Multistage tungsten mineralization was recently discovered in the Mamupu copper-polymetallic deposit in the southern Yulong porphyry copper belt(YPCB),Tibet.This study reports the results of cathodoluminescence,trace ...Multistage tungsten mineralization was recently discovered in the Mamupu copper-polymetallic deposit in the southern Yulong porphyry copper belt(YPCB),Tibet.This study reports the results of cathodoluminescence,trace element and Sr isotope analyses of Mamupu scheelite samples,undertaken in order to better constrain the mechanism of W mineralization and the sources of the ore-forming fluids.Three different types of scheelite are identified in the Mamupu deposit:scheelite A(Sch A)mainly occurs in breccias during the prograde stage,scheelite B(Sch B)forms in the chlorite-epidote alteration zone in the retrograde stage,while scheelite C(Sch C)occurs in distal quartz sulfide veins.The extremely high Mo content and negative Eu anomaly in Sch A represent high oxygen fugacity in the prograde stage.Compared with ore-related porphyries,Sch A has a similar REE pattern,but with higher ΣREE,more depleted HREE and slightly lower(^(87)Sr/^(86)Sr)i ratios.These features suggest that Sch A is genetically related to ore-related porphyries,but extensive interaction with carbonate surrounding rocks affects the final REE and Sr isotopic composition.Sch B shows dark(Sch B-I)and light(Sch B-II)domains under CL imaging.From Sch B-I to Sch B-II,LREEs are gradually depleted,with MREEs being gradually enriched.Sch C has the highest LREE/HREE ratio,which indicates that it inherited the geochemical characteristics of fluids after the precipitation of HREE-rich minerals,such as diopside and garnet,in the early prograde stage.The Mo content in Sch B and Sch C gradually decreased,indicating that the oxygen fugacity of the fluids changed from oxidative in the early stages to reductive in the later,the turbulent Eu anomaly in Sch B and Sch C indicating that the Eu anomaly in the Mamupu scheelite is not solely controlled by oxygen fugacity.The extensive interaction of magmatic-hydrothermal fluids and carbonate provides the necessary Ca^(2+)for the precipitation of scheelite in the Mamupu deposit.展开更多
The Yangla Cu skarn deposit is located in the central part of the Jinshajiang Suture Zone,southwest China,with a total reserve of 150 Mt Cu@1.03%.The newly discovered antimony orebodies at the depth of Yangla are stri...The Yangla Cu skarn deposit is located in the central part of the Jinshajiang Suture Zone,southwest China,with a total reserve of 150 Mt Cu@1.03%.The newly discovered antimony orebodies at the depth of Yangla are strictly controlled by the stratum,structure,and lithology,which are lenticular and vein-like within the marble fracture zone,which can provide a window into multistage miner-alization and ore genesis at Yangla.Mineralization can be divided into three types,Cu–Pb–Zn(skarn)pyrite,galena,and sphalerite,Cu(porphyry)chalcopyrite and pyrite,and Sb(hydrothermal)stibnite and pyrite.The mineral assem-blages were stibnite+pyrite+calcite+quartz±minor scheelite in antimony ores.This study presents quantitative measurements of the trace element compositions of pyrite and stibnite from the Yangla antimony ores.Analysis of pyrite with electron probe microanalysis(EPMA)showed enrichment in Co,Ni,Sb,As,and Mo,and deficit in its S and Fe contents when compared to the stoichiometric con-centrations of S and Fe in pyrite.The Sb-related pyrite may belong to sedimentary-reworked genesis and may be modi-fied by hydrothermalfluids,thereby presenting a certain dif-ference(i.e.,crystal morphology,texture,and chemical com-position)compared to the skarn and porphyry Cu-related pyrite in the Yangla Cu skarn deposit.Analysis of stibnite with EPMA and inductively coupled plasma-mass spectrom-etry showed enrichment in As,Pb,Sn,Pb,Cu,and Zn,and presented much higher Sb contents and slightly lower S con-tents when compared to the stoichiometric concentrations of Sb and S in stibnite.Statistical analysis of the stibnite trace elements showed correlations for the elemental pairs Cu–Pb,As–Sb,and Sn–Pb,and the coupled substitution equations Sb^(3+)↔Cu^(+)+Pb^(2+),Sb^(3+)↔As^(3+),and Sn^(2+)↔Pb^(2+)may be the major factors governed the incorporating Cu,Pb,As and Sn within the stibnite.Moreover,this study preliminary shows that the antimony mineralization may belong to a car-bonate replacement hydrothermal genesis at Yangla.展开更多
The Wangjiazhuang Cu(-Mo)deposit,located within the Zouping volcanic basin in western Shandong Province,China,is unique in this area for having an economic value.In order to expound the metallogenetic characteristics ...The Wangjiazhuang Cu(-Mo)deposit,located within the Zouping volcanic basin in western Shandong Province,China,is unique in this area for having an economic value.In order to expound the metallogenetic characteristics of this porphyry-like hydrothermal deposit,a detailed fluid inclusion study has been conducted,employing the techniques of representative sampling,fluid inclusion petrography,microthermometry,Raman spectroscopy,LA-ICP-MS analysis of single fluid inclusions,as well as cathode fluorescence spectrometer analysis of host mineral quartz.The deposit contains mainly two types of orebodies,i.e.veinlet-dissemination-stockwork orebodies in the K-Si alteration zone and pegmatiticquartz sulfide veins above them.In addition,minor breccia ore occurs locally.Four types of fluid inclusions in the deposit and altered quartz monzonite are identified:L-type one-or two-phase aqueous inclusions,V-type vapor-rich inclusions with V/L ratios greater than 50%-90%,D-type multiphase fluid inclusions containing daughter minerals or solids and S-type silicate-bearing fluid inclusions containing mainly muscovite and biotite.Ore petrography and fluid inclusion study has revealed a three-stage mineralization process,driven by magmatic-hydrothermal fluid activity,as follows.Initially,a hydrothermal fluid,separated from the parent magma,infiltrated into the quartz monzonite,resulting in its extensive K-Si alteration,as indicated by silicate-bearing fluid inclusions