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In this study, we investigated four different ferroan dolomite samples using in situ Raman spectroscopy and powder X-ray diffraction (XRD) at pressures up to 48 GPa and room temperature. Our results show that the transition from Dolomite-I (Dol-I) to Dolomite-II (Dol-II) occurs above 13–16 GPa, and the transition pressure depends on the composition of the solid solution. Compression above 32–35 GPa results in the appearance of Dolomite-IIIc (Dol-IIIc) or Dolomite-IIIb (Dol-IIIb). In the high-pressure XRD study, we found that the XRD patterns of Ca0.97(Mg0.77Fe0.23Mn0.03)(CO3)2(xFe = 0.23, Ank23) can be indexed as Dol-IIIc at 44 GPa, while the rhombohedral Dol-IIIb structure matches better with the XRD patterns of the xFe = 0.40 (Ank40) and 0.64 (Ank64) solid solutions. Additionally, in the Raman spectra of the Fe-richest sample (Ank64), we observed an abrupt frequency downshift of the CO3-stretching vibrations between 40–42 GPa, which may reflect a pressure-induced Fe2+spin transition.

The origin of Libyan Desert Glass (LDG) found in the western parts of Egypt close to the Libyan border is debated in planetary science. Two major theories of its formation are currently competing: (1) melting by airburst and (2) formation by impact-related melting. While mineralogical and textural evidence for a high-temperature event responsible for the LDG formation is abundant and convincing, minerals and textures indicating high shock pressure have been scarce. This paper provides a nanostructural study of the LDG, showing new evidence of its high-pressure and high-temperature origin. We mainly focused on the investigation of Zr-bearing and phosphate aggregates enclosed within LDG. Micro- and nanostructural evidence obtained with transmission electron microscopy (TEM) are spherical inclusions of cubic, tetragonal, and orthorhombic (Pnmaor OII) zirconia after zircon, which indicate high-pressure, high-temperature decomposition of zircon and possibly, melting of ZrO2. Inclusions of amorphous silica and amorphous Al-phosphate with berlinite composition (AlPO4) within mosaic whitlockite and monazite aggregates point at decomposition and melting of phosphates, which formed an emulsion with SiO2melt. The estimated temperature of the LDG melts was above 2750 °C, approaching the point of SiO2boiling. The variety of textures with different degrees of quenching immediately next to each other suggests an extreme thermal gradient that existed in LDG through radiation cooling. Additionally, the presence of quenched orthorhombic OII ZrO2provides direct evidence of high-pressure (>13.5 GPa) conditions, confirming theory 2, the hypervelocity impact origin of the LDG.

New petrographic and microanalytical studies of mineral inclusions in the Purang ophiolitic chromitites (SW Tibet) are used to scrutinize the evolution of the associated Cretaceous sub-oceanic lithospheric mantle section. Silicate inclusions in the chromite grains include composite and single-phase orthopyroxene, clinopyroxene, amphibole, and uvarovite. Most inclusions are sub-rounded or globular, whereas a few inclusions exhibit cubic/octahedral crystal morphologies. The latter are randomly distributed in the large chromite grains, though discrete aggregates are consistently confined to the grain centers. Abundant micrometer-scale, clinopyroxene inclusions are topotaxially aligned along crystallographic planes. Less-abundant sulfide, wüstite, apatite, and uvarovite inclusions are observed in some samples.

The new minerals wenjiite, Ti10(Si,P,◻)7(IMA2019-107c) and kangjinlaite, Ti11(Si,P)10(IMA2019-112b) occur with badengzhuite, zhiqinite, and a K-bearing dmisteinbergite-like mineral in a spheroid 20 μm across enclosed in corundum from the Cr-11 podiform chromitite orebody near the Kangjinla, Luobusa ophiolite, Tibet, China. In addition, wenjiite occurs with deltalumite, jingsuiite, osbornitekhambaraevite, and the K-bearing dmisteinbergite-like mineral in a lamellar intergrowth 100 μm long, also enclosed in corundum from the same locality. The new minerals were characterized by energy-dispersive spectroscopy and three-dimensional electron diffraction, which enabled us to obtain an ab initio structure solution and dynamical refinement from grains a few micrometers across hosted in a FIB lamella. Four analyses of wenjiite from the spheroid gave in wt% Si 21.67, P 6.24, Ti 66.39, V 1.37, Cr 2.20, Mn 0.97, and Fe 1.17 (normalized to 100), which corresponds to (Ti0.93Cr0.03Mn0.01Fe0.01V0.02)10(Si0.79P0.21)6.51on the basis of 10 cations excluding Si and P. The simplified formula is Ti10(Si,P)6.5, or more generally Ti10SixPy, where x > y and 6 ≤ (x + y) ≤ 7, i.e., Ti10(Si,P,◻)7. Wenjiite has hexagonal symmetry, space group: P63/mcm(no. 193), with a= 7.30(10) Å, c= 5.09(10) Å, V= 235(6) Å3, Z= 1, and is isostructural with xifengite, mavlyanovite, synthetic Ti5Si3, and synthetic Ti5P3.15. Four analyses of kangjinlaite gave in wt% Si 25.56, P 9.68, Ti 62.35, V 0.21, Cr 0.83, Mn 0.42, and Fe 0.95 (normalized to 100), which corresponds to (Ti10.65V0.03Cr0.13Mn0.06Fe0.14)Σ11.01(Si7.43P2.55)Σ9.99. The simplified formula is Ti11(Si,P)10. Kangjinlaite is tetragonal, with space group: I4/mmm(no. 139), a= 9.4(2) Å, c= 13.5(3) Å, V= 1210(50) Å3, Z= 4, and is isostructural with synthetic compounds of the Ho11Ge10type, being the most compact of these phases. Despite there now being over 70 compounds containing 38 elements isostructural with Ho11Ge10, synthesis of an analog of kangjinlaite has not been previously reported in either the Ti-P or Ti-Si binary systems or in a multicomponent system. The previously deduced crystallization sequence with decreasing temperature of the four minerals in the spheroid is wenjiite → kangjinlaite → zhiqinite + badengzhuite. This sequence is consistent with relationships reported in 9 binary systems containing intermetallic compounds of Ge and Sn isostructural with Mn5Si3and Ho11Ge10. In eight of these systems the Mn5Si3analog melts congruently, whereas the Ho11Ge10analog never does. Instead, the Ho11Ge10analog melts peritectically, generally to an Mn5Si3analog and less commonly to compounds with 5:4 stoichiometry. Final crystallization of the spheroid to zhiqinite + badengzhuite is expected to be well below the temperature of 1500 °C for the congruent melting of zhiqinite in the Ti-Si system, i.e., in the range of ~1100–1300 °C.

The synthesis of the Al2SiO5polymorphs kyanite, sillimanite and andalusite in a pure Al2O3–SiO2–H2O (ASH) system has long been known to be impeded. In order to decipher individual aspects of the reaction: corundum + SiO2aq, which repeatedly fails to produce thermodynamically stable Al2SiO5, we conducted experiments within the stability fields of kyanite and sillimanite (500–800 ℃; 0.2–1 GPa) with the aim of forming reaction coronas on corundum. Results showed that metastable corundum + quartz assemblages form persistently in pure ASH, even in Al2SiO5seeded experiments, despite the presence of catalyzing fluid and evidence of fast reaction kinetics. Coronas on corundum spontaneously formed when additional components (Na, K, N, and Mg) were added to the experiment. In a similar experiment with baddeleyite (ZrO2) instead of corundum in silica saturated water, a zircon corona formed readily. This implies that nucleation and growth of Al2SiO5is obstructed under conditions of Al and Si saturation in aqueous fluid, while both corundum and quartz saturated aqueous fluid are willing participants in other reactions towards stable corona formation. Instead of Al2SiO5precipitation, an unexpected fluid-aided silica diffusion process into corundum was documented. The latter included the formation of nanometer wide hydrous silicate layers along the basal plane of the corundum host, which enhanced the silica diffusion rate drastically, leading to silica supersaturation in the host mineral, and ultimately to precipitation of quartz inside corundum. We conclude that the natural metastable assemblage of quartz and corundum is not necessarily the result of dry or fluid absent conditions, given that the aqueous fluid in experiments does not promote Al2SiO5formation, but rather seems to support the formation and preservation of a metastable assemblage.

