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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 trace element geochemistry of the Purang chromitite evoke parental MORB- and boninite-like melts, consistent with the supra-subduction zone setting. The δ26Mg values of the high-Cr and high-Al chromitites range from –0.25 to –0.29‰ and –0.05 to –0.32‰, respectively. The associated harzburgite has nearly overlapping δ26Mg values of –0.13 to –0.37‰, but pyroxenite sills show distinct δ26Mg values (–0.61 to –0.67‰). The variable Mg isotope signatures, combined with abundant exotic, ultrahigh-pressure and super reduced (UHP-SuR) mineral inclusions in the chromite grains, suggest that recycling and recrystallization under different mantle conditions played an important role in the genesis and evolution of these rocks. Furthermore, discrete silicate, sulfide, and metal alloy inclusions in the Purang chromitites are comparable to those reported in other Tethyan ophiolites, and collectively suggest a common geodynamic evolution.

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 drill core sample that preserves a sharp reaction front between mineralized and unmineralized domains of the fine-grained siliciclastic compositional end member (carbonate free). Petrographic and mineralogical data provide evidence that oxidized hydrothermal fluids moved through the protolith via reaction permeability that developed from feldspar dissolution. The nature of reactive fluid flow was determined by reactions that took place at the fluid-mineral interface. Pyrite formation during the earliest stage of the hydrothermal paragenesis increased the mineral reactive surface area in the protolith. Acidity was then generated in situ via self-sustaining reactions involving pyrite oxidation, transient Fe sulfate formation, and sphalerite precipitation, which provided positive feedbacks to enhance porosity creation and further fluid infiltration and mineralization. In the absence of carbonate, however, ore fluid pH was buffered by K-feldspar dissolution (~4.5), thereby ensuring sphalerite precipitation was not inhibited under more acidic conditions. All CD-type deposits in the Carpentaria province are hosted by a protolith comprising carbonate, K-feldspar, pyrite, and organic matter; these phases set the boundary conditions for the development of self-sustaining reactions during ore formation. Importantly, these self-sustaining reactions represent a Goldilocks zone for ore formation that is applicable to other sediment-hosted deposits that formed via replacement of mixed siliciclastic-carbonate host rocks (e.g., stratiform Cu).

Wodegongjieite occurs in the Cr-11 chromitite orebody of the Luobusa ophiolite in the Kangjinla district, Tibet, China. It is found in two inclusions in corundum: (1) as a partial overgrowth (holotype) up to 1.5 μm thick around a spheroid 20 μm across of wenjiite (Ti10(Si,P,□)7), kangjinlaite (Ti11(Si,P)10), zhiqinite (TiSi2) and badengzhuite (TiP), and (2) as pools up to 0.25 μm wide filling interstices between wenjiite, jingsuiite (TiB2), osbornite–khamrabaevite (Ti[N,C]) and corundum. Energy dispersive analyses gave Al2O3 34.09, SiO2 49.11, K2O 2.56, CaO 11.71, SrO 2.53, total 100.0 wt.%, corresponding to K0.58Sr0.26Ca2.25Al7.20Si8.80O31.20, ideally KCa3(Al7Si9)O32, for Si + Al = 16 cations.Single-crystal studies were carried out with three-dimensional electron diffraction providing data for an ab initio structure solution in the hexagonal space group P6/mcc (#192) with a = 10.2(2) Å, c = 14.9(3) Å, V = 1340(50) Å3 and Z = 2. Density (calc.) = 2.694 g⋅cm–3. The refinement, which assumes complete Si–Al disorder, gives average T1–O and T2–O bond lengths both as 1.65 Å. It was not practical to use unconstrained refinement for the occupancies of the large cation sites 6f and 2a. The ab initio model shows clearly that the two cation sites have different sizes and coordination. Consequently, we imposed the condition (1) that all the K occupies the 2a site as the average K–O bond length of 3.07 Å is close to the average K–O bond lengths reported in kokchetavite and (2) that all the Ca occupies the 6f site as the average Ca–O bond length of 2.60 Å (2.36 Å and 2.84 Å for Ca–O1 and Ca–O3, respectively) is reasonable for Ca–O. Assuming that all K and all Ca are located at the 2a site and 6f site, respectively, Sr occupancies of these sites could be refined. Thermal parameters are positive and in a reasonable range. The structure is a sheet silicate isostructural with the K-feldspar polymorph kokchetavite, with two crystallographically distinct sites for K, but not with the topologically identical anorthite polymorph dmisteinbergite (CaAl2Si2O8) with only a single site for Ca. Substitution of K by Ca at the 6f site is associated with marked rotation of the Si,Al tetrahedra and a collapse of the structure to accommodate the smaller Ca ion.The spheroid of intermetallic phases is believed to have formed from the interaction of mantle-derived CH4 + H2 fluids with basaltic magmas at depths of ~30–100 km, resulting in precipitation of corundum that entrapped intermetallic melts. Associated immiscible silicate melt of granodioritic composition crystallised metastably to wodegongjieite instead of a mixture of anorthite and K-feldspar.