trapped in altered quartz monzonite.This is followed by the early mineralization,the formation of quartz veinlets and dissemination-stockwork ores.During the main mineralization stage,due to the participation and mixing of meteoric groundwater with magmatic-sourced hydrothermal fluid,the cooling and phase separation caused deposition of metals from the hydrothermal fluids.As a result,the pegmatitic-quartz sulfide-vein ores formed.In the late mineralization stage,decreasing fluid salinity led to the formation of L-type aqueous inclusions and chalcopyrite-sulfosalt ore.Coexistence of V-type and D-type inclusions and their similar homogenization temperatures with different homogenization modes suggest that phase separation or boiling of the ore-forming fluids took place during the early and the main mineralization stages.The formation P-T conditions of S-type inclusions and the early and the main mineralization stages were estimated as ca.156-182 MPa and 450-650℃,350-450℃,18-35 MPa and 280-380℃,8-15 MPa,respectively,based on the microthermometric data of the fluid inclusions formed at the individual stages.展开更多
Graphene(Gr)has unique properties including high electrical conductivity;Thus,graphene/copper(Gr/Cu)composites have attracted increasing attention to replace traditional Cu for electrical applications. However,the pro...Graphene(Gr)has unique properties including high electrical conductivity;Thus,graphene/copper(Gr/Cu)composites have attracted increasing attention to replace traditional Cu for electrical applications. However,the problem of how to control graphene to form desired Gr/Cu composite is not well solved. This paper aims at exploring the best parameters for preparing graphene with different layers on Cu foil by chemical vapor deposition(CVD)method and studying the effects of different layers graphene on Gr/Cu composite’s electrical conductivity. Graphene grown on single-sided and double-sided copper was prepared for Gr/Cu and Gr/Cu/Gr composites. The resultant electrical conductivity of Gr/Cu composites increased with decreasing graphene layers and increasing graphene volume fraction. The Gr/Cu/Gr composite with monolayer graphene owns volume fraction of less than 0.002%,producing the best electrical conductivity up to59.8 ×10^(6)S/m,equivalent to 104.5% IACS and 105.3% pure Cu foil.展开更多
The Dongnan Cu–Mo deposit,located in the southeast of the Zijinshan ore field(the largest porphyry–epithermal system in Southeast China),represents the complex magmatic and metallogenesis events in the region.The pe...The Dongnan Cu–Mo deposit,located in the southeast of the Zijinshan ore field(the largest porphyry–epithermal system in Southeast China),represents the complex magmatic and metallogenesis events in the region.The petrogenesis and metallogenesis of granitoids from the deposit are not determined,especially the interactions between ore-bearing(granodiorite porphyry)and barren samples(granodiorite and diorite).In the paper,the whole rock geochemical features shared a similar affinity to the middle-lower content and revealed that they derived from partial melting of the Cathaysian basement with the contribution of mantle materials,even represented that they generated in the plate subduction;LA-ICP-MS zircon U–Pb ages show that these granodiorites,granodioritic porphyry and diorite,were generated during 114–103 Ma.The ore-bearing samples mostly presented ε_(Hf)(t)of negative values(peak value is-4 to-3)with old two-stage Hf model ages(t_(DM)^(2))(peak value is 1.10–1.15 Ga),while the barren sample showed slightly negative ε_(Hf)(t)(peak value is-1 to 0)values with young t_(DM)^(2)(peak value is 1.00–1.05 Ga).The value of zircon Ce^(4+)/Ce^(3+)ratio mostly higher than 450 was first verified for the ore-bearing samples in the Dongnan Cu–Mo deposit,and the values of ore-bearing were found to be higher than those from the barren,which suggests that the ore-bearing formed in more oxidized parental magma with higher oxygen fugacity.Based on the geochemical characteristic of the element and isotope,we concluded that the Early Cretaceous multiphases magmatic activities,low melting temperature and low pressure of pluton,and high oxygen fugacity of zircon,were the favorable conditions for metallogenesis of Dongnan Cu–Mo deposit.展开更多
The Dexing porphyry deposit is the largest porphyry Cu–Mo–Au deposit in South China.Biotite composition can record the physicochemical conditions and evolution history of magmatic-hydrothermal system.Biotite from th...The Dexing porphyry deposit is the largest porphyry Cu–Mo–Au deposit in South China.Biotite composition can record the physicochemical conditions and evolution history of magmatic-hydrothermal system.Biotite from the Dexing porphyry deposit could be divided to three types:primary magmatic biotite(Bi-M),hydrothermal altered magmatic biotite(Bi-A)and hydrothermal biotite(Bi-H).The temperature of Bi-M and Bi-H range from 719 to 767℃ and 690 to 727℃,respectively.Both magmatic and hydrothermal biotite have high Fe^(3+)/Fe^(2+)ratios(from 0.18 to 0.24)and XMgvalues(from 0.57 to 0.66),indicating a high oxygen fugacity.BiM has F lower than Bi-A and Bi-H(up to 0.26 wt%),but has Cl(Cl=0.18–0.30 wt%)similar to Bi-A and Bi-H(Cl=0.21–0.35 wt%),suggesting that high Cl/F ratios of early hydrothermal fluid may result from the exsolution from high Cl magma.From potassic alteration zone to phyllic and propylitic alteration zones,Cl decreases with increasing Cu,whereas F increases roughly.Therefore,Cl mostly originate from magma,but enrichment of F possibly results from reaction of fluids and Neoproterozoic strata.Negative correlation between Cl and Cu indicates that Cl might act as an important catalyst during Cu mineralization process.Biotite from Dexing has similar halogen compositions to other porphyry Cu-/Mo deposits in the world.Chlorine contents of hydrothermal fluid may be critical for Cu transportation and enrichment,while consumption of Cl would promote Cu deposition.展开更多
