Unusual Mineral Research Articles

Kenorozhdestvenskayaite-(Fe), Ag6(Ag4Fe2)Sb4S12☐: A new tetrahedrite group mineral containing a natural [Ag6]4+ cluster and its relationship to the synthetic ternary phosphide (Ag6M4P12)M6′

Abstract [Ag6]4+ clusters are extremely rare in nature (only found in Ag-rich tetrahedrite group minerals). Due to their remarkable structures and some promising applications, a few synthesis phases that contain octahedral [Ag6]4+ clusters have been reported. However, the kinds of natural conditions that promote the formation of subvalent hexasilver clusters in tetrahedrite group minerals are still unclear. Kenorozhdestvenskayaite-(Fe), ideally Ag6(Ag4Fe2)Sb4S12☐ is a new tetrahedrite group mineral containing a natural [Ag6]4+ cluster, found in the Yindongpo gold deposit, Weishancheng ore field, Henan Province, China. This new species occurs at the edges of galena crystals as anhedral grains of 2 to 20 μm in size and is associated with pyrargyrite, pyrrhotite, and siderite. Kenorozhdestvenskayaite-(Fe) is black in color with metallic luster. It is brittle with conchoidal fracture and has a calculated density of 5.329 g/cm3. The empirical formula calculated on the basis of cation = 16 apfu is M(2)Ag6M(1)(Ag2.41Cu1.20Fe1.84Zn0.71)Σ6.16X(3)(Sb3.82As0.01)Σ3.83S(1)S11.60S(2)☐. It is cubic, with space group I43m, a = 10.7119(6) Å, V = 1229.1(2) Å3, and Z = 2. Since kenorozhdestvenskayaite-(Fe) is a new tetrahedrite group mineral containing a natural [Ag6]4+ cluster, its structure is comparable to the synthetic ternary phosphide (Ag6M4P12)M6′. The presence of the unusual mineral assemblages, i.e., pyrrhotite and pyrargyrite, as well as the other keno-end-member tetrahedrites, indicates a low-fS2 state for the mineralization stage, probably a result of the fluid boiling process in an open system that likely contributed to the formation of S-deficient tetrahedrites.

Chromian minerals and talc veins in the metasandstones of the Ochi nappe, southern Evia, Greece: The role of fluids in retrograde metamorphism during exhumation

Unusual minerals were formed during the retrograde metamorphism of high-pressure metamorphic rocks in the Ochi nappe, southern Evia, Greece, specifically widespread sub-mm-scale talc veins and chromian varieties of chlorite, phengite, biotite and allanite. Albite-quartz-calcite and calcite-quartz schists are cut by common 10–200 μm wide veins of talc, rimmed by Cr-chlorite with <0.6 apfu Cr. Hydraulic fracturing by fluids derived from dehydration of subducted chromite-rich serpentinite in the Ochi nappe created fractures in the schists where talc precipitated. Mineral chemistry and textures are related to regional metamorphic and tectonic phases, which included Eocene blueschist metamorphism followed by Oligocene syn-orogenic wedge extrusion. The overprint resulted in retrograde growth of albite porphyroblasts, emplacement of talc veins, and formation of phengite with <0.08 apfu Cr and later biotite with <0.3 apfu Cr. Late Oligocene shearing flattened many pre-existing minerals. Neogene exhumation within the North Cycladic detachment system produced decompression fractures that nucleated precipitation of allanite (some with <0.4 apfu Cr and > 0.8 apfu REE), apatite, titanite and zircon, reflecting the availability of halogen-rich fluids. The evolution of the retrograde metamorphic minerals assemblages can thus be tracked, with pervasive Cr-Mg infiltration in the Oligocene, and more focussed Miocene metasomatism by halogen-rich fluids.

Diamonds Discovered in the Forearc Harzburgites Hint at the Deep Mantle Source of the Skenderbeu Massif, Western Mirdita Ophiolite

The ultra-deep genesis of ophiolitic peridotite has reshaped our perception of the genesis of the oceanic mantle. Although ultra-high pressure (UHP) mineral assemblages have been unearthed in dozens of ophiolites in different orogenic belts around the world, the vast majority of them have been limited to podiform chromitites formed in suprasubduction zone (SSZ) settings, leaving uncertainty about whether such UHP minerals are intrinsic to the oceanic mantle or influenced by a specific mantle rock type. Here, we report on the occurrence of diamonds recovered from the harzburgites within the Skenderbeu massif, Mirdita ophiolite. The whole-rock, mineralogical major and trace element compositions, and redox states of the harzburgites align with modern abyssal harzburgites. Trace element modeling of clinopyroxene indicates that harzburgites have endured varying degrees of garnet-facies melting (~2%–5%) before progressing to spinel-facies melting (~10%–12%). Mineralogical characteristics further support that the Skenderbeu harzburgites underwent late-period MORB-like melt metasomatism in a forearc spreading center. An unusual mineral assemblage of diamonds has been separated from the studied harzburgites. The first occurrence of ophiolite-hosted diamonds discovered in the forearc harzburgites, together with previous similar discoveries in the SSZ ophiolitic chromitites, suggest that the ophiolite-hosted diamonds are not specific to certain mantle rocks.

