Geology and mineralization of the Daheishan supergiant porphyry molybdenum deposit(1.65 Bt),Jilin,China:A review

The Daheishan supergiant porphyry molybdenum deposit(also referred to as the Daheishan deposit)is the second largest molybdenum deposit in Asia and ranks fifth among the top seven molybdenum deposits globally with total molybdenum reserves of 1.65 billion tons,an average molybdenum ore grade of 0.081%,and molybdenum resources of 1.09 million tons.The main ore body is housed in the granodiorite porphyry plutons and their surrounding inequigranular granodiorite plutons,with high-grade ores largely located in the ore-bearing granodiorite porphyries in the middle-upper part of the porphyry plutons.Specifically,it appears as an ore pipe with a large upper part and a small lower part,measuring about 1700 m in length and width,extending for about 500 m vertically,and covering an area of 2.3 km^(2).Mineralogically,the main ore body consists of molybdenite,chalcopyrite,and sphalerite horizontally from its center outward and exhibits molybdenite,azurite,and pyrite vertically from top to bottom.The primary ore minerals include pyrite and molybdenite,and the secondary ore minerals include sphalerite,chalcopyrite,tetrahedrite,and scheelite,with average grades of molybdenum,copper,sulfur,gallium,and rhenium being 0.081%,0.033%,1.67%,0.001%,and 0.0012%,respectively.The ore-forming fluids of the Daheishan deposit originated as the CO_(2)-H_(2)O-NaCl multiphase magmatic fluid system,rich in CO_(2)and bearing minor amounts of CH4,N2,and H2S,and later mixed with meteoric precipitation.In various mineralization stages,the ore-forming fluids had homogenization temperatures of>420℃‒400℃,360℃‒350℃,340℃‒230℃,220℃‒210℃,and 180℃‒160℃and salinities of>41.05%‒9.8%NaCleqv,38.16%‒4.48%NaCleqv,35.78%‒4.49%NaCleqv,7.43%NaCleqv,and 7.8%‒9.5%NaCleqv,respectively.The mineralization of the Daheishan deposit occurred at 186‒167 Ma.The granites closely related to the mineralization include granodiorites(granodiorite porphyries)and monzogranites(monzogranite porphyries),which were mineralized after magmatic evolution(189‒167 Ma).Moreover,these mineralization-related granites exhibit low initial strontium content and high initial neodymium content,indicating that these granites underwent crust-mantle mixing.The Daheishan deposit formed during the Early-Middle Jurassic,during which basaltic magma underplating induced the lower-crust melting,leading to the formation of magma chambers.After the fractional crystallization of magmas,ore-bearing fluids formed.As the temperature and pressure decreased,the ore-bearing fluids boiled drops while ascending,leading to massive unloading of metal elements.Consequently,brecciated and veinlet-disseminated ore bodies formed.

Separation of macro amounts of tungsten and molybdenum by precipitation with ferrous salt

In order to develop a low-cost approach for separating macro amounts of Mo and W, the effects of parameters on the separation using FeSO4 as precipitation reagent were studied. The results show that the optimum reaction temperature is 10 °C, and the separation factor does not further improve after a reaction time of 7 h. Moreover, slow dropping speed of the precipitation reagent is beneficial for improving the separation efficiency. When the H＋/W molar ratio is below 1/1, the addition of acid to a neutral solution is favorable to the separation. For the solution with an ammonium concentration below 3 mol/L, the separation factor is high due to the high W-precipitation rate. Furthermore, the method is also effective when it is applied to industrial solution containing some other impurities. All these indicate the ferrous salts have great potential for removing W from Mo on a commercial scale.