Chemical vapor deposition (CVD) has shown great promise for the large-scale production of high-quality graphene films for industrial applications. Atomic-scale theoretical studies can help experiments to deeply unders...Chemical vapor deposition (CVD) has shown great promise for the large-scale production of high-quality graphene films for industrial applications. Atomic-scale theoretical studies can help experiments to deeply understand the graphene growth mechanism, and serve as theoretical guides for further experimental designs. Here, by using density functional theory calculations, ab-initio molecular dynamics simulations, and microkinetic analysis, we systematically investigated the kinetics of hydrogen constrained graphene growth on Cu substrate. The results reveal that the actual hydrogen-rich environment of CVD results in CH as the dominating carbon species and graphene H-terminated edges. CH participated island sp2 nucleation avoids chain cyclization process, thereby improving the nucleation and preventing the formation of non-hexameric ring defects. The graphene growth is not simply C-atomic activity, rather, involves three main processes: CH species attachment at the growth edge, leading to a localized sp3 hybridized carbon at the connecting site;excess H transfer from the sp3 carbon to the newly attached CH;and finally dehydrogenation to achieve the sp2 reconstruction of the newly grown edge. The threshold reaction barriers for the growth of graphene zigzag (ZZ) and armchair (AC) edges were calculated as 2.46 and 2.16 eV, respectively, thus the AC edge grows faster than the ZZ one. Our theory successfully explained why the circumference of a graphene island grown on Cu substrates is generally dominated by ZZ edges, which is a commonly observed phenomenon in experiments. In addition, the growth rate of graphene on Cu substrates is calculated and matches well with existing experimental observations.展开更多
Cu-phthalocyanine is widely studied as a hole-transport layer in organic electronic devices. Since Cu-phthalocyanine is a molecular solid, the crystal structure depends on a circumstance to a great extent. Vacuum depo...Cu-phthalocyanine is widely studied as a hole-transport layer in organic electronic devices. Since Cu-phthalocyanine is a molecular solid, the crystal structure depends on a circumstance to a great extent. Vacuum deposited layers were known to consist of two consecutive layers. In this article, Cu-phthalocyanine was deposited on the glass substrate inclined at several angles. The thickness of the first layer was found to be dependent on the substrate angle.展开更多
Transition metal catalyzed chemical vapor deposition (CVD) is considered as the most promising approach to synthesize highquality graphene films, and low-temperature growth of defect-free graphene films is long-term c...Transition metal catalyzed chemical vapor deposition (CVD) is considered as the most promising approach to synthesize highquality graphene films, and low-temperature growth of defect-free graphene films is long-term challenged because of the high energy barrier for precursor dissociation and graphitization. Reducing the growth temperature can also bring advantages on wrinkle-free graphene films owing to the minimized thermal expansion coefficient mismatch. This work focuses on density functional theory (DFT) calculations of the carbon source precursor with hydroxyl group, especially CH_(3)OH, on low-temperature CVD growth of graphene on Cu and CuNi substrate. We calculated all the possible cleavage paths for CH_(3)OH on transition metal substrates. The results show that, firstly, the cleavage barriers of CH_(3)OH on transition metal substrates are slightly lower than those of CH_(4), and once CO appears, it is difficult to break the C-O bond. Secondly, the CO promotes a better formation and retention of perfect rings in the early stage of graphene nucleation and reduces the edge growth barriers. Thirdly, these deoxidation barriers of CO are reduced after CO participates in graphene edge growth. This paper provides a strategy for the lowtemperature growth of wrinkles-free graphene on transition metal substrates using CH_(3)OH.展开更多
Three-dimensional geological modeling （3DGM） assists geologists to quantitatively study in three-dimensional （3D） space structures that define temporal and spatial relationships between geological objects. The 3D ...Three-dimensional geological modeling （3DGM） assists geologists to quantitatively study in three-dimensional （3D） space structures that define temporal and spatial relationships between geological objects. The 3D property model can also be used to infer or deduce causes of geological objects. 3DGM technology provides technical support for extraction of diverse geoscience information, 3D modeling, and quantitative calculation of mineral resources. Based on metallogenic concepts and an ore deposit model, 3DGM technology is applied to analyze geological characteristics of the Tongshan Cu deposit in order to define a metallogenic model and develop a virtual borehole technology; a BP neural network and a 3D interpolation technique were combined to integrate multiple geoscience information in a 3D environment. The results indicate： （1） on basis of the concept of magmatic-hydrothermal Cu polymetallic mineraliza- tion and a porphyry Cu deposit model, a spatial relational database of multiple geoscience information for mineralization in the study area （geology, geophysics, geochemistry, borehole, and cross-section data） was established, and 3D metallogenic geological objects including mineralization stratum, granodiorite, alteration rock, and magnetic anomaly were constructed; （2） on basis of the 3D ore deposit model, 23,800 effective surveys from 94 boreholes and 21 sections were applied to establish 3D orebody models with a kriging interpolation method; （3） combined 23,800 surveys involving 21 sections, using VC＋＋ and OpenGL platform, virtual borehole and virtual section with BP network, and an improved inverse distance interpolation （IDW） method were used to predict and delineate mineralization potential targets （Cu-grade of cell not less than 0.1%）; （4） comparison of 3D ore bodies, metallogenic geological objects of mineralization, and potential targets of mineralization models in the study area, delineated the 3D spatial and temporal relationship and causal processes among the ore bodies, alteration rock, metallo- genic stratum, intrusive rock, and the Tongshan Fault. This study provides important technical support and a scientific basis for assessment of the Tongshan Cu deposit and surrounding exploration and mineral resources.展开更多