Roman wall paintings from the Roman Forum district of Carthago Nova: Characterisation of mortars and pigments

This paper aims to study the construction technique and characterisation of original mortars and wall paintings at the Roman Forum district of Carthago Nova (Spain). A multi-analytical approach was conducted on original fragments using Optical Microscopy (OM), Field Emission Scanning Electron Microscopy (FESEM), colour tests (CIE L*a*b*) and contact angle measurements. Besides, the chemical composition was studied by X-fluorescence (XRF), Thermogravimetry (TG), X-ray diffraction (XRD) and Infrared spectroscopy using attenuated total reflectance (ATR-FTIR). The mortars showed a multi-layered pattern consisting of three distinguishable layers that were decorated with low-thickness coatings. The top layer composition was eminently calcitic, while the central and bottom layers were probably elaborated with pozzolanic materials. It is worth noting that unusual minerals as cerussite (PbCO3) were identified in some layers, and probably associated to subsequent activities carried out in the site after Roman times. The top coating was made of hematite (Fe2O3) for red decoration, whereas graphite (C) and hydroxyapatite (Ca5(PO4)3(OH)) were identified in black coatings, which suggests the use of animal bones in the production of black pigments. In addition, the outer surface of some fragments was most likely coated with organic substances to enhance colour and durability. Finally, SEM examination and EDX analyses also confirmed some of the above findings and the existence of NaCl surface crusts due to natural weathering.

Zeolitized fossil woods from alkaline volcaniclastic rocks: Unravelling an uncommon mineralization process

Mineralization of fossil woods with unusual mineral phases remains an underconstrained process despite its relatively common occurrences. Aside from common mineralization agents such as silica or carbonates, there are also atypical mineralization associations, such as zeolite-group phases, but the zeolitization process has not yet been investigated in detail. We studied zeolitized woods collected from two localities in the Cenozoic alkaline České Středohoří Volcanic Complex (Ohře Rift, Czech Republic), where fossil woods of diverse paleobotanical classification were deposited in volcaniclastic rocks of the same origin (lahar) and stratigraphic formation (Upper Oligocene). The identical geological setting allowed the investigation of potential variables influencing this type of mineralization by combining paleobotanical classification, detailed mineralogy, mineral chemistry, geochemistry, Sr isotope analysis and KAr chronology.The new results demonstrate the significant potential of fossil woods mineralized with zeolite-group minerals to be used to reconstruct the formation and deposition conditions of the lahars in which these woods are contained. The composition of zeolites is strongly dependent on thermal conditions and material exchange between wood and host rocks. Dominant mineral phases are phillipsite and chabazite in variable proportions. The phillipsite/chabazite ratio correlates well with the magnitude of the Eu anomaly, suggesting crystallization of phillipsite at a higher temperature under hot-lahar conditions of deposition. Chabazite lacking an Eu anomaly represents the later, colder mineralization stage. The 87Sr/86Sr ratios ranging 0.7042–0.7047 provide an additional line of evidence of fluid derivation from volcaniclastic deposits of the Upper Oligocene Děčín Fm.

Mineral–Geochemical and Geotectonic Features of the Lotmvara-II Ultrabasic Sill, Serpentinite Belt (Kola Peninsula)