Advances in Thermionic Cathode of Tungsten and Molybdenum

Several kinds of tungsten thermonic cathodes have been introduced. As a promising alternative for thoriated tungsten, rare earth doped molybdenum cathode has been studied. Compared with the traditional thoriated tungsten, La-Mo cathode has higher emission current density at lower temperature, but it has poor emission stability. In order to improve the emission stability, systematical study on the emission mechanism of La-Mo cathode has been carried out. The life of La-Mo cathode has been improved and has achieved 1400 It, which exceeds the minimum life for practical uses (1000 h). As another alternative for thoriated tungsten cathode, Y-Mo cathode has shown better performance. The thermionic emission capability of Y-Mo cathode is between that of La-Mo cathode and Th-W cathode.

Separation of tungsten and molybdenum with solvent extraction using functionalized ionic liquid tricaprylmethylammonium bis(2,4,4-trimethylpentyl)phosphinate

Functionalized ionic liquids(FILs)as extractants were employed for the separation of tungsten and molybdenum from a sulfate solution for the first time.The effects of initial pH,extractant concentration,metal concentrations in the feed were comprehensively investigated.The results showed that tricaprylmethylammonium bis(2,4,4-trimethylpentyl)phosphinate([A336][Cyanex272])could selectively extract W over Mo at an initial pH value of 5.5;the best separation factorβ_(W/Mo) of 25.61 was obtained for a solution with low metal concentrations(WO3:2.49 g/L,Mo:1.04 g/L).The[A336][Cyanex272]system performed effectively for solutions of different W/Mo molar ratios and different metal ion concentrations in the feed.The chemical reaction between[A336][Cyanex272]and W followed the ion association mechanism,which was further proved by the Fourier-transform infrared(FTIR)spectra of loaded[A336][Cyanex272]and the free extractant.The stripping experiments indicated that 95.48%W and 100.00%Mo were stripped using a 0.20 mol/L sodium hydroxide solution.Finally,the selective extractions of W and Mo from two synthetic solutions of different high metal concentrations were obtained;the separation factorβW/Mo reached 23.24 and 17.59 for the first and second solutions,respectively.The results suggest the feasibility of[A336][Cyanex272]as an extractant for the separation of tungsten and molybdenum.

Induction plasma spheroidization of tungsten and molybdenum powders

The melting, evaporation and oxidation behaviors as well as the solidification phenomena of tungsten and molybdenum in induction plasma were studied. Scanning electron microscopy was used to examine the morphology and the cross section of plasma-processed powders. X-ray diffraction was used to analyze the oxides formed on the particle surface of these two metals. The influence of spray chamber pressure on the spheroidization and oxidation phenomena was discussed. The results show that fewer Mo particles than W particles are spheroidized at the same powder feed rate under the same plasma spray condition although molybdenum has a lower melting point. A small fraction of tungsten is evaporized and condensed either on the surface of tungsten particles nearby or on the wall of spray chamber. Tungsten oxides were found in tungsten powder processed under soft vacuum condition. Extremely large grains form inside some spheroidized particles of tungsten powder.

Pressure leaching of bismuth sulfide concentrate containing molybdenum and tungsten in alkaline solution

The leaching results of bismuth sulfide concentrate containing molybdenum and tungsten in air-H2O2-NaOH system, pressure-O2-Na2CO3 system and pressure-O2-NaOH system were investigated. The results show that the extraction of molybdenum, tungsten and sulfur goes up with the increase of NaOH concentration, oxygen partial pressure and reaction time. The extraction of molybdenum and tungsten also rises up with temperature, but the leaching ratio of sulfur increases initially to a peak of 98% at 150℃ and then decreases with the increase of temperature. Under the optimal conditions, the extraction of molybdenum, tungsten and sulfur is more than 95.6%, 93.8% and 96.0%, respectively, and the main phases of residue are Bi2O3 and Fe2O3. Therefore, the method of pressure leaching in alkaline solution is provided as an effective separation of molybdenum, tungsten and sulfur from bismuth and a beneficial pretreatment for consequent process.

