Stratiform to stratabound replacement of a mixed siliciclastic-carbonate host rock is a defining ... more Stratiform to stratabound replacement of a mixed siliciclastic-carbonate host rock is a defining characteristic of many sediment-hosted base metal deposits. Mineralized rocks in clastic-dominated (CD-type) Zn-Pb ore deposits, which represent our highest value base metal resources, are generally thin (101 m), laterally extensive (103 m), and stratiform to stratabound in fine-grained siltstone and mudstone facies. At the recently discovered Teena CD-type Zn-Pb deposit (Proterozoic Carpentaria province, Australia), the host rock was undergoing burial diagenesis when altered and mineralized by hydrothermal fluids that moved up to 2 km lateral to the fluid input conduit (growth fault) through intraformational intervals. In much of the deposit, carbonate dissolution was an important reaction permeability control, although significant amounts of mineralization also occur in carbonate-free siliciclastic beds. In this study, transmission electron microscopy (TEM) data has been generated on a...
Meteorite impact processes are ubiquitous on the surfaces of rocky and icy bodies in the Solar Sy... more Meteorite impact processes are ubiquitous on the surfaces of rocky and icy bodies in the Solar System, including the Moon. One of the most common accessory minerals, zircon, when shocked, produces specific micro-structures that may become indicative of the age and shock conditions of these impact processes. To better understand the shock mechanisms in zircon from Apollo 15 and 16 impact breccias, we applied transmission electron microscopy (TEM) and studied nano-structures in eight lunar zircons displaying four different morphologies from breccias 15455, 67915, and 67955. Our observations revealed a range of shock-related features in zircon: (1) planar and non-planar fractures, (2) “columnar” zircon rims around baddeleyite cores, (3) granular textured zircon, in most cases with sub-µm-size inclusions of monoclinic ZrO2 (baddeleyite) and cubic ZrO2 (zirconia), (4) silica-rich glass and metal inclusions of FeS and FeNi present at triple junctions in granular zircon and in baddeleyite,...
Titanium minerals enclosed in corundum separated from the Cr-11 orebody include native Ti, zamboi... more Titanium minerals enclosed in corundum separated from the Cr-11 orebody include native Ti, zamboite (FeTiSi 2), osbornite (TiN)-khamrabaevite (TiC) solid solutions, and jingsuiite (TiB 2), as well as the new minerals badengzhuite (TiP) and zhiqinite (TiSi 2) and two potentially new minerals, Ti 11 (Si,P) 10 and Ti 10 (Si,P,) 7 , where indicates a vacancy. These minerals together constitute a spheroid 20 µm across inferred to have crystallized from a droplet of Ti-SiP intermetallic melt. Energy-dispersive spectroscopy and three-dimensional electron diffraction were applied to characterize the two new minerals. Badengzhuite has a primitive hexagonal cell with a = 3.49(7) Å, c = 11.70(23) Å, V = 124(4) Å 3 , and crystallizes in space group P 6 3 /mmc (Z = 4). It is isostructural with synthetic TiP. Two EDX (energy dispersive X-ray spectroscopy) analyses of badengzhuite gave 60.56 wt %Ti and 39.44 wt % P and 62.74 wt % Ti and 37.26 wt % P from which an empirical formula of Ti 1.020 P 0.980 was calculated on the basis of two atoms (ideally TiP). Zhiqinite has a primitive orthorhombic cell with a = 8.18(16) Å, b = 4.85(10) Å, c = 8.42(17) Å, V = 334(12) Å 3 , and crystallizes in space group Fddd (Z = 8). It is isostructural with synthetic TiSi 2 (C54 type). Four EDX analyses of zhiqinite gave 39.58-44.79 wt % Ti and 55.21-60.42 wt % Si, from which an empirical formula of Ti 0.905 Si 2.095 was calculated on the basis of three atoms (ideally TiSi 2). We suggest that interaction of mantle-derived CH 4 + H 2 fluids with basaltic magmas in the shallow lithosphere (depths of ∼ 30-100 km) under conditions more reducing than 6 log units below the oxygen fugacities corresponding to the iron-wüstite buffer resulted in precipitation of corundum that entrapped intermetallic melts, some of which crystallized to ultra-reduced TiP -Si phases. Experimental work on the Ti-Si and TiP systems indicates that the minerals enclosed in corundum could have crystallized from the alloy melt at the lowest temperature accessible on the liquidus. It has been alleged that these ultra-reduced phases are anthropogenic contaminants inadvertently introduced with fused alumina abrasive during preparation of mineral separates. Nonetheless, we conclude that the differences between the ultra-reduced minerals in the separates and the ultra-reduced phases in fused alumina are more convincing evidence for these minerals having a natural origin than the similarities between them are evidence for an anthropogenic origin.
Potassium feldspars (KAlSi3O8) are ubiquitous minerals in the Earth's upper crust. This family of... more Potassium feldspars (KAlSi3O8) are ubiquitous minerals in the Earth's upper crust. This family of minerals has been the subject of numerous experimental and theoretical investigations concerning their dissolution kinetics and the mechanisms controlling chemical alteration at acid and neutral pH, and at temperatures ranging from ambient to hydrothermal conditions. On the other hand, considerably less research on the dissolution behavior of K-feldspars has been carried out at alkaline conditions, in particular at pH > 9 and elevated temperatures. Filling in this gap in knowledge is the major motivation for this study. More specifically, we wanted to document and understand how the K-feldspar interface structurally and chemically evolves during alteration in order to determine the mechanism of dissolution. In this study we examined interfaces of orthoclase samples that were altered in separate experiments in a Ca(OH)2-H2O solution (pH25°C 12.4) at 190 °C for 24 hours. We used a combination of focused ion beam (FIB) milling and advanced analytical transmission electron microscopy (TEM) techniques to investigate the structure and chemistry of the near surface region of post-reaction grains, with particular attention being given to the fluid-solid interface. Even though each grain diminishes in volume due to dissolution, high-resolution TEM imaging indicates that the feldspar structure itself remains completely intact and crystalline, as evidenced by lattice fringes that abruptly terminate at the grain edge. Nanometer-scale chemical composition measurements and mapping by TEM-EDXS (energy dispersive X-ray spectroscopy) and EFTEM (energy filtered TEM) show that the chemistry of the parent feldspar also remains unchanged at the interface. In particular, there is no evidence for the incursion of Ca from the fluid solvent into the structure, either by interdiffusion or by a replacement process. Taken together, the TEM observations point to a sharp chemical reaction front characterized by the congruent (i.e. stoichiometric) release of all elements from the feldspar structure. Nanometer-scale measurements by high resolution analytical TEM also reveal that a surface alteration layer (SAL) of amorphous material forms in situ at the expense of the feldspar structure. The interface demarcates a spatially coincident and nm-sharp chemical and structural discontinuity between the parent feldspar and the amorphous phase. The amorphous SAL has a variable thickness, from under 10 nm up to ∼200 nm. This is likely one of the first observed occurrences of a significant surface amorphous layer on feldspar due to alteration in an alkaline solvent. The lack of a gap between the two phases points to an interfacial dissolution-reprecipitation process that continuously operates during hydrothermal alteration, and mostly likely right from the onset of contact with the fluid. After the initial formation of the amorphous layer, a 1-2 µm-thick porous amalgam of secondary crystalline phases comprised of calcite, tobermorite, and hydrogrossular, as well as other minor phases, precipitated over 3 the SAL. These authigenic crystalline minerals formed during the experiment (hydrothermal alteration, followed by fluid loss due to evaporation) by a classical thermodynamically-controlled precipitation process as the reactor bulk fluid became increasingly concentrated. We propose that a coupled interfacial dissolution-reprecipitation (CIDR) mechanism best explains the chemical and structural properties of the interface and the formation of an amorphous surface layer. In fact, many recent studies postulate that a CIDR process controls feldspar dissolution and the formation of SALs at acid and circumneutral pH over a wide range of temperatures. Combining these previous results with our new observations supports the idea that a unique and unifying mechanism likely controls chemical alteration of feldspars in all aqueous fluids.
