Enrichment Of Sn Research Articles

LA-ICP-MS Trace Element Characteristics and Geological Significance of Stibnite in the Zhaxikang Pb–Zn–Ag–Sb Deposit, Southern Tibet, SW China

Discovered within the North Himalayan Metallogenic Belt (NHMB), the Zhaxikang Pb–Zn–Ag–Sb deposit stands as the sole super-large scale ore deposit in the region. This deposit holds significant quantities of Pb and Zn (2.066 million tons at 6.38% average grade), Ag (2661 tons at an average of 101.64 g/t), and Sb (0.235 million tons at 1.14% average grade), making it one of China’s foremost Sb–polymetallic deposits. Stibnite represents the main carrier of Sb in this deposit and has been of great attention since its initial discovery. However, the trace element composition of stibnite in the Zhaxikang deposit has not yet been determined. This study carried out an analysis of the distribution patterns and substitution processes of trace elements within stibnite gathered from the Zhaxikang deposit, aiming to provide crucial information on ore-forming processes. Utilizing high-precision laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), we discovered that the studied stibnite is notably enriched in arsenic (~100 ppm) and lead (~10 ppm). Furthermore, the notably consistent time-resolved profiles suggest that elements such as Fe, Cu, As, In, Sn, Hg, and Pb predominantly exist as solid solutions within stibnite. Consequently, it is probable that the enrichment of Cu, Pb, and Sn in stibnite is due to isomorphic substitution reactions, including 3Pb2+↔2Sb3+, Cu+ + Pb2+↔Sb3+, and In3+ + Sn3+↔2Sb3+. Apart from that, Mn, Pb, and Hg with the spiky signals indicate their existence within stibnite as micro-inclusions. Overall, we found that the trace element substitutions in stibnite from the Zhaxikang Pb–Zn–Ag–Sb deposit are complicated. Incorporations of trace elements such as Pb, Cu, and In into stibnite are largely influenced by a variety of factors. The simple lattice structure and constant trace elements in studied stibnite indicate a low-temperature hydrothermal system and a relatively stable process for stibnite formation.

Detailing the redox ability of supported Pt-Sn and Pt-In catalysts for CO2-assisted PDH

Alloying Pt with In or Sn crucially improves Pt-based propane dehydrogenation (PDH) catalysts. CO2-assisted PDH (CO2-PDH) offers further benefits through H2 and carbon oxidation, but adds a complex interplay between alloy oxidation, nanoparticle (NP) sintering and carbon formation. Developing Pt-based CO2-PDH catalysts requires deconvoluting the hereto unidentified alloy properties and reaction mechanisms. This is studied through in situ Quick X-ray Absorption Spectroscopy and Temporal Analysis of Products on Pt:Sn/MgAl2O4 (Pt:Sn) and Pt:In/MgAl2O4 (Pt:In) catalysts (3 wt% Pt and 3 wt% In/Sn). Pure CO2 segregates the alloys while cofeeding CO2 and H2 largely retains Pt3Sn and Pt13In9 phases. On Pt:Sn, CO2 mainly interacts with H2 and carbon deposits via a Langmuir-Hinshelwood mechanism. Regenerative H2/O2 cycles cause Sn enrichment with a constant 0.9 nm NP size. Pt:In retained the Pt13In9 phase but showed NP growth from 0.8 to 2.1 nm, with greater susceptibility to alloy segregation and vaporization of In. This highlights Pt:Sn as more promising catalyst.

Material Studies on Decorative Buttons from the Hallstatt Period Tumuli in Mitterkirchen, Marchland, Upper Austria

The burial ground at Mitterkirchen belongs to the Early Iron Age, respectively, to the Hallstatt culture. A remarkable find from Mitterkirchen is approximately 3,000 buttons that were attached to a magnificent coat. Five of these buttons were provided for nondestructive material examinations using computed tomography (CT). Two of these buttons could be examined by metallography, light optical microscope (LOM), scanning electron microscope (SEM) with energy-dispersive X-ray analysis (EDX) and X-ray fluorescence examination (XRF). Based on the results of the investigation, it can be assumed that the bronze buttons were manufactured by a casting process. The bronze alloys are very different, which suggests the use of various starting materials including recycled copper alloys. The microstructure of the bronzes is uniform and, depending on their compositions, contains precipitates like Pb and the intermetallic phase Cu41Sn11. The corrosion layers exhibit a pronounced Sn enrichment and contain malachite.