Geology and mineralization of the supergiant Shimensi granitic-type W-Cu-Mo deposit(1.168 Mt)in northern Jiangxi,South China:A Review

The Shimensi deposit is a recently discovered W-Cu-Mo polymetallic deposit located in the Jiangnan porphyry-skarn W belt in South China.The deposit has a resource of 0.74×10^(6)t of WO_(3)accompanied by 0.4×10^(6)t Cu and 28000 t Mo and other useful components like Ga,making it one of the largest W deposits in the world.This paper is aimed to reveal the ore-controlling mechanisms of the Shimensi deposit,involving the role of the ore-related granites,the tectonic background for its formation,and the metallogenesis model.The systematic geological survey suggests multi-types of alteration are developed in the deposit,mainly including greisenization,potassic-alteration,sericitization,chloritization,and silicification.Drilling engineering data and mining works indicate that the Shimensi deposit consists of two main orebodies of I and II.Therein,the W resource has reached a supergiant scale,and the accompanied Cu,Mo,Au,Bi,Ga,and some other useful components are also of economic significance.The main ore-minerals consist of scheelite,wolframite and chalcopyrite.Disseminated mineralization is the dominant type of the W-Cu-Mo polymetallic orebodies,and mainly distributes in the inner and external contact zone that between the Neoproterozoic biotite granodiorite and the Yanshanian granites.The main orebody occurs at the external contact zone,and the pegmatoid crust near the inner contact zone is an important prospecting marker of the W mineralization.Of them,the disseminated W ores within the wall rock of the Neoproterozoic biotite granodiorite is a new mineralization type identified in this paper.Combining previous geochronological and isotopic data,we propose that the mineralization of the Shimensi deposit is closely related to the intruding of the Yanshanian porphyritic biotite granite and granite porphyry.Geochemical data suggest that the biotite granodiorite is rich in Ca and had provided a large amount of Ca for the precipitation of scheelite in this area.Thus,it is a favorable wall rock type for W mineralization.The Shimensi deposit belongs to granitic-type W polymetallic deposit related to post-magmatic hydrothermal,and the ore-forming fluid was initially derived from the Yanshanian magmas.

Cathodoluminescence and Trace Element Composition of Scheelite from the Middle-Lower Yangtze River Metallogenic Belt(MLYB): Implications for Mineralization and Exploration

The Middle-Lower Yangtze River Metallogenic Belt(MLYB)is known to contain abundant copper and iron porphyry-skarn deposits,with an increasing number of tungsten deposits and scheelite in Fe-Cu deposits being discovered in the MLYB during recent decades.The ore genesis of the newly-discovered tungsten mineralization in the MLYB is poorly understood.We investigate four sets of scheelite samples from tungsten,iron and copper deposits,using CL imaging and LA-ICP-MS techniques to reveal internal zonation patterns and trace element compositions.The REE distribution patterns of four studied deposits show varying degrees of LREE enrichment with negative Eu anomalies.The oxygen fugacity of ore-forming fluid increased in Donggushan,while the oxygen fugacity of ore-forming fluid decreased in Ruanjiawan,Guilinzheng and Gaojiabang.The scheelites from the Donggushan,Ruanjiawan,Guilinzheng and Gaojiabang deposits show enrichment in LREEs and HFSE,with Nb/La ratios ranging from 1.217 to 52.455,indicating that the four tungsten deposits are enriched in the volatile fluorine.A plot of(La/Lu)N versus Mo/δEu can be used to distinguish quartz vein type,porphyry and skarn tungsten deposits.This study demonstrates that scheelite grains can be used to infer tungsten mineralization and are effective in identifying magmatic types of tungsten deposits in prospective mining sites.

Origin and Evolution of the Hydrothermal System in Namiihu Samlaozhuaiig Molybdenum (Tungsten) Ore Deposit, Luanchuan County, Henan Province

Thoroughgoing studies of the homogenization temperatures, pressures and chendcal compositions offluid inclusions and the stable isotopes of hydrothermal minerals (quartz. calcite, pyrite and molybdenite)have thrown light on the evolution trend of the molybdenum-bearing hydrothermal system which originatedfrom magmatic processus and underwent significant mixing with meteoric waters in the later stages ofhydrothermal activity.