Laser ablation–inductively coupled plasma–mass spectrometry（LA–ICP–MS） was used to determine the trace element concentrations of magnetite from the Heifengshan, Shuangfengshan, and Shaquanzi Fe（–Cu） deposits ...Laser ablation–inductively coupled plasma–mass spectrometry（LA–ICP–MS） was used to determine the trace element concentrations of magnetite from the Heifengshan, Shuangfengshan, and Shaquanzi Fe（–Cu） deposits in the Eastern Tianshan Orogenic Belt. The magnetite from these deposits typically contains detectable Mg, Al, Ti, V, Cr, Mn, Co, Ni, Zn and Ga. The trace element contents in magnetite generally vary less than one order of magnitude. The subtle variations of trace element concentrations within a magnetite grain and between the magnetite grains in the same sample probably indicate local inhomogeneity of ore–forming fluids. The variations of Co in magnetite between samples are probably due to the mineral proportion of magnetite and pyrite. Factor analysis has discriminated three types of magnetite： Ni–Mn–V–Ti（Factor 1）, Mg–Al–Zn（Factor 2）, and Ga– Co（Factor 3） magnetite. Magnetite from the Heifengshan and Shuangfengshan Fe deposits has similar normalized trace element spider patterns and cannot be discriminated according to these factors. However, magnetite from the Shaquanzi Fe–Cu deposit has affinity to Factor 2 with lower Mg and Al but higher Zn concentrations, indicating that the ore–forming fluids responsible for the Fe–Cu deposit are different from those for Fe deposits. Chemical composition of magnetite indicates that magnetite from these Fe（–Cu） deposits was formed by hydrothermal processes rather than magmatic differentiation. The formation of these Fe（–Cu） deposits may be related to felsic magmatism.展开更多
The Kalatongke Cu-Ni sulfide deposits located in the East Junggar terrane, northern Xinjiang, western China are the largest magmatic sulfide deposits in the Central Asian Orogenic Belt （CAOB）. The chemical and carbo...The Kalatongke Cu-Ni sulfide deposits located in the East Junggar terrane, northern Xinjiang, western China are the largest magmatic sulfide deposits in the Central Asian Orogenic Belt （CAOB）. The chemical and carbon isotopic compositions of the volatiles trapped in olivine, pyroxene and sulfide mineral separates were analyzed by vacuum stepwise-heating mass spectrometry. The results show that the released volatiles are concentrated at three temperature intervals of 200-400°C, 400-900°C and 900-1200°C. The released volatiles from silicate mineral separates at 400-900°C and 900-1200°C have similar chemical and carbon isotopic compositions, which are mainly composed of H2O （av. ~92 mol%） with minor H2, CO2, H2S and SO2, and they are likely associated with the ore-forming magmatic volatiles. Light δ13CCO2 values （from -20.86‰ to -12.85‰） of pyroxene indicate crustal contamination occurred prior to or synchronous with pyroxene crystallization of mantlederived ore-forming magma. The elevated contents of H2 and H2O in the olivine and pyroxene suggest a deep mantle-originated ore-forming volatile mixed with aqueous volatiles from recycled subducted slab. High contents of CO2 in the ore-forming magma volatiles led to an increase in oxygen fugacity, and thereby reduced the solubility of sulfur in the magma, then triggered sulfur saturation followed by sulfide melt segregation; CO2 contents correlated with Cu contents in the whole rocks suggest that a supercritical state of CO2 in the ore-forming magma system under high temperature and pressure conditions might play a key role in the assemblage of huge Cu and Ni elements. The volatiles released from constituent minerals of intrusion 1# have more CO2 and SO2 oxidized gases, higher CO2/CH4 and SO2/H2S ratios and lighter δ13CCO2 than those of intrusions 2# and 3#. This combination suggests that the higher oxidation state of the volatiles in intrusion 1# than intrusions 2# and 3#, which could be one of key ore-forming factors for large amounts of ores and high contents of Cu and Ni in intrusion 1#. The volatiles released at 200-400°C are dominated by H2O with minor CO2, N2＋CO and SO2, with δ13CCO2 values （-25.66‰ to -22.98‰） within the crustal ranges, and are considered to be related to secondary tectonic-hydrothermal activities.展开更多
Previous studies have obtained some petrogenetic and metallogenic chronological data with SHRIMP （sensitive high-resolution ion microprobe） zircon U-Pb, zircon LA-ICPMS （laser-ablation-inductively coupled plasma ma...Previous studies have obtained some petrogenetic and metallogenic chronological data with SHRIMP （sensitive high-resolution ion microprobe） zircon U-Pb, zircon LA-ICPMS （laser-ablation-inductively coupled plasma mass spectroscopy） U-Pb, molybdenite Re-Os isochron and muscovite Ar-Ar methods in southern Jiangxi Province and its adjacent areas. Based on these, the purpose of this paper is to study the petrogenetic and metallogenic ages and their time gap for different genetic types of W-Sn deposits, and thus to research their numerous episodes, zonal arrangement and their geodynamic background. The result shows that the large-scale W-Sn mineralization in southern Jiangxi Province occurred in the middle to late Jurassic （170-150 Ma）, the skarn W-Sn-polymetallic deposits formed much earlier （170-161 Ma）, and all of the wolframite-quartz vein type, greisen type, altered granite type and fractured zone type tungsten deposits formed in the late Jurassic （160-150 Ma）. In one ore field or ore district, greisen type tungsten deposits formed earlier than quartz vein type ones hosted in the endoor exo-contact zone; and quartz vein type hosted in the endocontact zone formed earlier than that of exocontact zone. There is no significant time difference between tungstentin