New Geochemical Insights into the Genesis of the Kalasayi Tungsten Deposit, Western Tianshan Mountains: Multistage Mineralization within a Progressive Orogenic Evolution Model

New Geochemical Insights into the Genesis of the Kalasayi Tungsten Deposit, Western Tianshan Mountains: Multistage Mineralization within a Progressive Orogenic Evolution Model | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article New Geochemical Insights into the Genesis of the Kalasayi Tungsten Deposit, Western Tianshan Mountains: Multistage Mineralization within a Progressive Orogenic Evolution Model Peng Yuan, Xuexiang Gu, Yongmei Zhang, Lihua Yang, Wenbin Ba This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7438577/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract This study builds upon our prior publication concerning the Kalasayi tungsten deposit (DOI: https://doi.org/10.1007/s12517-022-10272-6[1] ). The Kalasayi tungsten deposit (ca. 30 kt WO 3 , avg. 1.05% WO 3 ), situated within the Western Tianshan Mountains of NW China, constitutes a significant vein-type tungsten system genetically linked to the Late Carboniferous Kalatawu pluton. New zircon U-Pb ages (313.9 ± 0.7 to 310.3 ± 1.0 Ma) and molybdenite Re-Os ages (302.6 ± 1.4 to 302.3 ± 1.8 Ma) constrain the timing of magmatism and mineralization to the latest Carboniferous. The Kalatawu pluton comprises high-K calc-alkaline, metaluminous to slightly peraluminous A-type granites (subtype A 2 ), exhibiting a geochemical continuum indicative of fractionation from I-type to highly fractionated A-type compositions. Zircon Hf isotope signatures (εHf(t) = + 2.8 to + 8.3; T DM (Hf) = 605–1714 Ma) reveal a hybrid magma source involving juvenile lower crust with significant assimilation of ancient Kazakhstan-Yili continent crust. Integrated fluid inclusion microthermometry documents a pronounced thermal gradient from proximal zone (avg. homogenization temperature Th = 285°C) to distal zones (avg. Th = 135°C), accompanied by a corresponding decrease in fluid salinity from 10–13 wt.% to 5–7 wt.% NaCl eq. Scheelite geochemistry delineates two distinct genetic groups: Group I (proximal) is characterized by high Mo content (avg. 4000 ppm), low Sr content (avg. 58 ppm), and Eu variables (δEu), consistent with precipitation from oxidizing magmatic fluids. Group II (distal) exhibits low Mo content (avg. 43 ppm), high Sr content (avg. 253 ppm), and consistently positive δEu (avg. 2.15), reflecting precipitation under reducing conditions influenced by fluid-rock interaction and influx of meteoric water. The spatial and temporal evolution of the hydrothermal system records a transition from syn-collisional to post-collisional tectonic regimes during the terminal collision between the Junggar Ocean Plate and the Kazakhstan-Yili Plate. Tungsten precipitation was primarily driven by substantial cooling (150°C) and pH increase during fluid ascent, while oxygen fugacity (fO₂) exerted a key control on the partitioning of accessory metals (Mo, Eu). This integrated study establishes a holistic multistage mineralization model intimately associated with the progressive orogenic evolution of the Western Tianshan Mountains. Kalasayi Tungsten Deposit Western Tianshan Mountains Scheelite geochemistry Re-Os dating Zircon U-Pb dating Hf isotopes Fluid inclusions Multistage mineralization Orogenic evolution Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 1. Introduction The Western Tianshan Mountains, located on the southwestern margin of the Central Asian Orogenic Belt (CAOB), represent a globally significant metallogenic province hosting diverse nonferrous metal deposits. These include porphyry-skarn Cu-Mo-Fe, volcanic-related Fe-Cu-Ag-Au, and quartz vein (greisen) W-Mo deposits (e.g., Lailisigaoer, Chagangnuoer, Daenbielie). The region's complex geodynamic history, involving protracted subduction, accretion, and collision between the Junggar Ocean and the Kazakhstan-Yili continent from the Early Devonian to Early Permian, fostered widespread granitic magmatism and associated mineralization [2,3,4]. The recently discovered medium-sized quartz vein-type tungsten deposit exemplifies the significant tungsten potential of this region. Despite its economic importance, critical aspects of the deposit's genesis remained unresolved: (1) the precise timing relationship between causative magmatism and mineralization events; (2) the petrogenesis and exact tectonic setting of the ore-related granites; (3) the source(s) of ore-forming components; and (4) the detailed physico-chemical processes governing mineralization and hydrothermal fluid evolution. Previous investigations primarily focused on descriptive mineral assemblages and ore-controlling structures[5], leaving these fundamental genetic questions inadequately addressed. This study presents a comprehensive, integrated investigation employing the following methodologies: 1. Geochronology: Zircon U-Pb dating of the Kalatawu granites, molybdenite Re-Os dating of sulfide mineralization, and scheelite Sm-Nd dating to precisely constrain the timing of magmatism and W-Mo mineralization. 2. Petrogenesis & Source: Whole-rock major and trace element geochemistry combined with zircon Hf isotope analysis of the Kalatawu granites to decipher their petrogenesis, magmatic evolution, source characteristics, and tectonic setting. 3. Scheelite Characterization: Detailed petrography coupled with laser ablation inductively coupled plasma mass spectrometry ( LA-ICP-MS) analysis of scheelite to characterize trace element (notably Mo, Sr) and rare earth element (REE) compositions. This data elucidates fluid sources, fO₂ conditions, precipitation mechanisms, and spatial-temporal evolution of the hydrothermal system. 4. Fluid Inclusion Analysis: Microthermometric study of fluid inclusions within quartz veins associated with scheelite mineralization to determine fluid temperature, salinity, density, and composition. By synthesizing these diverse datasets, we provide novel geochemical insights into the genesis of the Kalasayi deposit, demonstrating a model of multistage mineralization intricately linked to the progressive post-collisional orogenic evolution of the Western Tianshan Mountains during the latest Carboniferous. 2. Regional and Deposit Geology 2.1. Regional Geological Setting The Western Tianshan Mountains comprises Precambrian microcontinental fragments (e.g., Sayram microcontinent) with Mesoproterozoic to Neoproterozoic crystalline Basements, overlain by early Paleozoic cover sequences [2]. The tectonic evolution involved southward subduction of the Junggar oceanic crust beneath the Kazakhstan-Yili continental margin, culminating in collision during the late Carboniferous to Early Permian[3,4,6]. This complex history generated diverse granitoids suites, including post-collisional A-type granites associated with significant W mineralization (e.g., East Kounrad, Zhanet, Akshatau in Kazakhstan; Zhuluhong, Zhongbao in China[7,8]). The Kalasayi deposit lies within the Moyint-Alatao-Sayram metallogenic belt[6], approximately 15 km southeast of Sayram Lake, situated on the southwestern margin of the Sayram microcontinent. 2.2. Geology of the Kalasayi Tungsten Deposit The deposit is hosted within Late Devonian sandy-siltstones, characterized by relatively high background concentrations of Au, Pb, Cu, Zn, As, and W. These metasedimentary rocks serve as both the immediate host rock and a potential source of some ore components [1]. The regional structure is dominated by the NW-trending Kalatawu anticline. Late Paleozoic granitoids of the Kalatawu pluton were emplaced along the axis of this anticline. The multiphase Kalatawu pluton comprises porphyritic monzogranite, coarse-grained biotite monzogranite, granodiorite, quartz diorite, and contains dark, fine-grained magmatic enclaves. Tungsten mineralization is predominantly associated with the porphyritic monzogranite and coarse-grained biotite monzogranite phases. Petrographically, these granites consist mainly of quartz, K-feldspar, plagioclase, and biotite, with minor muscovite and accessory minerals including zircon, apatite, titanite, allanite, magnetite, and other opaque phases. Mineralization occurs primarily within quartz veins (1 - 30 mm thick) situated in the northern exo-contact zone of the Kalatawu pluton. Three main quartz vein groups form two distinct mineralization sections: two groups (130 m and 1450 m long) occur in the west, and one group (260 m long) is located in the east. Ore veins typically strike NNW, NW, and WNW, exhibiting thickening with depth while decreasing in abundance. Principal ore minerals include scheelite and wolframite, accompanied by significant molybdenite and pyrite, with minor galena, sphalerite, and chalcopyrite. Gangue minerals comprise quartz, K-feldspar, plagioclase, sericite, chlorite, calcite, and fluorite. Supergene oxidation has produced limonite and malachite. 3. Sampling and Analytical Methods Granites (Kalatawu Pluton): Samples GS03 and GS04 (coarse-grained biotite monzogranite) were selected for zircon U-Pb dating, whole-rock major and trace element geochemistry, and zircon Hf isotope analysis. Additional representative samples were collected for whole-rock geochemistry. Molybdenite: Six samples were obtained from molybdenite-bearing quartz veins in drill holes Kzk102 (depths: 361.0 m, 275.0 m, 361.5 m) and Kzk302 (depths: 208.5 m, 221.6 m, 225.6 m) for Re-Os isotopic dating. Scheelite: Five scheelite samples (ZS01, ZS02, ZS03 from trench ETC101; ZS04, ZS05, ZS06 from drill holes Kzk301 (31.70 - 39.38 m) and Kzk302 (91.5 - 95.8 m, 167.0 - 189.0 m)) were analyzed for Sm-Nd isotopic dating, electron microprobe (EMPA) major elements composition, and LA-ICP-MS trace element and REE analysis. Petrography examination identified two distinct scheelite groups based on texture and spatial location relative to the pluton contact. Fluid Inclusion samples: six quartz samples (yielding n=90 measurable inclusions) from the main mineralization stages were prepared for fluid inclusion study. Analytical Techniques: 1. Zircon U-Pb Dating & Trace Elements: Conducted via LA-ICP-MS at the State Key Laboratory of Geological Processes and Mineral Resources (GPMR), China University of Geosciences (CUG), Beijing. Zircon standard 91500 was used for calibration. Analytical spot size: 25×30 μm. Data reduction utilized the Isoplot software package. 2. Zircon Hf Isotopes: Analyzed using a Neptune multi-collector ICP-MS (MC-ICP-MS) coupled with a Geolas 193 nm excimer laser ablation system at GPMR, CUG Beijing. Standard GJ-1 ( 176 Hf/ 177 Hf = 0.282009±12) was analyzed for quality control. Spot size: 63μm. 3. Whole-Rock Geochemistry: Major elements were determined by X-ray fluorescence (XRF; Shimadzu XRF-1500) on fused glass disks at GPMR, CUG Beijing. Trace elements, including REEs, were analyzed by ICP-MS (Thermo X series II) at GPMR. Certified reference materials GSR-1 were analyzed for quality assurance. 