Abstract —In this paper, we present a description of the characteristics of the Lotmvara-II sill, which is a representative of the Serpentinite Belt (SB) composed of a series of shallowly emplaced ultrabasic intrusive bodies. The Paleoproterozoic SB complexes were derived from a large-scale mantle plume of komatiitic melt. The sill consists predominantly of fine-grained (locally nearly micrograined) harzburgites with subordinate zones of dunites and orthopyroxenites, located in the central and marginal parts, respectively. It formed from an Al-undepleted komatiitic magma of extremely high Mg content and may represent a near-surface laccolithic “ridge.” In general, the sill is comparatively homogeneous and does not have distinct zoning in the distribution of Mg# values in rock compositions (Mg# = 84.2–88.9, average 86.7). Detailed studies show that olivine, chromian spinel, and ilmenite are the most strongly magnesian in the central part of the body. The maximum values of Mg# equal to 90.7–91.4 in the compositions of olivine at the center of the sill are interpreted as “centers of initial crystallization”. The low values of Mg# equal to 73.4–76.4 are attributed to manifestations of the recurrent generation of olivine. The values of Mg# of orthopyroxene in the sill are within the range 84.6 to 92.3. Orthopyroxene grains in a porphyritic texture are surrounded by a rim of calcic amphibole (autometasomatic in origin); they do not differ compositionally from normal grains. The Zn content of the chromian spinel generally decreases toward the marginal parts of the sill. There is an insignificant degree of magmatic differentiation in the sill with respect to the principal components, but incompatible elements (REE and HFSE) locally show increased levels of their relative enrichment, which is reflected in the nature of the mineral associations described. Thus, the sill has a cryptic zonal structure, which is consistent with its overall crystallization from the center to the edges. The data gathered suggest the presence and significant development of volatile components, halogens, CO2, and especially magmatic H2O, which are capable of strongly lowering the liquidus and reducing the density and viscosity of the high-magnesium melt, thereby improving its mobility during ascent from the mantle to the near-surface level of the crust. An increase in fO2 is observed during in situ subvolcanic crystallization of the sill, as noted earlier in the related complexes of the belt. The relatively small volume of the komatiitic magma in the sill crystallized fairly quickly, resulting in unusual mineral intergrowths. Thus, the Lotmvara-II sill is a novel member in the Serpentinite Belt–Tulppio Belt (SB–TB) in the Paleoproterozoic SB–TB megastructure of the Fennoscandian Shield.

Petrographic and geochemical evidence of calc-silicate xenolith – magma interaction in the western Bushveld Complex, South Africa

Abstract Underground workings at Rowland Shaft, Lonmin Platinum, near Marikana have exposed a large (&amp;gt;7 x 5 m) calc-silicate xenolith in mottled anorthosite ~20 m below the UG 1 chromitite of the upper Critical Zone. The xenolith comprises a monticellite + forsterite + spinel assemblage that is consistent with a metamorphic Tmax of ≥975°C being reached at P ~1 kbar and XCO2 ~1. Internal variations in the modal proportions of these phases are interpreted as an artefact of sedimentary layering in the xenolith. The xenolith is flanked by a 20 to 30 cm wide magmatic skarn that contains several small, cm- to dm-scale, calc-silicate fragments displaying the same peak assemblage as the main xenolith, as well as a dm-scale chromitite autolith and mm- to dm-scale lenses and stringer-like masses of fine-grained uvarovite. The skarn matrix is mineralogically zoned, with an up to 10 cm wide clinopyroxenite layer proximal to the xenolith contact and calc-silicate fragments grading outwards into a gabbroic, plagioclase-clinopyroxene assemblage in which plagioclase becomes progressively more dominant distally. Notwithstanding its pseudo-ophitic texture, the distal skarn matrix displays a range of features consistent with crystallisation of magma contaminated by Ca from the decomposing xenolith under elevated fO2 conditions, including: (a) the unusual mineral compositions (zoned aluminian-ferrian diopside and anorthite, An&amp;gt;99), (b) the presence of calcite as inclusions in plagioclase and as a minor interstitial phase, (c) corroded wollastonite inclusions in clinopyroxene, and (d) thin grossular reaction rims between clinopyroxene and plagioclase. This chemical evolution is further substantiated by zoned spinel grains comprising Cr-rich cores and Al-enriched rims, which are, in turn, enclosed in garnet aggregates that grade outwards from uvarovite to grossular. Local development of grossular-vesuvianite symplectite indicates limited retrograde hydrous (XCO2 &amp;lt;0.1) fluid influx under subsolidus conditions (T &amp;lt;750°C). Bedding in the xenolith displays a steep westerly dip, approximately orthogonal to the magmatic layering. This, together with evidence in the skarn of both plastic shear strain and out-of-sequence magmatic autoliths, suggests that the xenolith underwent density-driven foundering within the RLS magma from an initial location above the UG 1 chromitite layer.

Post-magmatic hydrothermal activities in the Bursa ophiolite (NW Turkey): Implications for unusual minerals recovered from ophiolites

