan 2015 Accepted: 27 Jan 2015 First Online: 09 Mar 2017 Online ISSN: 1943-2682 Print ISSN: 0091-7613 © 2015 Geological Society of America Geology (2015) 43 (4): 315–318. https://doi.org/10.1130/G36489.1 Article history Received: 28 Nov 2014 Revision Received: 22 Jan 2015 Accepted: 27 Jan 2015 First Online: 09 Mar 2017 Cite View This Citation Add to Citation Manager Share Icon Share Facebook Twitter LinkedIn MailTo Tools Icon Tools Get Permissions Search Site Citation Aaron J. Cavosie, Timmons M. Erickson, Nicholas E. Timms; Nanoscale records of ancient shock deformation: Reidite (ZrSiO4) in sandstone at the Ordovician Rock Elm impact crater. Geology 2015;; 43 (4): 315–318. doi: https://doi.org/10.1130/G36489.1 Download citation file: Ris (Zotero) Refmanager EasyBib Bookends Mendeley Papers EndNote RefWorks BibTex toolbar search Search Dropdown Menu toolbar search search input Search input auto suggest filter your search All ContentBy SocietyGeology Search Advanced Search Abstract The terrestrial record of meteorite impacts is difficult to decipher because unequivocal evidence of impact is increasingly destroyed with time by erosion, burial, and tectonics. Zircon survives these processes as a shocked mineral, and above 20 GPa transforms to reidite, a high-pressure ZrSiO4 polymorph diagnostic of impact. However, the utility of reidite has been limited by its occurrence; it has only been reported from three relatively young (<36 Ma) impact craters globally. Here we report a new occurrence of reidite in brecciated sandstone from the Ordovician Rock Elm impact crater in Wisconsin, United States. Electron backscatter diffraction mapping was used to identify reidite and microtwins within shocked zircons smaller than 50 µm in diameter. Reidite occurs both as 200–500-nm-wide lamellar intergrowths and as nanoparticulate grains, and not only provides the first diagnostic evidence for ultrahigh-pressure shock metamorphism at Rock Elm, but is also the oldest reported occurrence of reidite. Considering its small size, and the ubiquitous presence of detrital zircon in siliciclastic rocks, reidite may be more common in the rock record than has been reported but has potentially gone undetected. The recognition that nanoscale reidite can be preserved over deep time within zircon in shock-metamorphosed sandstone presents new opportunities for investigating Earth’s impact record, as it could potentially preserve nanoscopic evidence of impact events much older than the one that formed Rock Elm. Given that shocked zircons have been shown to survive sedimentary cycling, the identification of reidite within zircons in siliciclastic rocks could facilitate investigating the impact chronology over much of the geological time scale, as the oldest terrestrial minerals known are detrital zircons. You do not have access to this content, please speak to your institutional administrator if you feel you should have access.

High-temperature induced dehydration, phase transition and exsolution in amicite: A single-crystal X-ray study

Temperature dependent single-crystal X-ray data were collected on amicite K4Na4(Al8Si8O32)·11H2O from Kola Peninsula (Russia) in steps of 25°C from room temperature to 175°C and of 50°C up to 425°C. At room temperature amicite has space group I2 with a=10.2112(1), b=10.4154(1), c=9.8802(1)Å, β=88.458(1)°, V=1050.416(18) Å3. Its crystal structure is based on a Si–Al ordered tetrahedral framework of the GIS type with two systems of eight-membered channels running along the a and c axes. Extraframework K and Na cations are ordered at two fully occupied sites.Above 75°C amicite was found to partly dehydrate into two separate but coherently intergrown phases, both of space group I2/a, one K-rich ∼K8(Al8Si8O32) ·4H2O (at 75°C: a=10.038(2), b=9.6805(19), c=9.843(2) Å, β=89.93(3)°, V=956.5(3)Å3) and the other Na-rich ∼Na8(Al8Si8O32)·2H2O (at 75°C: a=9.759(2), b=8.9078(18), c=9.5270(19) Å, β=89.98(3)°, V=828.2(3)Å3).Upon further heating above 75°C the Na- and K-phases lost remaining H2O with only minor influence on the framework structure and became anhydrous at 175°C and 375°C, respectively. The two anhydrous phases persisted up to 425°C.Backscattered electron images of a heated crystal displayed lamellar intergrowth of the K- and Na-rich phases. Exposed to ambient humid conditions K- and Na-rich phases rehydrated and conjoined to the original one phase I2 structure.