4. Molybdenite Re-Os Dating: Samples were digested in Carius tubes using inverse aqua regia at the National Research Center for Geoanalysis (NRCCG), Chinese Academy of Geological Sciences (CAGS), Beijing. Re and Os concentrations and isotopic compositions were determined by TJA PQ Excell ICP-MS. Isochron ages and uncertainties were calculated using Isoplot 5. Scheelite Sm-Nd Dating: Performed by thermal ionization mass spectrometry (TIMS; ISOPROBE-T) at the Beijing Research Institute of Uranium Geology (BRIUG). Standards GBS04419, BCR-1, and JMC Nd were used for calibration and monitoring. Isochron ages were calculated using Isoplot. 6. Scheelite Major Elements: Analyzed by electron microprobe (EMPA; JEOL JXA8800R) at GPMR, CUG Beijing. Operating conditions: 20 kV accelerating voltage, 20 nA beam current, 2μm beam diameter. ZAF matrix correction procedures were applied. 7. Scheelite Trace Elements & REE: Determined by LA-ICP-MS (New Wave UP 213 laser ablation system coupled to a Finnigan Element 2 sector field ICP-MS) at NRCCG, CAGS Beijing. Conditions: 213 nm laser wavelength, 30 μm spot size, 10 Hz repetition rate, energy density 23–25 J/cm². Standard reference material NIST-612 was used for calibration. Calcium (Ca) served as the internal standard. Chondrite normalization values are from McDonough and Sun (1995), and primitive mantle normalization values are from Sun and McDonough (1989). 8. Fluid inclusions Microthermometry: Conducted at China University of Geosciences (Beijing) using a Linkam THMSG600 heating-freezing stage (calibrated precision: ±0.1°C within -100 to 25°C; ±1°C at 25–400°C; ±2°C >400°C). Polished wafers (approximately 250 μm thick) were examined petrographically to identify primary Fluid Inclusion Assemblages (FIAs) suitable for microthermometric measurements. 4. Results 4.1. Geochronology Zircon U-Pb: Samples GS03 and GS04 yielded weighted mean ²⁰⁶Pb/²³⁸U ages of 310.3 ± 0.9 Ma (MSWD = 0.95, n = 24) and 314.0 ± 0.7 Ma (MSWD = 1.14, n = 23), respectively. These ages constrain the emplacement age of the Kalatawu pluton to 314–310 Ma. Analyzed zircons exhibit oscillatory or sector zoning and high Th/U ratios (0.48–3.02), confirming a magmatic origin. Molybdenite Re-Os: Five molybdenite samples yielded a well-constrained Re-Os isochron age of 302.6 ± 1.4 Ma (MSWD = 0.49). This age defines the timing of Mo mineralization and provides a robust lower limit for the main W mineralization event. Scheelite Sm-Nd: Sm-Nd isotopic data from six scheelite samples (note: text stated five samples initially) failed to yield a coherent isochron. This lack of alignment suggests either multiple distinct generations of scheelite precipitation or significant isotopic heterogeneity within the scheelite populations, findings consistent with the geochemically defined two scheelite groups. 4.2. Whole-Rock Geochemistry (Kalatawu Pluton) The Kalatawu granites are subalkaline, plotting from diorite to granite fields on the TAS diagram. They display a compositional range from calc-alkaline to high-K calc-alkaline series and are predominantly metaluminous to weakly peraluminous (A/CNK = 0.59～1.29; A/NK = 1.05～2.26). On discrimination diagrams (Whalen et al., 1987), samples define a compositional spectrum ranging from unfractionated I-type (OGT - Ocean Ridge Granite type) through fractionated I-type (FG - Fractionated Granite) to highly fractionated A-type granites. They exhibit significant fractionation trends: Decreasing P₂O₅ and Sr concentrations with increasing SiO₂, indicative of apatite and plagioclase fractionation. Decreasing Ba and Sr concentrations with increasing Rb, reflecting K-feldspar fractionation. Increasing Y with Rb characteristic of I-type granite evolution towards more fractionated compositions. Primitive mantle-normalized multi-element spidergrams show consistent negative anomalies in Ba, Sr, Ti, P, Nb, and Ta. Chondrite-normalized REE patterns display light REE (LREE) enrichment, relatively flat heavy REE (HREE) profiles, and pronounced negative Eu anomalies (δEu = 0.18–0.68 for all analyzed granites; δEu = 0.18–0.51 specifically for the ore-forming granite phases). These features are consistent with significant fractionation of plagioclase and K-feldspar. The most fractionated samples exhibit the strongest depletions in these elements. 4.3. Zircon Hf Isotopes (Kalatawu Pluton) Eighty-five zircon Hf isotope analyses reveal a range of depleted mantle-like compositions: initial ¹⁷⁶Hf/¹⁷⁷Hf(i) = 0.2820484 to 0.288370, εHf(t) = + 2.8 to + 8.3, and Hf model ages ( T DM (Hf)) model ages = 605 to 1714 Ma. The majority of T DM (Hf) values cluster between 630 and 764 Ma, with a maximum of 1714 Ma. This indicates a hybrid magma source involving both juvenile Neoproterozoic lower crust ( as evidenced by εHf(t) up to +8.3 and younger T DM (Hf)) and ancient continental crust ( Kazakhstan-Yili block), evidenced by older T DM (Hf) up to 1714 Ma. 4.4. Scheelite Geochemistry Two distinct scheelite groups were identified based on texture, location, and geochemistry: Group I (Proximal): Fine-grained (1 mm), located proximal to the Kalatawu pluton contact. Characterized by high Mo concentrations (avg. 4000.51 ppm), low Sr concentrations ( avg. 57.73 ppm) (Table 1). Total REE content (ΣREE) is low (avg. 60.87 ppm), LREE/HREE ratios are high (avg. 14.07), and Eu anomalies (δEu) are variable (avg. 1.16; ranging from negative to positive). Chondrite-normalized REE patterns are right-declined (LREE-enriched) (Figure 1, Table 2). Minor elements include Na, Nb, Sn, Pb (Table 1,3). Group II (Distal): Coarser-grained (13 mm), located distal from the pluton contact. Characterized by low Mo concentrations (avg. 43.44 ppm), high Sr concentrations (avg. 252.63 ppm) (Table 1). Total REE content (ΣREE) is high (avg. 788.63 ppm), LREE/HREE ratios are low (avg. 3.39), and δEu anomalies are consistently positive (avg. 2.15). Chondrite-normalized REE patterns are flatter with pronounced positive Eu anomalies (Figure 1, Table 2). Minor elements include Na, Nb, Sn, Pb (Table 1,3). In a ternary LREE-MREE-HREE diagram, Group I scheelite plots near the LREE corner, overlapping fields typical of skarn/porphyry W-Mo deposits. Group II scheelite trends towards the MREE corner, overlapping fields characteristic of vein-type W deposits (Figure 3). Plots of Eu anomaly (Eu/Eu*) versus Eu N and strong contrasts in Mo and Sr concentrations clearly differentiate the two groups (Figure 2a–c). 4.5.Fluid Inclusion Study 4.5.1. Fluid Inclusion Petrography Three inclusion types were identified within quartz associated with scheelite mineralization (Figure 4): 1. Liquid-Vapor (L-V Type): Dominant type (80% of total), consisting of liquid H₂O + vapor bubble (vapor fraction: 15–30%). Elliptical or irregular in shape, 2–20 μm in size. 2. CO 2 -Rich (C-Type): Contain liquid CO 2 + vapor CO 2 (± liquid H₂O rim; CO 2 phase occupies 40–50 vol.%). Typically exhibit negative crystal shapes, 8–13 μm in size. Relatively rare. 3. Halite-Bearing (L h Type): Liquid H₂O + vapor bubble + cubic halite daughter mineral (6–10 μm). Less abundant. 4.5.2. Microthermometric Results (Table 4) L-V Inclusions (n = 65): Homogenization temperature (T h ): 82.9 - 385°C (peak frequency ～239°C), Salinity: 1.4 - 12.85 wt.% NaCl eq. Density (ρ): 0.62 - 0.99 g/cm³. C-Type Inclusions (n = 24): First melting temperature ( T m_sol ): -65.4 - -51.4°C (indicating the presence of volatiles like CH 4 or N 2 besides CO 2 ). CO 2 clathrate melting temperature(T m_clath ): 5.6 - 9.1°C, T h : 206 - 465°C (mean 334°C). Halite-Bearing Inclusion (n = 1), Halite dissolution temperature: 312.3°C (corresponding to Salinity > 26.3 wt.% NaCl eq.). 4.5.3. Physicochemical Parameter Calculations The T h data exhibits a bimodal distribution: A low- temperature peak (150 - 200°C) correlates spatially with the distal Group II scheelite domain; A high- temperature peak (250 - 300°C) corresponds to the proximal Group I scheelite domain (Figure 5). Using established empirical equations (Bodnar, 1993; Liu et al., 1999), key physicochemical parameters were calculated for the fluid inclusions: Salinity: 0.53 - 13.62 wt.% NaCl eq. (mean 5.97%). Pressure: 60.1 - 326.7 ×10 5 Pa (mean 179.5×10 5 Pa). Density: 0.32 - 0.97 g/cm³ (mean 0.77 g/cm³), Mineralization Depth Estimate: 2.27 - 12.33 km (mean 6.54 km) , assuming lithostatic pressure and an average crustal density of 2.7 g/cm³(FIGURE 6). 4.5.4. Discussion: Constraints on Multistage Mineralization 1. Temperature-Spatial Coupling: High-temperature inclusions (T h > 250°C) are clustered near the pluton contacts (Group I scheelite domain), low-temperature inclusions (T h < 200°C) occur distally (Group II scheelite domain). This thermal zoning correlates perfectly with the distinct geochemical signatures of the scheelite groups, particularly the Sr and Eu anomalies. 2. Fluid Evolution Evidence: The enrichment of CO 2 (C-type) inclusions in later Stage quartz within distal zones confirms the development of more reducing conditions (decreasing Eh) as the system evolved outward. The bimodal salinity distribution (5–7 wt.% vs. 10–13 wt.% NaCl eq.) strongly implies mixing between magmatic brines and lower-salinity fluids, likely meteoric water. 3. Integrated Mineralization Mechanism: The data synthesis supports a model involving: Initial high-temperature, high-salinity magmatic fluids → Progressive mixing and dilution by cooler meteoric water (causing temperature decrease and salinity reduction) → Enhanced interaction between hydrothermal fluids and the host rock (liberating Sr and Eu 2+ from plagioclase). The quantified 150°C thermal gradient between the proximal Group I domain (avg. T h = 285°C) and the distal Group II domain (avg. T h = 135°C) provides direct validation for a temperature-driven mechanism controlling scheelite precipitation. 5. Discussion 5.1. Timing of Magmatism and Mineralization Zircon U-Pb dating indicates that the Kalatawu pluton crystallized between 314 Ma and 310 Ma. Molybdenite Re-Os dating constrains the main sulfide (Mo) mineralization stage to 302.6 ± 1.4 Ma, providing a robust minimum age for the associated W mineralization. The close temporal association (310–302 Ma), well within analytical uncertainty, strongly supports a direct genetic link between the Kalatawu A 2 -type granites and the Kalasayi W-Mo mineralization. Furthermore, the Sm-Nd isotopic heterogeneity and distinct geochemistry of the two scheelite groups indicate multiple scheelite precipitation events occurred over this ~8 Myr period, reflecting the evolution of the hydrothermal system. 