Low-temperature hydrothermal activities in ophiolites and their modification of chromite have been less studied compared to the magmatic processes. Here we present evidence of hydrothermal modification of chromitites from the mantle sequence of the Bursa ophiolite (NW Turkey). The chromitites are composed mainly of chromite with variable amounts of magnesite and quartz in the matrix. Many chromite grains contain various inclusions such as monophase magnesite or quartz, as well as multi-phase inclusions of quartz + chlorite ± magnesite associated with or without ferrian chromite, which are unusual in ophiolitic chromitites worldwide. Ferrian chromite intergrown with chlorite and quartz inclusions, has higher Cr# values (88.3–94.1) but lower MgO (6.11–9.74 wt%), and Fe3+/(Fe3++Fe2+) ratios (0.13–0.25) than primary chromite (Cr#: 78.3–79.1); MgO: 15.4–15.6 wt%; Fe3+/(Fe3++Fe2+): 0.36–0.40), indicating the infiltration of reducing and SiO2-rich serpentinizing fluids. The pyroxene and olivine were likely broken down by the pre-existing fluids and contributed to the SiO2-rich characteristic of serpentinizing fluid. Fluxing by CO2-rich fluids produced carbonation of the previous serpentine matrix and formed interstitial magnesite and quartz. Lower MgO contents and overall higher Cr# values of small chromite grains hosted in magnesite matrix compared to those hosted in quartz matrix (MgO: 13.2–15.0 wt% vs. 14.8–15.4 wt%; Cr#: 78.7–79.8 vs. 78.2–78.8) suggest that the carbonated fluids redistributed Mg2+ into magnesite and subtly increased Cr solubility in the fluids. Recrystallization may have prompted fracture healing in chromite grains and preservation of quartz when not associated with ferrian chromite. The carbon and oxygen isotope compositions of magnesite (δ13C: −3.35‰; δ18O: 17.29‰) indicate that the CO2-rich fluids were likely derived by decarbonation of marble and metaclastic rocks from the Tavşanlı zone metamorphic rocks in the Bursa ophiolite.

Mineral Formation at the East Pauzhetka Thermal Field (South Kamchatka) as an Indication of Influence of a Deep-Seated Alkaline Fluid and an Epithermal Ore-Forming System

Abstract —A sequence of argillized rocks and hydrothermal clays of the East Pauzhetka thermal field was studied in detail by means of drilling and trenching. We have identified zones composed of unusual mineral associations; their formation conditions are considered. The structure of the base of the hydrothermal-clay mass is shown. The source rocks (brecciated andesites) of the base are altered by hydrothermal–metasomatic processes and are represented by smectite–chlorite–K-feldspar–zeolite–carbonate–siliceous aggregate with sulfides, phosphates, titanium silicates and zircon silicates, and other mineral phases, including rare metals. A conceptual geological and geochemical model for the formation of argillisites and zones with mineral associations has been plotted. It is assumed that modern mineral formation in the East Pauzhetka thermal field inherits an epithermal ore-forming system located in the influence zone of a deep-seated fluid, the derivates of which are outflowing near the surface as alkaline metal-bearing solutions of the Pauzhetka hydrothermal system.

Nb–Ta mineralization in Ti-oxide minerals from the Bagolyhegy Metarhyolite Formation (Bükk Mountains, NE Hungary)

Abstract The foliated low-grade metamorphic rocks of the Triassic Bagolyhegy Metarhyolite Formation, mainly of pyroclastic origin, host post-metamorphic quartz-albite veins containing abundant tourmaline and occasionally rutile/ilmenite. The study of the Ti-oxide-mineralized veins with SEM-EDX revealed an unusual mineral assemblage comprising fine-grained Nb–Ta-bearing oxides (columbite-tantalite series, fluorcalciomicrolite and other Nb–Ti–Y–Fe-REE-oxide minerals) intergrown with Nb-rich polymorphs of TiO2 (anatase, rutile), ilmenite and zircon enriched with hafnium. This high field strength elements (HFSE)-bearing paragenesis is unexpected in this lithology, and was not described from any formation in the Paleozoic-Mesozoic rock suite of the Bükk Mountains (NE Hungary) before. The host metavolcanics are significantly depleted in all HFSE compared to the typical concentrations in felsic volcanics and the mineralized quartz-albite veins have even lower Ti–Nb–Ta concentration than the host rock, so the mineralization does not mean any enrichment. From proximal outcrops of the Triassic Szentistvánhegy Metavolcanics, potassic metasomatized lenses with albite-quartz vein fillings containing rutile/ilmenite are known. We studied them for comparison, but they only contain REE mineralization (allanite-monazite-xenotime); the Nb–Ta-content of Ti-oxide minerals is undetectably low. LA-ICP-MS measurements for U–Pb dating of Hf-rich zircon of the Nb–Ta-rich mineral assemblage gave 71.5 ± 5.9 Ma as lower intercept age while dating of allanite of the REE mineralized quartz-albite veins gave 113 ± 11 Ma as lower intercept age. The REE-bearing vein fillings formed during a separate mineralization phase in the Early Cretaceous, while the Nb–Ta mineralization was formed by post-metamorphic alkaline fluids in the Late Cretaceous., controlled by fault zones and fractures.