Precise target capture and the dynamic separation of Sn(IV) in highly acidic media by combining N and P donor covalent organic framework silica-based composite adsorbents

A silica-based adsorbent (P507@COF-TpAzo/SiO2) with nitrogen and phosphorus donors was prepared for industrial separation and recovery of Sn(IV) by in-situ growth of covalent organic framework (COF) on a silica substrate combined with vacuum impregnation. The materials were tested and analyzed by the scanning electron microscope (SEM), X-ray diffraction (XRD) and other characterization techniques, which demonstrated that the adsorbent has an enormous specific surface area, excellent heat resistance, and a regular morphological structure. The static experimental results showed that the adsorbent displayed remarkable selectivity for Sn(IV) in high HCl and HNO3 concentration environments, with excellent kinetics (∼60 min) and outstanding adsorption capacities (60.02 mg/g in 3 M HCl, 92.59 mg/g in 3 M HNO3) in different media at 3 M acidity. Cycle performance testing demonstrated that the adsorbent exhibited excellent stability (cycle times ≥8). Analysis using Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) showed that the synergistic adsorption results of N and P were reflected, mainly by the synergistic complexation of P=O and N=N-C. The potential sites for the adsorption of the adsorbent towards Sn(IV) were predicted by density functional theory (DFT) calculations, and the adsorbent demonstrated a more stable binding energy with Sn(IV). Finally, dynamic separation and efficient enrichment (>210) of Sn(IV) in highly acidic wastewater were realized by designing a penetrating column separation process. P507@COF-TpAzo/SiO2 satisfied the requirements of the dynamic adsorption experiments, bridging the research gap of dynamic separation, and provides a new strategy for the industrial removal and recovery of Sn(IV), as well as a way for environmental protection and industrial green production.

Features of ore-forming magma and fluid revealed by apatite and zircon geochemistry: A case study from the Huanggang skarn Fe-Sn deposit, NE China

The large-scale Huanggang Skarn Fe-Sn deposit is located in the southern part of the Great Xing’an Range (SGXR), NE China. The causative granitic rocks in the Huanggang ore district are characterized by consistently high SiO2 contents, low EuN/EuN* (0.02–0.24) and Sr/Y (0.2–1.9). The pre-ore granite porphyry and syn-ore syenogranite have been dated through zircon and monazite U-Pb dating at 144.6 ± 1.4 Ma and 138.6 ± 1.3 to 135.9 ± 0.8 Ma, respectively. The U-Pb dating of garnet from ore-associated skarn reveals that the mineralization was happened at 136.5 ± 1.3 Ma, which is consistent with the emplacement age of the ore-related syenogranite.Zircon geochemistry shows that the pre-ore granite porphyry has relatively low oxygen fugacity (average zircon Ce4+/Ce3+ = 14.74), whereas the syn-ore syenogranite is more oxidized (average zircon Ce4+/Ce3+ = 178.9). We suggest that the elevation of oxygen fugacity was most likely caused by degassing. The textural features indicate that apatite crystals from the pre-ore granite porphyry are magmatic in origin. In contrast, textural and chemical characteristics of apatite grains from syn-ore syenogranite reveal that they have been modified by hydrothermal fluids in different degrees. The apatite in both pre- and syn-ore granites display relatively high F and low Cl contents, and very low SO3 concentrations (i.e., <0.032 wt%), indicate extremely low content of S in the causative magma. Apatite from syn-ore syenogranite display more strong and variable enrichment of LREE relative to HREE compared to those from pre-ore granite porphyry. The extensive present of new REE mineral inclusions (monazite and xenotime) in the altered apatite suggests that the concentrations of Ca and Na must be low in the ore-forming fluid. Apatite from syn-ore syenogranite have higher concentrations of Mo, W, Zn, Sn, and Be than those from pre-ore granite porphyry.Combined with zircon and apatite geochemistry, and whole rock components of the ore-related granites in the Huanggang deposit, we propose that the ore-forming magma has undergone long-term evolution under relatively reduced conditions with extensive fractional crystallization of plagioclase. The reduced and S-poor evolved magma could have promoted the enrichment of Sn and prevented Fe from precipitating as sulfide. This study also reveals that the compositional characteristics of ore-forming fluid, such as the enrichment of ore-forming materials, could be revealed by altered apatite geochemistry.

Magmatic evolution and sources of metals and fluids in the large granite-related Xiasai vein-type Ag–Pb–Zn(–Sn) deposit, northern Yidun terrane, SW China

The Xiasai Ag–Pb–Zn–(Sn) deposit in the northern Yidun terrane (eastern Tethys), hosted in Late Triassic metasandstones, is genetically associated with Late Cretaceous granites. We present chemical and Sr–Nd–Pb–Li–B isotope data of Late Cretaceous granites and their mafic microgranular enclaves (MME), late aplites, and Late Triassic metasedimentary rocks. The narrow range of 87Sr/86Sr99 (0.70627–0.70953) and εNd99 (–6.1 to –5.2) values of most Late Cretaceous granites reflects a mixed source with contributions from the mantle and Paleoproterozoic felsic crust. These granites have high SiO2 contents (>69 wt%) and strong depletions in Sr, Ba, and Eu. Major and trace element contents correlate with the fractionation index 1/TiO2, indicating that they experienced extensive fractionation. Local late aplite dikes were derived from similar source rocks, but seem to be younger.The Pb isotopic compositions reflect that the metal Pb was derived from the granite with variable contributions from the Late Triassic sedimentary rocks. Weakly and moderately altered metasandstones have similar δ7Li and δ11B values as most granites (δ7Li: 0.00 to 2.68 ‰; δ11B values: –14.93 to –12.36 ‰), indicating magmatic fluid sources. The magmatic fluids resulted in the initial enrichment of Sn, Cu, Pb, and Zn. Strong alteration of feldspar and biotite resulted in the metasandstones in negligible change of Li concentrations, significant loss of Sr, Na2O, CaO, MgO, and Fe2O3, but significant addition of B. This alteration lowered δ7Li from 1.01 to –3.65 ‰ and lowered δ11B from –9.43 to –19.18 ‰. The low δ7Li values and extremely low δ11B values reflect external fluids from the Late Triassic sedimentary wall rocks, which interacted with granites and mobilized metals (e.g., Sn, Ag, Pb, and Zn) from the granite and/or the sedimentary wall rocks. The location of the Xiasai deposit is controlled by regional NNW-trending faults induced by Late Cretaceous extension.