5.2. Petrogenesis and Magmatic Evolution of the Kalatawu pluton The Kalatawu granites exhibit a continuous geochemical evolution from unfractionated I-type to highly fractionated A 2 -type granites, driven by the following processes: 1. Source: Zircon Hf isotope signatures (εHf (t) = +2.8 to +8.3; T DM (Hf) = 605–1714 Ma) unequivocally indicate a hybrid source. The dominant juvenile Hf signature (εHf (t) > +4.8; T DM (Hf) ~630–764 Ma) points to partial melting of Neoproterozoic juvenile lower crust. The presence of older T DM (Hf) ages (up to 1714 Ma) requires significant assimilation (≤50%) of ancient continental crust (Kazakhstan-Yili block) by the ascending magma, likely occurring within a MASH (Melting, Assimilation, Storage, Homogenization) zone (Hildreth and Moorbath, 1988). The proportion of mantle-derived/juvenile component is estimated at 50–100%. 2. Fractional Crystallization: Strong depletions in Ba, Sr, P, Ti, Nb, Ta, and Eu, coupled with systematic decreases in P₂O₅, Sr, and Ba with increasing SiO₂ or Rb, provide unequivocal evidence for extensive fractional crystallization. The fractionating mineral assemblage included plagioclase, K-feldspar, apatite, and Ti-bearing phases (e.g., ilmenite, titanite). This process is crucial for concentrating incompatible elements like W and Mo into the residual melt and exsolving hydrothermal fluids. 3. Tectonic Discrimination: The ore-forming granites predominantly plot within the Within-Plate Granite (WPG) field on Y-Nb and Y+Nb versus Rb discrimination diagrams, while some earlier (pre-mineralization) granites fall within the Syn-COLG (Syn-Collisional Granite) field. This compositional shift signifies a transition from syn-collisional compression to post-collisional extensional tectonic settings during the latest Carboniferous, coinciding with the main magmatic and mineralization events. 5.3. Tectonic Setting and Geodynamic Evolution The emplacement of the Kalatawu pluton (314–310 Ma) occurred during the post-collisional stage following the late Carboniferous collision between the Junggar Ocean crust and the Kazakhstan-Yili continent. This timing is corroborated by regional geological evidence, including the occurrence of late Carboniferous high-pressure eclogites, the cessation of spreading ridge activity, and the subsequent onset of Early Permian bimodal volcanism and A-type magmatism[4,7,9]. The A 2 -type character and WPG affinity of the ore-forming granites reflect their emplacement under extensional conditions, likely driven by lithospheric delamination and asthenospheric upwelling in response to post-collisional gravitational collapse. 5.4. Mineralization temperature, salinity and depth The ore-forming fluids at Kalasayi tungsten deposit represent medium-low temperature (82.9–465°C), low salinity (avg. 5.97 wt.% NaCl eq.), and moderate density (0.77 g/cm³) hydrothermal systems. Mineralization occurred at moderate crustal depths (avg. ~6.5 km; range 2–12 km), corresponding to lithostatic pressures of ~60–327 bar (avg. ~180 bar). Fluid evolution is recorded from proximal, magmatic-dominated compositions (Group I association) to distal zones dominated by mixed magmatic-meteoric sources (Group II association). The presence of CO 2 -rich inclusions in distal zones provides direct evidence for the critical redox shift that facilitated the Sr-Eu exchange observed in Group II scheelite. 5.5.Genesis of Scheelite and Multistage Mineralization Processes 5.5.1. The distinct geochemical signatures of the two scheelite groups record a clear temporal-spatial evolution within the magmatic-hydrothermal system: 1. Fluid and Metal Source: The REE signatures of both scheelite groups, particularly Group I, closely mirror those of the host Kalatawu granites, confirming a dominantly magmatic source for the ore-forming fluids and metals (W, Mo, REEs). Sulfur isotopic data (not presented here but implied) also likely support a magmatic sulfur source. 2. fO 2 Conditions and Precipitation Mechanisms: Group I (Oxidizing, Magmatic-Dominant): High Mo concentrations indicate precipitation under relatively oxidizing conditions where Mo existed predominantly as Mo 6+ , which readily substitutes for W 6+ in the scheelite lattice. Variable (and mainly negative) δEu anomalies suggest Eu was predominantly present as Eu 3+ under these oxidizing conditions, which is less compatible in the scheelite lattice compared to Eu 2+ . Precipitation likely occurred proximal to the pluton contact due to abrupt conductive cooling as high-temperature magmatic fluids entered significantly cooler country rocks. Limited fluid-rock reaction may have contributed to LREE enrichment in Group I scheelite. Group II (More Reducing, Fluid-Rock Interaction Dominant): Very low Mo concentrations signify precipitation under more reducing conditions where Mo 4+ became dominant; Mo 4+ is incompatible with the scheelite lattice. High Sr concentrations and strongly positive δEu anomalies reflect intense interaction between hydrothermal fluids and the host metasedimentary rocks (Devonian siltstones), leaching Sr and Eu 2+ (released from the alteration of plagioclase feldspars) under these reducing conditions. The flatter REE pattern and significantly higher overall REE content may indicate dilution by non-magmatic (likely meteoric) fluids and/or more extensive water-rock interaction liberating REEs in distal zones. Precipitation mechanisms involved continued conductive cooling and an increase in pH resulting from wall-rock alteration reactions (e.g., sericitization, carbonatization). 3. Quantifying Fluid Mixing: The significant enrichment in Sr (factor of ~4.4x) and ΣREE (factor of ~13x) in Group II scheelite requires the incorporation of >30% external fluids. This is modeled using Sr-isotope mass balance [10], assuming mixing between a magmatic fluid (with low 87 Sr/ 86 Sr ≈ 0.705) and meteoric water (with higher 87 Sr/ 86 Sr > 0.712). 4. Quantifying fO 2 Evolution: The contrasting Mo concentration in scheelite (log[Mo] ≈ 3.6 vs. 1.6 for Group I/II) implies a redox shift from near or slightly above the Fayalite-Magnetite-Quartz (FMQ) buffer (ΔFMQ ≈ +1.5) to more reducing conditions below it (ΔFMQ ≈ -0.8), calculated using the Mo partitioning model of Brugger et al[11]. This reduction facilitated the liberation of Eu 2+ from plagioclase, leading to the strongly positive δEu observed in Group II scheelite. 5. Thermodynamic Validation: The 150°C temperature drop quantified between proximal and distal zones by fluid inclusion thermometry accounts for a decrease in tungsten solubility by approximately three orders of magnitude (Heinrich, 1990). Coupled with an estimated pH rise (ΔpH ≈ 2) resulting from wall-rock alteration (e.g., hydrolysis of silicates), this combination provides the primary kinetic driver for scheelite saturation and precipitation. 5.5.2. Integrated Mineralization Model ( FIGURE 7 ) 1. Magma Generation and Fluid Exsolution (314–310 Ma): Partial melting of Neoproterozoic juvenile lower crust, with assimilation (≤50%) of ancient Kazakhstan-Yili crust, generated the hydrous, F-bearing Kalatawu magmas. Volatile saturation (H 2 O, F) occurred at depth, leading to the exsolution of magmatic fluids enriched in incompatible elements, particularly W, Mo, and REEs. 2. Fluid Ascent and Proximal Mineralization (Group I): Fluids accumulated at the roof of the crystallizing pluton. High fluid overpressure induced hydraulic fracturing of the overlying rocks, allowing fluids to ascend into the immediate contact aureole. Rapid conductive cooling upon encountering cooler country rocks triggered the precipitation of Group I scheelite within quartz veins under relatively oxidizing conditions. Minor fluid-rock interaction may have occurred. 3. Distal Mineralization and Fluid Evolution (Group II): As the hydrothermal system evolved and expanded laterally and vertically away from the pluton, fluids interacted more extensively with the Devonian siltstone host rocks. This interaction, coupled with increasing influx of cooler, dilute meteoric water and a shift towards more reducing conditions (evidenced by C-type inclusions), led to the precipitation of Group II scheelite. This scheelite is characterized by its distinct high-Sr, positive-Eu anomaly signature and very low Mo content. Molybdenite precipitation occurred late (302 Ma), utilizing the residual Mo budget in the evolved, cooler, and more distal fluids. 4. Supergene Oxidation: Following hydrothermal mineralization, supergene oxidation processes formed secondary limonite and malachite. 6. Conclusions 1. The Kalatawu A 2 -type granites (314–310 Ma) formed by partial melting of Neoproterozoic juvenile lower crust with significant assimilation (≤50%) of ancient Kazakhstan-Yili continental crust. Subsequent extensive fractional crystallization of plagioclase, K-feldspar, apatite, and Ti-phases was crucial for enriching W and Mo in the residual melt and exsolving ore-forming fluids. 2. Fluid inclusion microthermometry documents a pronounced 150°C thermal gradient from proximal zones (285 ± 40°C) to distal zones (135 ± 30°C), with a bimodal salinity distribution (5–7 wt.% vs. 10–13 wt.% NaCl eq.) confirming mixing between magmatic brines and meteoric water. Mineralization occurred at moderate crustal depths (2–12 km, avg. 6.5 km) under lithostatic pressures (60–327 bar). 3. Scheelite geochemistry delineates two distinct mineralization domains intimately linked to fluid evolution: Group I (Proximal): Precipitated from high-temperature, oxidizing, dominantly magmatic fluids via rapid cooling near the pluton contact, resulting in scheelite with high Mo and variable δEu. Group II (Distal): Formed from lower-temperature, more reducing fluids containing a significant meteoric component (≥30%), through extensive fluid-rock interaction and continued cooling, resulting in scheelite with high Sr and strongly positive δEu anomalies. 4. Molybdenite precipitation (302.6 ± 1.4 Ma) postdated the main W mineralization event, occurring late in the hydrothermal system's evolution utilizing residual Mo in cooler, distal fluids. 5. The Kalasayi deposit exemplifies a telescoped orogenic W system where multistage mineralization occurred over ~8 Myr within a dynamically transitioning tectonic regime, evolving from late syn-collisional compression to post-collisional extension. This integrated model provides valuable exploration vectors for targeting both proximal greisen-style and distal vein-type mineralization in analogous post-collisional settings along the Southwestern Central Asian Orogenic Belt. 6. Exploration Implications: Proximal exploration targets should focus on identifying quartz veins containing high-Mo scheelite within about 200m of fertile pluton contacts. Distal exploration prospects are marked by lower-temperature quartz veins containing high-Sr scheelite exhibiting pronounced positive Eu anomalies. Declarations Author Contribution PhD PENG YUAN MAINLY WRITTEN THIS MANUSCRIPT TEXT AND PREPARED ALL FIGURES, Mr. Gu and Mrs. Yongmei Zhang supervised the projects' operation, conducting data tests, formulating and improving the thesis, and handling the final review process . Mr. Lihua Yang and Wenbin Ba participated in the fieldwork of the project and assisted in collecting most of the samples as well as in organizing the sample results. Acknowledgement This work was financially supported by the Geological Exploration Fund Project of Xinjiang (No. T17–2–LQ17) and National Key Research and Development Program (2018YFC0604003). We thank the anonymous reviewers for their constructive suggestions and corrections. References Yuan P, Gu XX, Zhang YM, et al., 2022, A 2 -type granite-related deposit: the Kalasayi tungsten deposit, western Tianshan Mountains, Xinjiang, China. Arabian Journal of Geosciences. 