The discovery of ultrahigh pressure (UHP) minerals in orogenic belts has revolutionized our under... more The discovery of ultrahigh pressure (UHP) minerals in orogenic belts has revolutionized our understanding of subduction and the return flow of previously deeply subducted material to Earth's surface as part of the cycling and interaction of crustal and mantle systems. One class of UHP minerals is found as inclusions in orogenic peridotite-hosted podiform-chromite systems, within Phanerozoic ophiolites and ophiolitic mélanges. Such inclusions have opened a window into processes of recycling of crustal materials to the deep mantle and back through subduction and mantle convection in Phanerozoic orogens. Here, we document the first occurrence of an UHP mineral hosted in an ophiolitic podiform chromitite mélange from the Neoarchean paired metamorphic belt of the Central (Taihang) Orogenic Belt, Northern China. Numerous inclusions of rutile, apatite, dolomite, and amphibole are interpreted to be crustal-derived; they occur in podiform chromite grains hosted in a 2.6-2.5 Ga ophiolitic mélange now part of the North China Craton and formed by subduction of oceanic and continental material. Microstructures and phase relationships in a multi-phase inclusion of TiO2(II), rutile, apatite, and tremolite yield minimum P-T conditions of 7.5 GPa at 1000°C, indicating that the crustal host, including carbonates, were subducted to depths > 270 km, transferred to the mantle of the overriding plate, and returned to the surface by 2.5 Ga. We suggest that slab rollback forced upward mantle flow, incorporating entities from the lower plate, perhaps in serpentinite diapirs, resulting in adiabatic melting that allowed crustal material to be trapped in chromite grains crystallizing in high-Mg melts. Contrasting bulk moduli and thermal contraction of the inclusions and host chromite protected the inclusions from P-induced back-reaction during exhumation. Together, these features show that the 1600 km long Central (Taihang) Orogenic Belt is emerging as the world's first welldocumented Phanerozoic style orogen, with classic tectonic zonation, ophiolitic mélanges, paired metamorphism, local evidence for UHP conditions, foreland basins, and late to post orogenic magmatism. Applying the null hypothesis, we explain this high degree of similarity by invoking the operation of Phanerozoic style plate tectonics, at least throughout the 1600 km length of the COB, and by geological comparison, in other similar aged geological terrains globally. From this we infer modern-style plate tectonics was operating in the Neoarchean.
Recent studies have identified gold nanoparticles in ores in a range of deposit types, but little... more Recent studies have identified gold nanoparticles in ores in a range of deposit types, but little is known about their formation processes. In this contribution, gold-bearing magnetite from the well-documented, world-class Beiya Au deposit, China, was investigated in terms of microstructure and crystallography at the nanoscale. We present the first three-dimensional (3D) focused ion beam/scanning electron microscopy (FIB/SEM) tomography of the distribution of gold nanoparticles in nanopores in the low-Si magnetite. The porous low-Si magnetite, which overprints an earlier generation of silician magnetite, was formed by a coupled dissolution-reprecipitation reaction (CDRR). The extrinsic changes in thermodynamic conditions (e.g., S content and temperature) of the hydrothermal fluids resulted in the CDRR in magnetite and the disequilibrium of Au-Bi melts. The gold nanoparticles crystallized from Au-supersaturated fluids originating from the disequilibrium of Au-Bi melts and grew in two...
The Volyn pegmatites from Volodarsk-Volynskyi in the Zhytomyr Oblast, NW Ukraine, are associated ... more The Volyn pegmatites from Volodarsk-Volynskyi in the Zhytomyr Oblast, NW Ukraine, are associated with granites genetically related to the Paleoproterozoic Korosten pluton. Their late-stage evolution is characterized by the formation of opal-cemented breccia. A polymineralic pseudomorph after beryl within the breccia includes bertrandite (±euclase) + Fmuscovite (with tobelite component) + buddingtonite + OM (organic matter) + opal (+ traces of K-feldspar, albite, columbite, FeS 2 , barite, REE-minerals). Sector zoned and platy to fibrous buddingtonite has variable (K+Na)-vs. NH 4-contents (electron microprobe analyses) and some H 2 O or H 3 O + , as indicated by microscope infrared spectroscopy. We suggest that ammonium was produced by decay of OM, which is partly preserved in the pseudomorph. Energy-dispersive electron microprobe data of the OM show with increasing O-decreasing C-N-content due to degassing; the OM contains the high-field strength elements Zr (≤7 atom%), Y (≤3 atom%), Sc (≤0.8 atom%), REE (≤0.3 atom%), Th (≤0.2 atom%) and U (≤1.25 atom%), which increase with increasing O-content. Transmission electron microscopy of the OM confirms the presence of N; Zr, Si, and O (with other HFSE) are concentrated in nanometersized areas and at the transition from OM to opal in nanometer-sized platy Zr-Si-O crystals. Crich areas are amorphous but show poorly developed lattice fringes. OM is present in the pseudomorph is available, textural arguments and phase equilibria indicate its formation in a late stage of the pegmatite evolution, at P-T-conditions below ~100 MPa/150°C. We favor a conceptual model for the formation of the Volyn buddingtonite in analogy to Phanerozoic occurrences of buddingtonite, where over and around the shallow anorthosite-granite Korosten pluton hydrothermal convection cells introduced N-bearing hydrocarbons and its precursors into the cooling igneous rocks. Due to the elevated temperature, the OM disintegrated into degassing volatile and non-volatile residual components analogous to petroleum maturation. Organic N, released as NH 4 , was then incorporated into buddingtonite.