Zircon and cassiterite geochronology of Sn-polymetallic pegmatite from the Xianghualing ore field, South China: Implications for multi-stage magmatic-hydrothermal events

The Nanling metallogenic belt (South China) is one of the largest W-Sn polymetallic provinces in the world. The ore bodies are mainly hosted in Triassic-Jurassic granitoids which formed during a complex history of magmatic evolution. Among them, the Laiziling pluton, which forms the northern part of the Xianghualing district, is an example of Sn-polymetallic deposits that underwent multiple Mesozoic episodes. In this study, the first in-situ U-Pb age dating of zircon and cassiterite minerals, trace element, and Lu-Hf isotopic data are reported for Laiziling NYF-type pegmatites. Four types of pegmatites are identified: stock-like pegmatite, vein-type pegmatite, peripheral vein-type pegmatite, and cap/sill-like pegmatite. Zircon LA-ICP-MS U-Pb geochronology of pegmatites yields an age of ~150 Ma, which is consistent with the age of the associated mineralized granitic pluton. Results of cassiterite age dating indicate that the W-Sn mineralization took place at ca. 150 Ma coeval with pegmatite emplacement. Combined with structure and trace element composition, two young ages (i.e., ~130 and 90 Ma) can be identified from pegmatite veins, suggesting that the studied zircon crystals experienced two distinct periods of magmatic-hydrothermal evolution during the Cretaceous (related to Late Yanshanian magmatism). In addition, some zircon grains are obviously enriched in LREE, which is associated with hydrothermal metasomatism. Compared to the narrow range of magmatic zircons, a wide range of inherited zircons (Proterozoic to Paleozoic) are observed in the studied Late Jurassic pegmatite (Pg1 and Pg2b), suggesting that they were incorporated from pre-existing basement rocks during magma ascent and/or emplacement. Furthermore, U-Pb data for 14 disseminated cassiterite grains yield a 206Pb/238U age of 221.5 ± 4.2 Ma, documenting evidence of cassiterite inheritance during melt ascension from country rocks or representing the initial stage of Sn enrichment. The εHf values of magmatic zircons show negative εHf values from −4.4 to −16.6 and their crustal model ages (TDM2) vary between 1328 Ma to 2200 Ma, suggesting the parent magma of the Laiziling pegmatites were derived from partial melting of older crustal components (Proterozoic basement in the Cathaysian Block of South China) and the mixing of mantle materials. This study proposes that multi-stage magmatic-hydrothermal events may have occurred not only in the Xianghualing area but also in the whole Nanling Range, and provides fresh insights into the formation processes of rare metal-bearing pegmatites in South China.

GEOCHEMISTRY AND GENETIC IMPLICATIONS OF BASEMENT ROCKS AROUND MAKARFI AREA, NORTHWESTERN NIGERIA BASEMENT COMPLEX

Major and trace element analysis of rocks around Makarfi were carried out using Inductively Coupled Plasma Mass Spectrometry (ICP-MS) to determine the geochemical characteristics of the lithological components of the area. The area is composed of migmatite gneiss, biotite gneiss, granite gneiss, schists and granites. Analysis for major, trace and REE revealed that the gneisses, are paragneisses and metaluminous. The granites are peraluminous (A/CNK&gt;1) and calc-alkaline. The granites had undergone changes from a more primitive hornblende-biotite I-type variety to a more fractionated muscovite bearing S-type variety. Chemical data shows that the peraluminosity and enrichment in Li, Rb, Cs, Ta, Sn, Nb and Ga increases in the course of differentiation and evolution from hornblende-biotite granite to muscovite granite. Signatures of biotite and muscovite granites suggest emplacement in a syn-collisional tectonic setting while those of hornblende-biotite granite suggest a post-collisional tectonic setting.