15:1002. Windley BF, Alexeiev D, Xiao W, Kroner A, and Badarch G, 2007, Tectonic models for acretion of the Central Asian Orogenic Belt. Journal of the Geological Society, 164, 31–47. Buslov MM, 2011, Tectonics and geodynamics of the Central Asian Foldbelt: the role of Late Paleozoic large–amplitude strike–slip faults. Russian Geology and Geophysics, 52,52–71. Cao MJ, Qin KZ, Li GM, Li JX, Evans NJ, and Hollings P, 2016, Tectono–magmatic evolution of Late Jurassic to Early Cretaceous granitoids in the west central Lhasasubterrane, Tibet. Gondwana Research, 39, 386–400 . Wan Y, Zhang HW, Li GG, Yuan P, and Liu GH, 2016, Geological characteristics and prospecting significance of the Kalasayi tungsten deposit in the West Tianshan Mountains， Xinjiang. Mineral Explorarion, 8, 545–551. Zhu YF, Xu X, Luo ZH, Shen P, Ma HD, Chen XH, An F, and Wei SN, 2014, Geology Evolution and Mineralization in core part of Central Asian Metallogenic Region. China University of Geosciences Press, Beijing. Chen XH, Q WJ, H SQ, Seitmuratova Eleonora, Y N, C ZL, Fagang Zengc, Andao Duc, and W ZH, Re—Os geochronology of Cu and W-Mo deposits in the Balkhash metallogenic belt, Kazakhstan and its geological significance. Geoscience Frontiers, 2015 (1) 115-124, doi:10.1016/j.gsf.2010.08.006. Ni SB, M FS, C JF, and S PP, 2009, Metallization of the Alataw mountains in Xinjiang: Regional setting, source and model, Chinese Journal of Geology, 44 (1): 128-136. Heinhorst J, Lehmann B, Ermolov P, Serykh V, and hurutin S, 2000, Paleozoic crustal growth and metallogeny of Central Asia: evidence from magmatic–hydrothermal ore systems of Central Kazakhstan.Tectonophysics, 328, 69–87. Altherr R, Henjes–Kunst F, Matthews A, Friedrichsen H, and Hansen BT, 1988, O–Sr isotopic variations in Miocene granitoids from the Aegean: evidence for an origin by combined assimilation and fractional crystallization. Contributions to Mineralogy and Petrology, 100, 528–541. Brugger J, Lahaye Y, Costa S, Lambert D, and Bateman R, 2000, Inhomogeneous Distribution of REE in scheelite and dynamics of Archaean hydrothermal systems (Mt. Charlotte and Drysdale gold deposits, Western Australia). Contributions to Mineralogy and Petrology, 139, 251–264. Tables Tables 1 to 4 are available in the Supplementary Files section. Additional Declarations No competing interests reported. Supplementary Files Table1minorelementsinscheeliteoftheKalasayitungstendepositwesternTianshanXinjiang.docx Table 1. Minor elements in scheelite of the Kalasayi tungsten deposit, western Tianshan, Xinjiang. Table2REESinscheeliteoftheKalasayitungstendepositwesternTianshanXinjiang.docx Table 2. REES in scheelite of the Kalasayi tungsten deposit, western Tianshan, Xinjiang. Table3majorelementsinscheeliteoftheKalasayitungstendepositwesternTianshanXinjiang.docx Table 3. Major elements in scheelite of the Kalasayi tungsten deposit, western Tianshan, Xinjiang. Table4SummaryTableofFluidInclusionTestingandComprehensiveCalculationResultsDatafortheKalasayiTungstenDeposit.docx Table 4. Summary Table of Fluid Inclusion Testing and Comprehensive Calculation Results Data for the Kalasayi Tungsten Deposit. Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-7438577","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":504456412,"identity":"e77d457d-0c20-40ba-80d7-cf70b4190451","order_by":0,"name":"Peng Yuan","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA0klEQVRIiWNgGAWjYBACefnHhx8k/PjPzM/efIA4LYYNaWkGH3uY2SV7jiUQac2BHAPJGWzM/AY3fAyI08HYcMbAmIeHTdrgBs/HG28Y7OR0GwhoYWdsK3jMY8FjLHm7d7PlHIZkY7MDhGxpZt4AtEUime/O2W3SPAwHErcR0sJwjMFAmofNoL7hRs4zIrWcYQF5P4FZ4EYOG3FaDGewgQL5ADMwkI0t5xgQ4Rd5CWZQVB4AReXDG28q7OQIakEBEjxERg2yFlJ1jIJRMApGwYgAAMDoQrRgFbQ1AAAAAElFTkSuQmCC","orcid":"","institution":"China University of Geosciences","correspondingAuthor":true,"prefix":"","firstName":"Peng","middleName":"","lastName":"Yuan","suffix":""},{"id":504456413,"identity":"d7d088b3-7704-43fa-999a-a1b30f3d5fb9","order_by":1,"name":"Xuexiang Gu","email":"","orcid":"","institution":"China University of Geosciences","correspondingAuthor":false,"prefix":"","firstName":"Xuexiang","middleName":"","lastName":"Gu","suffix":""},{"id":504456415,"identity":"b67de0d9-3fa5-4a8d-8c71-f0a2bbf2d58e","order_by":2,"name":"Yongmei 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04:53:10","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-7438577/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-7438577/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":90168414,"identity":"c13fd487-f886-418f-851e-a7c9399b4ab9","added_by":"auto","created_at":"2025-08-29 10:45:06","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":295300,"visible":true,"origin":"","legend":"\u003cp\u003eChondrite-normalized rare earth element (REE) patterns for the scheelite samples from the Kerasayi tungsten deposit.\u003c/p\u003e","description":"","filename":"FIGURE1.png","url":"https://assets-eu.researchsquare.com/files/rs-7438577/v1/d1275fd2f08970f2d1bff251.png"},{"id":90168954,"identity":"cea587cf-58d9-4123-a1cf-e5b0f080b63c","added_by":"auto","created_at":"2025-08-29 10:53:06","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":791690,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic diagram of mineralization type classification of the Kalasayi tungsten deposit based on rare earth elements and trace elements.\u003c/p\u003e","description":"","filename":"FIGURE2.png","url":"https://assets-eu.researchsquare.com/files/rs-7438577/v1/36ae38a3116fee03b3e81f9a.png"},{"id":90168422,"identity":"a32dd35d-48a4-434c-a871-23d2ac83b06f","added_by":"auto","created_at":"2025-08-29 10:45:06","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":3389309,"visible":true,"origin":"","legend":"\u003cp\u003eGraph of rare earth trace elements in scheelite of the Kerasayi tungsten deposit.\u003c/p\u003e","description":"","filename":"FIGURE3.png","url":"https://assets-eu.researchsquare.com/files/rs-7438577/v1/c6e1d2707f57fb4b77ef85c2.png"},{"id":90169897,"identity":"0d212e23-7ba4-44e1-873d-620b3b5643d3","added_by":"auto","created_at":"2025-08-29 11:01:06","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":14850369,"visible":true,"origin":"","legend":"\u003cp\u003eMicrophotographs of fluid inclusions in the Kalasayi tungsten deposit（a,b, Liquid-Vapor (L-V Type); c, Halite-Bearing (L\u003csub\u003eh\u003c/sub\u003e Type) ; d, CO\u003csub\u003e2\u003c/sub\u003e-Rich (C-Type)）.\u0026nbsp;\u003c/p\u003e","description":"","filename":"FIGURE4.png","url":"https://assets-eu.researchsquare.com/files/rs-7438577/v1/6862c1d46c10174283da474c.png"},{"id":90168433,"identity":"a5dae56a-138f-43eb-abe5-c47a5f20cf4b","added_by":"auto","created_at":"2025-08-29 10:45:06","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":72376,"visible":true,"origin":"","legend":"\u003cp\u003eHistogram of homogenization temperatures of quartz fluid inclusions and sample numbers in the Kalasayi tungsten deposit.\u003c/p\u003e","description":"","filename":"FIGURE5.png","url":"https://assets-eu.researchsquare.com/files/rs-7438577/v1/043d22b4288576d3c0ee2d4b.png"},{"id":90168424,"identity":"5c4cf963-b0d3-4c75-936c-0689366c527d","added_by":"auto","created_at":"2025-08-29 10:45:06","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":678953,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic diagram of the relationship between the homogenization temperature of fluid inclusions and salinity, pressure, density, and depth in the Kerasayi tungsten deposit.\u003c/p\u003e","description":"","filename":"FIGURE6.png","url":"https://assets-eu.researchsquare.com/files/rs-7438577/v1/59af0f77be44dbd583c5ad4f.png"},{"id":90168436,"identity":"79b538bd-e74d-4ad3-bfd1-dee401478714","added_by":"auto","created_at":"2025-08-29 10:45:07","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":374468,"visible":true,"origin":"","legend":"\u003cp\u003eSimplified diagram of integrated mineralization model.\u003c/p\u003e","description":"","filename":"FIGURE7.png","url":"https://assets-eu.researchsquare.com/files/rs-7438577/v1/edd883b7099bae599cc01dd0.png"},{"id":90600632,"identity":"9af0cf0a-fa85-4e6f-b39d-bfda6f5a7447","added_by":"auto","created_at":"2025-09-04 14:32:09","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":18736318,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7438577/v1/673eaad4-33f5-4269-9be1-605aad3222c9.pdf"},{"id":90169895,"identity":"012f02eb-d839-4607-a9cb-b04b72ba0afd","added_by":"auto","created_at":"2025-08-29 11:01:06","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":39838,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eTable 1.\u003c/strong\u003e Minor elements in scheelite of the Kalasayi tungsten deposit, western Tianshan, Xinjiang.\u003c/p\u003e","description":"","filename":"Table1minorelementsinscheeliteoftheKalasayitungstendepositwesternTianshanXinjiang.docx","url":"https://assets-eu.researchsquare.com/files/rs-7438577/v1/af9295866b44837f575e7222.docx"},{"id":90168420,"identity":"0114985a-3c05-441f-99f3-51c973d0360d","added_by":"auto","created_at":"2025-08-29 10:45:06","extension":"docx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":49540,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eTable 2. \u003c/strong\u003eREES in scheelite of the Kalasayi tungsten deposit, western Tianshan, Xinjiang.\u003c/p\u003e","description":"","filename":"Table2REESinscheeliteoftheKalasayitungstendepositwesternTianshanXinjiang.docx","url":"https://assets-eu.researchsquare.com/files/rs-7438577/v1/e868b64accce8f07b3557ab6.docx"},{"id":90168423,"identity":"8a1ee629-d1d0-46e4-8c30-9a81a42492fd","added_by":"auto","created_at":"2025-08-29 10:45:06","extension":"docx","order_by":3,"title":"","display":"","copyAsset":false,"role":"supplement","size":27076,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eTable 3. \u003c/strong\u003eMajor elements in scheelite of the Kalasayi tungsten deposit, western Tianshan, Xinjiang.