Petrogenetic peculiarities of Fe-Ti oxide minerals in the processes of crystallization and evolution of late Cretaceous volcanic complexes of the Lesser Caucasus

Drawing from the determined differences between iron-titanium oxide minerals, we analyzed the conditions of crystallization and evolution of late-Cretaceous magmatic complexes of the Lesser Caucasus. It was found that the rocks of basalt-andesibasalt complex, which correspond to the early substage (upper Coniacian-lower Santonian) of late-Cretaceous volcanism in the Qazakh, Agjakand, Agdara depressions, have crystallized in the conditions of relatively highly- thermobaric crystallization of titanomagnetite, poorly differentiated and evolutionized according to the Fenner trend. In the second substage of volcanism, due to decrease in permeability of the Earth’s crust, the elevation of the remaining magma to the upper horizons was hindered. Therefore, within the Qazakh depression, shallow intermediate sites of crystallization developed where moderately titaniferous magnetite crystallized with the participation of oxidized fluids earlier than hornblende, pyroxene and plagioclase. Thus, the remaining magma evolutionized its composition through Bowen’s reaction series. In the Agjakand and Agdara depressions, change of previous expansion to compaction was the cause of hindering of partly fractioned portion of the magma. The latter thermally interacted with the above-embedded maghemite, hematite and in a number of cases magnetite. In the Khojavand depression, rocks of trachibasalt- trachiodolerite complex, which characterize the late substage of the Santonian volcanism, contain moderately titanium magnetites and maghemites. In the second substage of volcano-plutonism, rocks of tephrite-teshenite complex developed. There, accompanied by oxidized fluids, highly-clayey titanomagnetite crystallized before chrome-diopside and salite. However, the ulvospinel titanomagnetite in teshenites, having associated with barkevikite and kaersutite, crystallized at a relatively higher temperature. Within the Senonian volcanites of the Azykh depression, along with the moderately-titanium magnetite, chromic titanomagnetite and rarely chromite was determined. Similar mineralogical diversities are also characteristic for the Gochas depression.

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

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.

Mineralogical Characterization of Manganese Oxide Minerals of the Devonian Xialei Manganese Deposit

The Guangxi Zhuang Autonomous Region is an important manganese ore district in Southwest China, with manganese ore resource reserves accounting for 23% of the total manganese ore resource reserves in China. The Xialei manganese deposit (Daxin County, Guangxi) is the first super-large manganese deposit discovered in China. The Mn oxide in the supergene oxidation zone of the Xialei deposit was characterized using scanning electron microscopy (SEM), energy spectrometer (EDS), transmission electron microscopy (TEM, HRTEM), and X-ray diffraction analysis (XRD). The Mn oxides have a gray-black/steel-gray color, a semi-metallic-earthy luster, and appear as oolitic, pisolitic, banded, massive, and cellular textures. Scanning electron microscopy images show that the manganese oxide minerals are present as fine-spherical particles with an earthy surface. TEM and HRTEM indicate the presence of oriented bundled and staggered nanorods, and nanopores between the crystals. The Mn oxide ore can be classified into two textural types: (1) oolitic and pisolitic (often with annuli) Mn oxide, and (2) massive Mn oxide. Pyrolusite, cryptomelane, and hollandite are the main Mn oxide minerals. The potassium contents of cryptomelane and pyrolusite are discussed. The unit cell parameters of pyrolusite are refined.

Hidden and apparent twins in uranyl-oxide minerals agrinierite and rameauite: a demonstration of metric and reticular merohedry