The new mineral jingsuiite (TiB2, IMA-2018-117b), together with osbornite-khamrabaevite solid solution (TiN-TiC), deltalumite, and a potential new mineral, hexagonal Ti10(Si,P,□)7, constitute four inclusions up to 50 μm across in corundum recovered from the Cr-11 podiform chromitite orebody near Kangjinla, Luobusa ophiolite, Tibet, China. EELS, EDS, and 3D electron diffraction were applied to study the phases. In one inclusion, jingsuiite forms a rounded grain 40 μm across. Associated osbornite-khamrabaevite solid solution forms an irregular mass up to 10 μm across having the composition Ti(N0.5C0.5) and the Ti10(Si,P,□)7phase forms an incomplete overgrowth up to 20 μm thick around the grain of jingsuiite. In a second inclusion, jingsuiite, osbornite-khamrabaevite solid solution, Ti10(Si,P,□)7and deltalumite form a lamellar intergrowth 100 μm long composed of tablets of the four phases up to 50 μm long × 4 μm in thickness. Jingsuiite has a primitive hexagonal cell with a= 3.04(6), b= 3.04(6), c= 3.22(6) Å, α = 90°, β = 90°, γ = 120°, V= 25.8 (9) Å3, space group P6/mmm, Z= 1. Its structure was determined ab initio and dynamically refined on the basis of three-dimensional electron diffraction data; it is equivalent to that of synthetic TiB2. Results of EELS analyses of jingsuiite in foil no. 5357 (N = 20) gave B 61.87(1.22), C 1.53 (1.26), Ti 36.62 (1.45) at% from which an empirical formula of Ti1.10(B1.86C0.05)Σ1.91was calculated on the basis of 3 atoms. The ideal formula is TiB2. Our preferred scenario is that corundum with entrapped Ti-Si-P-Fe intermetallic melts was precipitated from basaltic magmas during exhumation following deep subduction. Enrichment of B in the melt pockets is attributed to the highly reducing conditions that led to the segregation of siderophile elements into intermetallic melts and to the siderophile behavior of B, thereby concentrating it in the intermetallic melts in preference to silicate melt. Experimental work on the Ti-Fe-Si system indicates that minerals enclosed in corundum grains such as Ti, FeTiSi2, and TiSi2could have crystallized from alloy melts at the lowest Taccessible on the liquidus, i.e., <1300 °C. The presence of TiB2in four inclusions in the Cr-11 orebody suggests incorporation of crustal sediments in the ophiolite followed by deep subduction to the Transition Zone where qingsongite (cubic BN) is inferred to have crystallized and subsequently exhumed to shallower levels where hexagonal BN and jingsuiite presumably crystallized.

Several recent papers have purported to find ultra-reduced minerals—as natural examples—within ophiolitic mantle sections, including SiC moissanite, Fe-Si alloys, various metal carbides, nitrides, and borides. All those phases were interpreted to be mantle derived. The phases are recovered from mineral concentrates and are assigned to the deep mantle because microdiamonds and other ultrahigh-pressure (UHP) minerals are also found. Based on these findings, it is claimed that the mantle rocks of ophiolite complexes are rooted in the transition zone (TZ) or even in the lower mantle, at redox states so reduced that phases like SiC moissanite are stable.

The Equal Credit Opportunity Act defines impermissible bases for consumer credit decisions, including marital status, but there are certain situations when additional parties, such as guarantors of co-signers, may be required to share credit information. When credit-worthiness or enforceability is in question, the lender can require additional parties to the agreement, but the lender may not insist that the additional party be the spouse. These provisions may be used by spouses as in the defense of recoupment by use of the compulsory counterclaim or affirmative defense.

The development rights and special declarant rights of builders of condominium and cooperative apartments have become a collateral value in the financing of construction under the Uniform Common Interest Ownership Act. These rights give developers the option of using certain common areas for future construction of additional units. The true value of these rights, however, is not always accurately measured. The result is the loss of some of the value of a particular project when it is assumed by another party.

The high-pressure CaCO3phase diagram has been the most extensively studied within the carbonates group. However, both the diverse mineralogy of carbonates and the abundance of solid solutions in natural samples require the investigation of multi-component systems at high pressures (P) and temperatures (T). Here we studied a member of the CaCO3–SrCO3solid-solution series and revealed the effect of cationic substitution on the pressure-induced phase transitions in calcium carbonate.

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 ways depending on the intrinsic crystal structure and pore textures: (1) heteroepitaxial growth utilizing the (111) lattice planes of magnetite, and (2) randomly oriented nucleation and growth. Therefore, this study unravels how intrinsic and extrinsic factors drove the formation of gold nanoparticles at fluid-mineral interfaces.

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 CaAl4Si2O11crystals 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/mmcand 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 geologist Don E. Wilhelms. On the Moon, donwilhelmsite can form from the primordial feldspathic crust during impact cratering events. In the feldspatic lunar meteorite Oued Awlitis 001, needles of donwilhelmsite crystallized in ~200 mm sized shock melt pockets of anorthositic-like chemical composition. These melt pockets quenched within milliseconds during declining shock pressures. Shock melt pockets in meteorites serve as natural crucibles mimicking the conditions expected in the Earth’s mantle. Donwilhelmsite forms in the Earth’s mantle during deep recycling of aluminous crustal materials, and is a key host for Al and Ca of subducted sediments in most of the transition zone and the uppermost lower mantle (460–700 km). Donwilhelmsite bridges the gap between kyanite and the Ca-component of clinopyroxene at low pressures and the Al-rich Ca-ferrite phase and Ca-perovskite at high-pressures. In ascending buoyant mantle plumes, at about 460 km depth, donwilhelmsite is expected to break down into minerals such as garnet, kyanite, and clinopyroxene. This process may trigger minor partial melting, releasing a range of incompatible minor and trace elements and contributing to the enriched mantle (EM1 and EM2) components associated with subducted sedimentary lithologies.

Approximately 700 diamond crystals were identified in volcanic (mainly pyroclastic) rocks of the Tolbachik volcano, Kamchatka, Russia. They were studied with the use of SIMS, scanning and transmission electron microscopy, and utilization of electron energy loss spectroscopy and electron diffraction. Diamonds have cube-octahedral shape and extremely homogeneous internal structure. Two groups of impurity elements are distinguished by their distribution within the diamond. First group, N and H, the most common structural impurities in diamond, are distributed homogeneously. All other elements observed (Cl, F, O, S, Si, Al, Ca, and K) form local concentrations, implying the existence of inclusions, causing high concentrations of these elements. Most elements have concentrations 3–4 orders of magnitude less than chondritic values. Besides N and H, Si, F, Cl, and Na are relatively enriched because they are concentrated in micro- and nanoinclusions in diamond. Mineral inclusions in the studied diamonds are 70–450 nm in size, round- or oval-shaped. They are represented by two mineral groups: Mn-Ni alloys and silicides, with a wide range of concentrations for each group. Alloys vary in stoichiometry from MnNi to Mn2Ni, with a minor admixture of Si from 0 to 5.20–5.60 at%. Silicides, usually coexisting with alloys, vary in composition from (Mn,Ni)4Si to (Mn,Ni)5Si2and Mn5Si2, and further to MnSi, forming pure Mn-silicides. Mineral inclusions have nanometer-sized bubbles that contain a fluid or a gas phase (F and O). Carbon isotopic compositions in diamonds vary from –21 to –29‰ δ13CVPDB(avg. = –25.4). Nitrogen isotopic compositions in diamond from Tolbachik volcano are from –2.32 to –2.58‰ δ15NAir. Geological, geochemical, and mineralogical data confirm the natural origin of studied Tolbachik diamonds from volcanic gases during the explosive stage of the eruption.