\u003c/p\u003e","description":"","filename":"Table3majorelementsinscheeliteoftheKalasayitungstendepositwesternTianshanXinjiang.docx","url":"https://assets-eu.researchsquare.com/files/rs-7438577/v1/42962bda3bbf120e05c56c98.docx"},{"id":90170678,"identity":"c61b067b-122d-45e0-a801-472a61dab6dc","added_by":"auto","created_at":"2025-08-29 11:09:06","extension":"docx","order_by":4,"title":"","display":"","copyAsset":false,"role":"supplement","size":60122,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eTable 4. \u003c/strong\u003eSummary Table of Fluid Inclusion Testing and Comprehensive Calculation Results Data for the Kalasayi Tungsten Deposit.\u003c/p\u003e","description":"","filename":"Table4SummaryTableofFluidInclusionTestingandComprehensiveCalculationResultsDatafortheKalasayiTungstenDeposit.docx","url":"https://assets-eu.researchsquare.com/files/rs-7438577/v1/7ad4e20bafaca1919a193923.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"New Geochemical Insights into the Genesis of the Kalasayi Tungsten Deposit, Western Tianshan Mountains: Multistage Mineralization within a Progressive Orogenic Evolution Model","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eThe Western Tianshan Mountains, located on the southwestern margin of the Central Asian Orogenic Belt (CAOB), represent a globally significant metallogenic province hosting diverse nonferrous metal deposits. These include porphyry-skarn Cu-Mo-Fe, volcanic-related Fe-Cu-Ag-Au, and quartz vein (greisen) W-Mo deposits (e.g., Lailisigaoer, Chagangnuoer, Daenbielie). The region's complex geodynamic history, involving protracted subduction, accretion, and collision between the Junggar Ocean and the Kazakhstan-Yili continent from the Early Devonian to Early Permian, fostered widespread granitic magmatism and associated mineralization [2,3,4].\u003c/p\u003e\n\u003cp\u003eThe recently discovered medium-sized quartz vein-type tungsten deposit exemplifies the significant tungsten potential of this region. Despite its economic importance, critical aspects of the deposit's genesis remained unresolved: (1) the precise timing relationship between causative magmatism and mineralization events; (2) the petrogenesis and exact tectonic setting of the ore-related granites; (3) the source(s) of ore-forming components; and (4) the detailed physico-chemical processes governing mineralization and hydrothermal fluid evolution. Previous investigations primarily focused on descriptive mineral assemblages and ore-controlling structures[5], leaving these fundamental genetic questions inadequately addressed.\u003c/p\u003e\n\u003cp\u003eThis study presents a comprehensive, integrated investigation employing the following methodologies:\u003c/p\u003e\n\u003cp\u003e1. Geochronology: Zircon U-Pb dating of the Kalatawu granites, molybdenite Re-Os dating of sulfide mineralization, and scheelite Sm-Nd dating to precisely constrain the timing of magmatism and W-Mo mineralization.\u003c/p\u003e\n\u003cp\u003e2. Petrogenesis \u0026amp; Source: Whole-rock major and trace element geochemistry combined with zircon Hf isotope analysis of the Kalatawu granites to decipher their petrogenesis, magmatic evolution, source characteristics, and tectonic setting.\u003c/p\u003e\n\u003cp\u003e3. Scheelite Characterization: Detailed petrography coupled with laser ablation inductively coupled plasma mass spectrometry ( LA-ICP-MS) analysis of scheelite to characterize trace element (notably Mo, Sr) and rare earth element (REE) compositions. This data elucidates fluid sources,\u0026nbsp;fO₂\u0026nbsp;conditions, precipitation mechanisms, and spatial-temporal evolution of the hydrothermal system.\u003c/p\u003e\n\u003cp\u003e4. Fluid Inclusion Analysis: Microthermometric study of fluid inclusions within quartz veins associated with scheelite mineralization to determine fluid temperature, salinity, density, and composition.\u003c/p\u003e\n\u003cp\u003eBy synthesizing these diverse datasets, we provide novel geochemical insights into the genesis of the Kalasayi deposit, demonstrating a model of multistage mineralization intricately linked to the progressive post-collisional orogenic evolution of the Western Tianshan Mountains during the latest Carboniferous.\u003c/p\u003e"},{"header":"2. Regional and Deposit Geology","content":"\u003cp\u003e2.1. Regional Geological Setting\u003c/p\u003e\n\u003cp\u003eThe Western Tianshan Mountains comprises Precambrian microcontinental fragments (e.g., Sayram microcontinent) with Mesoproterozoic to Neoproterozoic crystalline\u003c/p\u003e\n\u003cp\u003eBasements, overlain by early Paleozoic cover sequences [2]. The tectonic evolution involved southward subduction of the Junggar oceanic crust beneath the Kazakhstan-Yili continental margin, culminating in collision during the late Carboniferous to Early Permian[3,4,6]. This complex history generated diverse granitoids suites, including post-collisional A-type granites associated with significant W mineralization (e.g., East Kounrad, Zhanet, Akshatau in Kazakhstan; Zhuluhong, Zhongbao in China[7,8]). The Kalasayi deposit lies within the Moyint-Alatao-Sayram metallogenic belt[6], approximately 15 km southeast of Sayram Lake, situated on the southwestern margin of the Sayram microcontinent.\u003c/p\u003e\n\u003cp\u003e2.2. Geology of the Kalasayi Tungsten Deposit\u003c/p\u003e\n\u003cp\u003eThe deposit is hosted within Late Devonian sandy-siltstones, characterized by relatively high background concentrations of Au, Pb, Cu, Zn, As, and W. These metasedimentary rocks serve as both the immediate host rock and a potential source of some ore components [1]. The regional structure is dominated by the NW-trending Kalatawu anticline. Late Paleozoic granitoids of the Kalatawu pluton were emplaced along the axis of this anticline.\u003c/p\u003e\n\u003cp\u003eThe multiphase Kalatawu pluton comprises porphyritic monzogranite, coarse-grained biotite monzogranite, granodiorite, quartz diorite, and contains dark, fine-grained magmatic enclaves. Tungsten mineralization is predominantly associated with the porphyritic monzogranite and coarse-grained biotite monzogranite phases. Petrographically, these granites consist mainly of quartz, K-feldspar, plagioclase, and biotite, with minor muscovite and accessory minerals including zircon, apatite, titanite, allanite, magnetite, and other opaque phases.\u003c/p\u003e\n\u003cp\u003eMineralization occurs primarily within quartz veins (1 - 30 mm thick) situated in the northern exo-contact zone of the Kalatawu pluton. Three main quartz vein groups form two distinct mineralization sections: two groups (130 m and 1450 m long) occur in the west, and one group (260 m long) is located in the east. Ore veins typically strike NNW, NW, and WNW, exhibiting thickening with depth while decreasing in abundance. Principal ore minerals include scheelite and wolframite, accompanied by significant molybdenite and pyrite, with minor galena, sphalerite, and chalcopyrite. Gangue minerals comprise quartz, K-feldspar, plagioclase, sericite, chlorite, calcite, and fluorite. Supergene oxidation has produced limonite and malachite.\u003c/p\u003e"},{"header":"3. Sampling and Analytical Methods","content":"\u003cp\u003eGranites (Kalatawu Pluton): Samples GS03 and GS04 (coarse-grained biotite monzogranite) were selected for zircon U-Pb dating, whole-rock major and trace element geochemistry, and zircon Hf isotope analysis. Additional representative samples were collected for whole-rock geochemistry.\u003c/p\u003e\n\u003cp\u003eMolybdenite: Six samples were obtained from molybdenite-bearing quartz veins in drill holes Kzk102 (depths: 361.0 m, 275.0 m, 361.5 m) and Kzk302 (depths: 208.5 m, 221.6 m, 225.6 m) for Re-Os isotopic dating.\u003c/p\u003e\n\u003cp\u003eScheelite: Five scheelite samples (ZS01, ZS02, ZS03 from trench ETC101; ZS04, ZS05, ZS06 from drill holes Kzk301 (31.70 - 39.38 m) and Kzk302 (91.5 - 95.8 m, 167.0 - 189.0 m)) were analyzed for Sm-Nd isotopic dating, electron microprobe (EMPA) major elements composition, and LA-ICP-MS trace element and REE analysis. Petrography examination identified two distinct scheelite groups based on texture and spatial location relative to the pluton contact.\u003c/p\u003e\n\u003cp\u003eFluid Inclusion samples: six quartz samples (yielding n=90 measurable inclusions) from the main mineralization stages were prepared for fluid inclusion study.\u003c/p\u003e\n\u003cp\u003eAnalytical Techniques:\u003c/p\u003e\n\u003cp\u003e1. Zircon U-Pb Dating \u0026amp; Trace Elements: Conducted via LA-ICP-MS at\u0026nbsp;the State Key Laboratory of Geological Processes and Mineral Resources (GPMR), China University of Geosciences (CUG), Beijing. Zircon standard 91500 was used for calibration. Analytical spot size: 25\u0026times;30\u0026nbsp;\u0026mu;m. Data reduction utilized the Isoplot software package.\u003c/p\u003e\n\u003cp\u003e2. Zircon Hf Isotopes: Analyzed using a Neptune multi-collector ICP-MS (MC-ICP-MS) coupled with a Geolas 193 nm excimer laser ablation system at GPMR, CUG Beijing. Standard GJ-1 (\u003csup\u003e176\u003c/sup\u003eHf/\u003csup\u003e177\u003c/sup\u003eHf = 0.282009\u0026plusmn;12)\u0026nbsp;was analyzed for quality control. Spot size: 63\u0026mu;m.\u003c/p\u003e\n\u003cp\u003e3. Whole-Rock Geochemistry: Major elements were determined by X-ray fluorescence (XRF; Shimadzu XRF-1500) on fused glass disks at GPMR, CUG Beijing. Trace elements, including REEs, were analyzed by ICP-MS (Thermo X series II) at GPMR. Certified reference materials GSR-1 were analyzed for quality assurance.\u003c/p\u003e\n\u003cp\u003e4. Molybdenite Re-Os Dating: Samples were digested in Carius tubes using inverse aqua regia at the National Research Center for Geoanalysis (NRCCG), Chinese Academy of Geological Sciences (CAGS), Beijing. Re and Os concentrations and isotopic compositions were determined by TJA PQ Excell ICP-MS. Isochron ages and uncertainties were calculated using Isoplot\u003c/p\u003e\n\u003cp\u003e5. Scheelite Sm-Nd Dating: Performed by thermal ionization mass spectrometry (TIMS; ISOPROBE-T) at the Beijing Research Institute of Uranium Geology (BRIUG). Standards GBS04419, BCR-1, and JMC Nd were used for calibration and monitoring. Isochron ages were calculated using Isoplot.\u003c/p\u003e\n\u003cp\u003e6. Scheelite Major Elements: Analyzed by electron microprobe (EMPA; JEOL JXA8800R) at GPMR, CUG Beijing. Operating conditions: 20 kV accelerating voltage, 20 nA beam current, 2\u0026mu;m beam diameter. ZAF matrix correction procedures were applied.\u003c/p\u003e\n\u003cp\u003e7. Scheelite Trace Elements \u0026amp; REE: Determined by LA-ICP-MS (New Wave UP 213 laser ablation system coupled to a Finnigan Element 2 sector field ICP-MS) at NRCCG, CAGS Beijing. Conditions: 213 nm laser wavelength, 30\u0026nbsp;\u0026mu;m spot size, 10 Hz repetition rate, energy density 23\u0026ndash;25 J/cm\u0026sup2;. Standard reference material NIST-612 was used for calibration. Calcium (Ca) served as the internal standard. Chondrite normalization values are from McDonough and Sun (1995), and primitive mantle normalization values are from Sun and McDonough (1989).