Mathematical model and reaction mechanism of molybdenum and tungsten extraction with TRPO from peroxide solution

To understand the behavior of molybdenum and tungsten extracted by tri-alkyl phosphine oxide(TRPO)from peroxide solution,the extraction mechanism was studied by slope method and Raman and FTIR spectroscopy.The empirical formulas of molybdenum and tungsten extraction distribution ratio(D_(Mo)and D_(W))as functions of equilibrium pH,TRPO concentration and temperature were obtained by establishing mathematical models.Furthermore,the reliability of the empirical formula was verified in the H^(+)-W-Mo-H_(2)O_(2) solution.The results indicate that the calculated values of D_(Mo)or D_(W)were consistent with the experimental values.The apparent extraction equilibrium constants of molybdenum and tungsten wereK_(Mo)^(app)=8.51×10^(3)(0.74≤pH_(e)≤1.7),K_(Mo)^(app)=99.89×10^(3)(1.7<pH_(e)≤4.62)andK_(W)^(app)=2.65×10^(3)(0.92<pH_(e)<2.16)at 20°C,respectively.The main extraction complex of molybdenum or tungsten was[H_(2)(Mo or W)_(2)O_(3)(O_(2))_(4)(H_(2)O)_(2)]·2TRPO.These empirical formulas can be used to analyze and estimate the extraction and separation of Mo and W from low molybdenum and tungsten concentration solutions.

Microscopic Damage of Tungsten and Molybdenum Exposed to Low-Energy Helium Ions

Polycrystalline tungsten（W）and molybdenum（Mo）materials both non-annealed and annealed at temperatures of 800-1750~C have been irradiated with low-energy（220 eV）,high-flux（~10^（21）ions/m^2.s）He~＋at an irradiation temperature of 600℃and at a dose of1.0×10^（25）ions/m^2.This non-destructive conductive atomic force microscopy technique provides direct observation and comparison of surface swellings with growth of nanoscale defects in the irradiated materials.A coral-like surface structure and nanostructured defects were formed in W when irradiated at a He＋dose of 1.0×10^（25）ions/m^2.Increasing the annealing temperature resulted in an increase in the size of nanostructured defects and serious surface damage of W.Compared to W,Mo suffered much less surface damage after being irradiated at various He~＋doses.

DETERMINATION OF DIFFUSIVITY ON TUNGSTEN AND MOLYBDENUM IN DOUBLE GLOW DISCHARGE

This article introduces a method determining the equation of penetration curve by multielement regression(MER) in study of double glow discharge plasma metallizing(DGM) and the slope of the penetration curve can be calculated by derivation,the xdy can also be obtained.This method is more reliable and accurate than graphical integration.The variation of diffusion coefficient with the concentration of W and Mo are determined.

Application of specific ion interaction theory and parabolic models for the molybdenum(Ⅵ) and tungsten(Ⅵ) complexes with NTA and IDA at different ionic strengths

The interaction of nitrilotriacetic acid （NTA） and iminodiacetic acid （IDA） with tungsten（VI） （pH 7.5） and molybdenum（VI） （pH 6.00） has been studied in aqueous solutions at 25℃, and different ionic strengths （0.1 〈 1 （mol dm^-3） 〈 1.0 for NaClO4） by a combination of potentiometric and UV spectroscopic（260-270 nm） measurements. Dependence on ionic strength was taken into account by using the Bronsted-Guggenheim-Scatchard specific ion interaction theory （SIT） and parabolic model. The data included in this work, together with some previously published data, make it possible to calculate parameters for dependence on ionic strength by using the aforementioned models.

THE FIRST BINUCLEAR MOLYBDENUM AND TUNGSTEN COMPLEXES WITH DOUBLY-BRIDGING PYRIDINE-2-THIOLATO LIGANDS.X-RAY CRYSTAL STRUCTURE OF THE COMPLEX[Mo_2(CO)_4(μ-pyS)_2(PPh_3)_2].2C_7H_8

The title complex was obtained by reactions of [Mo(CO)_3(MeCN)_3] with [CuBr(pySH)(PPh_3)_2]or directly with pySH and PPh_3. The latter method can be used to synthesize the corresponding tungsten complex [W_2(CO)_4(μ-pyS)_2(PPh_3)_2].The molecular structure of the title compound was determined by X-ray diffraction method.