TEM studies of the ThMn12–type and Th2Zn17–type phases in the Nd-Fe-Ti system

Rare-earth intermetallic compounds with high Fe concentrations and adopting the ThMn12–type and Th2Zn17-type structures have attracted considerable attention in the field of permanent magnets. A large number of experimental studies has been done on these compounds, which are usually measured on alloys structurally characterized only by powder X-ray diffraction (XRD). However, the materials are often multiphasic and their quenched or annealed microstructures evidence homogenization ranges, second phases (resulting from segregation) and on-going phase transformations that may not be easily detectable by XRD. Additional microstructural studies on these systems are therefore required.Among the Fe-based systems, the ThMn12–type and Th2Zn17–type structures usually require stabilization by a third element, such as Ti. In the present work Nd:11Fe:Ti has been prepared by melting Nd, Fe and Ti in an arc furnace followed by subsequent splat-quenching and/or annealing treatments. The resulting materials have been characterized by XRD, scanning and transmission electron microscopy coupled with energy dispersive spectroscopy.The results have shown that the presence of α-Fe(Ti) could not be avoided during the solidification of the Nd:11Fe:Ti alloy. Furthermore, the microstructure morphologies and elemental analyses showed that at moderate cooling rates a secondary crystallization phase of Th2Zn17–type appeared in the Nd:11Fe:Ti alloy as result of a peritectic reaction. This lower temperature phase was however not detected in the splat-quenched material, where the high cooling rate route suppressed its crystallization. Nevertheless during a subsequent heat-treatment at 800 ºC the following decomposition took place: NdFe11Ti → Nd2(Fe,Ti)17 + α-Fe(Ti) + Fe2Ti. This reaction had already been proposed by Jang and Stadelmaier, who suggested that the NdFe11Ti compound is unstable at temperatures below 1000 °C. The current study shows that this transformation results in the fine lamellar intergrowth of the Th2Zn17-type phase in ThMn12-type grains, displaying random distribution of planar defects (Figure 1). The reciprocal space of the combined parent and intergrown phases has been mapped through a series of 3-D microdiffraction experiments (Figure 2). This allowed to establish that the preferred orientation relation between the two phases is (020)1:12//(003)2:17 and [100]1:12//[110]2:17, with the invariant plane sitting at 1:12//(333)2:17 planes.The work was supported by the Portuguese Science Foundation through the CTM/48617/2002, PEst-OE/CTM-UI0084/2011 and CFMC-PEst-OE/FIS/UI0261/2011 grants.

Metallic phases and siderophile elements in main group ureilites: Implications for ureilite petrogenesis