Deep origin of mantle peridotites from the Aladağ ophiolite, Turkey: Implication from trace element geochemistry of pyroxenes and mineralogy of ophiolitic diamonds

The Aladağ peridotites mainly consist of harzburgites with subordinary dunites. High olivine Fo [100 × Mg/(Mg + Fe2+) = 90.8–92.0] and spinel Cr# [100 × Cr/(Cr + Al) = 61.5–71.6] values indicate the Aladağ harzburgites have experienced high degrees of partial melting. Significant depletion of middle rare earth element in the clinopyroxene and orthopyroxene implies that the partial melting of mantle source initiated in the garnet stability field. Occurrences of the interstitial clinopyroxene and spinel-hosted hydrous mineral inclusions, as well as variable enrichments of light rare earth element (LREE) and large-ion lithophile element in the clinopyroxene and orthopyroxene, suggest that the harzburgites suffered pervasive melt-rock interaction. The modeled interacting melts show enrichments of LREE and have a boninite-like affinity. In the dunites, olivines have higher contents of Fo (92.3–92.7), Ca (476–1830 ppm), and Ti (3.4–9.8 ppm) than those in the harzburgites (90.8–92.0, 50–319 ppm, and 0.6–6.4 ppm, respectively). Spinels in dunites have high Cr# (73.4–77.4) values and Ti (569–722 ppm) concentrations. Such mineral chemical characteristics imply extensive melt-rock interaction. We propose that the dunite was produced by early-stage interaction of harzburgite with migrating Si-undersaturated melt in asthenosphere. Subsequently, dunite and harzburgite together experienced late-stage interaction with boninite-like melt as incorporated into thermal boundary layer above a supra-subduction zone. An unusual mineral assemblage of ophiolitic diamond, moissanite, zircon, corundum and rutile, separated from the Aladağ harzburgites, indicates that relatively deep processes involved in the formation of the Aladağ mantle peridotites.

Neobvyklá asociace minerálů s willemitem z prostoru centrální části příbramského uran - polymetalického revíru (Česká republika)

The unusual mineralization with willemite, rare Cu arsenides (koutekite, kutinaite) and balkanite was found at a sample originating from the Jerusalém deposit (shaft No. 9), Příbram uranium and base-metal ore district (Czech Republic). The gangue is formed by earlier siderite and quartz intensively replaced by abundant willemite and younger dolomite group minerals with hematite inclusions and the youngest calcite. The ore mineralization represented by sphalerite, djurleite, anilite, covellite, stromeyerite, balkanite, koutekite, kutinaite, primary anglesite and Hg-rich silver is accompanied by Zn-rich hisingerite, baileychlore and Fe-oxides with variable but significant Si contents. The detailed description and quantitative chemical data for individual mineral phases are given. The studied mineralization was formed in significantly changing redox conditions (from reducing to highly oxidizing) with a distinct decrease of temperature (down to below 70(3) °C).

Diamond and Other Exotic Mineral-Bearing Ophiolites on the Globe: A Key to Understand the Discovery of New Minerals and Formation of Ophiolitic Podiform Chromitite

Ophiolite-hosted diamond from peridotites and podiform chromitites significantly differs from those of kimberlitic diamond and ultra-high pressure (UHP) metamorphic diamond in terms of occurrence, mineral inclusion, as well as carbon and nitrogen isotopic composition. In this review, we briefly summarize the global distribution of twenty-five diamond-bearing ophiolites in different suture zones and outline the bulk-rock compositions, mineral and particular Re-Os isotopic systematics of these ophiolitic chromitites and host peridotites. These data indicate that the subcontinental lithospheric mantle is likely involved in the formation of podiform chromitite. We also provide an overview of the UHP textures and unusual mineral assemblages, including diamonds, other UHP minerals (e.g., moissanite, coesite) and crustal minerals, which robustly offer evidence of crustal recycling in the deep mantle along the suprasubduction zone (SSZ) and then being transported to shallow mantle depths by asthenospheric mantle upwelling in mid-ocean-ridge and SSZ settings. A systematic comparison between four main genetic models provides insights into our understanding of the origin of ophiolite-hosted diamond and the formation of podiform chromitite. Diamond-bearing peridotites and chromitites in ophiolites are important objects to discover new minerals from the deep earth and provide clues on the chemical composition and the physical condition of the deep mantle.

