Enlarging Zn deposition space via regulating Sn-induced effective interface for high areal capacity zinc-based flow battery

Zinc-based flow batteries(ZFBs)have aroused great favor in large-scale energy storage due to the high security and low cost.However,the low areal capacity arising from the limited space for Zn plating hinders the further development.Herein,a novel carbon felt-Sn-carbon felt sandwich host(CSCH)is designed and constructed.Benefiting from the strong chemical absorption and the dehydration effect on Zn(H_(2)O)_(6)^(2+),the Sn activation layer in the CSCH demonstrates the lowest comprehensive resistance for Zn deposition.Thus,Zn is induced to nucleate preferentially on the Sn activation layer,and grows towards the membrane,regulating the spatial distribution of Zn electrochemical deposits,which remarkably improves the areal capacity and cyclic stability of Zn anode.Consequently,the zinc-bromine flow batteries equipped with CSCH electrodes can achieve the ultra-high areal capacity of 120 mA h cm^(-2)at 80 mA cm^(-2),and run stably for 140 h with average energy efficiency of 80.3%in the extreme condition(80 mA cm^(-2),80 mA h cm^(-2)).This innovative work will inspire future advanced designs for high areal capacity electrodes in ZFBs.

Sediment-hosted Pb-Zn Deposits in Southwest Sanjiang Tethys and Kangdian Area on the Western Margin of Yangtze Craton

The western margin of Yangtze Craton is known as a significant sediment-hosted base-metal aggregate cluster,especially for Pb-Zn deposits in China,e.g.Jinding,Daliangzi,Tianbaoshan, Kuangshanchang and Qinlinchang deposits.In comparison with the classic MVT deposits in the world, based on the basic geology of the sediment-hosted Pb-Zn deposits,this paper focuses on temporal-spatial distribution of this deposit to further discuss its large scale mineralization and tectonic evolution history.In the SW Sanjiang Thethys,Jinding deposit is typically thrust fault-controlled and hosted mainly in the sandstones and breccia-bearing sandstones,whereas MVT-type deposits are controlled by lithology and faulting/fracturing with a strong preference for carbonate-hosted rocks.Most importantly,Jinding Pb-Zn deposit differs from the other types of sediment-hosted Pb-Zn deposits in which it was formed in a strongly deformed foreland basin within a continental collision zone.In the Kangdian area,the sediment-hosted Pb-Zn deposits were formed in the extensional basin on the side of the continental orogenic belt along the Yangtze Craton.Compared with classic MVT deposits,the Pb-Zn deposits in the Kangdian area belong to MVT deposits.This paper is significant not only for interpretation of the genesis of sediment-hosted Pb-Zn deposits but also for exploiting large base metal deposits in large sedimentary target areas.

REE and C-O Isotopic Geochemistry of Calcites from the World-class Huize Pb-Zn Deposits,Yunnan,China:Implications for the Ore Genesis

The world-class Huize Pb-Zn deposits of Yunnan province,in southwestern China,located in the center of the Sichuan-Yunnan-Guizhou Pb-Zn polymetallic metallogenic province,has Pb＋Zn reserves of more than 5 million tons at Pb＋Zn grade of higher than 25%and contains abundant associated metals,such as Ag,Ge,Cd,and Ga.The deposits are hosted in the Lower Carboniferous carbonate strata and the Permian Emeishan basalts which distributed in the northern and southwestern parts of the orefield.Calcite is the only gangue mineral in the primary ores of the deposits and can be classified into three types,namely lumpy,patch and vein calcites in accordance with their occurrence.There is not intercalated contact between calcite and ore minerals and among the three types of calcite,indicating that they are the same ore-forming age with different stages and its forming sequence is from lumpy to patch to vein calcites. This paper presents the rare earth element（REE） and C-O isotopic compositions of calcites in the Huize Pb-Zn deposits.From lumpy to patch to vein calcites,REE contents decrease as LREE/ HREE ratios increase.The chondrite-normalized REE patterns of the three types of calcites are characterized by LREE-rich shaped,in which the lumpy calcite shows（La）_N〈（Ce）_N〈（Pr）_N≈（Nd）_N with Eu/Eu~＊〈1,the patch calcite has（La）_N〈（Ce）_N〈（Pr）_N≈（Nd）_N with Eu/Eu~＊〉1,and the vein calcite displays（La）_N〉（Ce）_N〉（Pr）_N〉（Nd）_N with Eu/Eu~＊〉1.The REE geochemistry of the three types of calcite is different from those of the strata of various age and Permian Emeishan basalt exposed in the orefield.Theδ^（13） C_（PDb） andδ^（18）O_（Smow） values of the three types of calcites vary from-3.5‰to-2.1‰and 16.7‰to 18.6‰,respectively,falling within a small field between primary mantle and marine carbonate in theδ^（13）C_（PDb） vsδ^（18）O_（Smow） diagram. Various lines of evidence demonstrate that the three types of calcites in the deposits are produced from the same source with different stages.The ore-forming fluids of the deposits resulted from crustal -mantle mixing processes,in which the mantle-derived fluid components might be formed from degassing of mantle or/and magmatism of the Permian Emeishan basalts,and the crustal fluid was mainly provided by carbonate strata in the orefield.The ore-forming fluids in the deposits were homogenized before mineralization,and the ore-forming environment varied from relatively reducing to oxidizing.