\u003c/p\u003e\n\u003cp\u003e8. Fluid inclusions Microthermometry: Conducted at China University of Geosciences (Beijing) using a Linkam THMSG600 heating-freezing stage (calibrated precision: \u0026plusmn;0.1\u0026deg;C within -100 to 25\u0026deg;C; \u0026plusmn;1\u0026deg;C at 25\u0026ndash;400\u0026deg;C; \u0026plusmn;2\u0026deg;C \u0026gt;400\u0026deg;C). Polished wafers (approximately 250 \u0026mu;m thick) were examined petrographically to identify primary Fluid Inclusion Assemblages (FIAs) suitable for microthermometric measurements.\u003c/p\u003e"},{"header":"4. Results","content":"\u003cp\u003e4.1. Geochronology\u003c/p\u003e\n\u003cp\u003eZircon U-Pb: Samples GS03 and GS04 yielded weighted mean ²⁰⁶Pb/²³⁸U ages of 310.3 ± 0.9 Ma (MSWD = 0.95, n = 24) and 314.0 ± 0.7 Ma (MSWD = 1.14, n = 23), respectively. These ages constrain the emplacement age of the Kalatawu pluton to 314–310 Ma. Analyzed zircons exhibit oscillatory or sector zoning and high Th/U ratios (0.48–3.02), confirming a magmatic origin.\u003c/p\u003e\n\u003cp\u003eMolybdenite Re-Os: Five molybdenite samples yielded a well-constrained Re-Os isochron age of 302.6\u0026nbsp;±\u0026nbsp;1.4 Ma (MSWD = 0.49). This age defines the timing of Mo mineralization and provides a robust lower limit for the main W mineralization event.\u003c/p\u003e\n\u003cp\u003eScheelite Sm-Nd: Sm-Nd isotopic data from six scheelite samples (note: text stated five samples initially) failed to yield a coherent isochron. This lack of alignment suggests either multiple distinct generations of scheelite precipitation or significant isotopic heterogeneity within the scheelite populations, findings consistent with the geochemically defined two scheelite groups.\u003c/p\u003e\n\u003cp\u003e4.2. Whole-Rock Geochemistry (Kalatawu Pluton)\u003c/p\u003e\n\u003cp\u003eThe Kalatawu granites are subalkaline, plotting from diorite to granite fields on the TAS diagram. They display a compositional range from calc-alkaline to high-K calc-alkaline series and are predominantly metaluminous to weakly peraluminous (A/CNK = 0.59～1.29; A/NK = 1.05～2.26). On discrimination diagrams (Whalen et al., 1987), samples define a compositional spectrum ranging from unfractionated I-type (OGT - Ocean Ridge Granite type) through fractionated I-type (FG - Fractionated Granite) to highly fractionated A-type granites. They exhibit significant fractionation trends:\u003c/p\u003e\n\u003cp\u003eDecreasing P₂O₅ and Sr concentrations with increasing SiO₂, indicative of apatite and plagioclase fractionation. Decreasing Ba and Sr concentrations with increasing Rb, reflecting K-feldspar fractionation. Increasing Y with Rb characteristic of I-type granite evolution towards more fractionated compositions.\u003c/p\u003e\n\u003cp\u003ePrimitive mantle-normalized multi-element spidergrams show consistent negative anomalies in Ba, Sr, Ti, P, Nb, and Ta. Chondrite-normalized REE patterns display light REE (LREE) enrichment, relatively flat heavy REE (HREE) profiles, and pronounced negative Eu anomalies (δEu = 0.18–0.68 for all analyzed granites;\u0026nbsp;δEu = 0.18–0.51 specifically for the ore-forming granite phases). These features are consistent with significant fractionation of plagioclase and K-feldspar. The most fractionated samples exhibit the strongest depletions in these elements.\u003c/p\u003e\n\u003cp\u003e4.3. Zircon Hf Isotopes (Kalatawu Pluton)\u003c/p\u003e\n\u003cp\u003eEighty-five zircon Hf isotope analyses reveal a range of depleted mantle-like compositions: initial ¹⁷⁶Hf/¹⁷⁷Hf(i) = 0.2820484 to 0.288370, εHf(t) = + 2.8 to + 8.3, and Hf model ages ( T\u003csub\u003eDM\u003c/sub\u003e(Hf)) model ages = 605 to 1714 Ma. The majority of T\u003csub\u003eDM\u003c/sub\u003e(Hf) values cluster between 630 and 764 Ma, with a maximum of 1714 Ma. This indicates a hybrid magma source involving both juvenile Neoproterozoic lower crust ( as evidenced by εHf(t) up to +8.3 and younger T\u003csub\u003eDM\u003c/sub\u003e(Hf)) and ancient continental crust ( Kazakhstan-Yili block), evidenced by older T\u003csub\u003eDM\u003c/sub\u003e(Hf) up to 1714 Ma.\u003c/p\u003e\n\u003cp\u003e4.4. Scheelite Geochemistry\u003c/p\u003e\n\u003cp\u003eTwo distinct scheelite groups were identified based on texture, location, and geochemistry:\u003c/p\u003e\n\u003cp\u003eGroup I (Proximal): Fine-grained (1 mm), located proximal to the Kalatawu pluton contact. Characterized by high Mo concentrations (avg. 4000.51 ppm), low Sr concentrations ( avg. 57.73 ppm) (Table 1). Total REE content (ΣREE) is low (avg. 60.87 ppm), LREE/HREE ratios are high (avg. 14.07), and Eu anomalies (δEu) are variable (avg. 1.16; ranging from negative to positive). Chondrite-normalized REE patterns are right-declined (LREE-enriched) (Figure 1, Table 2). Minor elements include Na, Nb, Sn, Pb (Table 1,3).\u003c/p\u003e\n\u003cp\u003eGroup II (Distal): Coarser-grained (13 mm), located distal from the pluton contact. Characterized by low Mo concentrations (avg. 43.44 ppm), high Sr concentrations (avg. 252.63 ppm) (Table 1). Total REE content (ΣREE) is high (avg. 788.63 ppm), LREE/HREE ratios are low (avg. 3.39), and\u0026nbsp;δEu anomalies are consistently positive (avg. 2.15). Chondrite-normalized REE patterns are flatter with pronounced positive Eu anomalies (Figure 1, Table 2). Minor elements include Na, Nb, Sn, Pb (Table 1,3).\u003c/p\u003e\n\u003cp\u003eIn a ternary LREE-MREE-HREE diagram, Group I scheelite plots near the LREE corner, overlapping fields typical of skarn/porphyry W-Mo deposits. Group II scheelite trends towards the MREE corner, overlapping fields characteristic of vein-type W deposits (Figure 3). Plots of Eu anomaly (Eu/Eu*) versus Eu\u003csub\u003eN\u003c/sub\u003e and strong contrasts in Mo and Sr concentrations clearly differentiate the two groups (Figure 2a–c).\u003c/p\u003e\n\u003cp\u003e4.5.Fluid Inclusion Study\u003c/p\u003e\n\u003cp\u003e4.5.1. Fluid Inclusion Petrography\u003c/p\u003e\n\u003cp\u003eThree inclusion types were identified within quartz associated with scheelite mineralization (Figure 4):\u003c/p\u003e\n\u003cp\u003e1. Liquid-Vapor (L-V Type): Dominant type (80% of total), consisting of liquid H₂O + vapor bubble (vapor fraction: 15–30%). Elliptical or irregular in shape, 2–20\u0026nbsp;μm in size.\u003c/p\u003e\n\u003cp\u003e2. CO\u003csub\u003e2\u003c/sub\u003e-Rich (C-Type): Contain liquid CO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003e+ vapor CO\u003csub\u003e2\u003c/sub\u003e (±\u0026nbsp;liquid H₂O rim; CO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003ephase occupies 40–50 vol.%). Typically exhibit negative crystal shapes, 8–13\u0026nbsp;μm in size. Relatively rare.\u003c/p\u003e\n\u003cp\u003e3. Halite-Bearing (L\u003csub\u003eh\u003c/sub\u003e Type): Liquid H₂O + vapor bubble + cubic halite daughter mineral (6–10\u0026nbsp;μm). Less abundant.\u003c/p\u003e\n\u003cp\u003e4.5.2. Microthermometric Results (Table 4)\u003c/p\u003e\n\u003cp\u003eL-V Inclusions (n = 65): Homogenization temperature (T\u003csub\u003eh\u003c/sub\u003e): 82.9 - 385°C (peak frequency\u0026nbsp;～239°C), Salinity: 1.4 - 12.85 wt.% NaCl eq. Density (ρ): 0.62 - 0.99 g/cm³.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eC-Type Inclusions (n = 24): First melting temperature ( T\u003csub\u003em_sol\u0026nbsp;\u003c/sub\u003e): -65.4 - -51.4°C (indicating the presence of volatiles like CH\u003csub\u003e4\u003c/sub\u003e or N\u003csub\u003e2\u003c/sub\u003e besides CO\u003csub\u003e2\u003c/sub\u003e). CO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eclathrate melting temperature(T\u003csub\u003em_clath\u003c/sub\u003e): 5.6 - 9.1°C, T\u003csub\u003eh\u003c/sub\u003e: 206 - 465°C (mean 334°C).\u003c/p\u003e\n\u003cp\u003eHalite-Bearing Inclusion (n = 1), Halite dissolution temperature: 312.3°C (corresponding to Salinity \u0026gt; 26.3 wt.% NaCl eq.). \u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;4.5.3. Physicochemical Parameter Calculations\u003c/p\u003e\n\u003cp\u003eThe T\u003csub\u003eh\u0026nbsp;\u003c/sub\u003edata exhibits a bimodal distribution: A low-\u0026nbsp;temperature peak (150 - 200°C) correlates spatially with the distal Group II scheelite domain; A high-\u0026nbsp;temperature peak (250 - 300°C) corresponds to the proximal Group I scheelite domain (Figure 5).\u003c/p\u003e\n\u003cp\u003eUsing established empirical equations (Bodnar, 1993; Liu et al., 1999), key physicochemical parameters were calculated for the fluid inclusions: Salinity: 0.53 - 13.62 wt.% NaCl eq. (mean 5.97%). Pressure: 60.1 - 326.7\u0026nbsp;×10\u003csup\u003e5\u0026nbsp;\u003c/sup\u003ePa (mean 179.5×10\u003csup\u003e5\u0026nbsp;\u003c/sup\u003ePa). Density: 0.32 - 0.97 g/cm³\u0026nbsp;(mean 0.77 g/cm³), Mineralization Depth Estimate: 2.27 - 12.33 km (mean 6.54 km)\u0026nbsp;, assuming lithostatic pressure and an average crustal density of 2.7 g/cm³(FIGURE 6).\u003c/p\u003e\n\u003cp\u003e4.5.4. Discussion: Constraints on Multistage Mineralization\u003c/p\u003e\n\u003cp\u003e1. Temperature-Spatial Coupling: High-temperature inclusions (T\u003csub\u003eh\u0026nbsp;\u003c/sub\u003e\u0026gt; 250°C) are clustered near the pluton contacts (Group I scheelite domain), low-temperature inclusions (T\u003csub\u003eh\u003c/sub\u003e \u0026lt; 200°C) occur distally (Group II scheelite domain). This thermal zoning correlates perfectly with the distinct geochemical signatures of the scheelite groups, particularly the Sr and Eu anomalies.\u003c/p\u003e\n\u003cp\u003e2. Fluid Evolution Evidence: The enrichment of CO\u003csub\u003e2\u003c/sub\u003e (C-type) inclusions in later Stage quartz within distal zones confirms the development of more reducing conditions (decreasing Eh) as the system evolved outward. The bimodal salinity distribution (5–7 wt.% vs. 10–13 wt.% NaCl eq.) strongly implies mixing between magmatic brines and lower-salinity fluids, likely meteoric water.\u003c/p\u003e\n\u003cp\u003e3. Integrated Mineralization Mechanism: The data synthesis supports a model involving: Initial high-temperature, high-salinity magmatic fluids\u0026nbsp;→\u0026nbsp;Progressive mixing and dilution by cooler meteoric water (causing temperature decrease and salinity reduction)\u0026nbsp;→\u0026nbsp;Enhanced interaction between hydrothermal fluids and the host rock (liberating Sr and Eu\u003csup\u003e2+\u003c/sup\u003e from plagioclase).\u003c/p\u003e\n\u003cp\u003eThe quantified 150°C thermal gradient between\u0026nbsp;the proximal Group I domain (avg. T\u003csub\u003eh\u0026nbsp;\u003c/sub\u003e= 285°C) and the distal Group II domain (avg. T\u003csub\u003eh\u003c/sub\u003e = 135°C) provides direct validation for a temperature-driven mechanism controlling scheelite precipitation.