The migrating fluid-mineral interface provides an opportunity for the uptake of trace elements as solid solutions in the newly formed crystal lattice during the non-equilibrium growth of the crystal. However, mineral nanoparticles could precipitate directly from the interfacial fluid when it evolves to a supersaturated situation. To better understand the role of mineral nanoparticles in this scenario, this study focuses on a well-documented magnetite with oscillatory zoning from a skarn deposit by using high-resolution transmission electron microscopy (TEM). Our results show that the Al concentration in magnetite measured on a micrometer-scale is caused by three different effects: Al solid solution, Al-rich nanometer-sized lamellae, and zinc spinel nanoparticles in the host magnetite. Here, we propose a genetic relationship among the three different phases mentioned above. At first, a continuous increase of the Al concentration in the interfacial fluid can be incorporated into the crystal lattice of magnetite forming a solid solution. During cooling in a later stage, aluminum in magnetite is oversaturated and exsolution of hercynite (Al-rich lamellae) occurs from the host magnetite. If the Al concentration at the fluid-magnetite interface still increases during further growth of magnetite, the substitution of Fe by Al has gradually reached saturation so that aluminum cannot be incorporated in the magnetite crystal structure any longer. Using the magnetite lattice as a template, nucleation of abundant zinc spinel nanoparticles occurs. This will, in turn, lead to a gradual depletion of Al concentration in the interfacial fluid until the available ions for zinc spinel nucleation and growth have been used up. As a result, the migrating fluid-magnetite interface will enrich the Al concentration in the interfacial fluid until the available ion concentration is sufficient for nucleation of zinc spinel phase again. The fluidmineral interface in this mechanism has been repeatedly utilized during crystal growth, providing an efficient way for the uptake of trace element from a related undersaturated bulk fluid.

Calcium sulfate minerals are found in nature as three hydrates: gypsum (CaSO4·2H2O), bassanite (CaSO4·0.5H2O), and anhydrite (CaSO4). Due to their relevance in natural and industrial processes, the formation pathways of calcium sulfates from aqueous solution have been the subject of intensive research, and there is a growing body of literature, suggesting that calcium sulfates form through nonclassical nanoparticle-mediated crystallization processes. We showed earlier (Stawski et al. Nat. Commun.2016, 7, 11177) that at the early stages in the precipitation reaction, calcium sulfate nanocrystals nucleate through the reorganization and coalescence of aggregates rather than through classical unit addition. Here, we used low-dose dark field (DF) transmission electron microscopy (TEM) and electron diffraction and document that these restructuring processes do not continue until a final near-perfectly homogeneous single crystal is obtained. Instead, we show that the growth process yields a final imperfect mesocrystal with an overall morphology resembling that of a single crystal, yet composed of smaller nanodomains. Our data reveal that organic-free calcium sulfate mesocrystals grown by a particle mediated-pathway may preserve in the final crystal structure a “memory” or “imprint” of their nonclassical nucleation process, something that has been overlooked until now. Furthermore, the nanoscale misalignment of the structural subunits within these crystals might propagate through the length-scales, which is potentially expressed macroscopically as misaligned zones/domains in large single crystals. This is akin to observations in some of the giant crystals from the Naica Mine, Chihuahua, Mexico.

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 (δ13CPDB~ −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 δ15Nair(−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 × 2 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 channeled 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.

A series of polycrystalline diamond grains were found within the Valizhgen Peninsula in Koryakia, northern Kamchatka, Russia. A grain from the Aynyn River area is studied in detail with TEM. Diamond crystallites, 2–40 μm in size are twinned and have high dislocation density. They are cemented with tilleyite Ca5(Si2O7)(CO3)2, SiC, Fe-Ni-Mn-Cr silicides, native silicon, graphite, calcite, and amorphous material. Among SiC grains, three polymorphs were discriminated: hexagonal 4H and 6H and cubic C3 (β-SiC). Silicides have variable stoichiometry with (Fe,Ni,Mn,Cr)/Si = 0.505–1.925. Native silicon is an open-framework allotrope of silicon S24, which has been observed, to date, as a synthetic phase only; this is a new natural mineral phase. Three types of amorphous material were distinguished: a Ca-Si-C-O material, similar in composition to tilleyite; amorphous carbon in contact with diamond, which includes particles of crystalline graphite; and amorphous SiO2. No regularity in the distribution of the amorphous material was observed. In the studied aggregate, diamond crystallites and moissanite are intensively twinned, which is characteristic for these minerals formed by gas phase condensation or chemical vapor deposition (CVD) processes. The synthetic analogs of all other cementing compounds (β-SiC, silicides, and native silicon) are typical products of CVD processes. This confirms the earlier suggested CVD mechanism for the formation of Avacha diamond aggregates. Both Avacha and Aynyn diamond aggregates are related not to “classic” diamond locations within stable cratons, but to areas of active and Holocene volcanic belts. The studied diamond aggregates from Aynyn and Avacha, by their mineralogical features and by their origin during the course of volcanic eruptions via a gas phase condensation or CVD mechanism, may be considered a new variety of polycrystalline diamond and may be called “kamchatite.” Kamchatite extends the number of unusual diamond localities. It increases the potential sources of diamond and indicates the polygenetic character of diamond.

Here, we report the first occurrence of two (Ca-Y)-phosphate phases in apatite crystals from ancient rocks from both the Barberton greenstone belt and the Pilbara Craton. First, a cubic Ca3Y(PO4)3phase was observed in a sample of silicified tuff from the Mendon Formation from the Barberton greenstone belt. A second phase, corresponding to a synthetic compound with the formula CaYP7O20, was observed in a sample of black banded chert from the Hooggenoeg Formation of the Onverwacht Group and in a sample of chert from the Strelley Pool Chert Formation (East Pilbara Terrane). Based on the presence of these phosphates and specific textures revealed by transmission electron microscopy, we argue for the importance of dissolution-reprecipitation processes in the formation of these phosphate phases. Temperature was likely not the primary parameter controlling the crystallization of the Ca3Y(PO4)3and CaYP7O20phases. Instead, the REE-F complexes in an H2O solution and the specific budget of REEs and Y in apatite were likely responsible for the nucleation and formation of the (Ca-Y)-phosphate phases in the Archean rocks of the Barberton greenstone belt and Pilbara Craton.

To define the liquidus and solidus of the system CaCO3-MgCO, rotating multi-anvil experiments were performed at 6 GPa in the temperature range 1300 to 1800 °C under anhydrous conditions. Additionally, experiments under hydrous conditions were performed in the Mg-rich part of the phase diagram. To determine the melting point of the end-member magnesite at 6 GPa falling sphere/body experiments were performed. The run products were analyzed using electron microprobe, Raman spectroscopy, and X-ray diffraction. Some of the run products were investigated by transmission electron microscopy (TEM).

The low-grade carbonate banded iron formation of the Aguas Claras mine, from the transition of the Caûe to the Gandarela Formation (2.4?Ga, Itabira Group, Brazil), is composed of porous and microsparitic dolomite, quartz, iron oxides and (oxy)hydroxides. Iron oxides occur as bands, veins and as inclusions in the dolomite crystals, whereas iron (oxy)hydroxides only occur as inclusions. Combined mineralogical analyses (X-ray diffraction, Raman spectroscopy, focused-ion-beam thinning and transmission electron microscopy) identified the inclusions in porous dolomite as hematite and minor goethite and/or ferrihydrite, whereas microsparitic dolomite only hosts hematite. Curie balance analysis on whole rock reveals that, at temperatures between ~680?°C and ~900?°C, hematite and iron (oxy)hydroxide inclusions react with the surrounding dolomite resulting in the assemblage: magnesioferrite (MgFe2O4), srebrodolskite (Ca2Fe2O5), lime (CaO), portlandite (Ca(OH)2) and periclase (MgO), whereas hematite and pure dolomite do so only at ~900?°C. This difference is an indirect argument for the presence of iron hydroxide inclusions within the dolomite. The inclusions are either single crystals or form clusters in pores. The fast-Fourier-transform diffraction pattern of one single crystal can be indexed as goethite and ferrihydrite. This finding suggests an incipient solid-state transformation of ferrihydrite to goethite rather than a dissolution-precipitation process. It is suggested that the clustered hematite and the goethite/ferrihydrite precipitated from Fe- and Si-bearing fluid inclusions, which were trapped during early diagenesis at about 2.4?Ga under oxygenated conditions. Microstructural evidence (e.g. dislocations in dolomite from hematite inclusions) point to maximum T?