In this work, the structures of chemically related uranyl-oxide minerals agrinierite and rameauite have been revisited and some corrections to the available structure data are provided. Both structures were found to be twinned. The two minerals are chemically similar, and though their structures differ considerably, their unit-cell metrics are similar. Agrinierite was found to be twinned by metric merohedry (diffraction type I), whereas the structure of rameauite is twinned by reticular merohedry (diffraction type II). The twinning of the monoclinic unit cells (true cells) leads to pseudo-orthorhombic or pseudo-tetragonal supercells in the single-crystal diffraction patterns of both minerals. According to the new data and refinement, agrinierite is monoclinic (space group Cm), with a = 14.069 (3), b = 14.220 (3), c = 13.967 (3) Å, β = 120.24 (12)° and V = 2414.2 (12) Å3 (Z = 2). The twinning can be expressed as a mirror in (101) (apart from the inversion twin), which leads to a supercell with a = 14.121, b = 14.276, c = 24.221 Å and V = 2 × 2441 Å3, which is F centered. The new structure refinement converged to R = 3.54% for 6545 unique observed reflections with I > 3σ(I) and GOF = 1.07. Rameauite is also monoclinic (space group Cc), with a = 13.947 (3), b = 14.300 (3), c = 13.888 (3) Å, β = 118.50 (3)° and V = 2434.3 (11) Å3 (Z = 2). The twinning can be expressed as a mirror in (101) (apart from the inversion twin), which leads to a supercell with a = 14.223, b = 14.300, c = 23.921 Å and V = 2 × 2434 Å3, which is C centered. The new structure refinement of rameauite converged to R = 4.23% for 2344 unique observed reflections with I > 3σ(I) and GOF = 1.48. The current investigation documented how peculiar twinning can be, not only for this group of minerals, and how care must be taken in handling the data biased by twinning.

Evolution of Nb–Ta Oxide Minerals and Their Relationship to the Magmatic-Hydrothermal Processes of the Nb–Ta Mineralized Syenitic Dikes in the Panxi Region, SW China

Previous geochemical and petrological studies have concluded that initially magmatic Nb–Ta mineralization is often modified by post-magmatic hydrothermal fluids; however, there is still a lack of mineralogical evidence for the syenite-related Nb–Ta deposit. From the perspective of Nb–Ta minerals, the pyrochlore supergroup minerals have significance for indicating the fluid evolution of alkaline rock or related carbonatite type Nb–Ta deposits. The Panzhihua–Xichang (Panxi) region is a famous polymetallic metallogenic belt in southwestern China, abound with a huge amount of Nb–Ta mineralized syenitic dikes. This study focuses on the mineral textures and chemical compositions of the main Nb–Ta oxide minerals (including columbite-(Fe), fersmite, fergusonite-(Y), and especially pyrochlore group minerals) in samples from the Baicao and Xiaoheiqing deposits, in the Huili area, Panxi region, to reveal the magma evolution process of syenitic-dike-related Nb–Ta deposits. The Nb–Ta oxides in the Huili syenites are commonly characterized by a specific two-stage texture on the crystal scale, exhibiting a complex metasomatic structure and compositional zoning. Four types of pyrochlore group minerals (pyrochlores I, II, III, and IV) formed in different stages were identified. The euhedral columbite-(Fe), fersmite, and pyrochlores I and II minerals formed in the magmatic fractional crystallization stage. Anhedral pyrochlore III minerals are linked to the activity of magma-derived hydrothermal fluids at the late stages of magma evolution. The pyrochlore IV minerals and fergusonite-(Y) tend to be more concentrated in areas that have undergone strong albitization, which is a typical phenomenon of hydrothermal alteration. These mineralogical phenomena provide strong evidences that the magmatic-hydrothermal transitional stage is the favored model for explaining the Nb–Ta mineralization process. It is also concluded that the changes in chemical composition and texture characteristics for pyrochlore group minerals could serve as a proxy for syenite-related Nb–Ta mineralization processes.

The effect of filtration size on the geochemistry of groundwater samples from a massive sulfide deposit at the Bathurst Mining Camp, New Brunswick, Canada