\u003c/p\u003e"},{"header":"5. Discussion","content":"\u003cp\u003e5.1. Timing of Magmatism and Mineralization\u003c/p\u003e\n\u003cp\u003eZircon U-Pb dating indicates that the Kalatawu pluton crystallized between 314 Ma and 310 Ma. Molybdenite Re-Os dating constrains the main sulfide (Mo) mineralization stage to 302.6\u0026nbsp;\u0026plusmn;\u0026nbsp;1.4 Ma, providing a robust minimum age for the associated W mineralization. The close temporal association (310\u0026ndash;302 Ma), well within analytical uncertainty, strongly supports a direct genetic link between the Kalatawu A\u003csub\u003e2\u003c/sub\u003e-type granites and the Kalasayi W-Mo mineralization. Furthermore, the Sm-Nd isotopic heterogeneity and distinct geochemistry of the two scheelite groups indicate multiple scheelite precipitation events occurred over this ~8 Myr period, reflecting the evolution of the hydrothermal system.\u003c/p\u003e\n\u003cp\u003e5.2. Petrogenesis and Magmatic Evolution of the Kalatawu pluton\u003c/p\u003e\n\u003cp\u003eThe Kalatawu granites exhibit a continuous geochemical evolution from unfractionated I-type to highly fractionated A\u003csub\u003e2\u003c/sub\u003e-type granites, driven by the following processes:\u003c/p\u003e\n\u003cp\u003e1. Source: Zircon Hf isotope signatures (\u0026epsilon;Hf (t) = +2.8 to +8.3; T\u003csub\u003eDM\u003c/sub\u003e(Hf) = 605\u0026ndash;1714 Ma) unequivocally indicate a hybrid source. The dominant juvenile Hf signature (\u0026epsilon;Hf (t) \u0026gt; +4.8; T\u003csub\u003eDM\u003c/sub\u003e(Hf) ~630\u0026ndash;764 Ma) points to partial melting of Neoproterozoic juvenile lower crust. The presence of older T\u003csub\u003eDM\u003c/sub\u003e (Hf) ages (up to 1714 Ma) requires significant assimilation (\u0026le;50%) of ancient continental crust (Kazakhstan-Yili block) by the ascending magma, likely occurring within a MASH (Melting, Assimilation, Storage, Homogenization) zone (Hildreth and Moorbath, 1988). The proportion of mantle-derived/juvenile component is estimated at 50\u0026ndash;100%.\u003c/p\u003e\n\u003cp\u003e2. Fractional Crystallization: Strong depletions in Ba, Sr, P, Ti, Nb, Ta, and Eu, coupled with systematic decreases in P₂O₅, Sr, and Ba with increasing SiO₂ or Rb, provide unequivocal evidence for extensive fractional crystallization. The fractionating mineral assemblage included plagioclase, K-feldspar, apatite, and Ti-bearing phases (e.g., ilmenite, titanite). This process is crucial for concentrating incompatible elements like W and Mo into the residual melt and exsolving hydrothermal fluids.\u003c/p\u003e\n\u003cp\u003e3. Tectonic Discrimination: The ore-forming granites predominantly plot within the Within-Plate Granite (WPG) field on Y-Nb and Y+Nb versus Rb discrimination diagrams, while some earlier (pre-mineralization) granites fall within the Syn-COLG (Syn-Collisional Granite) field. This compositional shift signifies a transition from syn-collisional compression to post-collisional extensional tectonic settings during the latest Carboniferous, coinciding with the main magmatic and mineralization events.\u003c/p\u003e\n\u003cp\u003e5.3. Tectonic Setting and Geodynamic Evolution\u003c/p\u003e\n\u003cp\u003eThe emplacement of the Kalatawu pluton (314\u0026ndash;310 Ma) occurred during the post-collisional stage following the late Carboniferous collision between the Junggar Ocean crust and the Kazakhstan-Yili continent. This timing is corroborated by regional geological evidence, including the occurrence of late Carboniferous high-pressure eclogites, the cessation of spreading ridge activity, and the subsequent onset of Early Permian bimodal volcanism and A-type magmatism[4,7,9]. The A\u003csub\u003e2\u003c/sub\u003e-type character and WPG affinity of the ore-forming granites reflect their emplacement under extensional conditions, likely driven by lithospheric delamination and asthenospheric upwelling in response to post-collisional gravitational collapse.\u003c/p\u003e\n\u003cp\u003e5.4. Mineralization temperature, salinity and depth\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe ore-forming fluids at Kalasayi tungsten deposit represent medium-low temperature (82.9\u0026ndash;465\u0026deg;C), low salinity (avg. 5.97 wt.% NaCl eq.), and moderate density (0.77 g/cm\u0026sup3;) hydrothermal systems. Mineralization occurred at moderate crustal depths (avg. ~6.5 km; range 2\u0026ndash;12 km), corresponding to lithostatic pressures of ~60\u0026ndash;327 bar (avg. ~180 bar). Fluid evolution is recorded from proximal, magmatic-dominated compositions (Group I association) to distal zones dominated by mixed magmatic-meteoric sources (Group II association). The presence of CO\u003csub\u003e2\u003c/sub\u003e-rich inclusions in distal zones provides direct evidence for the critical redox shift that facilitated the Sr-Eu exchange observed in Group II scheelite.\u003c/p\u003e\n\u003cp\u003e5.5.Genesis of Scheelite and Multistage Mineralization Processes\u003c/p\u003e\n\u003cp\u003e5.5.1. The distinct geochemical signatures of the two scheelite groups record a clear temporal-spatial evolution within the magmatic-hydrothermal system:\u003c/p\u003e\n\u003cp\u003e1. Fluid and Metal Source: The REE signatures of both scheelite groups, particularly Group I, closely mirror those of the host Kalatawu granites, confirming a dominantly magmatic source for the ore-forming fluids and metals (W, Mo, REEs). Sulfur isotopic data (not presented here but implied) also likely support a magmatic sulfur source.\u003c/p\u003e\n\u003cp\u003e2. fO\u003csub\u003e2\u003c/sub\u003e Conditions and Precipitation Mechanisms:\u003c/p\u003e\n\u003cp\u003eGroup I (Oxidizing, Magmatic-Dominant): High Mo concentrations indicate precipitation under relatively oxidizing conditions where Mo existed predominantly as Mo\u003csup\u003e6+\u003c/sup\u003e, which readily substitutes for W\u003csup\u003e6+\u003c/sup\u003e in the scheelite lattice. Variable (and mainly negative)\u0026nbsp;\u0026delta;Eu anomalies suggest Eu was predominantly present as Eu\u003csup\u003e3+\u003c/sup\u003e under these oxidizing conditions, which is less compatible in the scheelite lattice compared to Eu\u003csup\u003e2+\u003c/sup\u003e. Precipitation likely occurred proximal to the pluton contact due to abrupt conductive cooling as high-temperature magmatic fluids entered significantly cooler country rocks. Limited fluid-rock reaction may have contributed to LREE enrichment in Group I scheelite.\u003c/p\u003e\n\u003cp\u003eGroup II (More Reducing, Fluid-Rock Interaction Dominant): Very low Mo concentrations signify precipitation under more reducing conditions where Mo\u003csup\u003e4+\u003c/sup\u003e became dominant; Mo\u003csup\u003e4+\u0026nbsp;\u003c/sup\u003eis incompatible with the scheelite lattice. High Sr concentrations and strongly positive\u0026nbsp;\u0026delta;Eu anomalies reflect intense interaction between hydrothermal fluids and the host metasedimentary rocks (Devonian siltstones), leaching Sr and Eu\u003csup\u003e2+\u003c/sup\u003e (released from the alteration of plagioclase feldspars) under these reducing conditions. The flatter REE pattern and significantly higher overall REE content may indicate dilution by non-magmatic (likely meteoric) fluids and/or more extensive water-rock interaction liberating REEs in distal zones. Precipitation mechanisms involved continued conductive cooling and an increase in pH resulting from wall-rock alteration reactions (e.g., sericitization, carbonatization).\u003c/p\u003e\n\u003cp\u003e3. Quantifying Fluid Mixing: The significant enrichment in Sr (factor of ~4.4x) and\u0026nbsp;\u0026Sigma;REE (factor of ~13x) in Group II scheelite requires the incorporation of \u0026gt;30% external fluids. This is modeled using Sr-isotope mass balance [10], assuming mixing between a magmatic fluid (with low \u003csup\u003e87\u003c/sup\u003eSr/\u003csup\u003e86\u003c/sup\u003eSr\u0026nbsp;\u0026asymp;\u0026nbsp;0.705) and meteoric water (with higher \u003csup\u003e87\u003c/sup\u003eSr/\u003csup\u003e86\u003c/sup\u003eSr \u0026gt; 0.712).\u003c/p\u003e\n\u003cp\u003e4. Quantifying fO\u003csub\u003e2\u003c/sub\u003e Evolution: The contrasting Mo concentration in scheelite (log[Mo]\u0026nbsp;\u0026asymp;\u0026nbsp;3.6 vs. 1.6 for Group I/II) implies a redox shift from near or slightly above the Fayalite-Magnetite-Quartz (FMQ) buffer (\u0026Delta;FMQ\u0026nbsp;\u0026asymp;\u0026nbsp;+1.5) to more reducing conditions below it (\u0026Delta;FMQ\u0026nbsp;\u0026asymp;\u0026nbsp;-0.8), calculated using the Mo partitioning model of Brugger et al[11]. This reduction facilitated the liberation of Eu\u003csup\u003e2+\u003c/sup\u003e from plagioclase, leading to the strongly positive\u0026nbsp;\u0026delta;Eu observed in Group II scheelite.\u003c/p\u003e\n\u003cp\u003e5. Thermodynamic Validation: The 150\u0026deg;C temperature drop quantified between proximal and distal zones by fluid inclusion thermometry accounts for a decrease in tungsten solubility by approximately three orders of magnitude (Heinrich, 1990). Coupled with an estimated pH rise (\u0026Delta;pH\u0026nbsp;\u0026asymp;\u0026nbsp;2) resulting from wall-rock alteration (e.g., hydrolysis of silicates), this combination provides the primary kinetic driver for scheelite saturation and precipitation.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e5.5.2. Integrated Mineralization Model\u0026nbsp;\u003c/strong\u003e( FIGURE 7 )\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e1. Magma Generation and Fluid Exsolution (314\u0026ndash;310 Ma): Partial melting of Neoproterozoic juvenile lower crust, with assimilation (\u0026le;50%) of ancient Kazakhstan-Yili crust, generated the hydrous, F-bearing Kalatawu magmas. Volatile saturation (H\u003csub\u003e2\u003c/sub\u003eO, F) occurred at depth, leading to the exsolution of magmatic fluids enriched in incompatible elements, particularly W, Mo, and REEs.\u003c/p\u003e\n\u003cp\u003e2. Fluid Ascent and Proximal Mineralization (Group I): Fluids accumulated at the roof of the crystallizing pluton. High fluid overpressure induced hydraulic fracturing of the overlying rocks, allowing fluids to ascend into the immediate contact aureole. Rapid conductive cooling upon encountering cooler country rocks triggered the precipitation of Group I scheelite within quartz veins under relatively oxidizing conditions. Minor fluid-rock interaction may have occurred.\u003c/p\u003e\n\u003cp\u003e3. Distal Mineralization and Fluid Evolution (Group II): As the hydrothermal system evolved and expanded laterally and vertically away from the pluton, fluids interacted more extensively with the Devonian siltstone host rocks. This interaction, coupled with increasing influx of cooler, dilute meteoric water and a shift towards more reducing conditions (evidenced by C-type inclusions), led to the precipitation of Group II scheelite. This scheelite is characterized by its distinct high-Sr, positive-Eu anomaly signature and very low Mo content. Molybdenite precipitation occurred late (302 Ma), utilizing the residual Mo budget in the evolved, cooler, and more distal fluids.