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) + F-muscovite (with tobelite component) + buddingtonite + organic matter (OM) + opal (+ traces of K-feldspar, albite, columbite, FeS2, barite, REE-minerals). Sector-zoned and platy to fibrous buddingtonite has variable (K+Na)-vs. NH4,-contents (electron microprobe analyses) and some H2O or H3O+, 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 at%), Y (≤3 at%), Sc (≤0.8 at%), REE (≤0.3 at%), Th (≤0.2 at%), and U (≤1.25 at%), 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 nanometer-sized areas and at the transition from OM to opal in nanometer-sized platy Zr-Si-O crystals. C-rich areas are amorphous but show poorly developed lattice fringes. OM is present in the pseudomorph also as brown pigmentation of opal and in pegmatitic beryl from Volyn as a component in late stage fluid inclusions, identified by C-H vibrational bands in infrared spectra. Stable isotope investigations of C and N of buddingtonite, black opal and kerite (fibrous OM known from the literature to occur in the Volyn pegmatites and interpreted as microfossils) indicate a biogenic origin of the OM. We propose that OM in the pseudomorph is condensed kerite, which achieved the high concentrations of high field strength elements via fluid-pegmatite interaction. Although no age determination of minerals in the pseudomorph is available, textural arguments and phase equilibria indicate its formation in a late stage of the pegmatite evolution, at P-Tconditions 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 NH4, was then incorporated into buddingtonite.

The first finds of iron nitrides and carbonitride as inclusions in lower-mantle diamond from Rio Soriso, Brazil, are herein reported. These grains were identified and studied with the use of transmission electron microscopy (TEM), electron diffraction analysis (EDX), and electron energy loss spectra (EELS). Among nitrides, trigonal Fe3N and orthorhombic Fe2N are present. Carbonitride is trigonal Fe9(N0.8C0.2)4. These mineral phases associate with iron carbide, Fe7C3, silicon carbide, SiC, Cr-Mn-Fe and Mn-Fe oxides; the latter may be termed Mn-rich xieite. Our identified finds demonstrate a wide field of natural compositions from pure carbide to pure nitride, with multiple stoichiometries from M5(C,N)3to M23(C,N)6and with M/(C,N) from 1.65 to 3.98. We conclude that the studied iron nitrides and carbonitrides were formed in the lowermost mantle as the result of the infiltration of liquid metal, containing light elements from the outer core into the D″ layer, with the formation of the association: native Fe0+ iron nitrides, carbides, and transitional compounds + silicon carbide. They indicated that major reservoirs of nitrogen should be expected in the core and in the lowermost mantle, providing some solution to the problem of nitrogen balance in the Earth.

Petroleum is retained in shales either in a sorbed state or in a free form within pores and fractures. In shales with oil resource potential, organic matter properties (i.e., richness, quality, and thermal maturity) control oil retention in general. In gas shales, organic pores govern gas occurrence. Although some pores may originate via secondary cracking reactions, it is still largely unclear as to how these pores originate. Here we present case histories mainly for two classic shales, the Mississippian Barnett Shale (Texas) and the Toarcian Posidonia Shale (Lower Saxony, Germany). In both cases, shale intervals enriched in free oil or bitumen are not necessarily associated with the layers richest in organic matter but are instead associated with porous biogenic matrices. However, for the vast bulk of the shale, hydrocarbon retention and porosity evolution are strongly related to changes in kerogen density brought about by swelling and shrinkage as a function of thermal maturation. Secondary organic pores can form only after the maximum kerogen retention (swelling) ability is exceeded at Tmax (the temperature at maximum rate of petroleum generation by Rock-Eval pyrolysis) around 445°C (833°F), approximately 0.8% vitrinite reflectance. Shrinkage of kerogen itself leads to the formation of organic nanopores, and associated porosity increase, in the gas window. [ABSTRACT FROM AUTHOR]

Many studies dealing with the synthesis of tourmaline report a sharp intragranular chemical gradient and extensive porosity in the core zones of the crystals, both of which still lack a reliable explanation. Using the example of olenitic tourmaline, we show that these features are likely explained by the occurrence of a precursor phase during tourmaline formation. Time-dependent piston–cylinder synthesis experiments were performed in the system SiO2 – Al2 O3 – B2 O3 –NaCl–H2 O at 700° C/40 kbar with run durations of 0.5 h, 2.5 h and 216 h, starting from quartz–Al2 O3 – H3 BO3 solid mixtures and NaCl solutions. Sharply zoned olenitic tourmaline ([4] B-rich cores,[4] B-poor rims) formed in all experiments, with its abundance increasing with increasing run duration. The amount of the additional solid product phases coesite and jeremejevite decreased with time. Extensive porosity is recognized in jeremejevite and in the cores of early grown acicular tourmaline. Textural relationships indicate that olenitic tourmaline grows at the expense of jeremejevite which acts as a crystalline precursor in this system. A possible reaction is: 3Al6 (BO3) 5(OH)3 + (12 - 2x) SiO2(aq) + 2y NaCl (aq) ? 2NayAl3 Al6 (Si6-xBxO18 (BO3)3 (O3-x, OH1+x) + (4.5- x) B2 O3 (aq) + (2.5 - x) H2O + 2y HCl(aq). The transformation likely proceeds via a dissolution/re-precipitation mechanism, which triggers the sharp chemical zonation in olenite. Based on Rayleigh fractionation modelling, we estimate a minimum B isotope fractionation between jeremejevite and fluid with ?11 Bjer-fluid ˜ 2.8 ‰ at 700° C/40 kbar. Due to the progressive dissolution of jeremejevite, the fluids d11B values continuously decrease with increasing run duration. Hence, olenite growth concomitant with the dissolution of jeremejevite will produce scattered or inverse boron isotope patterns (heavy cores, light rims) in tourmaline, which cannot result from simple Rayleigh fractionation. Similar reactions involving jeremejevite or other precursor phases might explain chemical zonation and porous textures in tourmaline core zones reported in many experimental studies. The occurrence of natural tourmaline overgrowing jeremejevite in pegmatites of the Erongo Mountains, Namibia, gives rise to the assumption that jeremejevite might also act as a precursor for tourmaline formation in natural systems.

Fragments of optically flat silica discs embedded in synthetic gouge were deformed to examine the relationship between the development of striations and slickenlines, and deformation mechanisms, conditions, and fault rheology. Experiments were performed under hydrothermal conditions in a rotary shear apparatus at 100°C or 450°C, to shear strains of 2.02 < ?< 8.25. Slip hardening and softening prevail at low and high temperatures, respectively. In recovered samples, disc fragment surfaces are decorated by fine gouge, sometimes arranged in trails, pits, and scratch marks. Prominent grooves—inferred slickenlines—with constant orientation, wavelength <10 µm, and amplitude <0.7 µm are only observed on disc fragments deformed at 450°C. Some parts of the grooves below the original disc fragment surface contain scattered rounded beads of silica ~200 nm diameter. Conversely, close examination of pits in 100°C experiments reveals they contain angular particles <2 µm diameter. The 200 nm diameter crystalline quartz can precipitate at 450°C in only 250 s, well within the time frame of the experiments but precipitation at 100°C would take at least 8 years. No systematic dislocation arrays were observed in the quartz disc fragments, but microfractures are sporadically present. This indicates that at both temperatures brittle failure generated microfractures and microcomminution occurred where gouge particles impacted disc fragment surfaces. These observations suggest formation of silica beads by precipitation from amorphous silica facilitates slip weakening, smoothing of the fault surface parallel to the slip vector, development of undulations perpendicular to the slip vector by a pressure solution creep mechanism, weakening, and maintenance of a constant slip direction. Slickenlines form at 450°C but not 100°C in wet experiments, by brittle wear and solution-depositionThey are slip vector-perpendicular undulations decorated by silica beads in an amorphous silica matrixFormation accompanies strain softening, fault smoothing, and maintenance of a constant slip direction

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Using transmission electron microscopy we show that planar deformation lamellae occur within quartz in the substrate of a rock fulgurite, i.e., a lightning-derived glass. These lamellae exist only in a narrow zone adjacent to the quartz/fulgurite boundary and are comparable to planar deformation features (“shock lamellae”) caused by hypervelocity impacts of extra-terrestrial objects. Our observations strongly suggest that the lamellae described here have been formed as a result of the fulgurite-producing lightning strike. This event must have generated a transient pressure pulse, whose magnitude, however, is uncertain at this stage.

