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<jats:title>Abstract</jats:title> <jats:p>We report the formation of minerals from the tochilinite-valleriite group (TVG) during laboratory serpentinization experiments conducted at 300 and 328 °C. Minerals in the TVG are composed of a mixture of sulfide and hydroxide layers that can contain variable proportions of Fe, Mg, Cu, Ni, and other cations in both layers. Members of this group have been observed as accessory minerals in several serpentinites, and have also been observed in association with serpentine minerals in meteorites. To our knowledge, however, TVG minerals have not previously been identified as reaction products during laboratory simulation of serpentinization. The serpentinization experiments reacted olivine with artificial seawater containing 34S-labeled sulfate, with a small amount of solid FeS also added to the 300 °C experiment. In both experiments, the predominant reaction products were chrysotile serpentine, brucite, and magnetite. At 300 °C, these major products were accompanied by trace amounts of the Ni-bearing TVG member haapalaite, Ni,Fe-sulfide (likely pentlandite), and anhydrite. At 328 °C, valleriite occurs rather than haapalaite and the accompanying Ni,Fe-sulfide is proportionally more enriched in Ni. Reduction of sulfate by H2 produced during serpentinization evidently provided a source of reduced S that contributed to formation of the TVG minerals and Ni,Fe-sulfides. The results provide new constraints on the conditions that allow precipitation of tochilinite-valleriite group minerals in natural serpentinites.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>We present in situ LA-ICP-MS U-Pb dating of xenotime and monazite in assemblages with native gold and Au (Ag) tellurides from the Xiaoqinling lode gold district in central China. Composite xenotime and monazite grains formed through coupled dissolution-reprecipitation reactions reveal two discrete gold mineralization events. The first gold mineralization event, recorded by monazite (158.6 ± 3.3 Ma, Tera-Wasserburg lower intercept age) and xenotime cores (157.11 ± 0.83 Ma, weighted mean 206Pb/238U age), is characterized by the mineral assemblage of lingbaoite (AgTe3)-sylvanite ([Au,Ag]2Te4)-stützite (Ag5–xTe3)/native tellurium-sylvanite-stützite. The second gold mineralization event, recorded in the rims of xenotime (135.46 ± 0.93 Ma, weighted mean 206Pb/238U age), is characterized by the mineral assemblage of native gold-calaverite (AuTe2)-petzite (AuAg3Te2)-tellurobismuthite (Bi2Te3). Our study implies that the large-scale Jurassic mineralization event in eastern China, related to flat subduction of the paleo-Pacific plate beneath the eastern China continent, also caused widespread gold mineralization in the Qinling-Dabie Orogen, in addition to production of its world-class porphyry Mo deposits. The fact that only a few Jurassic gold mineralization ages have been reported before, may be due to the lack of suitable geochronometers to record the earlier Jurassic hydrothermal processes, which have been overprinted by the better-recognized Early Cretaceous gold mineralization event. This study also presents a rare example of xenotime compositional alterations and resetting of U-Pb ages induced by low to moderate salinity carbono-aqueous fluids at low temperatures. The textural relationships between gold minerals in contact with such composite xenotime crystals demonstrate that they could have precipitated before, coeval with, or after the dated domains. Since low to moderate salinity carbono-aqueous fluids are commonly involved in the formation of lode gold deposits, it is crucial to examine xenotime textures and recognize potential alteration textures before carrying out isotopic dating of xenotime collected from these deposits. Without prior compositional and textural characterization, attempts to date such composite crystals could yield mixed dates and meaningless ages.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>The origin of the common blue 450 nm (2.8 eV) cathodoluminescence (CL) emission in natural and synthetic quartz has been investigated using a combination of CL microscopy and spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, and trace-element analysis by electron micro-probe analysis as well as inductively coupled plasma-mass spectrometry (ICP-MS). The study shows that the appearance of the ~450 nm emission band can be attributed to two different defects in quartz. First, a transient luminescence can be explained by structural defects in oxygen deficient quartz. The luminescence model implies self-trapped exciton (STE) emission related to oxygen vacancies. This type of CL emission is frequent in high-purity synthetic quartz and natural quartz of hydrothermal origin. Second, in Ti-rich quartz from natural samples (e.g., quartz phenocrysts in rhyolites) and synthetic quartz of Ti-diffusion experiments, an additional 450 nm (2.8 eV) emission was detected, which is stable under the electron beam. The intensity of this ~450 nm emission band correlates with the concentration of trace Ti in quartz, and substitutional Ti4+ at the Si4+ position was proved by EPR spectroscopy. In quartz crystals with elevated Ti concentrations both intrinsic and extrinsic blue CL emissions at ~450 nm can coexist, hindering a thorough characterization and quantification of the CL signal. A reliable distinction of the two different CL emission bands is possible by fitting the peaks of the CL spectra, and the peak width of the 450 nm emission can be used to differentiate the STE from the Ti4+ emission. However, the definitive technique is through the observation of CL peak shape change over time at a point by collecting a time series of CL spectra in conjunction with EPR spectroscopy and trace-element analysis of the Ti concentration.