A Kinetic Approach to Photomineralization of Methane in Air by Membranes Based on TiO2/WO3

Photomineralization of methane in air(10.0-1,000 ppm(mass/volume)of C)at 100%relative humidity(dioxygen as oxygen donor),was systematically studied at 318±3 K,in an annular laboratory-scale reactor,by photocatalytic membranes immobilising titanium dioxide and tungsten trioxide as co-photocatalysts.Kinetics of both substrate disappearance,to yield intermediates,and total organic carbon(TOC)disappearance,to yield carbon dioxide,were followed.A kinetic model was employed,from which,by a set of differential equations,four final optimised parameters,k1 and K1,k2 and K2,were calculated,able to fit the whole kinetic profile adequately.Modelling of quantum yields,as a function of substrate concentration and irradiance,as well as of concentration of photocatalysts,was carried out very satisfactorily.Kinetics of hydroxyl radicals reacting between themselves,leading to hydrogen peroxide,other than with substrate or intermediates leading to mineralization,were considered,paralleled by second competition kinetics involving superoxide radical anion.When using appropriate blends of the two photocatalysts,limiting quantum yieldsF∞values increase considerably and approach the maximum allowable value for the investigated molecule,in a much wider range of irradiances than that shown by the single catalysts mainly at low irradiances.This may be interpreted by strong competition kinetics of superoxide radicals generated by the catalyst defects,in the corresponding range of high irradiances.By this way,operation at high irradiance values is possible,without losing any efficiency for the mineralization process.

A Novel Method for Separation of Tungsten and Molybdenum

Research on the separation of tungstenand molybdenum is of importance as it is a ba-sic problem in the metallurgy and industry oftungsten.Traditional methods for the separa-tion include precipitation with sulfides andsolvent extraction.There are,however,certaindisadvantages for these methods.A novelmethod was developed based on another

Developing new reagent for selectively precipitation of molybdenum from tungstate solution

Based on the difference of microscopic properties between MoS 2- 4 and WO 2- 4, a series of new reagents, CuS, NiS, CoS, PbS, HgS, as well as ZnS, were developed for separation of molybdenum from tungstate solution. GPT(Generalized Perturbation Theory) calculation reveals they are more reactive with MoS 2- 4 than WO 2- 4. In laboratory test, CoS, NiS and CuS can remove more than 99.3%Mo. PbS and FeS are also effective for precipitation of Mo, but HgS and ZnS are almost useless. Taking environment and economy factors into consideration, CuS is chosen as the most suitable reagent.

A machine learning approach to tungsten prospectivity modelling using knowledge-driven feature extraction and model confidenc

Novel mineral prospectivity modelling presented here applies knowledge-driven feature extraction to a datadriven machine learning approach for tungsten mineralisation.The method emphasises the importance of appropriate model evaluation and develops a new Confidence Metric to generate spatially refined and robust exploration targets.The data-driven Random ForestTM algorithm is employed to model tungsten mineralisation in SW England using a range of geological,geochemical and geophysical evidence layers which include a depth to granite evidence layer.Two models are presented,one using standardised input variables and a second that implements fuzzy set theory as part of an augmented feature extraction step.The use of fuzzy data transformations mean feature extraction can incorporate some user-knowledge about the mineralisation into the model.The typically subjective approach is guided using the Receiver Operating Characteristics(ROC)curve tool where transformed data are compared to known training samples.The modelling is conducted using 34 known true positive samples with 10 sets of randomly generated true negative samples to test the random effect on the model.The two models have similar accuracy but show different spatial distributions when identifying highly prospective targets.Areal analysis shows that the fuzzy-transformed model is a better discriminator and highlights three areas of high prospectivity that were not previously known.The Confidence Metric,derived from model variance,is employed to further evaluate the models.The new metric is useful for refining exploration targets and highlighting the most robust areas for follow-up investigation.The fuzzy-transformed model is shown to contain larger areas of high model confidence compared to the model using standardised variables.Finally,legacy mining data,from drilling reports and mine descriptions,is used to further validate the fuzzy-transformed model and gauge the depth of potential deposits.Descriptions of mineralisation corroborate that the targets generated in these models could be undercover at depths of less than 300 m.In summary,the modelling workflow presented herein provides a novel integration of knowledge-driven feature extraction with data-driven machine learning modelling,while the newly derived Confidence Metric generates reliable mineral exploration targets.