mineralization and its intimately associated parent granite emplacement （1-6 Ma）. They all formed in the same rock-forming and ore-forming system and under the same geodynamic setting. Regionally, rock-forming and ore-forming processes of the W-Sn deposits in the Nanling region （include southern Jiangxi Province, southern Hunan Province, northern Guangdong Province and eastern Guangxi Zhuang Autonomous Region） exhibit numerous episodes. The mineralization in the Nanling region mainly occurred at （240-210） Ma, （170-150） Ma and （130-90） Ma. The tungsten-tin deposits in this region are centered by the largest scale in southern Jiangxi Province and southern Hunan Province, and become small in the east, west, south and north directions. This displays a zonal arrangement and temporal and spatial distribution regularity. Integrated with the latest research results, it is concluded that the W-Sn mineralization in southern Jiangxi Province and its adjacent areas corresponds to the second large-scale mineralization in South China. The Indosinian W-Sn mineralization formed under the extensional tectonic regime between collisional compressional stages, while the Yanshanian large-scale petrogenetic and metallogenic processes occurred in the Jurassic intraplate extensional geodynamic setting of lithosphere extension.展开更多
基金jointly supported by the National Key Research and Development Program of China(Grant No.2022YFC2905001)the Basic Research Fund of the Chinese Academy of Geological Sciences(Grant No.JKYZD202316)+2 种基金the National Natural Science Foundation of China(Grant Nos.42272093,42230813,42002097)the Research Project of the Shengyuan Mining Co.,Ltd.,Tibet(Grant No.XZSYKYJT-JSFW2019-001)the China Scholarship Council project and the Geological Survey project(Grant Nos.DD20230054,DD20221684,DD20221690,DD20230031,DD20230049,DD20230338)。
文摘Multistage tungsten mineralization was recently discovered in the Mamupu copper-polymetallic deposit in the southern Yulong porphyry copper belt(YPCB),Tibet.This study reports the results of cathodoluminescence,trace element and Sr isotope analyses of Mamupu scheelite samples,undertaken in order to better constrain the mechanism of W mineralization and the sources of the ore-forming fluids.Three different types of scheelite are identified in the Mamupu deposit:scheelite A(Sch A)mainly occurs in breccias during the prograde stage,scheelite B(Sch B)forms in the chlorite-epidote alteration zone in the retrograde stage,while scheelite C(Sch C)occurs in distal quartz sulfide veins.The extremely high Mo content and negative Eu anomaly in Sch A represent high oxygen fugacity in the prograde stage.Compared with ore-related porphyries,Sch A has a similar REE pattern,but with higher ΣREE,more depleted HREE and slightly lower(^(87)Sr/^(86)Sr)i ratios.These features suggest that Sch A is genetically related to ore-related porphyries,but extensive interaction with carbonate surrounding rocks affects the final REE and Sr isotopic composition.Sch B shows dark(Sch B-I)and light(Sch B-II)domains under CL imaging.From Sch B-I to Sch B-II,LREEs are gradually depleted,with MREEs being gradually enriched.Sch C has the highest LREE/HREE ratio,which indicates that it inherited the geochemical characteristics of fluids after the precipitation of HREE-rich minerals,such as diopside and garnet,in the early prograde stage.The Mo content in Sch B and Sch C gradually decreased,indicating that the oxygen fugacity of the fluids changed from oxidative in the early stages to reductive in the later,the turbulent Eu anomaly in Sch B and Sch C indicating that the Eu anomaly in the Mamupu scheelite is not solely controlled by oxygen fugacity.The extensive interaction of magmatic-hydrothermal fluids and carbonate provides the necessary Ca^(2+)for the precipitation of scheelite in the Mamupu deposit.
基金This research was funded by the National Natural Science Foundation of China(No.41862007)the Key Disciplines Construction of Kunming University of Science and Technology(No.14078384)the Yunnan Ten Thousand Talents Plan Young&Elite Talents Project(YNWR-QNBJ-2018-093)。
文摘The Yangla Cu skarn deposit is located in the central part of the Jinshajiang Suture Zone,southwest China,with a total reserve of 150 Mt Cu@1.03%.The newly discovered antimony orebodies at the depth of Yangla are strictly controlled by the stratum,structure,and lithology,which are lenticular and vein-like within the marble fracture zone,which can provide a window into multistage miner-alization and ore genesis at Yangla.Mineralization can be divided into three types,Cu–Pb–Zn(skarn)pyrite,galena,and sphalerite,Cu(porphyry)chalcopyrite and pyrite,and Sb(hydrothermal)stibnite and pyrite.The mineral assem-blages were stibnite+pyrite+calcite+quartz±minor scheelite in antimony ores.This study presents quantitative measurements of the trace element compositions of pyrite and stibnite from the Yangla antimony ores.Analysis of pyrite with electron probe microanalysis(EPMA)showed enrichment in Co,Ni,Sb,As,and Mo,and deficit in its S and Fe contents when compared to the stoichiometric con-centrations of S and Fe in pyrite.The Sb-related pyrite may belong to sedimentary-reworked genesis and may be modi-fied by hydrothermalfluids,thereby presenting a certain dif-ference(i.e.,crystal morphology,texture,and chemical com-position)compared to the skarn and porphyry Cu-related pyrite in the Yangla Cu skarn deposit.Analysis of stibnite with EPMA and inductively coupled plasma-mass spectrom-etry showed enrichment in As,Pb,Sn,Pb,Cu,and Zn,and presented much higher Sb contents and slightly lower S con-tents when compared to the stoichiometric concentrations of Sb and S in stibnite.Statistical analysis of the stibnite trace elements showed correlations for the elemental pairs Cu–Pb,As–Sb,and Sn–Pb,and the coupled substitution equations Sb^(3+)↔Cu^(+)+Pb^(2+),Sb^(3+)↔As^(3+),and Sn^(2+)↔Pb^(2+)may be the major factors governed the incorporating Cu,Pb,As and Sn within the stibnite.Moreover,this study preliminary shows that the antimony mineralization may belong to a car-bonate replacement hydrothermal genesis at Yangla.