Five crystals of pegmatitic xenotime from Ås II feldspar quarry (Evje, S Norway) were studied with comprehensive analytical methods from microscale to nanoscale with respect to fluid-mediated alterations and their geochronological implications. Xenotime crystals are strongly altered during dissolution-reprecipitation processes that resulted in the formation of (Th, U)-depleted xenotime subdomains with numerous microinclusions of (Th, U)-silicate, uraninite and minor galena. Remains of a primary xenotime (Xtm1) yielded LA-ICPMS Usingle bondPb data characterized by a reverse discordance (from −10.5 to −2.6%) with a 208Pb/232Th mean age 988.4 ± 5.9 Ma (95% conf., MSWD = 0.75, n = 71), which is within uncertainty with a 207Pb/235U mean age 979.1 ± 5.0 Ma (95% conf., MSWD = 1.4, n = 22) yielded by data filtered to below ±5% discordance (i.e., from −5.0 to −2.6%). The altered xenotime domains (Xtm2) provided highly scattered dates, including 208Pb/232Th dates from 200 ± 14 to 2135 ± 120 Ma (n = 135). Discordant Usingle bondPb data yielded upper intercept age 909 ± 16 Ma (MSWD = 7.9). EPMA Th-U-total Pb measurements and compositional characteristics of uraninite inclusions indicate three age populations of ca. 852–983, 594–687 and 37–101 Ma. TEM investigations revealed initial alterations within domains Xtm1, representing a primary xenotime, which progressed along parallel submicron- to nanoscale fractures. These fractures represent partially open grain boundaries, which are empty or are filled with secondary inclusions of (Th, U)-silicates, uraninite or coffinite. The submicron-sized inclusions are accompanied by subdomains of (Th, U)-depleted xenotime. Altered xenotime (Xtm2) is well crystalline in TEM imaging and electron diffraction patterns in contrast to primary unaltered xenotime domains (Xtm1) that demonstrate, in Raman spectra, moderate degree of radiation damage caused by U and Th decay. Secondary inclusions of Th and U phases are nanocrystalline or amorphous, which increases their potential for Pb-loss or accumulation of Pb in excess. Some of them contain nanoinclusions of Pb3O4 or metallic Pb, whereas

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)6.51 on 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 Ho11Ge10 type, 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 Mn5Si3 and Ho11Ge10. In eight of these systems the Mn5Si3 analog melts congruently, whereas the Ho11Ge10 analog never does. Instead, the Ho11Ge10 analog melts peritectically, generally to an Mn5Si3 analog 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.

Ellinaite, a natural analog of the post-spinel phase β-CaCr2O4, was discovered at the Hatrurim Basin, Hatrurim pyrometamorphic formation (the Mottled Zone), Israel, and in an inclusion within the super-deep diamond collected at the placer of the Sorriso River, Juína kimberlite field, Brazil. Ellinaite at the Hatrurim Basin is confined to a reduced rankinite–gehlenite paralava, where it occurs as subhedral grains up to 30 µm in association with gehlenite, rankinite and pyrrhotite or forms the rims overgrowing zoned chromite–magnesiochromite. The empirical formula of the Hatrurim sample is (Ca0.960Fe0.0162+Na0.012Mg0.003)0.992(Cr1.731V0.1833+Ti0.0683+Al0.023Ti0.0034+)2.008O4. The mineral crystallizes in the orthorhombic system, space group Pnma, unit-cell parameters refined from X-ray single-crystal data: a 8.868(9), b 2.885(3), c 10.355(11) Å, V 264.9(5) Å3 and Z=4. The crystal structure of ellinaite from the Hatrurim Basin has been solved and refined to R1=0.0588 based on 388 independent observed reflections. Ellinaite in the Juína diamond occurs within the micron-sized polyphase inclusion in association with ferropericlase, magnesioferrite, orthorhombic MgCr2O4, unidentified iron carbide and graphite. Its empirical formula is Ca1.07(Cr1.71Fe0.063+V0.06Ti0.03Al0.03Mg0.02Mn0.02)Σ1.93O4. The unit-cell parameters obtained from HRTEM data are as follows: space group Pnma, a 9.017, b 2.874 Å, c 10.170 Å, V 263.55 Å3, Z=4. Ellinaite belongs to a group of natural tunnel-structured oxides of the general formula AB2O4, the so-called post-spinel minerals: marokite CaMn2O4, xieite FeCr2O4, harmunite CaFe2O4, wernerkrauseite CaFe23+Mn4+O6, chenmingite FeCr2O4, maohokite MgFe2O4 and tschaunerite Fe(FeTi)O4. The mineral from both occurrences seems to be crystallized under highly reduced conditions at high temperatures (>1000 ∘C), but under different pressure: near-surface (Hatrurim Basin) and lower mantle (Juína diamond).

In the Sri Lankan Highlands denudation and chemical weathering represent the low-end member in global weathering rates. Here we report on the causes for these low rates in corestones from a highly weathered saprolite profile. By using electron microprobe and transmission electron microscopy (TEM) analyses, we investigated weathering reactions, and derived rates of pyroxene and biotite oxidation. High-resolution TEM analyses on primary minerals showed that the initial weathering products are non-crystalline and that these form the precursors of secondary minerals (kaolinite and smectite). The dissolution of primary minerals is characterised by sharp reaction fronts in the absence of chemical gradients, hence, dissolution can best be described by a dissolution – reprecipitation process. The first observable weathering reaction is the oxidation of structural Fe(II) in pyroxene and biotite. This oxidation is restricted to distinct zones within the minerals without the formation of oxidized layers. While the oxidation is not accompanied by chemical changes, the oxidation of structural Fe(II) in biotite may cause lattice distortion. Pyroxene and biotite oxidation rates were calculated at the corestone-scale by using the gradient of bulk rock Fe(II)/Fetotal ratios, assuming that oxidation is coupled to the weathering front advance rate. At the mineral-scale, oxidation rates were calculated by using gradients of in situ Fe(II)/Fe(III) ratios measured with electron energy-loss spectroscopy (EELS) within the minerals assuming a coupled oxidation-cation diffusion process. The mineral-scale oxidation rates are significantly higher, log Ominin situ = −11 molmin m−2 s−1, than corestone-scale oxidation rates, log Omin = −13 to −15 mol m−2 s−1. We explain the difference to result from the fact that corestone-scale rates average the oxidation over the entire mineral surface. Because at the corestone-scale pyroxene oxidation rates are also similar to dissolution rates, we infer that oxidation preconditions Fe(II)- bearing primary silicate minerals to weathering. However, although oxidation is initiating chemical weathering in this setting and is limited by the supply of O2, overall conversion of bedrock to saprolite is driven by the formation of porosity by fracture formation during this reaction, which allows for fluid transport and subsequent plagioclase weathering. We conclude that in compact bedrock nm- to µm-scale fracture- and porosity generation are the processes that drive weathering in tectonically quiescent regions. They are also the processes at depth that couple the weathering zone with processes at its surface. Finally, the formation of secondary surface layers at the nm-scale is essential in controlling the equilibrium in the local weathering environment and hence mineral dissolution. These layers are likely also those that control isotope fractionation in the weathering zone.