A 3D Geological Model Constrained by Gravity and Magnetic Inversion and its Exploration Implications for the World-class Zhuxi Tungsten Deposit, South China

The Zhuxi tungsten deposit in Jiangxi Province,South China,contains a total W reserve of about 2.86 Mt at an average grade of 0.54 wt%WO3,representing the largest W deposit in the world.Numerous studies on the metallogeny of the deposit have included its timing,the ore-controlling structures and sedimentary host rocks and their implications for mineral exploration.However,the deep nappe structural style of Taqian-Fuchun metallogenic belt that hosts the W deposit,and the spatial shape and scale of deeply concealed intrusions and their sedimentary host rocks are still poorly defined,which seriously restricts the discovery of new deposits at depth and in surrounding areas of the W deposit.Modern 3 D geological modeling is an important tool for the exploration of concealed orebodies,especially in brownfield environments.There are obvious density contrast and weak magnetic contrast in the ore-controlling strata and granite at the periphery of the deposit,which lays a physical foundation for solving the 3 D spatial problems of the ore-controlling geological body in the deep part of the study area through gravity and magnetic modeling.Gravity data(1:50000)and aeromagnetic data(1:50000)from the latest geophysical surveys of 2016-2018 have been used,firstly,to carry out a potential field separation to obtain residual anomalies for gravity and magnetic interactive inversion.Then,on the basis of the analysis of the relationship between physical properties and lithology,under the constraints of surface geology and borehole data,human-computer interactive gravity and magnetic inversion for 18 cross-sections were completed.Finally,the 3 D geological model of the Zhuxi tungsten deposit and its periphery have been established through these 18 sections,and the spatial shape of the intrusions and strata with a depth of 5 km underground were obtained,initially realizing―transparency‖for ore-controlling bodies.According the analysis of the geophysical,geochemical,and geological characteristics of the Zhuxi tungsten deposit,we discern three principles for prospecting and prediction in the research area,and propose five new exploration targets in its periphery.

Hydrothermal alteration processes in the giant Dahutang tungsten deposit, South China: Implications from litho-geochemistry and mass balance calculation

The giant Dahutang tungsten(W)deposit has a total reserve of more than 1.31 Mt WO3.Veinlet-disseminated scheelite and vein type wolframite mineralization are developed in this deposit,which are related to Late Mesozoic biotite granite.Four major types of alterations,which include albitization,potassic-alteration,and greisenization,and overprinted silicification developed in contact zone.The mass balance calculate of the four alteration types were used to further understanding of the mineralization process.The fresh porphyritic biotite granite has high Nb,Ta,and W,but low Ca and Sr while the Jiuling granodiorite has high Ca and Sr,but low Nb,Ta,and W concentrations.The altered porphyritic biotite granite indicated that the Nb,Ta,and W were leached out from the fresh porphyritic biotite granite,especially by sodic alteration.The low Ca and Sr contents of the altered Neoproterozoic Jiuling granodiorite indicate that Ca and Sr had been leached out from the fresh granodiorite by the fluid from Mesozoic porphyritic biotite granites.The metal W of the Dahutang deposit was mainly derived from the fluid exsolution from the melt and alteration of W-bearing granites.This study of alteration presents a new hydrothermal circulation model to understand tungsten mineralization in the Dahutang deposit.