基金financially supported by the Natural Science Foundation of China(Grant Nos.42272104,42172094 and 41772076)。
文摘The Wangjiazhuang Cu(-Mo)deposit,located within the Zouping volcanic basin in western Shandong Province,China,is unique in this area for having an economic value.In order to expound the metallogenetic characteristics of this porphyry-like hydrothermal deposit,a detailed fluid inclusion study has been conducted,employing the techniques of representative sampling,fluid inclusion petrography,microthermometry,Raman spectroscopy,LA-ICP-MS analysis of single fluid inclusions,as well as cathode fluorescence spectrometer analysis of host mineral quartz.The deposit contains mainly two types of orebodies,i.e.veinlet-dissemination-stockwork orebodies in the K-Si alteration zone and pegmatiticquartz sulfide veins above them.In addition,minor breccia ore occurs locally.Four types of fluid inclusions in the deposit and altered quartz monzonite are identified:L-type one-or two-phase aqueous inclusions,V-type vapor-rich inclusions with V/L ratios greater than 50%-90%,D-type multiphase fluid inclusions containing daughter minerals or solids and S-type silicate-bearing fluid inclusions containing mainly muscovite and biotite.Ore petrography and fluid inclusion study has revealed a three-stage mineralization process,driven by magmatic-hydrothermal fluid activity,as follows.Initially,a hydrothermal fluid,separated from the parent magma,infiltrated into the quartz monzonite,resulting in its extensive K-Si alteration,as indicated by silicate-bearing fluid inclusions trapped in altered quartz monzonite.This is followed by the early mineralization,the formation of quartz veinlets and dissemination-stockwork ores.During the main mineralization stage,due to the participation and mixing of meteoric groundwater with magmatic-sourced hydrothermal fluid,the cooling and phase separation caused deposition of metals from the hydrothermal fluids.As a result,the pegmatitic-quartz sulfide-vein ores formed.In the late mineralization stage,decreasing fluid salinity led to the formation of L-type aqueous inclusions and chalcopyrite-sulfosalt ore.Coexistence of V-type and D-type inclusions and their similar homogenization temperatures with different homogenization modes suggest that phase separation or boiling of the ore-forming fluids took place during the early and the main mineralization stages.The formation P-T conditions of S-type inclusions and the early and the main mineralization stages were estimated as ca.156-182 MPa and 450-650℃,350-450℃,18-35 MPa and 280-380℃,8-15 MPa,respectively,based on the microthermometric data of the fluid inclusions formed at the individual stages.
基金supported substantially by the Southwest Jiaotong University for Material and Financial Support。
文摘Graphene(Gr)has unique properties including high electrical conductivity;Thus,graphene/copper(Gr/Cu)composites have attracted increasing attention to replace traditional Cu for electrical applications. However,the problem of how to control graphene to form desired Gr/Cu composite is not well solved. This paper aims at exploring the best parameters for preparing graphene with different layers on Cu foil by chemical vapor deposition(CVD)method and studying the effects of different layers graphene on Gr/Cu composite’s electrical conductivity. Graphene grown on single-sided and double-sided copper was prepared for Gr/Cu and Gr/Cu/Gr composites. The resultant electrical conductivity of Gr/Cu composites increased with decreasing graphene layers and increasing graphene volume fraction. The Gr/Cu/Gr composite with monolayer graphene owns volume fraction of less than 0.002%,producing the best electrical conductivity up to59.8 ×10^(6)S/m,equivalent to 104.5% IACS and 105.3% pure Cu foil.
基金provided by the Opening Foundation of State Key Laboratory of Continental Dynamics(Grant No.21LCD08),Northwest University,China.
文摘The Dongnan Cu–Mo deposit,located in the southeast of the Zijinshan ore field(the largest porphyry–epithermal system in Southeast China),represents the complex magmatic and metallogenesis events in the region.The petrogenesis and metallogenesis of granitoids from the deposit are not determined,especially the interactions between ore-bearing(granodiorite porphyry)and barren samples(granodiorite and diorite).In the paper,the whole rock geochemical features shared a similar affinity to the middle-lower content and revealed that they derived from partial melting of the Cathaysian basement with the contribution of mantle materials,even represented that they generated in the plate subduction;LA-ICP-MS zircon U–Pb ages show that these granodiorites,granodioritic porphyry and diorite,were generated during 114–103 Ma.The ore-bearing samples mostly presented ε_(Hf)(t)of negative values(peak value is-4 to-3)with old two-stage Hf model ages(t_(DM)^(2))(peak value is 1.10–1.15 Ga),while the barren sample showed slightly negative ε_(Hf)(t)(peak value is-1 to 0)values with young t_(DM)^(2)(peak value is 1.00–1.05 Ga).The value of zircon Ce^(4+)/Ce^(3+)ratio mostly higher than 450 was first verified for the ore-bearing samples in the Dongnan Cu–Mo deposit,and the values of ore-bearing were found to be higher than those from the barren,which suggests that the ore-bearing formed in more oxidized parental magma with higher oxygen fugacity.Based on the geochemical characteristic of the element and isotope,we concluded that the Early Cretaceous multiphases magmatic activities,low melting temperature and low pressure of pluton,and high oxygen fugacity of zircon,were the favorable conditions for metallogenesis of Dongnan Cu–Mo deposit.
基金supported by the Chinese National Science Fund for Distinguished Young Scholars to Dr.Gao Jian-Feng(42025301).
文摘The Dexing porphyry deposit is the largest porphyry Cu–Mo–Au deposit in South China.Biotite composition can record the physicochemical conditions and evolution history of magmatic-hydrothermal system.Biotite from the Dexing porphyry deposit could be divided to three types:primary magmatic biotite(Bi-M),hydrothermal altered magmatic biotite(Bi-A)and hydrothermal biotite(Bi-H).The temperature of Bi-M and Bi-H range from 719 to 767℃ and 690 to 727℃,respectively.Both magmatic and hydrothermal biotite have high Fe^(3+)/Fe^(2+)ratios(from 0.18 to 0.24)and XMgvalues(from 0.57 to 0.66),indicating a high oxygen fugacity.BiM has F lower than Bi-A and Bi-H(up to 0.26 wt%),but has Cl(Cl=0.18–0.30 wt%)similar to Bi-A and Bi-H(Cl=0.21–0.35 wt%),suggesting that high Cl/F ratios of early hydrothermal fluid may result from the exsolution from high Cl magma.From potassic alteration zone to phyllic and propylitic alteration zones,Cl decreases with increasing Cu,whereas F increases roughly.Therefore,Cl mostly originate from magma,but enrichment of F possibly results from reaction of fluids and Neoproterozoic strata.Negative correlation between Cl and Cu indicates that Cl might act as an important catalyst during Cu mineralization process.Biotite from Dexing has similar halogen compositions to other porphyry Cu-/Mo deposits in the world.Chlorine contents of hydrothermal fluid may be critical for Cu transportation and enrichment,while consumption of Cl would promote Cu deposition.
基金supported by the National Natural Science Foundation of China(NSFC,No.T2188101)National Natural Science Foundation Youth Fund(Nos.22105006 and 52202033)the National Key R&D Program of China(No.2022YFA1204900).