The origin of magnetite-(apatite) iron deposits (MtAp) is among the most contentious issue in ore geology with competing models involving purely hydrothermal to magmatic processes. We study here melt inclusions trapped in plagioclase phenocrysts in andesite hosting the emblematic MtAp mineralization at El Laco, Chile. Our high-resolution study reveals that individual melt inclusions preserve complex processes of melt immiscibility including the separation of Si- and Fe-rich melts, the latter hosting other Cu-sulfide, phosphate-rich, and C-O-HFSE-rich residual melts. This assemblage is a small-scale analogue of the ore mineralization and establishes the missing link between silicate and Fe-P-rich melts which subsequently produce extrusive magnetite. These results strongly indicate that El Laco mineralization derives from crystallization of Fe-P-rich melts providing insight into the formation of similar deposits elsewhere.

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. We challenge this view. We report high-temperature experiments carried out to define the conditions under which SiC can be stable in Earth’s mantle. Mineral separates from a fertile lherzolite xenolith of the Eifel and chromite from the LG-1 seam of the Bushveld complex were reacted with SiC at 1600 K and 0.7 GPa. At high temperature, a redox gradient is quickly established between the silicate/oxide assemblage and SiC, of ~12 log-bar units in fO2. Reactions taking place in this redox gradient allow us to derive a model composition of an ultra-reduced mantle by extrapolating phase compositions to 8 log units below the iron-wüstite equilibrium (IW-8) where SiC should be stable. At IW-8 silicate and oxide phases would be pure MgO end-members. Mantle lithologies at IW-8 would be Fe° metal saturated, would be significantly enriched in SiO2, and all transition elements with the slightest siderophile affinities would be dissolved in a metal phase. Except for the redox-insensitive MgAl2O4 end-member, spinel would be unstable. Relative to an oxidized mantle at the fayalite-magnetite-quartz (FMQ) buffer, an ultra-reduced mantle would be enriched in enstatite by factor 1.5 since the reduction of the fayalite and ferrosilite components releases SiO2. That mantle composition is unlike any natural mantle lithology ever reported in the literature. Phases as reduced as SiC or Fe-Si alloys are unstable in an FeO-bearing, hot, convecting mantle. Based on our results, we advise against questioning existing models of ophiolite genesis because of accessory diamonds and ultra-reduced phases of doubtful origin.

Metamorphic diamonds hosted by major and accessory phases in ultrahigh-pressure (UHP) metamorphic terranes represent important indicators of deep subduction and exhumation of continental crust at convergent plate boundaries. However, their nucleation and growth mechanisms are not well understood due to their small size and diversity. The Bohemian microdiamond samples represent a unique occurrence of monocrystalline octahedral and polycrystalline cubo-octahedral microdiamonds in two different metasedimentary rock types. By combining new and published data on microdiamonds (morphology, resorption, associated phases, carbon isotope composition) with P–T constraints from their host rocks, we demonstrate that the peak P–T conditions for the diamond-bearing UHP rocks cluster along water activity-related phase transitions that determine the microdiamond features. With increasing temperature, the diamond-forming medium changes from aqueous fluid to hydrous melt, and diamond morphology evolves from cubo-octahedral to octahedral. The latter is restricted to the UHP-UHT rocks exceeding 1100 °C, which is above the incongruent melting of phengite, where microdiamonds nucleate along a prograde P–T path in silicate-carbonate hydrous melt. The observed effect of temperature on diamond morphology supports experimental data on diamond growth and can be used for examining growth conditions of cratonic diamonds from kimberlites, which are dominated by octahedra and their resorbed forms.

A significant characteristic distinguishing Carlin-type Au deposits from other Au deposits is the abundance of invisible Au in arsenian pyrite. Gold occurs primarily as ionic Au1+ in arsenian pyrite and is unstable during subsequent thermal events. In this study, we used the focused ion beam combined with scanning electron microscope (FIB-SEM) techniques, and a transmission electron microscope (TEM) to examine invisible Au and how it evolved through later geologic events that eventually led to the formation of Au nanoparticles. FIB-SEM techniques were used to prepare site-specific TEM foils from four Carlin-type gold deposits, including Getchell and Cortez Hills, Nevada, USA, and Shuiyindong and Jinfeng, Guizhou Province, China. These samples were analyzed to quantify ore pyrite chemistry and evaluate textures at the nanometer scale. In 17 examined TEM foils, we observed widespread Au-rich domains in high-grade Au arsenian pyrites from the Getchell and Cortez Hills Au deposits and the Jinfeng deposit but only 10 Au-bearing nanoparticles, ~10 to 20 nm in diameter. The Au-rich domains exhibit Au (Sb), (Tl), (Hg), and (Cu) peaks in the energy dispersive X-ray (EDX) spectrum without the presence of recognizable nanoparticles. This confirms that Au is invisible even at a nanometer scale and is most likely present in the crystal structure of arsenian pyrite. Stacking faults and nanometer-sized fluid inclusions were commonly observed in Au-bearing arsenian pyrite from the four deposits, implying rapid crystallization. Moreover, unlike the coarsely crystalline arsenian pyrite from Guizhou Carlin-type Au deposits, arsenian pyrite from Carlin-type deposits in Nevada consists of fine-grained polycrystalline aggregates, further implying rapid crystallization. Additionally, curved dislocations were commonly pinned by solid inclusions, reflecting a former annealing process. Combining nanoscale textures with geologic information previously reported for Carlin-type deposits, invisible ionic Au was initially incorporated into the crystal structure of arsenian pyrite during rapid precipitation. Subsequent post-ore magmatic events in both districts initiated the annealing of the ionic Au-bearing arsenian pyrite, leading to the redistribution of trace elements and formation of Au-bearing nanoparticles in the arsenian pyrite. The presence of predominantly ionically bonded Au in arsenian pyrite confirms that ore fluids were not saturated in Au when Au-bearing arsenian pyrite formed, as previously reported for Carlin-type deposits. Ionic Au that was scavenged from an undersaturated ore fluid and incorporated into the arsenian pyrite crystal structure formed the giant Carlin-type Au deposits.