We report on the occurrence of a new high-pressure Ca-Al-silicate in localized shock melt pockets... more We report on the occurrence of a new high-pressure Ca-Al-silicate in localized shock melt pockets found in the feldspatic lunar meteorite Oued Awlitis 001 and discuss the implications of our discovery. The new mineral crystallized as tiny, micrometer-sized, acicular grains in shock melt pockets of roughly anorthitic bulk composition. Transmission electron microscopy based three-dimensional electron diffraction (3D ED) reveals that the CaAl4Si2O11 crystals are identical to the calcium aluminum silicate (CAS) phase first reported from static pressure experiments. The new mineral has a hexagonal structure, with a space group of P63/mmc and lattice parameters of a = 5.42(1) Å; c = 12.70(3) Å; V = 323(4) Å3; Z = 2. This is the first time 3D ED was applied to structure determination of an extraterrestrial mineral. The International Mineralogical Association (IMA) has approved this naturally formed CAS phase as the new mineral “donwilhelmsite” [CaAl4Si2O11], honoring the U.S. lunar geologi...
Apatites from Martian nakhlites NWA 10153 and NWA 10645 were used to obtain insight into their cr... more Apatites from Martian nakhlites NWA 10153 and NWA 10645 were used to obtain insight into their crystallization environment and the subsequent postcrystallization evolution path. The research results acquired using multi-tool analyses show distinctive transformation processes that were not fully completed. The crystallization history of three apatite generations (OH-bearing, Cl-rich fluorapatite as well as OH-poor, F-rich chlorapatite and fluorapatite) were reconstructed using transmission electron microscopy and geochemical analyses. Magmatic OH-bearing, Cl-rich fluorapatite changed its primary composition and evolved toward OH-poor, F-rich chlorapatite because of its interaction with fluids. Degassing of restitic magma causes fluorapatite crystallization, which shows a strong structural affinity for the last episode of system evolution. In addition to the three apatite generations, a fourth amorphous phase of calcium phosphate has been identified with Raman spectroscopy. This amorp...
We investigated lherzolitic peridotites in the Cretaceous Purang ophiolite along the Yarlung Zhan... more We investigated lherzolitic peridotites in the Cretaceous Purang ophiolite along the Yarlung Zhangbo suture zone (YZSZ) in SW Tibet to constrain their mantle-melt evolution history. Coarsegrained Purang lherzolites contain orthopyroxene (Opx) and olivine (Ol) porphyroclasts with embayments filled by small olivine (Ol) neoblasts. Both clinopyroxene (Cpx) and Opx display exsolution textures represented by lamellae structures. Opx exsolution (Opx1) in clinopyroxene (Cpx1) is made of enstatite, whose compositions (Al 2 O 3 = 3.85-4.90 wt%, CaO = <3.77 wt%, Cr 2 O 3 = 0.85-3.82 wt%) are characteristic of abyssal peridotites. Host clinopyroxenes (Cpx1) have higher Mg#s and Na 2 O, with lower TiO 2 and Al 2 O 3 contents than Cpx2 exsolution lamellae in Opx, and show variable LREE patterns. Pyroxene compositions of the lherzolites indicate 10-15% partial melting of a fertile mantle protolith. P-T estimates (1.3-2.3 GPa, 745-1067°C) and the trace element chemistry of pyroxenes with exsolution textures suggest crystallization depths of 75 km in the upper mantle, where the original pyroxenes became decomposed, forming exsolved structures. Further upwelling of lherzolites into shallow depths in the mantle resulted in crystal-plastic deformation of the exsolved pyroxenes. Combined with the occurrence of microdiamond and ultrahigh-pressure (UHP) mineral inclusions in chromites of the Purang peridotites, the pyroxene exsolution textures reported here confirm a multi-stage partial melting history of the Purang lherzolites and at least three discrete stages of P-T conditions in the course of their upwelling through the mantle during their intra-oceanic evolution.
The microinclusions in cuboid diamonds from Ebelyakh River deposits (northeastern Siberian craton... more The microinclusions in cuboid diamonds from Ebelyakh River deposits (northeastern Siberian craton) have been investigated by FIB/TEM techniques. It was found that these microinclusions have multiphase associations, containing silicates, oxides, carbonates, halides, sulfides, graphite, and fluid phases. The bulk chemical composition of the microinclusions indicates two contrasting growth media: Mg-rich carbonatitic and Al-rich silicic. Each media has their own specific set of daughter phases. Carbonatitic microinclusions are characterized by the presence of dolomite, phlogopite, apatite, Mg, Fe-oxide, KCl, rutile, magnetite, Fe-sulfides, and hydrous fluid phases. Silicic microinclusions are composed mainly of free SiO2 phase (quartz), high-Si mica (phengite), Al-silicate (paragonite), F-apatite, Ca-carbonates enriched with Sr and Ba, Fe-sulfides, and hydrous fluid phases. These associations resulted from the cooling of diamond-forming carbonatitic and silicic fluids/melts preserved i...
Geophysical investigations and laboratory experiments provide strong evidence for subduction of a... more Geophysical investigations and laboratory experiments provide strong evidence for subduction of ancient oceanic crust, and geological and mineralogical observations suggest that subducted oceanic crust is recycled into the upper mantle. This model is supported by some direct petrologic and mineralogical evidence, principally the recovery of super-deep diamonds from kimberlites and the presence of crustal materials in ophiolitic chromitites and peridotites, but many details are still unclear. Here we report the discovery of ophiolite-hosted diamonds in the podiform chromitites of the Skenderbeu massif of the Mirdita ophiolite in the western part of Neo-Tethys. The diamonds are characterized by exceedingly light C isotopes (δ 13 CPDB ~ −25‰), which we interpret as evidence for subduction of organic carbon from Earth's surface. They are also characterized by an exceptionally large range in δ 15 Nair (-12.9‰ to +25.5‰), accompanied by a low N aggregation state. Materials sparsely included in diamonds include amorphous material, Ni-Mn-Co alloy, nanocrystals (20 x 20 nm) of calcium silicate with an orthorhombic perovskite structure (Ca-Pv), and fluids. The fluids coexisting with the alloy and Ca-Pv provide clear evidence that the diamonds are natural rather than synthetic. We suggest that the Skenderbeu diamonds nucleated and grew from a C-saturated, NiMnCo-rich melt derived from a subducted slab of ocean crust and lithosphere in the deep mantle, at least in the diamond stability field, perhaps near the top of the mantle transition zone. The subsequent rapid upward transport in channelled networks related to slab rollback during subduction initiation may explain the formation and preservation of Skenderbeu diamonds. The discovery of diamonds from the Mirdita ophiolite not only provides new evidence of diamonds in these settings, but also provides a valuable opportunity to understand deep cycling of subducted oceanic crust and mantle composition. This is a preprint, the final version is subject to change, of the American Mineralogist (MSA) Cite as Authors (Year) Title. American Mineralogist, in press.