Calcite is one of the most ubiquitous minerals in the Earth’s crust and is mostly present as calcite or the slightly denser polymorph aragonite. In addition five different phases of CaCO3(calcite II-VI), which display similar structural features as calcite, have been observed with increasing pressure in different experiments by several authors. Experimentally, the CaCO3-III and CaCO3-IIIb polymorphs have recently been observed by Merlini et al. (2012) applying pressures between 2.5-15 GPa on natural samples of calcite using single-crystal synchrotron X‑ray diffraction.

Methane-rich gas occurs in the total organic carbon-rich Alum Shale (Furongian to Lower Ordovician) in southern Sweden. The lower part of the thermally immature Alum Shale was impregnated by bitumen locally generated by heating from magmatic intrusions from the Carboniferous to the Permian. Organic geochemical data indicate that the migrated bitumen is slightly degraded. In the upper Alum Shale, where methane is the main hydrocarbon in thermovaporization experiments, centimeter-size calcite crystals occur that contain fluid inclusions filled with oil, gas, or water. The Alum Shale is thus considered a mixed shale oil-biogenic shale gas play. The presented working hypothesis to explain the biogenic methane occurrence considers that water-soluble bitumen components of the Alum Shale were converted to methane. A hydrogeochemical modeling approach allows the quantitative retracing of inorganic reactions triggered by oil degradation. The modeling results reproduce the present-day gas and mineralogical composition. The conceptual model applied to explain the methane occurrence in the Alum Shale in southern Sweden resembles the formation of biogenic methane in the Antrim Shale (Michigan Basin, United States). In both models, melting water after the Pleistocene glaciation and modern meteoric water may have diluted the contents of total dissolved solids (TDS) in basinal brines. Such pore waters with low TDS contents create a subsurface aqueous environment favorable for microbes that have the potential to form biogenic methane. Today, biogenic methane production rates, with shale as the substrate using different hydrocarbon-degrading microbial enrichment cultures in incubation experiments, range from 10 to 620 nmol per gram and per day. [ABSTRACT FROM AUTHOR]

Opal has long fascinated scientists. It is one of the few minerals with an amorphous structure, and yet, compared to silica glass, it is highly organized on the mesoscale. By means of inelastic neutron scattering (INS), we could document that in four samples of opal at low temperature an ice-like structure of water is present, with details depending on microstructural characteristics. While FTIR spectra for all samples are nearly identical and thus not very informative, INS shows clear differences, highlighting the significance of microstructures. Neutron diffraction at 100 K on one of the opal samples provides evidence for crystalline cubic ice.

Two new mineral species of the mayenite group, fluormayenite Ca12Al14O32[4F2] (I43d, a = 11.9894(2) Å, V = 1723.42(5) Å3, Z = 2) and fluorkyuygenite Ca12Al14O32[(H2O)4F2] (I43d, a = 11.966(2) Å, V = 1713.4(1) Å3, Z = 2), are major constituents of larnite pyrometamorphic rocks of the Hatrurim Complex (Mottled Zone) distributed along the Dead Sea rift on the territory of Israel, Palestinian Autonomy and Jordan. Holotype specimens of fluormayenite and fluorkyuygenite were collected at the Jabel Harmun, Judean Mts., Palestinian Autonomy and in the Hatrurim Basin, Negev Desert, Israel, respectively. Mineral associations of holotype fluormayenite and fluorkyuygenite are similar and include larnite, shulamitite, Cr-containing spinel–magnesioferrite series, ye'elimite, fluorapatite–fluorellestadite, periclase, brownmillerite, oldhamite as well as the retrograde phases portlandite, hematite, hillebrandite, afwillite, foshagite, ettringite, katoite and hydrocalumite. Fluormayenite and fluorkyuygenite crystals, usually <20 µm in size, are colourless, in places with greenish or yellowish tint, the streak is white. Both minerals are transparent with a vitreous lustre; they do not show fluorescence. Fluormayenite and fluorkyuygenite are isotropic and have similar refractive indices: n = 1.612(3) and n = 1.610(3) (589 nm), respectively. The hardness of fluormayenite and fluorkyuygenite is H (Mohs) 5½ –6; VHN load 50 g, 771(38) kg mm2; and 5-5½; VHN load 50 g, 712(83) kg m2, respectively. Both minerals have the microporous tetrahedral framework structure characteristic of the mayenite supergroup. In fluormayenite 1/3 of the structural cages are occupied by fluorine. In fluorkyuygenite, in addition to fluorine and negligible amounts of OH, H2O molecules occupy about 2/3 of the cages. The holotype fluormayenite from Jabel Harmun has the crystal chemical formula (Ca11.951Na0.037)S11.987(Al13.675Fe3+ 0.270Mg0.040Si0.009P0.005S6+ 0.013)S14.013O31.503(OH)1.492[4.581F1.375Cl0.044]S6, fluorkyuygenite from the Hatrurim Basin has the composition Ca12.034(Al13.344Fe3+ 0.398Si0.224)S13.966O32[(H2O)3.810F1.894(OH)0.296]S6. Raman spectra of fluormayenite and fluorkyuygenite in the spectral region 200–1000 cm–1 are similar and are characterized by the four strong main bands at about 320 (?2 AlO4), 520 (?4 AlO4), 700, 770 (?1 AlO4) cm–1. In the O-H vibration region fluorkyuygenite shows a broad band between 2600–3500 cm–1 (?H2O). The molecular water is completely released from the fluorkyuygenite structure at about 400°C. Fluorkyuygenite crystallized initially as fluormayenite, which later was altered under influence of water vapour-enriched gases during a combustion process. Fluormayenite has been synthesized and fluorkyuygenite is an analogue of the recently discovered chlorkyuygenite, Ca12Al14O32[(H2O)4Cl2], from the Northern Caucasus, Russia.

Experiments were conducted to reproduce reaction rims of phlogopite ± diopside around olivine that have been observed within a wide range of potassic melts, including phonolite. Phlogopite is also a common secondary phase formed at the expense of olivine during metasomatic events involving K2Oand H2O-rich fluids or melts. Piston-cylinder experiments where olivine single crystals were reacted with synthetic phonolite melt at 10.7-14.7 kbar and 950-1000 °C recreate the mineralogy and textures documented in natural samples. Rim growth is parabolic with time, indicating a diffusion-controlled reaction. Fast diffusion in the melt and varying compositions across the phlogopite reaction rims suggest that diffusion through the rims, along grain boundaries is rate limiting. Reaction rates dramatically increase with temperature as well as the bulk water content of the sample charge. This is because of increasing amounts of atomically bound hydrous species along the grain boundaries that increase the rates of diffusion and thereby the rates of rim growth. Atomically bound hydrous species increase the rates of rim growth by lowering the activation energy for diffusion and by increasing the solubility of diffusing species in the grain boundary region. Transmission electron microscopy shows the presence of isolated pores and open grain boundaries. Most of these may have opened during quenching, but there is some evidence to suggest that a free fluid phase may have been locally present in experiments with high melt water contents (>8 wt%). The measured rim growth rates at different conditions are used to estimate residence times of reacting olivine crystals in natural systems.