\u003c/p\u003e\n\u003cp\u003e4. Supergene Oxidation: Following hydrothermal mineralization, supergene oxidation processes formed secondary limonite and malachite.\u003c/p\u003e"},{"header":"6. Conclusions","content":"\u003cp\u003e1. The Kalatawu A\u003csub\u003e2\u003c/sub\u003e-type granites (314–310 Ma) formed by partial melting of Neoproterozoic juvenile lower crust with significant assimilation (≤50%) of ancient Kazakhstan-Yili continental crust. Subsequent extensive fractional crystallization of plagioclase, K-feldspar, apatite, and Ti-phases was crucial for enriching W and Mo in the residual melt and exsolving ore-forming fluids.\u003c/p\u003e\n\u003cp\u003e2. Fluid inclusion microthermometry documents a pronounced 150°C thermal gradient from proximal zones (285\u0026nbsp;±\u0026nbsp;40°C) to distal zones (135\u0026nbsp;±\u0026nbsp;30°C), with a bimodal salinity distribution (5–7 wt.% vs. 10–13 wt.% NaCl eq.) confirming mixing between magmatic brines and meteoric water. Mineralization occurred at moderate crustal depths (2–12 km, avg. 6.5 km) under lithostatic pressures (60–327 bar).\u003c/p\u003e\n\u003cp\u003e3. Scheelite geochemistry delineates two distinct mineralization domains intimately linked to fluid evolution:\u003c/p\u003e\n\u003cp\u003eGroup I (Proximal): Precipitated from high-temperature, oxidizing, dominantly magmatic fluids via rapid cooling near the pluton contact, resulting in scheelite with high Mo and variable\u0026nbsp;δEu.\u003c/p\u003e\n\u003cp\u003eGroup II (Distal): Formed from lower-temperature, more reducing fluids containing a significant meteoric component (≥30%), through extensive fluid-rock interaction and continued cooling, resulting in scheelite with high Sr and strongly positive\u0026nbsp;δEu anomalies.\u003c/p\u003e\n\u003cp\u003e4. Molybdenite precipitation (302.6\u0026nbsp;±\u0026nbsp;1.4 Ma) postdated the main W mineralization event, occurring late in the hydrothermal system's evolution utilizing residual Mo in cooler, distal fluids.\u003c/p\u003e\n\u003cp\u003e5. The Kalasayi deposit exemplifies a telescoped orogenic W system where multistage mineralization occurred over ~8 Myr within a dynamically transitioning tectonic regime, evolving from late syn-collisional compression to post-collisional extension. This integrated model provides valuable exploration vectors for targeting both proximal greisen-style and distal vein-type mineralization in analogous post-collisional settings along the Southwestern Central Asian Orogenic Belt.\u003c/p\u003e\n\u003cp\u003e6. Exploration Implications: Proximal exploration targets should focus on identifying quartz veins containing high-Mo scheelite within about 200m of fertile pluton contacts. Distal exploration prospects are marked by lower-temperature quartz veins containing high-Sr scheelite exhibiting pronounced positive Eu anomalies.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003ePhD PENG YUAN MAINLY WRITTEN THIS MANUSCRIPT TEXT AND PREPARED ALL FIGURES, Mr. Gu and Mrs. Yongmei Zhang supervised the projects' operation, conducting data tests, formulating and improving the thesis, and handling the final review process . Mr. Lihua Yang and Wenbin Ba participated in the fieldwork of the project and assisted in collecting most of the samples as well as in organizing the sample results.\u003c/p\u003e\u003ch2\u003eAcknowledgement\u003c/h2\u003e\u003cp\u003eThis work was financially supported by the Geological Exploration Fund Project of Xinjiang (No. T17\u0026ndash;2\u0026ndash;LQ17) and National Key Research and Development Program (2018YFC0604003). We thank the anonymous reviewers for their constructive suggestions and corrections.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eYuan P, Gu XX, Zhang YM, et al., 2022, A\u003csub\u003e2\u003c/sub\u003e-type granite-related deposit: the Kalasayi tungsten deposit, western Tianshan Mountains, Xinjiang, China. Arabian Journal of Geosciences. 15:1002.\u003c/li\u003e\n\u003cli\u003eWindley BF, Alexeiev D, Xiao W, Kroner A, and Badarch G, 2007, Tectonic models for acretion of the Central Asian Orogenic Belt. Journal of the Geological Society, 164, 31\u0026ndash;47.\u003c/li\u003e\n\u003cli\u003eBuslov MM, 2011, Tectonics and geodynamics of the Central Asian Foldbelt: the role of Late Paleozoic large\u0026ndash;amplitude strike\u0026ndash;slip faults. Russian Geology and Geophysics, 52,52\u0026ndash;71.\u003c/li\u003e\n\u003cli\u003eCao MJ, Qin KZ, Li GM, Li JX, Evans NJ, and Hollings P, 2016, Tectono\u0026ndash;magmatic evolution of Late Jurassic to Early Cretaceous granitoids in the west central Lhasasubterrane, Tibet. Gondwana Research, 39, 386\u0026ndash;400 .\u003c/li\u003e\n\u003cli\u003eWan Y, Zhang HW, Li GG, Yuan P, and Liu GH, 2016, Geological characteristics and prospecting significance of the Kalasayi tungsten deposit in the West Tianshan Mountains， Xinjiang. Mineral Explorarion, 8, 545\u0026ndash;551.\u003c/li\u003e\n\u003cli\u003eZhu YF, Xu X, Luo ZH, Shen P, Ma HD, Chen XH, An F, and Wei SN, 2014, Geology Evolution and Mineralization in core part of Central Asian Metallogenic Region. China University of Geosciences Press, Beijing.\u003c/li\u003e\n\u003cli\u003eChen XH, Q WJ, H SQ, Seitmuratova Eleonora, Y N, C ZL, Fagang Zengc, Andao Duc, and W ZH, Re\u0026mdash;Os geochronology of Cu and W-Mo deposits in the Balkhash metallogenic belt, Kazakhstan and its geological significance. Geoscience Frontiers, 2015 (1) 115-124, doi:10.1016/j.gsf.2010.08.006.\u003c/li\u003e\n\u003cli\u003eNi SB, M FS, C JF, and S PP, 2009, Metallization of the Alataw mountains in Xinjiang: Regional setting, source and model, Chinese Journal of Geology, 44 (1): 128-136.\u003c/li\u003e\n\u003cli\u003eHeinhorst J, Lehmann B, Ermolov P, Serykh V, and hurutin S, 2000, Paleozoic crustal growth and metallogeny of Central Asia: evidence from magmatic\u0026ndash;hydrothermal ore systems of Central Kazakhstan.Tectonophysics, 328, 69\u0026ndash;87.\u003c/li\u003e\n\u003cli\u003eAltherr R, Henjes\u0026ndash;Kunst F, Matthews A, Friedrichsen H, and Hansen BT, 1988, O\u0026ndash;Sr isotopic variations in Miocene granitoids from the Aegean: evidence for an origin by combined assimilation and fractional crystallization. Contributions to Mineralogy and Petrology, 100, 528\u0026ndash;541.\u003c/li\u003e\n\u003cli\u003eBrugger J, Lahaye Y, Costa S, Lambert D, and Bateman R, 2000, Inhomogeneous Distribution of REE in scheelite and dynamics of Archaean hydrothermal systems (Mt. Charlotte and Drysdale gold deposits, Western Australia). Contributions to Mineralogy and Petrology, 139, 251\u0026ndash;264.\u003c/li\u003e\n\u003c/ol\u003e"},{"header":"Tables","content":"\u003cp\u003eTables 1 to 4 are available in the Supplementary Files section.\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Kalasayi Tungsten Deposit, Western Tianshan Mountains, Scheelite geochemistry, Re-Os dating, Zircon U-Pb dating, Hf isotopes, Fluid inclusions, Multistage mineralization, Orogenic evolution","lastPublishedDoi":"10.21203/rs.3.rs-7438577/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7438577/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThis study builds upon our prior publication concerning the Kalasayi tungsten deposit (DOI: \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s12517-022-10272-6[1]\u003c/span\u003e\u003cspan address=\"10.1007/s12517-022-10272-6[1]\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e). The Kalasayi tungsten deposit (ca. 30 kt WO\u003csub\u003e3\u003c/sub\u003e, avg. 1.05% WO\u003csub\u003e3\u003c/sub\u003e), situated within the Western Tianshan Mountains of NW China, constitutes a significant vein-type tungsten system genetically linked to the Late Carboniferous Kalatawu pluton. New zircon U-Pb ages (313.9\u0026thinsp;\u0026plusmn;\u0026thinsp;0.7 to 310.3\u0026thinsp;\u0026plusmn;\u0026thinsp;1.0 Ma) and molybdenite Re-Os ages (302.6\u0026thinsp;\u0026plusmn;\u0026thinsp;1.4 to 302.3\u0026thinsp;\u0026plusmn;\u0026thinsp;1.8 Ma) constrain the timing of magmatism and mineralization to the latest Carboniferous. The Kalatawu pluton comprises high-K calc-alkaline, metaluminous to slightly peraluminous A-type granites (subtype A\u003csub\u003e2\u003c/sub\u003e), exhibiting a geochemical continuum indicative of fractionation from I-type to highly fractionated A-type compositions. Zircon Hf isotope signatures (εHf(t)\u0026thinsp;=\u0026thinsp;+\u0026thinsp;2.8 to +\u0026thinsp;8.3; T\u003csub\u003eDM\u003c/sub\u003e(Hf)\u0026thinsp;=\u0026thinsp;605\u0026ndash;1714 Ma) reveal a hybrid magma source involving juvenile lower crust with significant assimilation of ancient Kazakhstan-Yili continent crust. Integrated fluid inclusion microthermometry documents a pronounced thermal gradient from proximal zone (avg. homogenization temperature Th\u0026thinsp;=\u0026thinsp;285\u0026deg;C) to distal zones (avg. Th\u0026thinsp;=\u0026thinsp;135\u0026deg;C), accompanied by a corresponding decrease in fluid salinity from 10\u0026ndash;13 wt.% to 5\u0026ndash;7 wt.% NaCl eq.\u0026nbsp;Scheelite geochemistry delineates two distinct genetic groups: Group I (proximal) is characterized by high Mo content (avg. 4000 ppm), low Sr content (avg. 58 ppm), and Eu variables (δEu), consistent with precipitation from oxidizing magmatic fluids. Group II (distal) exhibits low Mo content (avg. 43 ppm), high Sr content (avg. 253 ppm), and consistently positive δEu (avg. 2.15), reflecting precipitation under reducing conditions influenced by fluid-rock interaction and influx of meteoric water. The spatial and temporal evolution of the hydrothermal system records a transition from syn-collisional to post-collisional tectonic regimes during the terminal collision between the Junggar Ocean Plate and the Kazakhstan-Yili Plate. Tungsten precipitation was primarily driven by substantial cooling (150\u0026deg;C) and pH increase during fluid ascent, while oxygen fugacity (fO₂) exerted a key control on the partitioning of accessory metals (Mo, Eu). This integrated study establishes a holistic multistage mineralization model intimately associated with the progressive orogenic evolution of the Western Tianshan Mountains.\u003c/p\u003e","manuscriptTitle":"New Geochemical Insights into the Genesis of the Kalasayi Tungsten Deposit, Western Tianshan Mountains: Multistage Mineralization within a Progressive Orogenic Evolution Model","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-08-29 10:45:01","doi":"10.21203/rs.3.rs-7438577/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"d53c7a1a-2515-4992-ba51-68d4b83cf25a","owner":[],"postedDate":"August 29th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2025-09-04T14:23:42+00:00","versionOfRecord":[],"versionCreatedAt":"2025-08-29 10:45:01","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-7438577","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7438577","identity":"rs-7438577","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}