Organic synthesis on Mars occurs by the electrochemical reduction of CO 2 , a reaction that is hi... more Organic synthesis on Mars occurs by the electrochemical reduction of CO 2 , a reaction that is highly relevant for abiotic organic synthesis on early Earth.
Alkali feldspar crystals have been recognized in the troilite-graphite nodules of the Morasko IAB... more Alkali feldspar crystals have been recognized in the troilite-graphite nodules of the Morasko IAB iron meteorite. Their chemical, microtextural and structural properties were studied using electron microprobe analysis (EMPA), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), transmission electron microscopy (TEM) and Raman spectroscopy. The feldspars occur as perthitic or antiperthitic intergrowths, whereas the albite lamellae are perfectly twinned. The structural properties reveal intergrown phases with fairly disordered patterns. The electron microprobe analyses demonstrate that the intergrown phases are mainly rich in sodium or potassium, resulting in compositions that are close to those of albite or orthoclase. The compositions, calculated on the basis of a segmented perthite-antiperthite image, showed that the Or-to-Ab proportions in the homogenized crystals were almost 0.3:0.7, thus indicating that the anorthoclase crystallized under high-temperature conditions. Two hypotheses of crystal formation could account for these characteristics: crystallization from a melt or from a metasomatic solution. Relics with evidence of metasomatic replacement of former minerals were not found. Accordingly, this work focuses on arguments that support the other hypothesis. Large ion lithophile elements (LILEs, e.g., Ba, Sr, Rb, LREE, Pb, and Ga) were used to track the origin of the crystals. Their concentrations indicate crystallization from a parent melt strongly depleted in LILEs. Alkali feldspar is commonly a product of a highly differentiated melt. However, highly differentiated melts are typically enriched in LILEs, which here is not the case. The melt that crystallized the feldspar cannot be related to impact-induced partial melting of the chondritic material alone. The derived melt probably was contaminated by silica-rich target material during interaction between the IAB projectile and the target material and was accompanied by metal and sulphide melts that were both immiscible with a silicate melt.
A transmission electron microscope (TEM) study of Paleoproterozoic zircon that has experienced ul... more A transmission electron microscope (TEM) study of Paleoproterozoic zircon that has experienced ultra-high temperature (UHT) metamorphism at ca. 570 Ma in the Kerala Khondalite Belt (KKB), southern India, documents the occurrence of metallic Pb nanospheres. These results permit comparison with a previous report from UHT zircon in Enderby Land, Antarctica, and allow further constraints to be placed on possible mechanisms for nanosphere formation. As in Enderby Land, the nanospheres in the KKB occur in non-metamict zircon, emphasising that radiogenic Pb redistribution can occur with only partial interconnectivity of radiation damaged zircon. In contrast, the nanospheres reported here are not closely associated with Si-rich glass inclusions, which is inconsistent with a silicate liquid-metal immiscibility model proposed in the earlier study. Formation of these Pb nanospheres effectively halts Pb-loss from zircon, even under extreme conditions, and can adversely affect geochronological interpretations due to decoupling of Pb from U.
We have investigated a piece of the Netschaëvo IIE iron meteorite containing a silicate inclusion... more We have investigated a piece of the Netschaëvo IIE iron meteorite containing a silicate inclusion by means of electron microprobe analysis (EMPA) and transmission electron microscopy (TEM). Netschaëvo contains chondrule-bearing clasts and impact melt rock clasts were also recently found. The examined inclusion belongs to the latter and is characterized by a porphyritic texture dominated by clusters of coarse-grained olivine and pyroxene, set in a fine-grained groundmass that consists of new crystals of olivine and a hyaline matrix. This matrix material has a quasi-basaltic composition in the inner part of the inclusion, whereas the edge of the inclusion has a lower SiO 2 concentration and is enriched in MgO, P 2 O 5 , CaO, and FeO. Close to the metal host, the inclusion also contains euhedral Mg-chromite crystals and small (<2 lm), Si-rich globules. A TEM foil was cut from this glassy, silico-phosphate material. It shows that the material consists of elongated olivine crystallites containing up to 14 wt% P 2 O 5 , amorphous material, and interstitial Cl-apatite crystals. The Si-rich silicate glass globules show a second population of Ferich silicate glass droplets, indicating they formed by silicate liquid immiscibility. Together with the presence of phosphoran olivine and quenched Cl-apatite, these textures suggest rapid cooling and quenching as a consequence of an impact event. Moreover, the enrichment of phosphorus in the silicate inclusion close to the metal host (phosphoran olivine and Cl-apatite) indicates that phosphorus re-partitioned from the metal into the silicate phase upon cooling. This probably also took place in pallasite meteorites that contain late-crystallizing phases rich in phosphorus. Accordingly, our findings suggest that oxidation of phosphorus might be a general process in core-mantle environments, bearing on our understanding of planetesimal evolution. Thus, the Netschaëvo sample serves as a natural planetesimal core-mantle boundary experiment and based on our temperature estimates, the following sequence of events takes place: (i) precipitation of olivine (1400-1360°C), (ii) re-partitioning of phosphorus from the metal into the silicate phase, and (iii) formation of immiscible melts (1230-1115°C).
The banded iron formation of the Bababudan Group (Western Dhawar Craton, India) is composed of mi... more The banded iron formation of the Bababudan Group (Western Dhawar Craton, India) is composed of millimetric to centimetric alternating quartz and grey to red Fe-oxide bands. Major phases are quartz and martite (hematized magnetite) with minor Fe-sulfides and Ca-Mg-Fe-carbonates. Micrometric Fe-oxide spherules fill cavities in discontinuous micrometric layers of Fe-oxides that occur in the massive quartz layers and at the interface of massive Feoxide and quartz layers. The spherules are composed of micrometric radial plates of hematite intergrown with nanometric magnetite. These spherules contain carbonaceous matter (CM) with nanometric Fe-particles and have low N contents (~ 900 ppm; CM1). The spherule formation is attributed to a low temperature hydrothermal process (150-200°C) at around 2.52 Ga, possibly favored by the presence of CM. These hydrothermal fluids dissolved diagenetic interstitial sulfides or carbonates creating cavities which, provided space for the spherule precipitation. Carbonaceous matter of semi-anthracite maturity is encapsulated in quartz grains adjacent to the Fe-oxide spherules (CM2) and it is thus concluded that CM1 and CM2 are most likely contemporaneous and of the same origin, either incorporated at the time of BIF formation or during the hydrothermal event at 2.52 Ga from the underlying phyllitised black shales. Carbonaceous matter (CM3) was also found around the Fe-oxide spherules and the martite grains. CM3 has much higher N contents (> 5000 ppm) and is of a lower maturity than CM1 and CM2 and is related to weathering, also indicated by the presence of goethite and kaolinite. The 13 C of all CMs varies from-19.4 to-24.7 ‰, similar to values measured in the underlying phyllitised black shales and likely reflect denitrifying microbial activity.