The occurrence of a trioctahedral analog of illite, the dioctahedral interlayer-deficient K-mica, has long been debated. Due to the inherent difficulties of determining structure and chemical composition of the extremely fine-grained material, earlier descriptions based on separated material are equivocal. Here we describe low-temperature (diagenetic) formation of fluorophlogopite, which is interlayerdeficient and therefore analogous to illite, using high-resolution in situ methods (transmission electron microscopy, TEM, with preparation by focused ion beam milling, combined with wavelength-dispersive analysis by field-emission gun electron microprobe). The average composition is K0.5Mg2.8V0.01Fe0.005[Si3.15Al0.85O10(OH)0.65F1.35], including minor amounts of NH4for charge compensation as determined by electron energy loss spectroscopy. The K-deficient Mg-mica occurs in layer packages of ~10 layers, and no indications for interlayering with other sheet silicate layers such as chlorite or vermiculite could be identified with TEM. X-ray powder diffraction patterns of separated material confirm the absence of smectite components.

We report the synthesis of h-magnetite, ideally h-Fe3O4with considerable amounts of substitutional cations (Cr, Mg, Al, Si) and quenchable to ambient conditions. Two types of experiments were performed at 18 GPa and 1800 °C in a multi-anvil press. In one, we used an oxide mixture with a majoritic stoichiometry Mg1.8Fe1.2(Al1.4Cr0.2Si0.2Mg0.2)Si3O12, with Si and Mg in excess as starting material (MA-367, MA-380). In the second type of experiment (MA-376), we started from an oxide mixture on the composition of the Fe-oxide phase obtained in MA-367. The Fe-oxide phases of both experiments were investigated by electron microprobe and transmission electron microscopy including electron diffraction tomography. Our investigations show that the Fe-oxide phases crystallize in the structure-type of h-magnetite. However, electron diffraction data show that keeping the cell setting from literature, this phase crystallizes in space group Amam and not in space group Bbmm as previously proposed. In the experiment MA-367, the Fe-oxide phase are mutually intergrown with majorite, the major phase of the run products. The formula for h-magnetite in this run was calculated as Fe1(Fe2+ 0.75Mg0.26)Fe2(Fe3+ 0.70 Cr0.15Al0.11Si0.04)2O4. In the experiment on the bulk composition of the Fe-oxide, the main phase was h-magnetite with composition Fe1(Fe2+ 1.02)Fe2(Fe3+ 0.65Cr0.19Al0.13Si0.03)2O4and traces of nearly pure endmember wadsleyite and stishovite. Our results indicate that the substitution of 20 to 30% of Fe (0.7 to 0.9 atoms per formula unit) by smaller cations favored the preservation of the high-pressure form to ambient conditions. We prove that the h-magnetite-type oxide is also stable in chemical systems more complex than Fe-O. Based on our results, which were obtained at 18 GPa and 1800 °C in a system (MA-367) that is closely related to Fe-enriched oceanic lithospheric material, we suggest that a Fe3O4-rich phase may be present in environments connected to deeply subducted slabs and possibly associated with deep carbonatitic melting. Our observations show that Cr strongly partitions in the oxide phase such that the coexisting silicates are depleted in Cr compared to Fe3O4-free assemblages. This may significantly affect the chemical signature of melts produced in the deep mantle.

Continuous paleosecular variations reconstructed from sedimentary archives have remarkably deepened our insights into the dynamics of the Earth's magnetic field as well as the chronological purpose. Nevertheless, to construct reliable sedimentary paleomagnetic records in diagenetic reducing sediments is challenging generally due to the pervasive magnetic mineral diagenesis. The relict magnetic minerals are residuals after diagenesis and probably able to record a depositional remanent magnetization, thus it is worthy to explore their paleomagnetic potentials. For this study, two Black Sea sediment cores covering the past 8 ka were subjected to mineralogical and paleo‐ and rock magnetic analyses. Paramagnetic pyrite framboids are pervasive in the studied sediments deposited under anoxic bottom water conditions in the Black Sea. In addition, relict magnetic minerals of ferrous hemoilmenite, Fe‐Mn and Fe‐Cr spinels, and magnetite inclusions are also present in the studied cores. Compared to the previous published paleomagnetic results from the same cores over the last glacial period (20–30 ka) which are dominated by detrital (titano‐)magnetite particles, the studied relict magnetic mineral samples exhibit a similar behavior in recording the depositional remanent magnetization. Furthermore, the obtained paleosecular variations spanning the past 8 ka reproduce the high intensity patterns observed in the regional archeomagnetic and volcanic datasets. Thus, the successful reconstruction of paleomagnetic secular variations from the anoxic Black Sea sediments greatly extend the application of paleomagnetism in sediments deposited in water with a reducing sub‐surface environments from where paleomagnetic data are generally sparse. The Earth's magnetic field can be recorded by magnetic minerals during their deposition within a water column, and are later preserved in sediments. The geomagnetic field signal may be biased if the magnetic minerals are subsequently altered because of changes in bottom water redox conditions. However, relict magnetic minerals are resistant to ambient environmental changes and thus have great potentials to record reliable paleomagnetic signals. To attest this novel idea, we systematically investigated sediments form the Black Sea under strong anoxic bottom water conditions. Our results demonstrate that the relict magnetic minerals survived in the Black Sea sediments covering the past eight thousand years. By comparison with detrital (titano‐)magnetite samples, we found that relict magnetic mineral samples have similar behavior in recording the geomagnetic field. Moreover, the geomagnetic field variations reconstructed from the Black Sea sediments are comparable with other validated regional datasets for the past eight thousand years. Therefore, our new study significantly extends the application of paleomagnetic methods in a wider range of sedimentary redox conditions. Relict minerals of hemoilmenite, Fe‐Mn and Fe‐Cr spinels, and magnetic inclusions are magnetic carriers in studied Black Sea sedimentsThe ability in recording the DRM by relict magnetic minerals are comparable with detrital (titano‐)magnetiteThe obtained paleosecular variations resemble reginal field patterns observed in archeomagnetic and volcanic datasets for the past 8 ka Relict minerals of hemoilmenite, Fe‐Mn and Fe‐Cr spinels, and magnetic inclusions are magnetic carriers in studied Black Sea sediments The ability in recording the DRM by relict magnetic minerals are comparable with detrital (titano‐)magnetite The obtained paleosecular variations resemble reginal field patterns observed in archeomagnetic and volcanic datasets for the past 8 ka

Qingsongite (IMA 2013-30) is the natural analog of cubic boron nitride (c-BN), which is widely used as an abrasive under the name “Borazon.” The mineral is named for Qingsong Fang (1939-2010), who found the first diamond in the Luobusa chromitite. Qingsongite occurs in a rock fragment less than 1 mm across extracted from chromitite in deposit 31, Luobusa ophiolite, Yarlung Zangbu suture, southern Tibet at 29°13.86N and 92°11.41E. Five electron microprobe analyses gave B 48.54 ± 0.65 wt% (range 47.90-49.2 wt%); N 51.46 ± 0.65 wt% (range 52.10-50.8 wt%), corresponding to B1.113N0.887 and B1.087N0.913, for maximum and minimum B contents, respectively (based on 2 atoms per formula unit); no other elements that could substitute for B or N were detected. Crystallographic data on qingsongite obtained using fast Fourier transforms gave cubic symmetry, a = 3.61 ± 0.045 Å. The density calculated for the mean composition B1.100N0.900is 3.46 g/cm3, i.e., qingsongite is nearly identical to synthetic c-BN. The synthetic analog has the sphalerite structure, space group F43m. Mohs hardness of the synthetic analog is between 9 and 10; its cleavage is {011}. Qingsongite forms isolated anhedral single crystals up to 1 mm in size in the marginal zone of the fragment; this zone consists of ~45 modal% coesite, ~15% kyanite, and ~40% amorphous material. Qingsongite is enclosed in kyanite, coesite, or in osbornite; other associated phases include native Fe; TiO2II, a high-pressure polymorph of rutile with the αPbO2structure; boron carbide of unknown stoichiometry; and amorphous carbon. Coesite forms prisms several tens of micrometers long, but is polycrystalline, and thus interpreted to be pseudomorphic after stishovite. Associated minerals constrain the estimated pressure to 10-15 GPa assuming temperature was about 1300 °C. Our proposed scenario for formation of qingsongite begins with a pelitic rock fragment that was subducted to mid-mantle depths where crustal B originally present in mica or clay combined with mantle N (δ15N = -10.4 ± 3‰ in osbornite) and subsequently exhumed by entrainment in chromitite. The presence of qingsongite has implications for understanding the recycling of crustal material back to the Earth’s mantle since boron, an essential constituent of qingsongite, is potentially an ideal tracer of material from Earth’s surface.