文摘Chemical vapor deposition (CVD) has shown great promise for the large-scale production of high-quality graphene films for industrial applications. Atomic-scale theoretical studies can help experiments to deeply understand the graphene growth mechanism, and serve as theoretical guides for further experimental designs. Here, by using density functional theory calculations, ab-initio molecular dynamics simulations, and microkinetic analysis, we systematically investigated the kinetics of hydrogen constrained graphene growth on Cu substrate. The results reveal that the actual hydrogen-rich environment of CVD results in CH as the dominating carbon species and graphene H-terminated edges. CH participated island sp2 nucleation avoids chain cyclization process, thereby improving the nucleation and preventing the formation of non-hexameric ring defects. The graphene growth is not simply C-atomic activity, rather, involves three main processes: CH species attachment at the growth edge, leading to a localized sp3 hybridized carbon at the connecting site;excess H transfer from the sp3 carbon to the newly attached CH;and finally dehydrogenation to achieve the sp2 reconstruction of the newly grown edge. The threshold reaction barriers for the growth of graphene zigzag (ZZ) and armchair (AC) edges were calculated as 2.46 and 2.16 eV, respectively, thus the AC edge grows faster than the ZZ one. Our theory successfully explained why the circumference of a graphene island grown on Cu substrates is generally dominated by ZZ edges, which is a commonly observed phenomenon in experiments. In addition, the growth rate of graphene on Cu substrates is calculated and matches well with existing experimental observations.
文摘Cu-phthalocyanine is widely studied as a hole-transport layer in organic electronic devices. Since Cu-phthalocyanine is a molecular solid, the crystal structure depends on a circumstance to a great extent. Vacuum deposited layers were known to consist of two consecutive layers. In this article, Cu-phthalocyanine was deposited on the glass substrate inclined at several angles. The thickness of the first layer was found to be dependent on the substrate angle.
基金supported by the National Natural Science Foundation of China(No.T2188101)Beijing National Laboratory for Molecular Science(No.BNLMS-CXTD-202001)National Key R&D Program of China(No.2018YFA0703502).
文摘Transition metal catalyzed chemical vapor deposition (CVD) is considered as the most promising approach to synthesize highquality graphene films, and low-temperature growth of defect-free graphene films is long-term challenged because of the high energy barrier for precursor dissociation and graphitization. Reducing the growth temperature can also bring advantages on wrinkle-free graphene films owing to the minimized thermal expansion coefficient mismatch. This work focuses on density functional theory (DFT) calculations of the carbon source precursor with hydroxyl group, especially CH_(3)OH, on low-temperature CVD growth of graphene on Cu and CuNi substrate. We calculated all the possible cleavage paths for CH_(3)OH on transition metal substrates. The results show that, firstly, the cleavage barriers of CH_(3)OH on transition metal substrates are slightly lower than those of CH_(4), and once CO appears, it is difficult to break the C-O bond. Secondly, the CO promotes a better formation and retention of perfect rings in the early stage of graphene nucleation and reduces the edge growth barriers. Thirdly, these deoxidation barriers of CO are reduced after CO participates in graphene edge growth. This paper provides a strategy for the lowtemperature growth of wrinkles-free graphene on transition metal substrates using CH_(3)OH.
基金supported by the National Basic Research Program of China(Grant No.1212010881001 )the National Scicnce of the 12th "Five-Year Technology Support Program"(Grant No.2010BAE00281-6)+1 种基金the National Natural Science Foundation of China(Grant Nos.40772157,40972232, 41072070)the State Key Laboratory of Geological Processes and Mineral Resources(Grant Nos.GPMR0941,200624)
文摘Three-dimensional geological modeling （3DGM） assists geologists to quantitatively study in three-dimensional （3D） space structures that define temporal and spatial relationships between geological objects. The 3D property model can also be used to infer or deduce causes of geological objects. 3DGM technology provides technical support for extraction of diverse geoscience information, 3D modeling, and quantitative calculation of mineral resources. Based on metallogenic concepts and an ore deposit model, 3DGM technology is applied to analyze geological characteristics of the Tongshan Cu deposit in order to define a metallogenic model and develop a virtual borehole technology; a BP neural network and a 3D interpolation technique were combined to integrate multiple geoscience information in a 3D environment. The results indicate： （1） on basis of the concept of magmatic-hydrothermal Cu polymetallic mineraliza- tion and a porphyry Cu deposit model, a spatial relational database of multiple geoscience information for mineralization in the study area （geology, geophysics, geochemistry, borehole, and cross-section data） was established, and 3D metallogenic geological objects including mineralization stratum, granodiorite, alteration rock, and magnetic anomaly were constructed; （2） on basis of the 3D ore deposit model, 23,800 effective surveys from 94 boreholes and 21 sections were applied to establish 3D orebody models with a kriging interpolation method; （3） combined 23,800 surveys involving 21 sections, using VC＋＋ and OpenGL platform, virtual borehole and virtual section with BP network, and an improved inverse distance interpolation （IDW） method were used to predict and delineate mineralization potential targets （Cu-grade of cell not less than 0.1%）; （4） comparison of 3D ore bodies, metallogenic geological objects of mineralization, and potential targets of mineralization models in the study area, delineated the 3D spatial and temporal relationship and causal processes among the ore bodies, alteration rock, metallo- genic stratum, intrusive rock, and the Tongshan Fault. This study provides important technical support and a scientific basis for assessment of the Tongshan Cu deposit and surrounding exploration and mineral resources.