Stratiform to stratabound replacement of a mixed siliciclastic-carbonate host rock is a defining ... more Stratiform to stratabound replacement of a mixed siliciclastic-carbonate host rock is a defining characteristic of many sediment-hosted base metal deposits. Mineralized rocks in clastic-dominated (CD-type) Zn-Pb ore deposits, which represent our highest value base metal resources, are generally thin (101 m), laterally extensive (103 m), and stratiform to stratabound in fine-grained siltstone and mudstone facies. At the recently discovered Teena CD-type Zn-Pb deposit (Proterozoic Carpentaria province, Australia), the host rock was undergoing burial diagenesis when altered and mineralized by hydrothermal fluids that moved up to 2 km lateral to the fluid input conduit (growth fault) through intraformational intervals. In much of the deposit, carbonate dissolution was an important reaction permeability control, although significant amounts of mineralization also occur in carbonate-free siliciclastic beds. In this study, transmission electron microscopy (TEM) data has been generated on a...
Meteorite impact processes are ubiquitous on the surfaces of rocky and icy bodies in the Solar Sy... more Meteorite impact processes are ubiquitous on the surfaces of rocky and icy bodies in the Solar System, including the Moon. One of the most common accessory minerals, zircon, when shocked, produces specific micro-structures that may become indicative of the age and shock conditions of these impact processes. To better understand the shock mechanisms in zircon from Apollo 15 and 16 impact breccias, we applied transmission electron microscopy (TEM) and studied nano-structures in eight lunar zircons displaying four different morphologies from breccias 15455, 67915, and 67955. Our observations revealed a range of shock-related features in zircon: (1) planar and non-planar fractures, (2) “columnar” zircon rims around baddeleyite cores, (3) granular textured zircon, in most cases with sub-µm-size inclusions of monoclinic ZrO2 (baddeleyite) and cubic ZrO2 (zirconia), (4) silica-rich glass and metal inclusions of FeS and FeNi present at triple junctions in granular zircon and in baddeleyite,...
Titanium minerals enclosed in corundum separated from the Cr-11 orebody include native Ti, zamboi... more Titanium minerals enclosed in corundum separated from the Cr-11 orebody include native Ti, zamboite (FeTiSi 2), osbornite (TiN)-khamrabaevite (TiC) solid solutions, and jingsuiite (TiB 2), as well as the new minerals badengzhuite (TiP) and zhiqinite (TiSi 2) and two potentially new minerals, Ti 11 (Si,P) 10 and Ti 10 (Si,P,) 7 , where indicates a vacancy. These minerals together constitute a spheroid 20 µm across inferred to have crystallized from a droplet of Ti-SiP intermetallic melt. Energy-dispersive spectroscopy and three-dimensional electron diffraction were applied to characterize the two new minerals. Badengzhuite has a primitive hexagonal cell with a = 3.49(7) Å, c = 11.70(23) Å, V = 124(4) Å 3 , and crystallizes in space group P 6 3 /mmc (Z = 4). It is isostructural with synthetic TiP. Two EDX (energy dispersive X-ray spectroscopy) analyses of badengzhuite gave 60.56 wt %Ti and 39.44 wt % P and 62.74 wt % Ti and 37.26 wt % P from which an empirical formula of Ti 1.020 P 0.980 was calculated on the basis of two atoms (ideally TiP). Zhiqinite has a primitive orthorhombic cell with a = 8.18(16) Å, b = 4.85(10) Å, c = 8.42(17) Å, V = 334(12) Å 3 , and crystallizes in space group Fddd (Z = 8). It is isostructural with synthetic TiSi 2 (C54 type). Four EDX analyses of zhiqinite gave 39.58-44.79 wt % Ti and 55.21-60.42 wt % Si, from which an empirical formula of Ti 0.905 Si 2.095 was calculated on the basis of three atoms (ideally TiSi 2). We suggest that interaction of mantle-derived CH 4 + H 2 fluids with basaltic magmas in the shallow lithosphere (depths of ∼ 30-100 km) under conditions more reducing than 6 log units below the oxygen fugacities corresponding to the iron-wüstite buffer resulted in precipitation of corundum that entrapped intermetallic melts, some of which crystallized to ultra-reduced TiP -Si phases. Experimental work on the Ti-Si and TiP systems indicates that the minerals enclosed in corundum could have crystallized from the alloy melt at the lowest temperature accessible on the liquidus. It has been alleged that these ultra-reduced phases are anthropogenic contaminants inadvertently introduced with fused alumina abrasive during preparation of mineral separates. Nonetheless, we conclude that the differences between the ultra-reduced minerals in the separates and the ultra-reduced phases in fused alumina are more convincing evidence for these minerals having a natural origin than the similarities between them are evidence for an anthropogenic origin.
Potassium feldspars (KAlSi3O8) are ubiquitous minerals in the Earth's upper crust. This family of... more Potassium feldspars (KAlSi3O8) are ubiquitous minerals in the Earth's upper crust. This family of minerals has been the subject of numerous experimental and theoretical investigations concerning their dissolution kinetics and the mechanisms controlling chemical alteration at acid and neutral pH, and at temperatures ranging from ambient to hydrothermal conditions. On the other hand, considerably less research on the dissolution behavior of K-feldspars has been carried out at alkaline conditions, in particular at pH > 9 and elevated temperatures. Filling in this gap in knowledge is the major motivation for this study. More specifically, we wanted to document and understand how the K-feldspar interface structurally and chemically evolves during alteration in order to determine the mechanism of dissolution. In this study we examined interfaces of orthoclase samples that were altered in separate experiments in a Ca(OH)2-H2O solution (pH25°C 12.4) at 190 °C for 24 hours. We used a combination of focused ion beam (FIB) milling and advanced analytical transmission electron microscopy (TEM) techniques to investigate the structure and chemistry of the near surface region of post-reaction grains, with particular attention being given to the fluid-solid interface. Even though each grain diminishes in volume due to dissolution, high-resolution TEM imaging indicates that the feldspar structure itself remains completely intact and crystalline, as evidenced by lattice fringes that abruptly terminate at the grain edge. Nanometer-scale chemical composition measurements and mapping by TEM-EDXS (energy dispersive X-ray spectroscopy) and EFTEM (energy filtered TEM) show that the chemistry of the parent feldspar also remains unchanged at the interface. In particular, there is no evidence for the incursion of Ca from the fluid solvent into the structure, either by interdiffusion or by a replacement process. Taken together, the TEM observations point to a sharp chemical reaction front characterized by the congruent (i.e. stoichiometric) release of all elements from the feldspar structure. Nanometer-scale measurements by high resolution analytical TEM also reveal that a surface alteration layer (SAL) of amorphous material forms in situ at the expense of the feldspar structure. The interface demarcates a spatially coincident and nm-sharp chemical and structural discontinuity between the parent feldspar and the amorphous phase. The amorphous SAL has a variable thickness, from under 10 nm up to ∼200 nm. This is likely one of the first observed occurrences of a significant surface amorphous layer on feldspar due to alteration in an alkaline solvent. The lack of a gap between the two phases points to an interfacial dissolution-reprecipitation process that continuously operates during hydrothermal alteration, and mostly likely right from the onset of contact with the fluid. After the initial formation of the amorphous layer, a 1-2 µm-thick porous amalgam of secondary crystalline phases comprised of calcite, tobermorite, and hydrogrossular, as well as other minor phases, precipitated over 3 the SAL. These authigenic crystalline minerals formed during the experiment (hydrothermal alteration, followed by fluid loss due to evaporation) by a classical thermodynamically-controlled precipitation process as the reactor bulk fluid became increasingly concentrated. We propose that a coupled interfacial dissolution-reprecipitation (CIDR) mechanism best explains the chemical and structural properties of the interface and the formation of an amorphous surface layer. In fact, many recent studies postulate that a CIDR process controls feldspar dissolution and the formation of SALs at acid and circumneutral pH over a wide range of temperatures. Combining these previous results with our new observations supports the idea that a unique and unifying mechanism likely controls chemical alteration of feldspars in all aqueous fluids.