The distribution of Th and U in a crystal of pegmatitic xenotime-(Y) (henceforth named xenotime) from Ås II feldspar quarry (Evje, S Norway) has been studied with transmission electron microscopy (TEM) to determine submicron- to nanoscale processes that might have affected U-(Th-)Pb age record. Xenotime contains high Th and U unaltered domains, and Th and U depleted altered domains, which contain numerous inclusions of (Th, U)-silicate and uraninite. A focused ion beam foil (FIB-foil) prepared from the unaltered xenotime, examined with transmission electron microscopy (TEM), revealed a network of ca. 15–20 nm-thick and up to several hundred nanometers-long dislocations. The dislocation cores contain U, Th and Si enriched material, and are surrounded on both sides by radiation-damaged xenotime. Rarely present “empty” dislocations are indicative of nanoscale-sized porosity in xenotime. The presence of a network of line defects in xenotime indicates plastic deformation of the xenotime crystal, which resulted in an initial stage of the formation of partially open phase boundaries. The dislocations network has been infiltrated by fluid, which mediated coupled dissolution-reprecipitation reactions. Segregation of U and Th into the dislocation cores, and selective transport of highly fluid-mobile U outside of the xenotime is suggested to be a source of Pb-excess and reverse discordance in the 207Pb/235U vs. 206Pb/238U concordia diagrams. The new finding of migration and finally segregation of U and Th into dislocation cores at the atomic-scale demonstrates the importance of nanoscale investigations for better understanding of the obtained age data and provides crucial implications for applications of xenotime geochronology.

Fluids are the primary agents for mass transfer in subduction zones. These fluids can be captured as primary inclusions within minerals crystallizing during subduction processes. Some of these inclusions, referred to as multiphase solid inclusions (MSI), are characterized by the high proportion and variety of minerals, hence by a high concentration of solute in the trapped fluid. Kotková et al. (2021) have described primary MSI in garnets of subduction-related ultra-high pressure (UHP) peridotites (P-T of 1030-1150 ºC/3.6-4.8 GPa) of the Bohemian Massif. MSI range in size between ≈5-40 µm and are mostly composed of hornblende, the barian mica kinoshitalite, dolomite and magnesite. MSI have been interpreted as trapped residual liquids produced after partial UHP crystallization of carbonate-silicate melts that now form garnet pyroxenite veins in the peridotites. Experimental re-melting of MSI is the best procedure to investigate the precise nature of trapped fluids. We have conducted re-melting experiments of MSI present in garnets of a lherzolite, taking the inclusions to P-T around their entrapment conditions at or close to host rock peak P-T, 4-4.5 GPa and 1000-1225 ºC. The inclusions (re-)crystallized into a garnet fringe at the boundary between inclusions and host garnet, barian mica and carbonatite melt towards the center of the inclusion, and a large irregular and empty space in between the garnet fringe and the central silicate-carbonate component. Microstructures and mass balance indicate that the empty space was occupied by a Na-K-Cl-F-rich saline aqueous fluid (brine). Hence experiments did not produce a single melt at any experimental conditions, but systematically show the stability and coexistence of barian mica + carbonatite melt + brine at the entrapment conditions, and a garnet fringe indicating reaction between trapped fluids and host garnet. This suggest that growing garnet trapped a carbonatite melt and a saline aqueous fluid coexisting in the matrix, together with solid crystals of barian mica likely produced by metasomatism of the percolating fluids through the host peridotite. It is intriguing, however, that neither single mica crystals nor separate former carbonate melt and brine have been found included in garnets. Mass balance shows that carbonate melt is the main host for incompatible elements such as Ba. This presentation will discuss the bearings of the experimental results on the nature and origin of these MSI, potential links to diamond formation and their implication on mass transfer processes in subduction zones.Kotkova et al. (2021) Lithos 398-399, 106309

—We have studied volcanogenic diamonds in the context of a discussion of their genesis, including some assumption on their artificial origin. The carbon isotope composition of diamonds collected from the eruption products of Tolbachik volcano (δ13CVPDB from –22 to –29‰) is within the range of the δ13CVPDB values of natural diamonds, including those from kimberlites. The δ15NAir values of the Tolbachik diamonds, measured for the first time (–2.58 and –2.32‰), correspond to δ15NAir of volcanic gases and differ from that of atmospheric nitrogen (δ15NAir = 0‰), which may be expected in synthetic diamonds. In the studied volcanogenic diamonds, as in synthetic ones, the nitrogen impurity is unaggregated. However, such an unaggregated form of nitrogen is specific to many natural diamonds (e.g., variety II diamonds, according to Orlov’s classification). Impurity elements (Cl, F, O, S, Si, Al, Ca, and Na) are locally concentrated in volcanogenic diamonds; they are a constituent of micro- and nanoinclusions in them. The high contents of F and Cl in the studied diamonds are correlated with the composition of volcanic gases; there is no reason to expect a similar correlation in synthetic diamonds. Moreover, the studied cube-octahedral Tolbachik diamonds have a number of accessory forms, some of which are not observed in synthetic diamonds. Their surfaces are frequently covered with films composed of Mg–Fe and Ca–Mg silicates, aluminosilicates, sulfates, metal alloys, and native Al. Mineral inclusions in the studied diamonds are Mn–Ni–Si alloys and silicides varying in composition from (Mn,Ni)4Si to (Mn,Ni)5Si2, Mn5Si2, and pure Mn silicide MnSi. Summing up the obtained data, we conclude that volcanogenic diamonds form in a strongly reducing environment, in which silicides and native metals and their alloys are stable. The predominant cube-octahedral morphology of these diamonds and the unaggregated nitrogen impurity point to their short-term residence under high-temperature conditions. This makes them similar, to some extent, to synthetic diamonds. There are, however, clear differences as well. Volcanogenic diamonds are similar in compositional peculiarities, including isotope compositions, to natural diamonds that form under most unfavorable conditions, such as cuboids, balases, carbonado, and some diamonds of the eclogite paragenesis. They also resemble diamonds found in situ in harzburgite and chromitite of ophiolites. This suggests a specific mechanism of formation of both volcanogenic and ophiolitic diamonds in the oceanic lithosphere.