In hydrogeochemical studies, samples are commonly filtered to limit the fraction of analyte that is adsorbed or structurally bound to suspended particles, ensuring that only the dissolved fraction is analyzed, and thereby reducing analytical bias during measurement. The standard filter size that has been adopted is 0.45 μm, however, ultrafiltration can be used to remove colloidal particles two orders of magnitude smaller. In the following, we investigate the effect that standard (0.45 μm) and ultrafiltration (0.004 μm) have on the hydrogeochemistry of groundwaters from a volcanogenic massive sulfide (VMS) deposit at the Bathurst Mining Camp, New Brunswick, Canada. Groundwater samples were collected from six monitoring wells at the Nigadoo Mine tailings facility, and major and trace geochemistry were determined using a combination of inductively coupled plasma optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS), and ion chromatography. Waters at the Nigadoo deposit are generally enriched in Ca and SO4, relative to other major cations and anions. Some element contents - including those associated with VMS deposits - differ depending on the filtration technique used (e.g., As, Fe, Pb, rare earth elements and yttrium [REY]), some are equally affected by both techniques (e.g., Cu, Ni, Zn), and some are unaffected by filtration (e.g., Ba, Ca, Mn, Cl-). Shale-normalized REY anomalies (CeSN/CeSN*, EuSN/EuSN*, and YSN/HoSN) and overall patterns can differ greatly (e.g., changing the sign of the anomaly) depending on the filtration technique used. We observe previously undocumented, and, at this time, unexplainable fractionation of Ho and Yb (non-redox sensitive REYs, unaffected by the tetrad effect) in unfiltered waters from the Nigadoo deposit. Differences in groundwater geochemistry induced by filtration technique can result in false positive and negative anomalies during environmental and exploration projects and must therefore be carefully considered. At the Nigadoo site, oxidation of sulfide minerals can occur, resulting in the formation of relatively unstable oxide minerals. Away from the tailings, where carbonate minerals are scarce and can no longer act as a pH buffer, the unstable oxide minerals break down and release metals and metalloids into the surrounding environment. The filtration methods used in this study can provide insight into where the specific metals and metalloids are hosted and how they are likely to behave under different redox conditions. Because VMS deposit pathfinder elements are enriched in unfiltered water, and differ by degree of filtration, geochemical analysis of the filtride material may also make an effective exploration tool.Thematic collection: This article is part of the Hydrochemistry related to exploration and environmental issues collection available at: https://www.lyellcollection.org/cc/hydrochemistry-related-to-exploration-and-environmental-issues

Origin of Fe-Ni-Cu (Co) sulfide and Fe-Ti oxide minerals in the c. 1.77 Ga dolerite dyke, Singhbhum Craton (eastern India)

Dolerite dyke swarms are widespread within the Singhbhum Craton (eastern India) that emplaced from the Neoarchean to Paleoproterozoic era just after the stabilization of crust before c. 3 Ga. These dyke swarms are oriented in NE - SW to NNE - SSW, NW - SE to WNW - ESE, E - W, and N - S directions. The WNW - ESE trending c. 1.77 Ga Pipilia dyke swarm is sampled from the Satkosia area of the Orissa state. The dyke shows a noticeable disparity in terms of the modal proportion and grain size of pyroxenes, plagioclase, Fe-Ti-oxide minerals and texture across the trend. At places the primary silicates are altered to secondary hydrated mineral assemblages of amphibole, chlorite and sericite. Primary silicates are clinopyroxene (augite: Mg# = 65.7 - 82.6; En37-48Fs11-17Wo36-41), orthopyroxene (clinoenstatite: Mg# = 68.5 − 78; En63-70Fs20-29Wo4-5), plagioclase (An11-39Ab44-82Or1-7) and Fe-Ti oxides are titanomagnetite (FeO = 34.38 − 39.50 wt%, Fe2O3 = 48.26 − 56.21 wt%, TiO2 = 5.05 − 9.60 wt%) and ilmenite (FeO = 40.75 − 43.79 wt%, Fe2O3 = 3.54 − 10.03 wt%, TiO2 = 47.82 − 50.87 wt%). Application of two-pyroxene thermometry yields an equilibration temperature range of 1065oC to 978oC, and coexisting titanomagnetite-ilmenite pairs reveal 731.39oC to 573.37oC at the oxygen fugacity (fO2) condition NNO+0.3 to FMQ-1.03. The dyke contains disseminated sulfides at the interstices of Fe-Ti-oxides, and silicates. Major sulfide minerals are pyrite, chalcopyrite, and vaesite; Pyrite-vaesite assemblages occur in association with secondary silicate minerals. Pyrite grains contain variable concentration of Co = 0.01 − 5.70 wt% and Ni = 0.02 − 1.95 wt%. Coexisting vaesite contains Co = 2.42 − 10.44 wt%, Ni = 26.40 − 47.88 wt%, and Fe = 7.32 − 26.55 wt%. Texture, sulfide-silicate assemblage, and presence of low metal/S sulfides such as the pyrite-vaesite assemblage indicate primary Fe-Ni- sulfides (pyrrhotite-pentlandite) that segregated from immiscible sulfide liquid at high temperature is modified by late magmatic/hydrothermal fluid activities. Numerous sulfide-bearing deposits hosted in ultramafic-mafic intrusions of Paleoproterozoic age have been recorded globally and the occurrence of Fe-Ni-sulfides in the c. 1.77 Ga Pipilia dyke swarm in the Singhbhum Craton enhances the exploration potential of this craton in eastern India.Supplementary material at https://doi.org/10.6084/m9.figshare.c.5643989