The discovery of ultrahigh pressure (UHP) minerals in orogenic belts has revolutionized our under... more The discovery of ultrahigh pressure (UHP) minerals in orogenic belts has revolutionized our understanding of subduction and the return flow of previously deeply subducted material to Earth's surface as part of the cycling and interaction of crustal and mantle systems. One class of UHP minerals is found as inclusions in orogenic peridotite-hosted podiform-chromite systems, within Phanerozoic ophiolites and ophiolitic mélanges. Such inclusions have opened a window into processes of recycling of crustal materials to the deep mantle and back through subduction and mantle convection in Phanerozoic orogens. Here, we document the first occurrence of an UHP mineral hosted in an ophiolitic podiform chromitite mélange from the Neoarchean paired metamorphic belt of the Central (Taihang) Orogenic Belt, Northern China. Numerous inclusions of rutile, apatite, dolomite, and amphibole are interpreted to be crustal-derived; they occur in podiform chromite grains hosted in a 2.6-2.5 Ga ophiolitic mélange now part of the North China Craton and formed by subduction of oceanic and continental material. Microstructures and phase relationships in a multi-phase inclusion of TiO2(II), rutile, apatite, and tremolite yield minimum P-T conditions of 7.5 GPa at 1000°C, indicating that the crustal host, including carbonates, were subducted to depths > 270 km, transferred to the mantle of the overriding plate, and returned to the surface by 2.5 Ga. We suggest that slab rollback forced upward mantle flow, incorporating entities from the lower plate, perhaps in serpentinite diapirs, resulting in adiabatic melting that allowed crustal material to be trapped in chromite grains crystallizing in high-Mg melts. Contrasting bulk moduli and thermal contraction of the inclusions and host chromite protected the inclusions from P-induced back-reaction during exhumation. Together, these features show that the 1600 km long Central (Taihang) Orogenic Belt is emerging as the world's first welldocumented Phanerozoic style orogen, with classic tectonic zonation, ophiolitic mélanges, paired metamorphism, local evidence for UHP conditions, foreland basins, and late to post orogenic magmatism. Applying the null hypothesis, we explain this high degree of similarity by invoking the operation of Phanerozoic style plate tectonics, at least throughout the 1600 km length of the COB, and by geological comparison, in other similar aged geological terrains globally. From this we infer modern-style plate tectonics was operating in the Neoarchean.
Recent studies have identified gold nanoparticles in ores in a range of deposit types, but little... more Recent studies have identified gold nanoparticles in ores in a range of deposit types, but little is known about their formation processes. In this contribution, gold-bearing magnetite from the well-documented, world-class Beiya Au deposit, China, was investigated in terms of microstructure and crystallography at the nanoscale. We present the first three-dimensional (3D) focused ion beam/scanning electron microscopy (FIB/SEM) tomography of the distribution of gold nanoparticles in nanopores in the low-Si magnetite. The porous low-Si magnetite, which overprints an earlier generation of silician magnetite, was formed by a coupled dissolution-reprecipitation reaction (CDRR). The extrinsic changes in thermodynamic conditions (e.g., S content and temperature) of the hydrothermal fluids resulted in the CDRR in magnetite and the disequilibrium of Au-Bi melts. The gold nanoparticles crystallized from Au-supersaturated fluids originating from the disequilibrium of Au-Bi melts and grew in two...
The Volyn pegmatites from Volodarsk-Volynskyi in the Zhytomyr Oblast, NW Ukraine, are associated ... more The Volyn pegmatites from Volodarsk-Volynskyi in the Zhytomyr Oblast, NW Ukraine, are associated with granites genetically related to the Paleoproterozoic Korosten pluton. Their late-stage evolution is characterized by the formation of opal-cemented breccia. A polymineralic pseudomorph after beryl within the breccia includes bertrandite (±euclase) + Fmuscovite (with tobelite component) + buddingtonite + OM (organic matter) + opal (+ traces of K-feldspar, albite, columbite, FeS 2 , barite, REE-minerals). Sector zoned and platy to fibrous buddingtonite has variable (K+Na)-vs. NH 4-contents (electron microprobe analyses) and some H 2 O or H 3 O + , as indicated by microscope infrared spectroscopy. We suggest that ammonium was produced by decay of OM, which is partly preserved in the pseudomorph. Energy-dispersive electron microprobe data of the OM show with increasing O-decreasing C-N-content due to degassing; the OM contains the high-field strength elements Zr (≤7 atom%), Y (≤3 atom%), Sc (≤0.8 atom%), REE (≤0.3 atom%), Th (≤0.2 atom%) and U (≤1.25 atom%), which increase with increasing O-content. Transmission electron microscopy of the OM confirms the presence of N; Zr, Si, and O (with other HFSE) are concentrated in nanometersized areas and at the transition from OM to opal in nanometer-sized platy Zr-Si-O crystals. Crich areas are amorphous but show poorly developed lattice fringes. OM is present in the pseudomorph is available, textural arguments and phase equilibria indicate its formation in a late stage of the pegmatite evolution, at P-T-conditions below ~100 MPa/150°C. We favor a conceptual model for the formation of the Volyn buddingtonite in analogy to Phanerozoic occurrences of buddingtonite, where over and around the shallow anorthosite-granite Korosten pluton hydrothermal convection cells introduced N-bearing hydrocarbons and its precursors into the cooling igneous rocks. Due to the elevated temperature, the OM disintegrated into degassing volatile and non-volatile residual components analogous to petroleum maturation. Organic N, released as NH 4 , was then incorporated into buddingtonite.