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)5Si2 and 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.

In magmatic Nickel-Copper-Platinum-group elements (Ni-Cu-PGE) sulfide deposits, PGE occur as solid solution in base metal sulfides (BMS) or occur as platinum-group minerals (PGM). In different deposits, such as the world-class deposits at Jinchuan and Noril’sk district which formed from sulfide liquids with different oxygen fugacity (fO2), the proportion of PGE forming PGMs and entering BMS as solid solution are variable and the PGMs are different in mineral species and morphology. The early-cumulated massive ores from the two deposits were analyzed using Electron Probe Microanalysis (EPMA), Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS), Scanning Electron Microscope (SEM) and Focused Iron Beam and Transmission Electron Microscope (FIB-TEM). Combined with whole-rock PGE and semimetals data, this contribution discusses the effect of thermodynamic conditions (mostly fO2) and semimetals on the distribution of PGE and the mineral species and morphology of PGM in magmatic sulfide deposits. The Noril’sk massive ores commonly contain 5–12 vol% of magmatic magnetite whereas magnetite is absent in the Jinchuan massive ores, which suggests that the sulfide liquid at Noril’sk had a higher oxygen fugacity (fO2) compared to the sulfide liquid at Jinchuan. In the Jinchuan massive ores, only ∼ 39 % Ir and 37 % Rh are presented in solid solution within BMS. Meanwhile, many (Ir-Rh-Pt)AsS crystals with grain sizes of 200 nm to 2.5 μm were recognized enclosed in BMS grains and cobaltite-gersdorffite solid solution (CGSS) or rarely located at BMS grain boundaries. Microstructures of the (Ir-Rh-Pt)AsS minerals suggests that they probably crystallized from the sulfide liquid together with MSS. In contrast, more than 63 % Ir and 89 % Rh are presented in solid solution within BMS and no (Ir-Rh-Pt)AsS crystal was found in the Noril’sk massive ores. On the other hand, arsenides, stannide, antimonides, tellurides and bismuthides of Pd and/or Pt (Pt-Pd-semimetal minerals) were found in the Jinchuan and Noril’sk massive ores. This study suggests that thermodynamic conditions (especially fO2) control the valence states of semimetals (especially As) affecting the behavior of PGE in sulfide liquids. A relatively low fO2 of sulfide liquids leads to a relatively high Asn-/Asn+ ratio, which is atomical ratio of the anion to cation of As (n represents valence number), and results in relative more Ir-AsS, Rh-AsS and Pt-As pre-nucleation clusters. These pre-nucleation clusters were enriched in or near the migrating MSS grain boundaries and finally reaching oversaturation and nucleation of (Ir-Rh-Pt)AsS crystals occurred. In contrast, a relatively high oxygen fugacity (fO2) of sulfide liquids results in a low Asn-/Asn+ ratio and Ir-AsS, Rh-AsS and Pt-As pre-nucleation clusters forming a negligible amount of (Ir-Rh-Pt)AsS minerals and facilitating Ir and Rh to enter MSS crystal lattice. As for the deposits formed from sulfide liquids with a relatively low fO2, such as the deposits at Jinchuan, Yangliuping and Sudbury, the fractional crystallization of MSS together with (Ir-Rh-Pt)AsS minerals resulted in PGE differentiation.

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,☐)7 phase 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,☐)7 and 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)Σ1.91 was 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 TiSi2 could have crystallized from alloy melts at the lowest T accessible on the liquidus, i.e.

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, (5) inclusions of rutile in shocked baddeleyite, (6) amorphous domains, (7) recrystallized domains. In many grain aggregates, shock-related micro-structures overprint each other, indicating either different stages of a single impact process or multiple impact events. During shock, some zircons were transformed to diaplectic glass (6), and others (7) were completely decomposed into SiO2 and Zr-oxide, evident from the observed round shapes of cubic zirconia and silica-rich glass filling triple junctions of zircon granules. Despite the highly variable effect on textures and Zr phases, shock-related features show no correlation with relatively homogeneous U–Pb or 207Pb/206Pb ages of zircons. Either the shock events occurred very soon after the solidification or recrystallization of the different Zr phases, or the shock events were too brief to result in noticeable Pb loss during shock metamorphism.

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.

Eight late medieval to early modern red beads representative of a total of 41 from a cesspit of the “Fronerei auf dem Schrangen” in Lübeck, Germany, were investigated using micro X-ray computed tomography (3D-μXCT), X-ray microdiffraction (μ-XRD2), transmission electron microscopy (HRTEM) and Raman spectroscopy (RS). The microscopic properties of the material were characterised non- destructively or minimally invasively for colouration, mineralogical and chemical composition determination but also with regard to their macroscopic external appearance. The polished beads are spherical with flattered tops and boreholes perpendicular to the flattening and show partially traces of working. As base material for all examined beads, high Mg-Calcite with polyenes could be identified. Combined with density and microstructure data, the beads are undoubtedly red precious corals, identical with modern corallium rubrum from the Mediterranean also confirmed by C- and O-isotopic analyses. The studies provide general criteria for the determination of corallium rubrum, confirming the macroscopically determined identification of other coral artefacts associated with the Hanseatic League, and thus prove their iconographic importance as well as the trade contacts with the Mediterranean region. However, the extent to which the characteristics of the coral beads indicate accidental or intentional individual or collective societal or social circumstances is left to further study.