Albitization of K-feldspar has been studied experimentally at 500 and 750 °C and 200 MPa using concentrated NaCl solutions. The partially reacted feldspar grains were characterized using X-ray diffraction, electron probe microanalysis, transmission electron microscopy as well as Raman and laser-induced photoluminescence spectroscopy. The replacement of K-feldspar by albite occurs via coupled dissolution-reprecipitation due to the mobilization of K in exchange for Na and results in the mobilization of minor elements like Ba, Fe, Ti, and Mg. The release of tetrahedrally incorporated Fe3+ and Ti4+ in K-feldspar is temperature-dependent resulting in increasing mobilization with increasing temperature. Barium shows a positive correlation with K in the reacted areas. Replacement also leads to the formation of cogenetic rutile and Fe-rich pseudobrookite inclusions in the albitized regions. This supports the proposal that the Fe responsible for the formation of hematite inclusions in altered, natural alkali feldspars can originate from the feldspar.

All known forms of life require phosphorus, and biological processes strongly influence the global phosphorus cycle. Although the record of life on Earth extends back to 3.8?billion years ago and the advent of biological phosphate processing can be tracked to at least 3.5?billion years ago, the earliest known P-rich deposits appeared only 2?billion years ago. The onset of P deposition has been attributed to the rise of atmospheric oxygen 2.4–2.3?billion years ago and the related profound biogeochemical shifts, which increased the riverine input of phosphate to the ocean and boosted biological productivity and phosphogenesis. However, the P-rich deposits post-date the rise of oxygen by about 300?million years. Here we use microfabric, trace element and carbon isotope analyses to assess the environmental setting and redox conditions of the 2-billion-year-old P-rich deposits of the vent- or seep-influenced Zaonega Formation, northwest Russia. We identify phosphatized microorganism fossils that resemble modern methanotrophic archaea and sulphur-oxidizing bacteria, analogous to organisms found in modern seep settings and upwelling zones with a sharp redoxcline. We therefore propose that the P-rich deposits in the Zaonega Formation were formed by phosphogenesis mediated by sulphur bacteria, similar to modern sites, and by the precipitation of calcium phosphate minerals on microbial templates during early diagenesis.

The Al-B substitution in the system albite?reedmergnerite has been investigated experimentally by performing cold-seal hydrothermal and piston-cylinder synthesis experiments at temperatures of 450 °C and 750 °C in the pressure range 0.2?3.0 GPa. As starting material, glasses close to NaBSi3O8(R100), NaB0.75Al0.25Si3O8(R75), and NaB0.5Al0.5Si3O8(R50) composition were used. Run products were characterised by SEM, powder-XRD applying the Rietveld method, EMP- and TEM-analyses. In all but one experiment reedmergnerite or (Al, B)-bearing feldspar formed as the main phase beside quartz, coesite or jadeite in one run at 3.0 GPa, 750 °C. Amorphous phases were observed in the nominally dry experiments and were assumed to be due to incongruent melting under participation of absorbed water. Synthetic (Al, B)-feldspar from experimental runs show considerable Al-B solid solution. TEM-investigations show that the (Al, B)-feldspars are strongly twinned. No exsolution lamellae of varying compositions are visible, indicating that the (Al, B)-feldspars are chemically homogeneous. The reedmergnerite (Rd)-component in albite at constant temperature of 750 °C increases strongly with increasing pressure, with the highest Rd-content of about 50 mol% just below the albite ? jadeite + quartz equilibrium. The amount of Al substituting into reedmergnerite is small and the variation with pressure is not well constrained. At 3.0 GPa, 750 °C an albite content of 4 mol% is observed in reedmergnerite. Consequently, the wide miscibility gap of albite-reedmergnerite solid solution in albitic feldspars observed at low pressures strongly diminishes to higher pressures. The degree of ordering in the synthetic B-bearing feldspars was estimated from Rietveld-determined mean (T-O) distances of the four tetrahedral positions T1o, T1m, T2o, T2m. For reedmergnerite a pressure-induced high/low transition appears to occur within the pressure range 1.0?1.5 GPa at 750 °C. This experimental study indicates that albitic feldspars can reach maximum Rd-contents of up to about 20 mol% under late-stage Band Na-enriched pegmatitic conditions. At fluid-saturated conditions such feldspars can be transported during subduction to depths of about 40 km until their breakdown and formation of a B-bearing melt. Natural albitic feldspars, typically containing only traces of B, will decompose in subduction zones below about 50 km depths and produce a melt with low B-contents.

In this study, deuteric coarsening of a lamellar cryptoperthite to a patch perthite has been experimentally induced for the first time. An homogeneous alkali feldspar, bulk composition Ab60Or40, was produced by molten salt ion-exchange with a gem quality orthoclase from Madagascar. This was then annealed isothermally for 32 days at 550 °C. This resulted in a coherent lamellar cryptoperthite (periodicity 28 nm) probably by spinodal decomposition and subsequent coarsening. The cryptoperthite was then reacted with 20 wt% H2O or 0.1 M HCl at 400 and 500 °C at 200, 400, and 1000 MPa for 96 h and for 192 h at 1500 MPa. At 1000 and 1500 MPa and 500 °C, the cryptoperthitic crystal fragments were partially replaced by a mosaic of albite and sanidine subgrains in the form of a patch perthite. Other than the Gibb’s free energy of reaction as derived from the chemical potentials of the reactant and product phases, the second principle mechanism responsible for driving this reaction is interface-coupled dissolution-reprecipitation driven by a reduction in the coherency strain energy stored within the initial cryptoperthite. The main indicator of this is a change in the microtexture due to the destruction of the coherent lamellar cryptoperthite and its replacement by an assemblage of incoherent subgrains. Detailed mass balancing, based on XRD and EPMA data, indicate that conversion of cryptoperthite to patch perthite is not isochemical. Experimental formation of patch perthite appears to take place in two steps. Between the original cryptoperthite and the patch perthite, TEM investigation identified a “transition zone,” characterized by a significant coarsening of the preexisting lamellar microstructure, without any sign of a loss in lattice coherency. This zone is probably the result of hydrous species diffusing into the cryptoperthite causing the H2O-enhanced diffusion of Na and K and hence lamellar coarsening. In the second step, this coarsened microstructure is replaced by the patch perthite. The polycrystalline patch perthite is characterized by a very complex distribution of albite and sanidine sub-grains. Even the larger albite or sanidine patches are polycrystalline. This inevitably results in a three-dimensional network of grain boundaries characterized by high defect densities resulting from the structural misfit between the albite and sanidine sub-grains. An increase in average grain size with distance from the interface indicates that secondary coarsening of the initially, very fine-grained intergrowth occurred. This was driven by the reduction of interface and surface energy similar to the coarsening observed in multiphase ceramics. In addition, the newly formed patch perthite is highly porous despite the fact that the results obtained in this study show that the replacement of cryptoperthite by patch perthite is nearly isovolumetric (?V ~ -0.6%). The observed reaction-induced porosity results from differences in relative solubilities between the cryptoperthite and the patch perthite. Porosity abundance has been estimated at approximately 10 to 11 vol% based on the amount of quartz formed during the experiments. Three-dimensional investigations via FIB serial sectioning indicate almost no interconnectivity between pores. A consequence of albite and sanidine sub-grain coarsening is the constant redistribution of the porosity and the sub-grain boundaries within the patch perthite mosaic over time. This suggests that a dynamically evolving porosity could provide an important transport mechanism for fluid transport through rocks even when the abundance and interconnectivity of the reaction-induced porosity is low.