We report on the occurrence of a new high-pressure Ca-Al-silicate in localized shock melt pockets... more We report on the occurrence of a new high-pressure Ca-Al-silicate in localized shock melt pockets found in the feldspatic lunar meteorite Oued Awlitis 001 and discuss the implications of our discovery. The new mineral crystallized as tiny, micrometer-sized, acicular grains in shock melt pockets of roughly anorthitic bulk composition. Transmission electron microscopy based three-dimensional electron diffraction (3D ED) reveals that the CaAl4Si2O11 crystals are identical to the calcium aluminum silicate (CAS) phase first reported from static pressure experiments. The new mineral has a hexagonal structure, with a space group of P63/mmc and lattice parameters of a = 5.42(1) Å; c = 12.70(3) Å; V = 323(4) Å3; Z = 2. This is the first time 3D ED was applied to structure determination of an extraterrestrial mineral. The International Mineralogical Association (IMA) has approved this naturally formed CAS phase as the new mineral “donwilhelmsite” [CaAl4Si2O11], honoring the U.S. lunar geologi...
Apatites from Martian nakhlites NWA 10153 and NWA 10645 were used to obtain insight into their cr... more Apatites from Martian nakhlites NWA 10153 and NWA 10645 were used to obtain insight into their crystallization environment and the subsequent postcrystallization evolution path. The research results acquired using multi-tool analyses show distinctive transformation processes that were not fully completed. The crystallization history of three apatite generations (OH-bearing, Cl-rich fluorapatite as well as OH-poor, F-rich chlorapatite and fluorapatite) were reconstructed using transmission electron microscopy and geochemical analyses. Magmatic OH-bearing, Cl-rich fluorapatite changed its primary composition and evolved toward OH-poor, F-rich chlorapatite because of its interaction with fluids. Degassing of restitic magma causes fluorapatite crystallization, which shows a strong structural affinity for the last episode of system evolution. In addition to the three apatite generations, a fourth amorphous phase of calcium phosphate has been identified with Raman spectroscopy. This amorp...
We investigated lherzolitic peridotites in the Cretaceous Purang ophiolite along the Yarlung Zhan... more We investigated lherzolitic peridotites in the Cretaceous Purang ophiolite along the Yarlung Zhangbo suture zone (YZSZ) in SW Tibet to constrain their mantle-melt evolution history. Coarsegrained Purang lherzolites contain orthopyroxene (Opx) and olivine (Ol) porphyroclasts with embayments filled by small olivine (Ol) neoblasts. Both clinopyroxene (Cpx) and Opx display exsolution textures represented by lamellae structures. Opx exsolution (Opx1) in clinopyroxene (Cpx1) is made of enstatite, whose compositions (Al 2 O 3 = 3.85-4.90 wt%, CaO = <3.77 wt%, Cr 2 O 3 = 0.85-3.82 wt%) are characteristic of abyssal peridotites. Host clinopyroxenes (Cpx1) have higher Mg#s and Na 2 O, with lower TiO 2 and Al 2 O 3 contents than Cpx2 exsolution lamellae in Opx, and show variable LREE patterns. Pyroxene compositions of the lherzolites indicate 10-15% partial melting of a fertile mantle protolith. P-T estimates (1.3-2.3 GPa, 745-1067°C) and the trace element chemistry of pyroxenes with exsolution textures suggest crystallization depths of 75 km in the upper mantle, where the original pyroxenes became decomposed, forming exsolved structures. Further upwelling of lherzolites into shallow depths in the mantle resulted in crystal-plastic deformation of the exsolved pyroxenes. Combined with the occurrence of microdiamond and ultrahigh-pressure (UHP) mineral inclusions in chromites of the Purang peridotites, the pyroxene exsolution textures reported here confirm a multi-stage partial melting history of the Purang lherzolites and at least three discrete stages of P-T conditions in the course of their upwelling through the mantle during their intra-oceanic evolution.
The microinclusions in cuboid diamonds from Ebelyakh River deposits (northeastern Siberian craton... more The microinclusions in cuboid diamonds from Ebelyakh River deposits (northeastern Siberian craton) have been investigated by FIB/TEM techniques. It was found that these microinclusions have multiphase associations, containing silicates, oxides, carbonates, halides, sulfides, graphite, and fluid phases. The bulk chemical composition of the microinclusions indicates two contrasting growth media: Mg-rich carbonatitic and Al-rich silicic. Each media has their own specific set of daughter phases. Carbonatitic microinclusions are characterized by the presence of dolomite, phlogopite, apatite, Mg, Fe-oxide, KCl, rutile, magnetite, Fe-sulfides, and hydrous fluid phases. Silicic microinclusions are composed mainly of free SiO2 phase (quartz), high-Si mica (phengite), Al-silicate (paragonite), F-apatite, Ca-carbonates enriched with Sr and Ba, Fe-sulfides, and hydrous fluid phases. These associations resulted from the cooling of diamond-forming carbonatitic and silicic fluids/melts preserved i...
Geophysical investigations and laboratory experiments provide strong evidence for subduction of a... more Geophysical investigations and laboratory experiments provide strong evidence for subduction of ancient oceanic crust, and geological and mineralogical observations suggest that subducted oceanic crust is recycled into the upper mantle. This model is supported by some direct petrologic and mineralogical evidence, principally the recovery of super-deep diamonds from kimberlites and the presence of crustal materials in ophiolitic chromitites and peridotites, but many details are still unclear. Here we report the discovery of ophiolite-hosted diamonds in the podiform chromitites of the Skenderbeu massif of the Mirdita ophiolite in the western part of Neo-Tethys. The diamonds are characterized by exceedingly light C isotopes (δ 13 CPDB ~ −25‰), which we interpret as evidence for subduction of organic carbon from Earth's surface. They are also characterized by an exceptionally large range in δ 15 Nair (-12.9‰ to +25.5‰), accompanied by a low N aggregation state. Materials sparsely included in diamonds include amorphous material, Ni-Mn-Co alloy, nanocrystals (20 x 20 nm) of calcium silicate with an orthorhombic perovskite structure (Ca-Pv), and fluids. The fluids coexisting with the alloy and Ca-Pv provide clear evidence that the diamonds are natural rather than synthetic. We suggest that the Skenderbeu diamonds nucleated and grew from a C-saturated, NiMnCo-rich melt derived from a subducted slab of ocean crust and lithosphere in the deep mantle, at least in the diamond stability field, perhaps near the top of the mantle transition zone. The subsequent rapid upward transport in channelled networks related to slab rollback during subduction initiation may explain the formation and preservation of Skenderbeu diamonds. The discovery of diamonds from the Mirdita ophiolite not only provides new evidence of diamonds in these settings, but also provides a valuable opportunity to understand deep cycling of subducted oceanic crust and mantle composition. This is a preprint, the final version is subject to change, of the American Mineralogist (MSA) Cite as Authors (Year) Title. American Mineralogist, in press.