Eleven monazite grains, two from a migmatitic gneiss and nine from two felsic granulites from the Góry Sowie Block (SW Poland) were studied with transmission electron microscopy (TEM), electron probe microanalysis (EPMA), Raman microspectroscopy and laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) U-Th-Pb analysis in order to assess processes affecting U-Th-Pb age record. Two monazite grains from the migmatitic gneiss are patchy zoned in BSE imaging and overgrown by allanite, whereas Raman results indicate moderate radiation damage. Monazite in the corresponding TEM foils shows twins and nanoinclusions of fluorapatite, thorianite, goethite, titanite, chlorite and CaSO4. Furthermore, monazite is partially replaced by secondary monazite, forming ca. 100 nm-thick layers, and calcite along grain boundaries. The submicron alterations had little or no effect on the Pb/U and Pb/Th dates, when compared to earlier age constraints on the metamorphism in the studied region. In contrast, monazite from both granulites is homogeneous in eight investigated TEM foils, contains no solid or fluid nanoinclusions or any signs of fluid-induced alterations, with only one exception of a ca. 140 nm-thick crack filled with monazite. The 206Pb/238U and marginally older 208Pb/232Th mean dates pulled for all data show good coherence. However, the 207Pb/235U isotopic record is disturbed due the presence of common Pb within the entire monazite grain in one granulite and in the cores of two monazite grains in the second granulite, where the Usingle bondPb data of the rims are not compromised and concordant. Due to lack of TEM evidence for fluid-mediated alterations, the age discordance has to be related to addition of common Pb in the monazite lattice or in the micro-cracks. To summarize, the 208Pb/232Th data reveal the most accurate ages, which are consistent with previous geochronological studies in the region. Therefore, the Pb/Th chronometer, which is less compromised by age disturbance compared to Pb/U ages, is recommended for monazite geochronology. Application of the submicron scale investigations using TEM is recommended to evaluate potential presence of the submicron inclusions of Pb-bearing phases or compositional alterations of monazite that can remain unnoticed by using standard microanalytical instruments.

There are seven meteorite craters and several Neogene placers in the Ukrainian Shield containing impact apographitic diamond. In this work impact diamonds from the Bilylivka meteorite crater and from the Samotkan’ Neogene titanium-zirconium placer were studied in detail. The results of a comprehensive study of impact diamond crystals — morphology, microtopography, microstructure, carbon isotope composition, photoluminescence, optical, infrared, and Raman spectroscopy — are presented. The size of the impact diamonds is up to 0.5 mm. Impact diamond crystals are mostly two- or three-phase polycrystalline aggregates (diamond, lonsdaleite, graphite). They show external morphological and internal microstructural features of solid-state phase transition of graphite to diamond during impact shock metamorphism – they are paramorphoses on graphite crystals. Microstructural features of the graphite-diamond transition in the studied crystals of impact diamonds are their polysynthetic (11 2¯¯¯ 1) twinning and the polycrystalline structure of the twins themselves. The carbon isotopic composition of impact diamonds ranges: for Bilylivka diamonds – from –14.80 to –21.84 ‰ δ13C VPDB, with an average value of –17.21 ‰ δ13C and for Samotkan’ diamonds – from –10.35 to –23.06 ‰ δ13C VPDB, with an average value of –17.64 ‰ δ13C. The photo luminescent and spectroscopic features of the studied diamonds indicate the absence of nitrogen defects in crystals that are characteristic for mantle diamond. The location of the source rocks and potential routes how diamond have been incorporated into the Samotkan’ placer are discussed.

Transmission electron microscopy and 3D focused ion beam/scanning electron microscope nanotomography are applied to grain and phase boundaries between quartz, plagioclase, K-feldspar, clinopyroxene, amphibole, and calcite. The samples come from metamorphic, plutonic and volcanic rocks, and hydrothermal quartz, and experienced cooling and decompression after highly variable P–T peak conditions. Most of the boundaries are partially open in the range of up to several hundred nanometres and partly to totally filled with secondary minerals, such as actinolite, biotite, chlorite, sheet silicates, and quartz, as well as with amorphous matter. Cracking and opening of boundaries are suggested to be related to anisotropic thermoelastic response of crystals to cooling. It starts below the brittle–ductile transition of the involved minerals. The partially open grain and phase boundaries, together with dissolution-generated cavities, can form porosity of more than 2 vol.% and permeability under conditions of at least lowermost greenschist facies. Such networks of partially open or partially refilled boundaries potentially affect properties of crystalline rocks and processes in the upper crust, such as metasomatism, weathering, migration of radionuclides through bedrock of geological repositories of nuclear waste, and deformation in nature and in experiment., Journal of Metamorphic Geology, 40 (1), ISSN:0263-4929, ISSN:1525-1314

The microbial key players at methane seeps are methanotrophic archaea and sulfate-reducing bacteria. They form spherical aggregates and jointly mediate the sulfate-dependent anaerobic oxidation of methane (SD–AOM: CH4 + SO42− → HCO3− + HS− + H2O), thereby inducing the precipitation of authigenic seep carbonates. While seep carbonates constitute valuable archives for molecular fossils of SD–AOM-mediating microbes, no microfossils have been identified as AOM aggregates to date. We report clustered spherical microstructures engulfed in 13C-depleted aragonite cement (δ13C values as low as −33‰) of Pleistocene seep carbonates. The clusters comprise Mg-calcite spheres between ∼5 µm (single spheres) and ∼30 µm (clusters) in diameter. Scanning and transmission electron microscopy revealed a porous nanocrystalline fabric in the core area of the spheres surrounded by one or two concentric layers of Mg-calcite crystals. In situ measured sphere δ13C values as low as −42‰ indicate that methane-derived carbon is the dominant carbon source. The size and concentric layering of the spheres resembles mineralized aggregates of natural anaerobic methanotrophic archaea (ANME) of the ANME-2 group surrounded by one or two layers of sulfate-reducing bacteria. Abundant carbonate-bound 13C-depleted lipid biomarkers of archaea and bacteria indicative of the ANME-2-Desulfosarcina/Desulfococcus consortium agree with SD–AOM-mediating microbes as critical agents of carbonate precipitation. Given the morphological resemblance, in concert with negative in situ δ13C values and abundant SD–AOM-diagnostic biomarkers, the clustered spheres likely represent fossils of SD–AOM-mediating microbes.