The chromitites of the Neoproterozoic Bou Azzer ophiolite (central Anti-Atlas, Morocco) revisited

• Intermediate-Cr and high-Cr chromitites in the Bou Azzer ophiolite, Morocco. • Chromitites crystallized from fore-arc basalts (FAB) and boninites, respectively. • Fore-arc position of the ophiolite in a subduction-initiation geodynamic setting. • Super-reduced phases (moissanite and native Cu) formed during serpentinization. The Neoproterozoic Bou Azzer ophiolite in the Moroccan Anti-Atlas Panafrican belt hosts numerous chromitite orebodies within the peridotite section of the oceanic mantle. The chromitites are strongly affected by serpentinization and metamorphism, although they still preserve igneous relicts amenable for petrogenetic interpretation. The major, minor and trace element composition of unaltered chromite cores reveal two compositional groups: intermediate-Cr (Cr# = 0.60 – 0.74) and high-Cr (Cr# = 0.79 – 0.84) and estimates of parental melt compositions suggest crystallization from pulses of fore-arc basalts (FAB) and boninitic melts, respectively, that infiltrated the oceanic supra-subduction zone (SSZ) mantle. A platinum group elements (PGE) mineralization dominated by Ir-Ru-Os is recognized in the chromitites, which has its mineralogical expression in abundant inclusions of Os-Ir alloys and coexisting magmatic laurite (RuS 2 ) and their products of metamorphic alteration. Unusual mineral phases in chromite, not previously reported in this ophiolite, include super-reduced and/or nominally ultra-high pressure minerals moissanite (SiC), native Cu and silicates (oriented clinopyroxene lamellae), but “exotic” zircon and diaspore have also been identified. We interpret that clinopyroxene lamellae have a magmatic origin, whereas super-reduced phases originated during serpentinization processes and diaspore is linked to late circulation of low-silica fluids related to rodingitization. Zircon grains, on the other hand, with apatite and serpentine inclusions, could either have formed after the interaction of chromitite with mantle-derived melts or could represent subducted detrital sediments later incorporated into the chromitites. We offer a comparison of the Bou Azzer chromitites with other Precambrian ophiolitic chromitites worldwide, which are rather scarce in the geological record. The studied chromitites are very similar to the Neoproterozoic chromitites reported in the Arabian-Nubian shield, which are also related to the Panafrican orogeny. Thus, we conclude that the Bou Azzer chromitites formed in a subduction-initiation geodynamic setting with two-stages of evolution, with formation of FAB-derived intermediate-Cr chromitites in the early stage and formation of boninite-derived high-Cr chromitites in the late stage.

Investigating Possible Gastroliths in a Referred Specimen of Bohaiornis guoi (Aves: Enantiornithes)

Gastroliths, where preserved, can provide indirect evidence regarding diet in extinct avian and non-avian dinosaurs. Masses of gastroliths consistent with the presence of a gastric mill are preserved in many Early Cretaceous Jehol birds mostly belonging to the Ornithuromorpha. Gastroliths are also present in basal birds Sapeornis and Jeholornis in which herbivory is supported by direct evidence these taxa consumed seeds in the form of crop or stomach contents. Although gastroliths have been correlated with herbivory in non-avian dinosaurs, the presence of gastroliths and bone together in Ambopteryx calls this association in to question. Despite being known from greater numbers of specimens than other avian lineages, no unequivocal direct or indirect evidence of diet has been recovered from Jehol deposits for the Enantiornithes. A referred specimen of Bohaiornis guoi IVPP V17963 was described as preserving a small number of gastroliths interpreted as rangle, gastroliths whose function is cleaning the stomach in extant raptorial birds. However, based on comparison with gastroliths in other Jehol birds, it has alternatively been suggested that the identified structures are not ingested stones at all but some unusual mineral precipitate. Considering the limited evidence regarding diet in Enantiornithes and the importance of accurately identifying the traces in Bohaiornis in order to understand the enantiornithine digestive system, we extracted two samples of these purported gastroliths and explored these traces using computerized laminography scanning, scanning electron microscopy, energy dispersive x-ray spectroscopy, ground sections, and body size to gastral mass regressions. Similar analyses were conducted on gastroliths extracted from undisputed gastral masses of two Jehol ornithuromorphs and the non-avian pennaraptoran Caudipteryx. The combined results contradict the hypothesis that these traces are gastroliths and supports the interpretation they are mineral precipitate, most likely authigenic quartz (chalcedony). Although authigenesis is commonly responsible for the preservation of soft tissues, it is unclear if these traces record part of the tissues of this Bohaiornis. This study highlights the importance of a multidisciplinary approach in understanding unusual traces in the fossil record and reveal a previously unidentified taphonomic phenomenon in fossils from Jehol deposits.