Organic synthesis on Mars occurs by the electrochemical reduction of CO 2 , a reaction that is hi... more Organic synthesis on Mars occurs by the electrochemical reduction of CO 2 , a reaction that is highly relevant for abiotic organic synthesis on early Earth.
Alkali feldspar crystals have been recognized in the troilite-graphite nodules of the Morasko IAB... more Alkali feldspar crystals have been recognized in the troilite-graphite nodules of the Morasko IAB iron meteorite. Their chemical, microtextural and structural properties were studied using electron microprobe analysis (EMPA), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), transmission electron microscopy (TEM) and Raman spectroscopy. The feldspars occur as perthitic or antiperthitic intergrowths, whereas the albite lamellae are perfectly twinned. The structural properties reveal intergrown phases with fairly disordered patterns. The electron microprobe analyses demonstrate that the intergrown phases are mainly rich in sodium or potassium, resulting in compositions that are close to those of albite or orthoclase. The compositions, calculated on the basis of a segmented perthite-antiperthite image, showed that the Or-to-Ab proportions in the homogenized crystals were almost 0.3:0.7, thus indicating that the anorthoclase crystallized under high-temperature conditions. Two hypotheses of crystal formation could account for these characteristics: crystallization from a melt or from a metasomatic solution. Relics with evidence of metasomatic replacement of former minerals were not found. Accordingly, this work focuses on arguments that support the other hypothesis. Large ion lithophile elements (LILEs, e.g., Ba, Sr, Rb, LREE, Pb, and Ga) were used to track the origin of the crystals. Their concentrations indicate crystallization from a parent melt strongly depleted in LILEs. Alkali feldspar is commonly a product of a highly differentiated melt. However, highly differentiated melts are typically enriched in LILEs, which here is not the case. The melt that crystallized the feldspar cannot be related to impact-induced partial melting of the chondritic material alone. The derived melt probably was contaminated by silica-rich target material during interaction between the IAB projectile and the target material and was accompanied by metal and sulphide melts that were both immiscible with a silicate melt.
A transmission electron microscope (TEM) study of Paleoproterozoic zircon that has experienced ul... more A transmission electron microscope (TEM) study of Paleoproterozoic zircon that has experienced ultra-high temperature (UHT) metamorphism at ca. 570 Ma in the Kerala Khondalite Belt (KKB), southern India, documents the occurrence of metallic Pb nanospheres. These results permit comparison with a previous report from UHT zircon in Enderby Land, Antarctica, and allow further constraints to be placed on possible mechanisms for nanosphere formation. As in Enderby Land, the nanospheres in the KKB occur in non-metamict zircon, emphasising that radiogenic Pb redistribution can occur with only partial interconnectivity of radiation damaged zircon. In contrast, the nanospheres reported here are not closely associated with Si-rich glass inclusions, which is inconsistent with a silicate liquid-metal immiscibility model proposed in the earlier study. Formation of these Pb nanospheres effectively halts Pb-loss from zircon, even under extreme conditions, and can adversely affect geochronological interpretations due to decoupling of Pb from U.
We have investigated a piece of the Netschaëvo IIE iron meteorite containing a silicate inclusion... more We have investigated a piece of the Netschaëvo IIE iron meteorite containing a silicate inclusion by means of electron microprobe analysis (EMPA) and transmission electron microscopy (TEM). Netschaëvo contains chondrule-bearing clasts and impact melt rock clasts were also recently found. The examined inclusion belongs to the latter and is characterized by a porphyritic texture dominated by clusters of coarse-grained olivine and pyroxene, set in a fine-grained groundmass that consists of new crystals of olivine and a hyaline matrix. This matrix material has a quasi-basaltic composition in the inner part of the inclusion, whereas the edge of the inclusion has a lower SiO 2 concentration and is enriched in MgO, P 2 O 5 , CaO, and FeO. Close to the metal host, the inclusion also contains euhedral Mg-chromite crystals and small (<2 lm), Si-rich globules. A TEM foil was cut from this glassy, silico-phosphate material. It shows that the material consists of elongated olivine crystallites containing up to 14 wt% P 2 O 5 , amorphous material, and interstitial Cl-apatite crystals. The Si-rich silicate glass globules show a second population of Ferich silicate glass droplets, indicating they formed by silicate liquid immiscibility. Together with the presence of phosphoran olivine and quenched Cl-apatite, these textures suggest rapid cooling and quenching as a consequence of an impact event. Moreover, the enrichment of phosphorus in the silicate inclusion close to the metal host (phosphoran olivine and Cl-apatite) indicates that phosphorus re-partitioned from the metal into the silicate phase upon cooling. This probably also took place in pallasite meteorites that contain late-crystallizing phases rich in phosphorus. Accordingly, our findings suggest that oxidation of phosphorus might be a general process in core-mantle environments, bearing on our understanding of planetesimal evolution. Thus, the Netschaëvo sample serves as a natural planetesimal core-mantle boundary experiment and based on our temperature estimates, the following sequence of events takes place: (i) precipitation of olivine (1400-1360°C), (ii) re-partitioning of phosphorus from the metal into the silicate phase, and (iii) formation of immiscible melts (1230-1115°C).
The banded iron formation of the Bababudan Group (Western Dhawar Craton, India) is composed of mi... more The banded iron formation of the Bababudan Group (Western Dhawar Craton, India) is composed of millimetric to centimetric alternating quartz and grey to red Fe-oxide bands. Major phases are quartz and martite (hematized magnetite) with minor Fe-sulfides and Ca-Mg-Fe-carbonates. Micrometric Fe-oxide spherules fill cavities in discontinuous micrometric layers of Fe-oxides that occur in the massive quartz layers and at the interface of massive Feoxide and quartz layers. The spherules are composed of micrometric radial plates of hematite intergrown with nanometric magnetite. These spherules contain carbonaceous matter (CM) with nanometric Fe-particles and have low N contents (~ 900 ppm; CM1). The spherule formation is attributed to a low temperature hydrothermal process (150-200°C) at around 2.52 Ga, possibly favored by the presence of CM. These hydrothermal fluids dissolved diagenetic interstitial sulfides or carbonates creating cavities which, provided space for the spherule precipitation. Carbonaceous matter of semi-anthracite maturity is encapsulated in quartz grains adjacent to the Fe-oxide spherules (CM2) and it is thus concluded that CM1 and CM2 are most likely contemporaneous and of the same origin, either incorporated at the time of BIF formation or during the hydrothermal event at 2.52 Ga from the underlying phyllitised black shales. Carbonaceous matter (CM3) was also found around the Fe-oxide spherules and the martite grains. CM3 has much higher N contents (> 5000 ppm) and is of a lower maturity than CM1 and CM2 and is related to weathering, also indicated by the presence of goethite and kaolinite. The 13 C of all CMs varies from-19.4 to-24.7 ‰, similar to values measured in the underlying phyllitised black shales and likely reflect denitrifying microbial activity.
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Papers by Richard Wirth