Amphibole geochemistry in the Haobugao skarn Zn-Fe-Sn deposit in the southern Great Xing’an Range: Implications for the ore-forming process

The Haobugao Zn-Fe-Sn deposit is a typical skarn deposit in the southern Great Xing’an Range of NE China. Despite many advances in understanding its genesis, the detailed ore-forming processes of Zn, Fe and Sn are still unclear. Amphibole, a rock-forming mineral, has been well studied as an indicator of diverse magmatic and metamorphic processes; however, the geochemistry of hydrothermal amphibole has previously received less attention. The Haobugao deposit contains two generations of hydrothermal amphibole (Amp-I and Amp-Ⅱ), which provides a good opportunity to use amphibole geochemistry to trace the mineralization process. Early Amp-I coexists with cassiterite, magnetite and quartz, whereas late Amp-II coexists with quartz and sulfides and can be further divided into two subgroups: Amp-Ⅱa (in skarn) and Amp-Ⅱb (in the country rocks of siltstone). The oxygen isotopic compositions of the fluid (δ18Ofluid 2.9‰) responsible for the Amp-I formation indicate that the amphiboles formed from mixed magmatic fluid with meteoric water. Amp-I is LREE-depleted and HREE-enriched with obvious negative Eu anomalies. Amp-Ⅱ is generally slightly LREE-depleted with negative or positive Eu anomalies and positive Ce anomalies. The incorporation of trace and rare elements is mainly controlled by the fluid composition. Detailed petrological observations and amphibole geochemistry, combined with previous research results, confirm that Sn, Fe, Pb and Zn mineralization occurred during a single mineralization event. From the oxide to the quartz sulfide stage, the ore-forming fluid evolved from high-temperature and oxidized conditions with enrichment of Sn, Li, Be and REEs to low-temperature and reduced or oxidized conditions with enrichment of Cu, Co and Zn. The concentrations of Cu, Co and Zn in different amphiboles vary with the mineral crystallization sequence. This study shows that amphibole geochemistry can be useful for tracing fluid evolution and mineralization processes in hydrothermal systems.

Magmatic–Hydrothermal Evolution at the Barren Wushan Pluton, Southeast China: Insight into Controls on Mineralization Potential

Abstract A-type granites typically exhibit enrichment and mineralization of critical metals such as molybdenum and tin, essential for emerging technologies. However, the key factors influencing their mineralization potential remain elusive. The scarcity of studies on barren systems impedes the understanding of this question. Here, a detailed melt and fluid inclusion study was conducted on the barren Wushan pluton to reconstruct its magmatic evolution and magmatic–hydrothermal transition and explore the factors controlling the metallogenic potential of Mo and Sn in A-type granites. The Wushan pluton displays apparent lithological zoning consisting of two major phases, i.e., medium-grained seriate to porphyritic alkali feldspar granite and fine-grained porphyritic granite. Miarolitic cavities are widely developed in each lithofacies. The silicate melt inclusions from two granitic phases are rhyolitic, with moderate F contents (0.06–0.53 wt %) and depleted H2O contents (2.0–3.5 wt %). Melt inclusions show a wide range of incompatible element contents, such as Cs (9–1977 μg/g) and Rb (268–2601 μg/g), suggesting that Wushan has undergone a high degree of magma evolution. Mo behaves incompatibly in the magmatic evolution, and its content is enriched with the increasing degree of fractional crystallization, but remains constant after the Cs content exceeds 50 μg/g. Rayleigh fractionation model suggests that a large amount of Mo is extracted from fluid exsolution, which restrains Mo from further enrichment. In contrast, Sn behaves as a mildly incompatible element during the entire magmatic evolution history. The contents of Sn increase slowly compared to the trend of Mo, and the maximum contents reach ~30 μg/g in the highly evolved melts. The separation and crystallization of Sn-bearing minerals such as biotite, magnetite, and titanite inhibit the enrichment of Sn. Intermediate-density (ID-type) fluid inclusions hosted in the miarolitic quartz, representing the initial fluid exsolving from magma, display high Mo but low Sn concentrations. Constrained from two assemblages of coexisting ID-type fluid and melt inclusions, the fluid/melt partition coefficients of metals are obtained, with DMo, fluid/melt at 16–19, while DSn, fluid/melt is only about 1. The comparison between Mo-mineralized and barren intrusions worldwide shows that the metal contents in melts and fluids are not fundamentally different. The mineralized intrusions are characterized by the lower melt viscosity and the development of apophyses, both of which facilitate the extraction of metals and fluids from large magma chambers, followed by their concentration into a small rock volume. Consequently, it appears that physical and structural conditions rather than chemical compositions play a crucial role in the Mo mineralization process. Enrichment of Sn in melts is necessary but not decisive for Sn mineralization, whereas Sn enrichment in the initial exsolving fluid determines the Sn mineralization potential of a given granitic system. Compared to Sn enrichment in source melting and fractional crystallization which commonly enhance final Sn fertility in the highly evolved melts, the efficiency of Sn partitioning between melt and fluid plays a fundamental role in converting melt fertility into Sn-enriched fluids and thereby high mineralization potential of the magmatic–hydrothermal system. Our findings suggest a prospect for Mo exploration in the coastal A-type granite belt in South China, while the potential for Sn mineralization is expected to be limited.