Why Tolbachik Diamonds Cannot be Natural

AbstractTaking into account recent publications, we provide additional comprehensive evidence that type Ib cuboctahedral diamonds and some other microcrystalline diamonds from Kamchatka volcanic rocks and alluvial placers cannot be natural and undoubtedly represent synthetic materials, which appear in the natural rocks by anthropogenic contamination. The major arguments provided in favor of the natural origin of those diamonds can be easily disproved. They include the coexistence of diamond and deltalumite from Koryaksky volcano; coexistence with super-reduced corundum and moissanite, Mn-Ni silicide inclusions, F-Cl enrichment and F/Cl ratios, and carbon and nitrogen isotopes in Tolbachik diamonds, as well as microtwinning, Mn-Ni silicides, and other inclusions in microcrystalline diamond aggregates from other Kamchatka placers. We emphasize the importance of careful comparison of unusual minerals found in nature, which include type Ib cuboctahedral diamonds and super-reduced phase assemblages resembling industrial slags, with synthetic analogs. The cavitation model proposed for the origin of Tolbachik diamonds is also unreliable since cavitation has only been shown to cause the formation of nanosized diamonds only.

Nitrogen isotopic compositions in NH4+-mineral-bearing coal: Origin and isotope fractionation

Coals containing ammonium-bearing aluminosilicates usually have highly-elevated concentrations of critical elements, including Ga, Al, U, V, Re, Se, and rare earth elements. Coals from the Moxinpo and Yishan coalfields of southern China and the Daqingshan Coalfield of northern China are unusual in containing abundant ammonium-bearing minerals (buddingtonite and ammonian illite). Understanding the source of N in the ammonium-bearing minerals could provide useful information, not only for the enrichment of the critical elements, but also for the formation of these unusual minerals. A geochemical and nitrogen isotope study was undertaken in order to investigate the origin and behavior of nitrogen in the minerals and associated coals. The N contents decrease as rank increases from low volatile bituminous to semi-anthracite, indicating that substantial N was thermally lost during coalification. The isotopic composition of organic nitrogen (δ15Norg) ranges from 3.7 to 7.7‰ and increases with coal rank in the studied samples. However, this does not indicate that the isotope fractionation of organic N was due to the coal rank advance; rather, it is largely caused by the depositional environments of peat accumulation and coal-precursor plant assemblages.δ15N values of inorganic N (δ15Nino) in NH4+-minerals generally have a wider range (5.1 to 12.4‰) than those of organic matter (3.7 to 7.5‰) in coal and are commonly higher than those of δ15Norg in the same coal sample. The N in the ammonium-bearing aluminosilicates was derived from the decomposition of the organic matter of the coals that were subjected to increased geothermal gradient (and fluid flow) as a consequence of igneous intrusion or infiltration of high-temperature hydrothermal fluids. The N released from organic matter was transported by high-T fluids, from which 14N was preferentially converted into volatile matter and 15N readily remained in the fluids. Subsequently NH4+ in the high-T fluids substituted for K+ in pre-existing minerals or NH4+ − bearing high-T fluids reacted with pre-existing kaolinite in the coals, leading to more positive δ15N values for the NH4+-bearing minerals than those of the organic matter in these coals. Therefore, the δ15Nino values in coal, in a wider context, could be potentially used to estimate the degree of high-T heating on coal metamorphism, to trace the pathway of hydrothermal fluids circulating within the coal basin, and to provide useful information on the sources of critical elements that are enriched in coals.

The geochemical behaviour of Be and F in historical mine tailings of Yxsjöberg, Sweden

The speciation, mobility, transport, and fate of beryllium (Be) in the terrestrial environment is poorly studied even though it is considered to be one of the most hazardous elements in the periodic table. Historical tailings containing the unusual mineral danalite [Be3(Fe4.4Mn0.95Zn0.4)(SiO4)3.2S1.4] together with Fe-sulfides and fluorite has been stored open to the atmosphere for more than 50y. Environmental mineralogy, which combines geochemical and mineralogical techniques, was used to elucidate the weathering of danalite and fluorite. Danalite is unstable in oxic conditions due to the occurrence of Fe (II) and S-(II) in the crystal lattice and has oxidized at the same pace as pyrrhotite in the tailings. The acidic conditions generated from sulfide oxidation and the release of F from fluorite weathering have most likely enhanced Be mobility in the tailings. Secondary gypsum, hydrous ferric oxides and Al-oxyhydroxides are hypothesized to have played an important role regarding the mobility of Be in the tailings. The results indicate that Be released from danalite was first scavenged by these secondary minerals through co-precipitation. However, the dissolution of secondary gypsum due to changing geochemical conditions has also released Be to the groundwater. The groundwater at the shore of the tailings revealed the highest Be concentrations measured anywhere in the world (average: 4.5 mg/L) even though the water has a circumneutral pH. This extraordinary finding can be explained by high concentrations of F (73 mg/L), as F and Be have been shown to form strong complexes. The weathering of danalite and fluorite will continue for hundreds of years if remediation measures are not taken. Re-mining the tailings could be an appropriate remediation method.