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>A solid solution of the mineral feiite (Fe3TiO5) was recently discovered in a shock-induced melt pocket of the Shergotty martian shergottite. It is particularly interesting for its potential as an indicator of pressure-temperature (P-T) and oxygen fugacity in martian crustal and mantle material. To date, complete crystallographic analysis of feiite has not been conducted, as the mineral was previously analyzed by electron backscatter diffraction on micrometer-size grains (Ma et al. 2021). Here we report a convergent crystal-structure model for feiite based on synchrotron single-crystal X-ray diffraction data collected on three grains of feiite synthesized at 12 GPa and 1200 °C. Feiite adopts the CaFe3O5 structure type (Cmcm, Z = 4), which is composed of two octahedral M1 and M2 sites and one trigonal prismatic M3 site (M = metal) in a ratio of 1:2:1. The three feiite grains with composition Ti0.46–0.60Fe3.54–3.40O5 were best modeled by substituting Ti4+ into only the octahedral M2 site, accounting for 30% of this site. Comparisons of the measured average bond lengths in the coordination polyhedra with the optimized Ti4+–O, Fe2+–O, and Fe3+–O bond lengths suggest that ferrous iron occupies the trigonal M3 site, while iron is mixed valence in the octahedral M1 and M2 sites. The Ti4+ and Fe3+ content constrained by our crystal-chemical analyses suggests that at least ~30% of the available iron must be ferric (i.e., Fe3+/Fetotal = 0.3) for the sample synthesized at 12 GPa and 1200 °C and higher P-T conditions may be needed to form the end-member feiite (Fe32+TiO5).</jats:p>

<jats:title>Abstract</jats:title> <jats:p>The results of investigations into enrichment of precious metals in sphalerite and pyrite from the Maluntou epithermal gold deposit, China, are reported. The obtained data suggest intimate associations of Au- and Ag-bearing nanoparticles with chalcopyrite inclusions in sphalerite and pyrite. The origins of chalcopyrite inclusions involved different hydrothermal processes, including recrystallization-driven phase separation from parent chalcopyrite-sphalerite solid solutions and replacement of pre-existing pyrite in the presence of Cu-bearing fluids. The chalcopyrite blebs/lamellae follow sphalerite {111} planes, which define a shared sulfur layer for both chalcopyrite and sphalerite. This study indicates that mixing and boiling during the evolution of ore-forming fluids for the Maluntou deposit are key processes for the abnormal enrichment of precious metals in sphalerite and pyrite. The chalcopyrite micro/nano inclusions enhanced enrichment of precious metals in sphalerite provides new insights into the controls on the enrichment of precious metals in sulfides.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>Synthetic flux-grown end-member gahnite, ZnAl2O4, and several different colored crystals doped with one or more transition metals including Mn, Ni, Cr, Co, and Fe were studied by electron microprobe methods and UV/Vis/NIR single-crystal optical absorption spectroscopy. The first major objective was to measure and assign the various electronic absorption features. The second was to analyze quantitatively the crystal colors using the experimental spectra and the CIE 1931 color-space-chromaticity diagram. The microprobe results show that the doped gahnites have transition metal concentrations between about 0.001 and 0.1 cations per formula unit. The spectrum of colorless, nominally pure ZnAl2O4 displays no absorption in the visible region. Microprobe analysis of a light-blue gahnite crystal reveals small amounts of Ni and Mn. The UV/Vis/NIR spectrum does not indicate any dd-electronic transitions relating to Mn. All absorption features also cannot be fully interpreted using Tanabe-Sugano diagrams for Ni2+ in either octahedral or tetrahedral coordination. A series of seven slightly different colored gahnites with differing concentrations of Cr3+ and most also containing smaller amounts of Ni was investigated. The spectrum of a one pink crystal shows two intense absorption features in the visible region. They are assigned to spin-allowed 4A2g → 4T2g (4F) and 4A2g → 4T1g (4F) transitions of VICr3+. Other spectra display additional weak bands and lines that are most probably spin-forbidden dd-transitions of Ni2+. These gahnites with Ni and Cr show varying purple colorations depending on the concentrations of both metals. Two more deeply blue gahnites contain Co2+ as demonstrated by their UV/Vis spectra but not by microprobe analysis. Two intense absorption features at ~7440 and ~16 850 cm–1 are observed and assigned to the spin-allowed transitions 4A2 → 4T1 (4F) and 4A2 → 4T1 (4P) of Co2+, respectively. Complex absorption fine structure, caused by spin-orbit and/or vibronic interactions, is also observed. Three different gahnites with yellow to orange colorations contain measurable Mn. Their spectra are similar in appearance and display several weak IVMn2+ spin-forbidden transitions located above 20 000 cm–1. The spectra of two green gahnites show several Fe spin-forbidden electronic transitions arising from single, isolated IVFe2+ and VIFe3+ cations between 10 000 and 25 000 cm–1. The intensities of some of the VIFe3+-related bands can be increased through exchange-coupled interactions with next nearest IVFe2+ neighbors. The colors of various doped gahnites and the end-member galaxite are analyzed using their single-crystal absorption spectra in the visible region. Their dominant wavelength, λk, and hue saturation, pc, values are given on the CIE 1931 color-space-chromaticity diagram and are discussed. The Hex colors of all crystals are calculated and can be compared to those of the studied crystals.