Partitioning of tin between mafic minerals, Fe-Ti oxides and silicate melts: Implications for tin enrichment in magmatic processes

The partition coefficients of Sn (tin) between minerals and silicate melts (DSnmin/melt) are vital for understanding the Sn enrichment during magmatic processes related to tin-granites. However, experimentally determined DSnmin/melt values remain scarce due to the difficulty in avoiding severe Sn loss to noble metal capsules. In this study, we performed mineral/melt Sn partitioning experiments at 0.5–1.0 GPa, 850–1000 °C, and fO2 of FMQ + 8 to ∼ FMQ − 1. The fO2s were imposed by solid buffers of Ru–RuO2, Re–ReO2, Ni–NiO, Co–CoO and graphite using three improved capsule designs: 1) a single sample capsule (Pt) for the Ru–RuO2 buffered runs, 2) double capsules with Pt95Rh05 as outer capsule and Re as inner sample capsule for the graphite and Re–ReO2 buffered runs, and 3) triple capsules for the Co–CoO and Ni–NiO buffered runs, with Pt95Rh05 (or Au) as outer capsule, Re lined Pt as inner sample capsule. These new capsule designs avoided significant Sn loss and enabled us to obtain accurate DSnmin/melt at a controlled fO2. The experimental results show that DSnmin/melt values are 0.08–12.66 for amphibole, 0.01–5.55 for biotite, 0.09–10.39 for clinopyroxene, 0.004–0.97 for orthopyroxene, < 0.01 for olivine, 1.34–108.43 for Ti-magnetite, 0.04–4.17 for spinel and 0.10–0.64 for ilmenite. The large variation of DSn for each mineral was mainly ascribed to the effect of fO2, which results in an arresting decrease of DSn with decreasing fO2. Under the reducing conditions (fO2 < FMQ), Sn is highly incompatible (DSn < 0.1) in almost all the minerals. Modeling results indicate that partial melting at low fO2 conditions results in Sn enrichment in the derived magma, while subsequent high degree of fractional crystallization is also important for the Sn enrichment in the residual melt. The experimental and modeling results thus explain why major primary tin deposits are always related to reducing and highly fractionated granites.

Interfacial Segregation of Sn during the Continuous Annealing and Selective Oxidation of Fe-Mn-Sn Alloys.

The effect of Mn on interfacial Sn segregation during the selective oxidation of Fe-(0-10)Mn-0.03Sn (at.%) alloys was determined for annealing conditions compatible with continuous galvanizing. Significant Sn enrichment was observed at the substrate free surface and metal/oxide interface for all annealing conditions and Mn levels. Sn enrichment at the free surface was insensitive to the Mn alloy concentration, which was partially attributed to the opposing effects of Mn on segregation thermodynamics and kinetics: Mn increases the driving force for Sn segregation via reducing Sn solubility in Fe but also reduces the effective Sn diffusivity by increasing the austenite volume fraction. This insensitivity was exacerbated by the depletion of solute Mn near the surface due to the selective oxidation of Mn. Thus, Sn segregation occurred in regions with a local Mn concentration lower than the nominal bulk composition of the alloys suggested. Sn enrichment at the metal/external oxide interface was reduced compared to the free surface and decreased with increasing bulk Mn content, which was attributed to changes in the external oxide morphology and metal/internal oxide interfaces acting as Sn sinks.

Skarn Formation and Zn–Cu Mineralization in the Dachang Sn Polymetallic Ore Field, Guangxi: Insights from Skarn Rock Assemblage and Geochemistry

The Dachang is a world-class, super-giant Sn polymetallic ore field mainly composed of Zn–Cu ore bodies proximal to the granitic pluton and Sn polymetallic ore bodies distal to the granitic pluton. In this study, we used petrographic studies and major and trace element geochemistry with calc-silicates from the Zn–Cu ore bodies to constrain the physicochemical conditions of hydrothermal fluids during skarn rock formation and the evolution of ore-forming elements. Two skarn stages were identified based on petrographic observations: Prograde skarn rocks (Stage I), containing garnet, vesuvianite, pyroxene, wollastonite, and retrograde skarn rocks (Stage II), containing axinite, actinolite, epidote, and chlorite. The retrograde skarn rocks are closely associated with mineralization. The geochemical results show that the garnets in the Dachang ore field belong to the grossular–andradite solid solution, in which the early generation of garnet is mainly composed of grossular (average Gro72And25), while the later generation of garnet is mainly composed of andradite (average Gro39And59); the vesuvianites are Al-rich vesuvianites; the pyroxenes form a diopside–hedenbergite solid solution with a composition of Di3–86Hd14–96; the axinites are mainly composed of ferroaxinite; and the actinolites are Fe-actinolite. The mineral assemblage of the skarn rocks indicates that the ore-forming fluid was in a relatively reduced state in the early prograde skarn stage. As the ore-forming fluid evolved, the oxygen fugacity of the ore-forming fluid increased. During the final skarn stage, the ore-forming fluid changed from a relatively oxidized state to a reduced state. The skarn rocks have evolved from early Al-rich to late Fe-rich characteristics, indicating that the early ore-forming fluid was mainly magmatic exsolution fluid, which may mainly reflect the characteristics of magmatic fluids, and the late Fe-rich characteristics of the skarn rocks may indicate that the late hydrothermal fluid was strongly influenced by country rocks. Trace element analyses showed that the Sn content decreased from the prograde skarn stage to the retrograde skarn stage, indicating that Sn mineralization was not achieved by activating and extracting Sn from prograde skarn rocks by hydrothermal fluids. The significant enrichment of Sn in the magmatic hydrothermal fluid is a necessary condition for Sn mineralization. There are various volatile-rich minerals such as axinite, vesuvianite, fluorite, and tourmaline in the Dachang ore field, indicating that the ore-forming fluid contained extensive volatiles B and F, which may be the fundamental reason for the large-scale mineralization of the Dachang ore field.