Monocrystalline type Ia diamonds with octahedral growth morphology prevail among lithospheric diamonds, including precious stones. Unlike less common ‘fibrous’ diamonds that grew from alkali-rich carbonate-bearing melts and fluids, the growth medium of ‘monocrystalline’ type Ia diamonds remains debatable. Here we report the first finding of an optically visible (~30 μm in size) carbonate inclusion in the center of a gem type Ia octahedral diamond from the Sytykanskaya kimberlite pipe, Yakutia. We found that the inclusion consists of submicron size carbonate phases represented by K 2 Ca(CO 3 ) 2 butschliite (~15 vol%), Na 2 Mg(CO 3 ) 2 eitelite (~5 vol%), and dolomite (~80 vol%). Although neither butschliite nor eitelite can coexist with dolomite under mantle P-T conditions, these phases readily appear all together in the quenched products of carbonatite melt under mantle pressures. Thus, at the moment of capture, the inclusion material was a carbonatite melt with the following composition 10(K 0.75 Na 0.25 ) 2 CO 3 ∙90(Ca 0.57 Mg 0.43 )CO 3 . The content of alkali carbonates at the level of 10 mol% indicates that the melt was formed at a temperature of ≥1300 °C. The high K/Na and Ca/(Ca + Mg) ratios in this melt indicate its derivation by partial melting of recycled marine sediments (pelites). Considering an age of the last subduction event beneath the Siberian craton, our new finding implies that subducting slabs drag carbonated material of the continental crust beneath ancient cratons, where it experiences partial melting to form a potassic dolomitic melt responsible for the formation of most diamonds, since the Late Archean.

Nanospheres of lead (Pb) have recently been identified in zircon (ZrSiO4) with the potential to compromise the veracity of U-Pb age determinations. The key assumption that the determined age is robust against the effects of Pb mobility, as long as Pb is not lost from the zircon during subsequent geological events, is now in question. To determine the effect of nanosphere formation on age determination, and whether analysis of nanospheres can yield additional information about the timing of both zircon growth and nanosphere formation, zircons from the Napier Complex in Enderby Land, East Antarctica, were investigated by high-spatial resolution NanoSIMS (Secondary Ion Mass Spectrometry) mapping. Conventional SIMS analyses with >µm resolution potentially mixes Pb from multiple nanospheres with the zircon host, yielding variable average values and therefore unreliable ages. NanoSIMS analyses were obtained of 207Pb/206Pb in nanospheres a few nanometres in diameter that were resolved from 207Pb/206Pb measurements in the zircon host. We demonstrate that analysis for 207Pb/206Pb in multiple individual Pb nanospheres, along with separate analysis of 207Pb/206Pb in the zircon host, can not only accurately yield the age of zircon crystallization, but also the time of nanosphere formation resulting from Pb mobilization during metamorphism. Model ages for both events can be derived that are correlated due to the limited range of possible solutions that can be satisfied by the measured 207Pb/206Pb ratios of nanospheres and zircon host. For the Napier Complex zircons, this yields a model age of ca 3110 Ma for zircon formation and a late Archean model age of 2610 Ma for the metamorphism that produced the nanospheres. The Nanosphere Model Age (NMA) method constrains both the crystallization age and age of the metamorphism to ~±135 Ma, a significant improvement on errors derived from counting statistics.

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. Coarse-grained 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 (Al2O3 = 3.85–4.90 wt%, CaO =

Sphalerite and arsenopyrite can host trace elements (e.g., Ge, Cd and Au) that are important for high technology applications. These trace elements are incorporated into the structure of the host mineral (e.g., by substitution) if inclusions are apparently absent. Focused ion beam technique and transmission electron microscopy combined with electron microprobe analysis allow for the correlation from micrometre to the nanometre scale in order to investigate the locations of trace elements in situ within the host minerals. Therefore, Ge-rich sphalerite from the Tres Marias Zn–Pb–Ge deposit in Mexico and auriferous arsenopyrite from the Ashanti Au mine in Ghana are investigated. Sphalerite from Tres Marias contains Ge concentrations of up to 1430 μg/g and is characterised by elevated Fe contents. Germanium is homogeneously distributed within the sphalerite lattice without the presence of distinct Ge-bearing phases in the form of inclusions or exsolutions. In arsenopyrite from the Ashanti mine, Au occurs as oriented sub-microscopic discrete phases showing at least two distinct orientations, which cause the observed trace-element concentrations visible at larger scale. The formation of nanometre-sized gold particles in arsenopyrite is interpreted as enrichment of Au at the interface of crystallising arsenopyrite with the hydrothermal fluid and subsequent crystallisation of nanometre-sized gold grains at the surface of arsenopyrite after the critical concentration for nucleation was overstepped.

The metastable paragenesis of corundum and quartz is rare in nature but common in laboratory experiments where according to thermodynamic predictions aluminum–silicate polymorphs should form. We demonstrate here that the existence of a hydrous, silicon-bearing, nanometer-thick layer (called “HSNL”) on the corundum surface can explain this metastability in experimental studies without invoking unspecific kinetic inhibition. We investigated experimentally formed corundum reaction products synthesized during hydrothermal and piston–cylinder experiments at 500–800 °C and 0.25–1.8 GPa and found that this HSNL formed inside and on the corundum crystals, thereby controlling the growth behavior of its host. The HSNL represents a substitution of Al with Si and H along the basal plane of corundum. Along the interface of corundum and quartz, the HSNL effectively isolates the bulk phases corundum and quartz from each other, thus apparently preventing their reaction to the stable aluminum silicate. High temperatures and prolonged experimental duration lead to recrystallization of corundum including the HSNL and to the formation of quartz + fluid inclusions inside the host crystal. This process reduces the phase boundary area between the bulk phases, thereby providing further opportunity to expand their coexistence. In addition to its small size, its transient nature makes it difficult to detect the HSNL in experiments and even more so in natural samples. Our findings emphasize the potential impact of nanometer-sized phases on geochemical reaction pathways and kinetics under metamorphic conditions in one of the most important chemical systems of the Earth’s crust.