基金financially supported by the Chinese 973 project(2012CB416804)the ‘‘CAS Hundred Talents’’ Project from the Chinese Academy of Sciences(KZCX2-YW-BR-09)to Qi Liang
文摘Laser ablation–inductively coupled plasma–mass spectrometry（LA–ICP–MS） was used to determine the trace element concentrations of magnetite from the Heifengshan, Shuangfengshan, and Shaquanzi Fe（–Cu） deposits in the Eastern Tianshan Orogenic Belt. The magnetite from these deposits typically contains detectable Mg, Al, Ti, V, Cr, Mn, Co, Ni, Zn and Ga. The trace element contents in magnetite generally vary less than one order of magnitude. The subtle variations of trace element concentrations within a magnetite grain and between the magnetite grains in the same sample probably indicate local inhomogeneity of ore–forming fluids. The variations of Co in magnetite between samples are probably due to the mineral proportion of magnetite and pyrite. Factor analysis has discriminated three types of magnetite： Ni–Mn–V–Ti（Factor 1）, Mg–Al–Zn（Factor 2）, and Ga– Co（Factor 3） magnetite. Magnetite from the Heifengshan and Shuangfengshan Fe deposits has similar normalized trace element spider patterns and cannot be discriminated according to these factors. However, magnetite from the Shaquanzi Fe–Cu deposit has affinity to Factor 2 with lower Mg and Al but higher Zn concentrations, indicating that the ore–forming fluids responsible for the Fe–Cu deposit are different from those for Fe deposits. Chemical composition of magnetite indicates that magnetite from these Fe（–Cu） deposits was formed by hydrothermal processes rather than magmatic differentiation. The formation of these Fe（–Cu） deposits may be related to felsic magmatism.
基金financially supported by NSF of China(Grant 41072056, 40772058, 91014003, 40534020 and40772062)Key Projects of China Geological Survey(1212011121092)MOE (311010)
文摘The Kalatongke Cu-Ni sulfide deposits located in the East Junggar terrane, northern Xinjiang, western China are the largest magmatic sulfide deposits in the Central Asian Orogenic Belt （CAOB）. The chemical and carbon isotopic compositions of the volatiles trapped in olivine, pyroxene and sulfide mineral separates were analyzed by vacuum stepwise-heating mass spectrometry. The results show that the released volatiles are concentrated at three temperature intervals of 200-400°C, 400-900°C and 900-1200°C. The released volatiles from silicate mineral separates at 400-900°C and 900-1200°C have similar chemical and carbon isotopic compositions, which are mainly composed of H2O （av. ~92 mol%） with minor H2, CO2, H2S and SO2, and they are likely associated with the ore-forming magmatic volatiles. Light δ13CCO2 values （from -20.86‰ to -12.85‰） of pyroxene indicate crustal contamination occurred prior to or synchronous with pyroxene crystallization of mantlederived ore-forming magma. The elevated contents of H2 and H2O in the olivine and pyroxene suggest a deep mantle-originated ore-forming volatile mixed with aqueous volatiles from recycled subducted slab. High contents of CO2 in the ore-forming magma volatiles led to an increase in oxygen fugacity, and thereby reduced the solubility of sulfur in the magma, then triggered sulfur saturation followed by sulfide melt segregation; CO2 contents correlated with Cu contents in the whole rocks suggest that a supercritical state of CO2 in the ore-forming magma system under high temperature and pressure conditions might play a key role in the assemblage of huge Cu and Ni elements. The volatiles released from constituent minerals of intrusion 1# have more CO2 and SO2 oxidized gases, higher CO2/CH4 and SO2/H2S ratios and lighter δ13CCO2 than those of intrusions 2# and 3#. This combination suggests that the higher oxidation state of the volatiles in intrusion 1# than intrusions 2# and 3#, which could be one of key ore-forming factors for large amounts of ores and high contents of Cu and Ni in intrusion 1#. The volatiles released at 200-400°C are dominated by H2O with minor CO2, N2＋CO and SO2, with δ13CCO2 values （-25.66‰ to -22.98‰） within the crustal ranges, and are considered to be related to secondary tectonic-hydrothermal activities.
基金financially supported by the National Key Basic Research Program (Grant2012CB416704) from the Ministry of Science and Technology, Chinagrant No. 40772063 from the National Natural Science Foundation of China+1 种基金the Program of Excellent Young Scientists from the Ministry of Land and Resources (200809)Geological Survey Program Grant 1212010561603-2 from the China Geological Survey
文摘Previous studies have obtained some petrogenetic and metallogenic chronological data with SHRIMP （sensitive high-resolution ion microprobe） zircon U-Pb, zircon LA-ICPMS （laser-ablation-inductively coupled plasma mass spectroscopy） U-Pb, molybdenite Re-Os isochron and muscovite Ar-Ar methods in southern Jiangxi Province and its adjacent areas. Based on these, the purpose of this paper is to study the petrogenetic and metallogenic ages and their time gap for different genetic types of W-Sn deposits, and thus to research their numerous episodes, zonal arrangement and their geodynamic background. The result shows that the large-scale W-Sn mineralization in southern Jiangxi Province occurred in the middle to late Jurassic （170-150 Ma）, the skarn W-Sn-polymetallic deposits formed much earlier （170-161 Ma）, and all of the wolframite-quartz vein type, greisen type, altered granite type and fractured zone type tungsten deposits formed in the late Jurassic （160-150 Ma）. In one ore field or ore district, greisen type tungsten deposits formed earlier than quartz vein type ones hosted in the endoor exo-contact zone; and quartz vein type hosted in the endocontact zone formed earlier than that of exocontact zone. There is no significant time difference between tungstentin mineralization and its intimately associated parent granite emplacement （1-6 Ma）. They all formed in the same rock-forming and ore-forming system and under the same geodynamic setting. Regionally, rock-forming and ore-forming processes of the W-Sn deposits in the Nanling region （include southern Jiangxi Province, southern Hunan Province, northern Guangdong Province and eastern Guangxi Zhuang Autonomous Region） exhibit numerous episodes. The mineralization in the Nanling region mainly occurred at （240-210） Ma, （170-150） Ma and （130-90） Ma. The tungsten-tin deposits in this region are centered by the largest scale in southern Jiangxi Province and southern Hunan Province, and become small in the east, west, south and north directions. This displays a zonal arrangement and temporal and spatial distribution regularity. Integrated with the latest research results, it is concluded that the W-Sn mineralization in southern Jiangxi Province and its adjacent areas corresponds to the second large-scale mineralization in South China. The Indosinian W-Sn mineralization formed under the extensional tectonic regime between collisional compressional stages, while the Yanshanian large-scale petrogenetic and metallogenic processes occurred in the Jurassic intraplate extensional geodynamic setting of lithosphere extension.