Liquid Metal Doping Induced Asymmetry in Two-Dimensional Metal Oxides.

The emergence of ferroelectricity in two-dimensional (2D) metal oxides is a topic of significant technological interest; however, many 2D metal oxides lack intrinsic ferroelectric properties. Therefore, introducing asymmetry provides access to a broader range of 2D materials within the ferroelectric family. Here, the generation of asymmetry in 2D SnO by doping the material with Hf0.5Zr0.5O2 (HZO) is demonstrated. A liquid metal process as a doping strategy for the preparation of 2D HZO-doped SnO with robust ferroelectric characteristics is implemented. This technology takes advantage of the selective interface enrichment of molten Sn with HZO crystallites. Molecular dynamics simulations indicate a strong tendency of Hf and Zr atoms to migrate toward the surface of liquid metal and embed themselves within the growing oxide layer in the form of HZO. Thus, the liquid metal-based harvesting/doping technique is a feasible approach devised for producing novel 2D metal oxides with induced ferroelectric properties, represents a significant development for the prospects of random-access memories.

In situ analysis of mica from the Daguanshan granites in Western Yunnan: Implication for Sn enrichment and mineralization

The potential of tin mineralization associated with the Triassic Lincang granite batholith in Western Yunnan, China, has been poorly understood, despite the batholith being considered the northern extension of the Southeast Asian Tin Belt. To address this issue and gain insights into the mechanism of tin enrichment, we investigate the major and trace element compositions of biotite and muscovite from four granite units in Daguanshan, including hornblende-biotite granite, biotite granite, two-mica granite, and muscovite granite in the Hongmaoling Sn deposit. From the hornblende-biotite granite to two-mica granite, the biotite composition varies from Mg-biotite to Fe-biotite with increasing MnO and decreasing K/Rb. The Fe3+-Fe2+-Mg2+ diagram and decreasing Mg/(Fe + Mg) ratios of the biotite indicate reducing conditions. From two-mica granite to muscovite granite, the muscovite Li, F, Rb and Cs concentrations generally increase with decreasing K/Rb, suggesting a magmatic fractionation trend. The variations in zoned muscovite composition reflect a high degree of magmatic fractionation and a lack of fluid interaction. Biotite tin concentrations increase from ∼ 18 ppm in the hornblende-biotite granite to ∼ 36 ppm in the biotite granite and further to ∼ 62 ppm in the two-mica granite. In addition, tin concentrations increase from ∼ 180 ppm in the core to ∼ 330 ppm in the rim of muscovite in the muscovite granite. These data indicate that magmatic fractionation is critical to Sn enrichment in the Hongmaoling deposit. The Nb/Ta ratio and tin concentration in mica from tin mineralized granites are generally higher than those from barren granites, indicating they could be used as reliable indicators for assessing tin metallogenic potential.

Tin Mineralization in the Triassic Chacaltaya District (Cordillera Real, Bolivia) Traced by In Situ Chemical and δ18O-δ11B Compositions of Tourmaline

Abstract We present a petrographic and geochemical study of tourmaline from the Triassic Chacaltaya Sn-polymetallic district in the Cordillera Real of Bolivia. Tourmaline is associated with greisens, breccias, and veins, which occur around the Triassic Chacaltaya peraluminous granitic stock hosted by Silurian metasedimentary rocks. Three main petrographic types of hydrothermal tourmaline have been identified: pre-ore greisen-related (Tur-1), syn-ore breccia-related (Tur-2), and syn-ore vein-related (Tur-3). The three types of tourmaline belong to the alkali group and have Fe-rich compositions mostly close to the schorl end member. Overlapping Fe/(Fe + Mg) ratios suggest broadly similar compositions of the hydrothermal fluids during the deposition of tourmaline. The most notable differences in minor and trace element contents include relative enrichment in Zn and Li in Tur-1 and relative enrichment in Ca, Sc, V, Cr, Sr, Sn, Y, Cs, Be, and Zr in Tur-3, with Tur-2 showing intermediate compositions between those of Tur-1 and Tur-3. The progressive enrichment in Sn from Tur-1 (avg = 14 ppm) through Tur-2 (avg = 311 ppm) and Tur-3 (avg = 476 ppm) indicates an increase of Sn concentrations in the hydrothermal system coinciding with cassiterite deposition in breccias and veins. The transition from high Li and Zn contents in Tur-1 to elevated Ca, Sr, V, and Cr contents in Tur-3 is interpreted as reflecting interaction between a hydrothermal fluid of magmatic origin and the metasedimentary country rocks. Strong and relatively steady positive Eu anomalies in all tourmaline types suggest dominantly reduced hydrothermal conditions. In situ δ18O and δ11B analyses of greisen-related Tur-1 reveal crystallization in isotopic equilibrium with magmatic water derived from a peraluminous S-type granite. In contrast, higher δ18O values of breccia-related Tur-2 and vein-related Tur-3 indicate crystallization in isotopic equilibrium with a fluid of metamorphic origin or a magmatic fluid that variably interacted with the metasedimentary host rocks. Geochemical modeling reproduces interactions between a fluid of magmatic origin and the host metasedimentary rocks at moderate water/rock ratios between 0.1 and 0.5. We conclude that cassiterite mineralization in the Chacaltaya district was formed primarily through interaction between B-Sn–rich magmatic fluids and the metasedimentary country rocks.