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>Regolith-hosted rare earth elements (REEs) deposits received great attention due to the increasing incorporation of REEs in modern technologies. In lateritic Sc deposits and ion-adsorption deposits (IADs), Sc behaves quite differently from REEs: REEs adsorb as outer-sphere complexes on clay surface in IADs, while Sc could enter the lattice of clay minerals in lateritic Sc deposits. The unique behavior of Sc has not been well understood yet. Here, by using first-principles molecular dynamics techniques, we show that the complexation mechanisms of Y3+ and Sc3+ on clay edge surfaces are distinctly different. Y3+ preferentially adsorbs on Al(OH)2SiO site with its coordination water protonated. Sc3+ is found to behave similarly to other first-row transition metals (e.g., Ni2+) due to its smaller ionic radius and prefers adsorbing on the vacancy site, from where Sc3+ can be readily incorporated in the clay lattice. The H2O ligands of Sc3+ get deprotonated upon complexation, providing new binding sites for further enrichment of Sc3+. These processes prevent Sc3+ from being leached during weathering and lead to the formation of Sc-rich clay minerals found in lateritic deposits. Based on these results, it is revealed that the small ionic radius and high affinity to enter the vacancy on edge surfaces make Sc compatible with clay minerals and are the origin of its unique geochemical behavior.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>Nelsonite (Fe-Ti oxide-apatite rock) devoid of silicates offers a rare opportunity to investigate the magma processes for the formation of magmatic Fe-Ti oxide deposits. Both fractional crystallization and silicate liquid immiscibility have been put forward, but the lack of robust evidence has hindered unambiguously distinguishing the role of these two processes in Fe-Ti mineralization. The nelsonite and associated Fe-Ti-P-rich rocks hosted in the Proterozoic Damiao anorthosite complex represent a typical example for studying Fe-Ti ore-forming processes. We recognized a new type of nelsonite (type-I) in the Damiao complex, which is distinct from the two known types of nelsonite (type-II and type-III) from the same complex. The type-I nelsonite is characterized by its coexistence with oxide-apatite gabbronorite and granite in the same dike, and all these rocks have identical emplacement ages (1740 ± 7 Ma), subparallel REE patterns, and major-element compositions lacking intermediate compositions, suggesting derivation from conjugate Fe- and Si-rich melts generated by silicate liquid immiscibility. The large type-II nelsonite bodies form irregular dikes along fractures in anorthosite and constitute the major ore type. The type-III nelsonite occurs as conformable layers or pods within oxide-apatite gabbronorite and pyroxenite, and occupies the end part of the type-II dike. The latter two types of nelsonites formed by extensive fractional crystallization of residual magma with crystal accumulation and subsequent hydrothermal replacement. During residual magma evolution, silicate liquid immiscibility was crucial for Fe-Ti-P enrichment, fractional crystallization was responsible for enhancing oxide-apatite concentrations, and hydrothermal replacement was effective for mobilizing oxide-apatite concentrations. Our newly recognized nelsonite provides an unambiguous, outcrop-scale, field evidence for the operation of silicate liquid immiscibility process. We show that giant magmatic Fe-Ti oxide orebodies can form by a combination of processes involving silicate liquid immiscibility, fractional crystallization and hydrothermal mobilization.</jats:p>

<jats:title>Abstract</jats:title> <jats:p>Gold in Carlin-type gold ores is commonly hosted in the arsenian pyrite rim, but the formation of arsenian pyrite and its contribution to Au adsorption are poorly understood. Based on our previous NanoSIMS Au mapping, we conducted SEM and HR-TEM analyses to examine the Au deportment and nanoscale texture of individual auriferous arsenian pyrite grains from the giant Carlin-type Lannigou gold deposit, SW China. The results indicate that the arsenian pyrite rim is composed of numerous nanoparticulate pyrite grains (rather than a single crystal), and gold nanoparticles (Au0) occur mainly in sub-rim with the highest Au content, which are porous and have lower degrees of order. We propose that nanoparticulate arsenian pyrite attachment and aggregation is the main mechanism for the arsenian pyrite rim growth, and such mechanism is crucial for the Au efficient enrichment for this giant gold deposit.</jats:p>