Metallic phases and siderophile elements are critical to understanding the petrogenesis of the enigmatic ureilite meteorites. We obtained petrographic, major and minor element, and the first in situ trace element data for metallic phases (metal, sulfides, phosphide, carbide) in 24 main group ureilites of various petrographic types with Fo ∼75–95. The most abundant type of metal (∼1–3vol.%) occurs as ∼10–40μm-wide strips along silicate grain boundaries. Ni contents of this metal range from ∼0 to 7.3wt.% and are correlated with Co among all samples (Ni/Co=0.64×CI). A less abundant type of metal occurs as ∼5–150μm diameter metallic spherules, consisting of cohenite (Fe3C), metal, phosphide and sulfide, enclosed in silicates (preferentially low-Ca pyroxene). Most samples contain 2 types of sulfide: (1) low-Cr (<0.1wt.%) troilite, and (2) lamellar intergrowths of daubreelite (FeCr2S4) and troilite.Abundances of 17 (mostly siderophile) elements were measured by LA-ICP-MS in grain boundary metal, spherules, graphite, sulfides and silicates. Average compositions of grain boundary metal in 10 samples show decreasing CI-normalized abundance with increasing volatility, interrupted by depletions in W, Mo, Ni and Zn, and enrichments in Au, As, Ga and Ge. CI-normalized Os abundances range from ∼2 to 65, and are correlated with increasing Os/Pt, Os/Ni and Os/Pd ratios. CI-normalized Pt/Os ratios range from ∼0.3 to 1. Bulk cohenite-bearing spherules have siderophile element abundances indistinguishable from those of grain boundary metal in the same sample. CI-normalized patterns of most siderophile elements in the metal are, within error, identical to those of the bulk rock (at 25–40× higher abundances) in each sample. There are no correlations between siderophile element abundances and Fo.We infer that at T⩾1200°C ureilites contained immiscible Fe–C (3–4wt.% C) and Fe–S melts, small samples of which were trapped as the spherules within silicates. The Fe–S melt was largely extracted from the rocks, and the bulk of the residual Fe–C melt is now represented by the grain boundary metal. Assuming that ureilite precursor materials had CI or CV abundances of siderophile elements, the large fractionations of HSE observed in metal in 7 of the 10 samples require extremely high degrees (>98%) of batch Fe–S melt extraction, which implies very high xFeS (=wt. FeS/[Fe+FeS]) in the precursors. Furthermore, at such high degrees of fractionation, the HSE are so strongly concentrated into the residual metal that to match their relatively low absolute abundances in the ureilite metal, very high initial metal contents are required. Together, these constraints would imply that ureilite precursors had abundances of Fe metal and FeS (∼20–35wt.% each) far exceeding those of known CC or OC. These requirements could be relaxed, permitting lower (more plausible) degrees of melting and lower initial metal and sulfide abundances, if ureilite precursors were volatile-depleted to a greater extent than bulk CV. We suggest that ureilite precursors contained, to various degrees, an overabundance (relative to chondrites) of refractory-enriched material such as CAIs. Excess CAIs could also account for observed depletions of W and Mo (otherwise difficult to explain) in the ureilite metal, and lead to the observed range of siderophile element patterns and abundances among samples. Such a model can potentially explain the lack of correlation between siderophile element abundances and FeO (or olivine Fo), and reconcile the metal and siderophile element data with a redox model for ureilite petrogenesis.

Oriented feldspar-feldspathoid intergrowths in rocks of the Khibiny massif: genetic implications

Poikilitic megacrysts of alkali feldspar with abundant inclusions of feldspar-nepheline and feldspar-kalsilite micrographic or lamellar intergrowths are characteristic for the rischorrites of the Khibiny massif. Strict crystallographic orientation relations were identified among the intergrowth phases based on optical investigation using a 4-axes universal stage and crystal orientation imaging using electron back scatter diffraction. The most frequently observed orientation relation is the parallel orientation of the kalsilite and nepheline [001] directions with the [010] direction of the alkali feldspar host and concomitant coincidence of the feldspathoid [100] directions with the [100]-, [101]- and [001] directions of the alkali feldspar. The presence of relic nepheline within intergrowth domains and the successive replacement of precursor nepheline by alkali feldspar and associated formation of feldspar-feldspathoid intergrowth suggest development of the rischorrites from feldspar urtites, in which nepheline is the dominant felsic phase. The metasomatic nature of the transformation of urtites to rischorrites is identified from massive introduction of potassium and silica and removal of sodium. Metasomatism occurred at high temperature; the gigantic apatite deposits of the Khibiny massif seem to be related to this metasomatic event.