TEM and SEM/FIB sequential imaging of quartz grain boundaries from contact and regional metamorphic rocks show that most of the grain boundaries are open on the nanometer scale. Three types of voids occur. (i) Roughly 40–500?nm wide open zones parallel to the grain boundaries. They are suggested to be caused by general volume reduction as a result of anisotropic cooling contraction at temperatures decreasing below ca. 300°C, the threshold temperature of diffusion in quartz and of decompression expansion at pressures decreasing below several hundred MPa. (ii) Cavities of variable shape and up to micrometer size along the open grain boundaries and (iii) cone-shaped, nanometer-sized depressions at sites where dislocation lines meet the open grain boundaries. The latter two types are generated by dissolution–precipitation processes. Open grain boundaries, cavities, and depressions form a connected network of porosity, which allows fluid circulation and may affect physical properties of the rocks. The same process is suggested to occur along grain and phase boundaries in other rocks as exemplified in this study, and it should be expected along intracrystalline cracks or cleavage planes. TEM and SEM/FIB sequential imaging show voids along quartz grain boundariesThermal contraction probably leads to up to 500 nm wide open grain boundariesA network of cavities allows fluid circulation and affects rock properties

Ringwoodite [(Mg,Fe)2SiO4] is the high-pressure polymorph of olivine stable in the upper mantle between ~525 to 660 km. Information on its temperature-dependent water content and Fe-oxidation state bears important implications on the hydrogen cycle and oxidation state of the Earth’s interior. We conducted several multi-anvil experiments to synthesize iron-bearing (0.11 = xFe= 0.24) hydrous ringwoodite under oxidizing and reducing conditions. The experiments were performed at 1200 °C and pressures between 16.5 and 18.3 GPa. The incorporation of hydrogen and iron in ringwoodite was studied using Fourier transform infrared (FTIR), Mössbauer (MB), ultraviolet-visible (UV-VIS), and electron energy loss (EEL) spectroscopy. For MB spectroscopy, ringwoodite enriched in 57Fe was synthesized. The IR spectra of ringwoodite show a broad OH band around 3150 cm-1and two shoulders on the high-energy side: one intense at 3680 cm-1and one weak at around 3420 cm-1. The water content of the samples was determined using FTIR spectroscopy to have a maximum value of 1.9(3) wt% H2O. UV-VIS spectra display a broad band around 12 700 cm-1and a shoulder at 9900 cm-1representing the spin-allowed dd-transitions of VIFe2+. The weaker band around 18 200 cm-1is a distinct feature of Fe2+-Fe3+intervalence charge transfer indicating the presence of Fe3+in the samples. EEL spectra yield Fe3+fractions ranging from 6(3)% at reducing conditions to 12(3)% at oxidizing conditions.

The assemblage strontium anorthite, quartz, and kyanite was reacted with H2O+CaCl2solutions at 500 °C and pressures between 460 and ~1300 MPa using a hydrothermal diamond-anvil cell. Information on the kinetics was obtained in situ based on time-resolved synchrotron-radiation X-ray fluorescence analyses of the Sr concentration in the fluid. The reaction products (anorthite or zoisite) were studied using transmission electron microscopy to obtain information on the reaction mechanism and mineral-fluid partitioning of strontium. The time required for equilibration was primarily controlled by the reaction mechanism, but not discernibly affected by pressure or chloride concentration. Nucleation and growth of zoisite at the expense of strontium anorthite was much faster than the Sr-Ca exchange reaction of strontium anorthite to anorthite, and resulted in chemically homogeneous crystals. The anorthite had developed a high nanoporosity during the reaction, which is indicative of coupled dissolution-precipitation. A zoisite-fluid exchange coefficient

The thermal maturity of samples of the Posidonia Shale collected from the Hils Syncline, northern Germany, varies significantly as a function of location indicating variations in local history. Synchrotron X-ray diffraction was used to document the composition and the preferred orientation of four samples of the Posidonia Shale with different degrees of maturity (0.68–1.45%, Ro) to determine possible effects on diagenesis and preferred orientation. Overall, the degree of preferred orientation of all clay minerals (illite-smectite, illite-mica, and kaolinite) and in all samples is similar, with (001) pole figure maxima ranging from 3.7 to 6.3 multiples of a random distribution (m.r.d.). Calcite displays weak preferred orientation, with c axes perpendicular to the bedding plane (1.1–1.3 m.r.d.). Other constituent phases such as quartz, feldspars, and pyrite have a random orientation distribution. The difference in thermal history, which causes significant changes in the maturity of organic matter, influenced the preferred orientation of clay minerals only marginally as most of the alignment seems to have evolved early in their history. Synchrotron X-ray microtomography was used to characterize the three-dimensional microstructure of a high-maturity sample. Low-density features, including porosity, fractures, and kerogen, were observed to be elongated and aligned roughly parallel to the bedding plane. The volume of low-density features was estimated to be ~7 vol.%, consistent with previous petrophysical measurements of porosity of 8–10 vol.%. Transmission electron microscopy analysis of samples with different degrees of maturity (0.74%Roand 1.45%Ro) was used to document microstructures at the nanoscale as well as the presence of kerogen. In the high-maturity sample, pores were less abundant while minerals were more deformed as shown by fractured calcite and by kinked and folded illite. Some of the porosity was aligned with clay platelets.

Atomic diffusion along grain boundaries in solids is a key process in many geological environments and in ceramics research. It is closely related to the grain boundary width, which is an important parameter in numerous equations describing diffusional or rheological processes, including plastic deformation of polycrystals, intergranular failure, and recrystallization. Here, we studied diffusion along a single well-characterized, near Σ5 grain boundary in yttrium aluminum garnet (YAG) using different transmission electron microscopy methods at atomic resolution. For the diffusion experiment, YAG thin-films containing Yb as diffusant were deposited perpendicular to the grain boundary on the bicrystal. We investigated the grain boundary using a focal series in combination with multislice calculations that yield the electron exit wave. This, coupled with chemically sensitive Z-contrast images, as well as the Yb distribution over the grain boundary measured using electron energy loss spectroscopy, show the zone of enhanced Yb diffusion parallel to the grain boundary. This zone of enhanced diffusion is often considered as the effective grain boundary width.

The 3.65 Å phase, a member of the family of dense hydrous magnesium silicates (DHMS) in the system MgO-SiO2-H2O, was synthesized in a 77 h multi-anvil press experiment at conditions of 10 GPa and 425 °C by using a gel of composition MgSiO3plus water in excess as starting materials. From our multi-methodical study including SEM, TEM, EMP, IR, and Raman analysis, we determined the composition of the 3.65 Å phase to be MgSi(OH)6. Powder XRD combined with Rietveld refinement revealed the 3.65 Å phase to be isostructural with δ-Al(OH)3. The 3.65 Å phase can be described as a hydrous A-site vacant perovskite with probably long-range random distribution of Si and Mg at octahedral sites. Locally, some ordering of Mg and Si might exist, as indicated from the spectroscopic measurements. The 3.65 Å phase represents the second DHMS with exclusively sixfold-coordinated Si, the other being phase D. The 3.65 Å phase is stable at pressures above about 9.0 GPa and temperatures below 500 °C. This limited P-T stability together with its high water content makes the 3.65 Å phase an unrealistic mantle component. If at all, it might only occur under hydrous conditions in the coldest parts of deeply and extremely fast subducted old oceanic slabs.