Mineralogical-geochemical features of corundum Miaskite-pegmatite from mine no. 210 (Ilmeny mountains, South Urals): preliminary results

Miaskite-pegmatite of mine no. 210 exhibits an unusual mineral composition for the Ilmeny Mountains. It contains a signifcant amount of sapphire-like corundum (uncommon of nepheline-bearing pegmatites) and various Th-bearing minerals («thoro-aeschinite», pyrochlore, phosphates). Pegmatite has a zonal structure, in which the central nepheline and lateral feldspar zones difer in composition of rock-forming and accessory minerals. Corundum is found in all zones of pegmatite. Accessory minerals of the central, eastern, and western zones include (i) Ti-niobates (columbite, pyrochlore, srilankite), zircon, spinel and thorianite, (ii) columbite, pyrochlore and zircon, and (iii) columbite, «ilmenorutile», toro-aeschinite, monazite-La and Ce, and zircon, respectively. The calculations based on two-feldspar thermometer for diferent pegmatite zones show a decrease in temperature from the periphery toward the center, which is in agreement with the variability of mineral assemblages. Pegmatite is strongly altered, which is expressed in the formation of cancrinite and sodalite, hydration of pyrochlore of the central zone, and signifcant compositional changes of Ti-niobates in the lateral zones of pegmatite. The Rb-Sr age of corundum miaskite-pegmatite is ~275 Ma, but the Rb-Sr system is signifcantly destroyed. The initial 87Sr/86Sr(275) isotopic ratio and ?Nd(275) value of the mineral indicate its crustal formation conditions. The geochemistry of corundum points to its multistage crystallization. The data points on Fe vs. Ga / Mg and FeO – Cr2O3 – MgO – V2O3 vs. FeO + TiO2 + Ga2O3 plots correspond to both «magmatic» and «metasomatic» corundum.

Polymineralic inclusions as tracers of multistage metasomatism in a paleo mantle wedge

Paleosubduction zones are key areas where slab-derived fluids interact with the overlying mantle wedge. Slab fluids play therefore an important role in the deep element cycle and can metasomatize ultramafics showing particular mineral assemblages. The nature of slab fluids is usually investigated from fluid inclusions and/or multiphase solid inclusions, as well as from incompatible elements in mantle minerals. We have made a study on a garnet-peridotite from the Variscan Ulten Zone (Eastern Alps, Italy) in which peculiar polymineralic inclusions (PI) in garnet provide a wealth of information on the interaction between mantle wedge and slab fluids. The selected sample shows a fine-grained amphibole-olivine-orthopyroxene-spinel-clinopyroxene matrix and a fractured large garnet porphyroclast, surrounded by a kelyphitic corona. Garnet core and rim host randomly distributed PI, which may be as large as 284,000 μm2. The PI show irregular, fracture-controlled shapes and often contain unusual mineral associations. Many PI are directly associated with Mg-hornblende- or chlorite-sealed micro-fractures crosscutting garnet. The most abundant PI contain spinel and amphibole as the main minerals. Spinel-bearing PI consists of high-Cr spinel (Cr# = 0.31–0.41) surrounded by amphiboles (magnesio-hornblende), locally associated with dolomite, sapphirine, calcite, sulphides and kinoshitalite (i.e. a Ba-rich phlogopite). Amphibole-bearing PI contain zoned amphiboles (tschermakitic cores surrounded by Mg-hornblende, which is rimmed by tremolite and Mg-amphibole), dissakisite (an REE-bearing epidote), apatite, dolomite, calcite, spinel, sapphirine, chlorite, kinoshitalite, and sulfides. The retrieved mineral reaction history and the major and some incompatible elements (Cl, Ba, Sr) of PI minerals provide clues about the composition of metasomatic fluids. The studied PI formed in garnet fractures during exhumation by reactions between garnet and (1) slab-derived COH fluids and (2) late-stage saline brines. Metasomatic fluids/brines were rich in volatile elements and had a crustal signature (enrichment in LILE and LREE) with variable Cl contents and CO2/H2O ratios. Products of early garnet-fluid reactions became reactants of later reactions, thus generating complex textures, including replacement textures of sapphirine over spinel, calcite over dolomite and chlorite over Mg-hornblende. Textures and compositions of the PI testify to a multistage metasomatic overprint at peak P-T conditions above 2 GPa (M1), during the first exhumation stage at 775–1000 °C, below 2 GPa (M2) and finally at 775 °C and 1 GPa (M3). In this study we demonstrate that Gibbs free energy minimization may aid in distinguishing between multiphase solid inclusions and polymineralic inclusions; the latter do provide valuable information on the evolution of retrograde P-T paths in the paleosubduction channel, the relative chronology of metasomatic events and clues on the chemical signature of the fluids.