Tracing tungsten-tin mineralization processes with tourmaline geochemistry in the Wangxianling-Hehuaping district, Nanling Range (South China)

The mechanisms controlling the enrichment and separate precipitation of tungsten and tin ores are obscure. To unravel the physicochemical changes in the mineralization system during the magmatic-hydrothermal transition, we investigate the petrography, geochemistry, and boron isotopes of tourmaline in the Wangxianling-Hehuaping district (Nanling Range, South China). Four types of tourmalines were identified: Magmatic (Tur-WG) and hydrothermal (Tur-WV) tourmaline in the Triassic W-mineralized tourmaline-two-mica granite (ca. 220 Ma); Magmatic (Tur-SnG) and hydrothermal (Tur-SnV) tourmaline in the Jurassic Sn-mineralized biotite granite (ca. 155 Ma). Tur-WV and Tur-SnV have lower Fe3+/(Fe2+ + Fe3+) ratios than those of Tur-WG and Tur-SnG, suggesting that W-Sn mineralization occurred in a relatively reducing environment. In addition, the δ11B values of all four types of tourmalines are similar, suggesting that the ore-forming fluids were primarily exsolved from the granitic magma. Significant chemical variations (e.g., Mg, Fe, Sc, V, Ni, and REEs) between Tur-SnG and Tur-SnV may have been resulted from fractionation and intense ore fluid-wall rock reactions. In contrast, Tur-WG has similar chemical compositions to Tur-WV, suggesting that the Triassic W mineralization may have undergone a magmatic-hydrothermal process with little ore fluid-wall reaction. Tur-SnV has exceptionally high F content, which could enhance the Sn solubility and enrichment. This explains the low Sn content of granitic magmas with large-scale Jurassic tin mineralization. Considering that W has a large melt-fluid partition coefficient, we conclude that in the Triassic, W is enriched in the exsolved fluid from the granitic magma and precipitated with temperature drop. This may have caused the decrease in W content in the protolith and limited the Jurassic W mineralization. Subsequently, the mantle-derived F addition along the Chenzhou-Linwu fault in the Jurassic had led to Sn enrichment in the fluids, and mineralization is triggered by temperature drop and fluid-rock reactions. Eventually, the extensive Triassic W mineralization and Jurassic Sn mineralization exhibit the separation of tungsten-tin mineralization. The separated tungsten-tin mineralization model based on different volatile components could also be applicable to other tungsten-tin metallogenic belts.

Distribution and enrichment of rare metal elements in the basement rocks of South China: Controls on rare-metal mineralization

The southeastern part of the South China Block (SCB) is composed of the Nanling-Yunkai and Wuyi terranes and the Jiangnan Orogenic Belt (JOB), of which the Nanling and the JOB are two world-famous rare-metal metallogenic belts. Rare-metal deposits in both areas are closely associated with crustally-derived granites. However, rare-metal abundances and enrichment mechanisms in Precambrian basement rocks, which probably are sources of the ore-forming granites in the SCB, have not been well understood. Bulk compositions of more than 800 basement rock samples are used to unravel the abundances, variation and enrichment mechanism of the rare-metal elements in Precambrian basement rocks of the SCB and their genetic links with rare-metal mineralization. The basement meta-sedimentary rocks of the westernmost section of the JOB have the highest Sn (10.2 ppm), W (7.7 ppm), Be (3.46 ppm) and Cs (17.1 ppm) abundances, whereas those of the eastern JOB have low Sn (2.4–3.2 ppm), W (1.2–2.1 ppm), Nb (12.9–13.9 ppm) and Be (2.22–2.34 ppm), but relatively high Li (53.3–57.0 ppm) contents. The eastern Nanling basement rocks show high Sn (4.5 ppm), W (3.0 ppm) and U (3.67 ppm) relative to upper continental crust (UCC), similar to the western Nanling basements (4.2 ppm, 3.0 ppm and 4.03 ppm, respectively), but have significantly higher Rb/Sr, Li, Be, Cs and lower CaO/Na2O and Ba than the western Nanling basements, implying the presence of more meta-pelitic rocks in the eastern Nanling basements. The Wuyi terrane is characterized by low rare-metal abundances, e.g Sn (2.1 ppm), W (1.3 ppm), Cs (5.7 ppm) and Li (36.4 ppm). Rare-metal enrichment mechanisms are also distinct in the basement rocks of different terranes of the SCB. Four types of enrichment mechanism are identified: magmatic recycling, chemical weathering, source enrichment and alternative redox depositional environments. The enrichment of Sn, W, Cs and Be in the westernmost basement of the JOB is attributed to a higher proportion of old and multi-cycled materials and alternating depositional environments, and the enrichment of Sn, W, REE and U in the Nanling basement is ascribed to the higher proportion of recycled detritus and an enriched source. Chemical weathering (clay adsorption) is an important initial enrichment mechanism in the eastern JOB basement. Comparisons of rare-metal mineralization in the SCB with the basement compositions suggest that rare-metal mineralization of the granites is not only related to the rare-metal contents of the source, but also is closely related to the lithology of the source. Stronger W mineralization in the eastern JOB and eastern Nanling than in their western parts is probably related to their more pelite-rich basements.