Feedback between deformation mechanisms, fluid-rock interactions and porosity evolution in fault zone rocks has a crucial impact on their bulk rheology. Porosity formation within mid-crustal fault rocks (typically mylonites) can facilitate fluid flow, formation of mineral and geothermal resources, and can promote strain localization. On the contrary, porosity reduction in rocks from a brittle fault core (typically cataclasites) can cause elevated pore fluid pressures, and consequently influence the recurrence time of earthquakes.We characterized the porosity distribution within the New Zealand’s Alpine Fault zone in cataclasite samples recovered during the first phase of the Deep Fault Drilling Project and outcropping mylonitic rocks collected at Stoney Creek, New Zealand. Synchrotron X-ray microtomography-derived analyses of open pore spaces show total microscale porosity values in the range of 0.1-0.24% within the cataclasites and up to 0.44% in the mylonites. Synchrotron nanotomography datasets reveal additional 0.03 to 0.19% pore volumes within the mylonites. In all samples, pores are very small, not connected, with mainly non-spherical, elongated, flat shapes and show subtle bipolar orientation. Scanning and transmission electron microscopy reveal the samples’ microstructural organization, where nanoscale pores ornament grain boundaries of the constituent minerals. Pores are mostly associated with (often newly formed) clay minerals in the cataclasite samples, suggesting the orientation of clays controls the shape and orientation of the associated pores. In the mylonitic samples, pores are sub-parallel to the foliation, and often associated with C’-type shear bands, indicating formation during creep cavitation.Our observations imply that porosity within the Alpine Fault core was reduced due to pressure solution processes and the associated mineral precipitation. Simultaneously propagation of fluids triggered by cavity formation in the ductile regime is likely to cause further mineral precipitation in fluid filled pores within the fault zone. Such precipitation can affect the mechanical behavior of the Alpine Fault by decreasing the already critically low total porosity of the fault core, causing elevated pore fluid pressures, and/or introducing weak mineral phases, and thus lowering the overall fault frictional strength. We conclude that the current state of porosity in the Alpine Fault zone is likely to play a key role in the initiation of the next fault rupture.

An intergrowth of zircon and xenotime, formed at ca. 2.09 Ga, was significantly altered after incorporation as a restite into pegmatite at ca. 370 Ma (Piława Górna, Góry Sowie Block, SW Poland; Budzyń et al., 2018). Alteration involved fluid-induced coupled dissolution-reprecipitation processes, which resulted in compositional alteration and development of patchy zoning and porosity in the xenotime and the rim of zircon. Diffusion-reaction processes affected the metamict core of zircon and resulted in nano- to microscale patchy zoning and submicron-scale porosity. This study evaluates the alteration processes with respect to structural and compositional characteristics by using TEM and LA-ICPMS trace element analysis.Nanoscale observations revealed nanoporosity in the metamict core of zircon and a continuation of patchy zoning on a submicron level, which resulted from heterogeneous metamictization correlating with variation in U and Th contents. The altered xenotime and the zircon rim are dominated by microporosity filled with a variety of secondary phases such as U, Th, Pb and Fe rich oxides and silicates. In rare cases, secondary PbS formed nano inclusions in zircon, occasionally surrounded by amorphous apatite. Aside of known substitution mechanisms in xenotime, such as thorite and cheralite components, a correlation of Zr with LREE and Si contents indicates substitution of the zircon component. Furthermore, the zircon-xenotime interface revealed dissolution pits, filled with secondary zircon that formed at the expense of primary xenotime via coupled dissolution-reprecipitation reactions. This indicates local penetration of the fluid-mineral reaction front into xenotime. Major (Si, Zr and P) and trace elements, including U, Th and Pb, which are geochronologically relevant, have been mobilized in the metamict core of zircon due to alteration induced by an alkali-rich fluid with high activities of F, Na and Ca. The altered xenotime and porous rim of zircon were affected by alteration induced by a fluid containing Fe, which resulted in precipitation of Fe-rich phases, such as Fe-oxides and silicates often accompanied by relevant contents of Pb. In conclusion, nanoscale structural observations and LA-ICP-MS trace element data support the complex geochronological implications of the altered zircon-xenotime intergrowth, emphasising the necessity of understanding alteration processes of zircon and xenotime taking into account element transport and thus the disturbance of their geochronological clock.Acknowledgements: This work was supported by the National Science Centre grant no. 2017/27/B/ST10/00813.References:BudzyńB., Sláma J., Kozub-Budzyń G.A., Konečný P., HolickýI., RzepaG.,Jastrzębski M. (2018) Lithos 310-311, 65-85.

The high-pressure CaCO3 phase 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–SrCO3 solid-solution series and revealed the effect of cationic substitution on the pressure-induced phase transitions in calcium carbonate. A synthetic solid solution Ca0.82Sr0.18CO3 was studied in situ by Raman spectroscopy in a diamond-anvil cell (DAC) up to 55 GPa and 800 K. The results of this work show significant differences in the high-pressure structural and vibrational behavior of the (Ca,Sr)CO3 solid solution compared to that of pure CaCO3. The monoclinic CaCO3-II-type structure (Sr-calcite-II) was observed already at ambient conditions instead of the “expected” rhombohedral calcite. The stress-induced phase transition to a new high-pressure modification, termed here as Sr-calcite-IIIc, was detected at 7 GPa. Sr-calcite-VII formed already at 16 GPa and room T, which is 14 GPa lower compared to CaCO3-VII. Finally, crystallization of Sr-aragonite was detected at 540 K and 9 GPa, at 200 K lower T than pure aragonite. Our results indicate that substitution of Ca2+ by bigger cations, such as Sr2+, in CaCO3 structures can stabilize phases with larger cation coordination sites (e.g., aragonite, CaCO3-VII, and post-aragonite) at lower P-T conditions compared to pure CaCO3. The present study shows that the role of cationic composition in the phase behavior of carbonates at high pressures should be carefully considered when modeling the deep carbon cycle and mantle processes involving carbonates, such as metasomatism, deep mantle melting, and diamond formation.

s of the International Symposium on Deep Earth Exploration and Practices, 1–5 Nov 2021, Nanjing, China