Determining multiple fluid pulse and evolution using zoned garnet in Mengya’a skarn Pb-Zn-polymetallic deposit, Tibet

Skarn deposits, which serve as a significant source of Pb, Zn, Fe, W, Cu, and Au, are typically formed through interactions between fluids and carbonate rocks. However, the discovery of skarn deposits faces obstacles due to a limited understanding of the factors influencing their size. Many studies increasingly assume that the presence of large skarn deposits may be closely associated with multi-stage fluid pulses. Nonetheless, this assumption has not undergone explicit testing. In this study, zoned garnet grains from the large Mengya’a Pb-Zn-polymetallic deposits were used to unravel the multi-stage fluid pulse and evolution within a magmatic-hydrothermal system. In-situ major and trace elemental analysis reveals that the garnets exhibit two distinct zones, namely Ti-Al-enriched (G1) and Ti-Al-poor (G2) zones. The G1 domains are characterized by high HFSEs, slight enrichment in heavy rare earth elements (HREE), and minor variable Eu anomalies, as well as a linear relationship between REE and Y concentrations. These observations suggest that their formation reflects the fluid flux in a nearly closed system. The G2 domains exhibit oscillatory zoning in Al, Fe, Sn, HFSE, and various other elements, reflecting the intermittent flow of fluids originating from a degassing magma reservoir. The Al-, Zn-, and HFSE-rich characteristics of G2, along with their low δEu anomalies in comparison to G1, are associated with fluids that have undergone multiple recharge events from a magma chamber containing a significant amount of meteoric water in an open system. The presence of Sn-rich and In-rich zones within G2, accompanied by high δEu anomalies, indicates a gradual cooling and evolution of the pulsed fluids, resulting in the enrichment of Sn and volatile elements in the remaining fluid. Consequently, it can be concluded that the contribution of multiple fluid flows from a recharged magma chamber, undergoing extended cooling and evolution, plays a pivotal role in the formation of large skarn deposits. An additional implication of this study is that the zoning of Sn in garnet serves as a crucial indicator of Sn mineralization within skarn deposits.

Early Paleozoic granitic magmatism and mineralization in the Debao Sn-Cu deposit, South China: Constraints from zircon and cassiterite U-Pb geochronology and whole-rock geochemistry

Numerous W-Sn deposits are developed in South China. While the majority of these deposits are related to the Yanshanian granites, a few of them are associated with the Early Paleozoic granites, and their geological significance is poorly understood. The Debao deposit is a typical skarn Sn-Cu polymetallic deposit that is spatially related to the Early Paleozoic Qinjia granites. Zircon U-Pb dating of three lithofacies (coarse-grained biotite granite, medium-grained porphyritic biotite granite and fine-grained porphyritic biotite granite) of the Qinjia granites yielded emplacement ages of 437.8 ± 3.0 Ma, 440.2 ± 2.0 Ma and 441.0 ± 3.0 Ma, respectively, consistent with cassiterite U-Pb ages of skarn ore (439.6 ± 2.7 Ma), indicating a close genetic relationship between the granitic magmatism and Sn mineralization. Biotite from the Qinjia granites belong to the ferro-biotite series with relatively high F contents (up to 0.70 wt. %). The Biotite compositions plot near the Ni-NiO (NNO) buffer on a Fe3+-Fe2+-Mg2+ diagram, suggesting formation under relatively low oxygen fugacity. The Qinjia granites are characterized by highly silicious (70.37–72.88 wt. %), high alkali (Na2O + K2O = 6.98–8.88 wt. %) and metaluminous to strongly peraluminous with the A/CNK ratios of 0.92–1.21, belonging to the I-S transform-type granites. They are enriched in U, Th, Zr, Nd and Hf, and depleted in Ba, Sr, Nb, Ta and Ti. They display right-declining chondrite-normalized REE patterns with significant negative Eu anomalies (EuN/Eu* = 0.33–0.66), and have low Nb/Ta and K/Rb ratios, indicating that the Qinjia granites experienced a high degree of fractional crystallization. The zircon εHf(t) values (−2.7 to +1.4), together with TDMC of 1.59 to 1.33 Ga, indicate that the granites formed via partial melting of Mesoproterozoic crustal with minor addition of mantle materials. The reduced (fO2 near NNO and Ce4+/Ce3+ ratios of zircon < 100), fractionated and volatile-rich magma facilitated the enrichment of Sn in the residual melt and hydrothermal fluids. Combined with previous studies on the Early Paleozoic magmatic rocks and tectonic activities in South China, we suggest that the Qinjia granites and associated Sn-Cu mineralization were likely formed in the post-collisional extensional environment during the Wuyi-Yunkai orogeny.