Regulating Zn Deposition via an Artificial Solid–Electrolyte Interface with Aligned Dipoles for Long Life Zn Anode

Aqueous zinc ion batteries show prospects for next-generation renewable energy storage devices.However,the practical applications have been limited by the issues derived from Zn anode.As one of serious problems,Zn dendrite growth caused from the uncontrollable Zn deposition is unfavorable.Herein,with the aim to regulate Zn deposition,an artificial solid–electrolyte interface is subtly engineered with a perovskite type material,BaTiO3,which can be polarized,and its polarization could be switched under the external electric field.Resulting from the aligned dipole in BaTiO3 layer,zinc ions could move in order during cycling process.Regulated Zn migration at the anode/electrolyte interface contributes to the even Zn stripping/plating and confined Zn dendrite growth.As a result,the reversible Zn plating/stripping processes for over 2000 h have been achieved at 1 mA cm^(−2) with capacity of 1 mAh cm−2.Furthermore,this anode endowing the electric dipoles shows enhanced cycling stability for aqueous Zn-MnO2 batteries.The battery can deliver nearly 100%Coulombic efficiency at 2 Ag^(−1) after 300 cycles.

Re-Os and U-Pb Geochronology of the Erlihe Pb-Zn Deposit,Qinling Orogenic Belt,Central China,and Constraints on Its Deposit Genesis

The Erlihe Pb-Zn deposit is an important mine of the Pb-Zn metallogenic zone in the South Qinling Orogen.It has been considered a sedimentary exhalative deposit in previous investigations because the ore body occurs concordantly at the transitional location of an upright fold.Re and Os isotopic analyses for paragenetic pyrites with sphalerite and galena from the ore body have been used to determine the timing of mineralization and to trace the source of metallogenic materials.The Re-Os isotopic data of four pyrite samples construct an isochron,yielding a weighted average age of 226±17 Ma（mean square weighted deviation=1.7）,which is considered the main mineralization age.A dioritic porphyrite vein sample,showing weaker mineralization,was also dated using the SHRIMP zircon UPb isotopic method to constrain the youngest metallogenic age of the ore deposit,because it distributes along a group of tensional joints cutting not only the upright fold in the deposit field,but also the main ore bodies.The dioritic porphyrite sample yields a weighted mean ^（206）Pb/^（238）U age of 221±3 Ma,which is slightly younger than the Re-Os isotopic isochron age of the pyrites,considered as the upper age limit of the mineralization,namely the ending age of the mineralization.The Os isotopic compositions of sulfide minerals distribute within a range between Os isotopic compositions of the crust and the mantle, indicating that the ore deposit can be derived from magma-related fluid,and the metallogenic materials are most likely derived from the mixing source of the crust and the mantle.The Erlihe Pb-Zn deposit and associated dioritic porphyrite vein,important records of Qinling tectonic-magmatism-mineralization activities,were formed during the Triassic collisional orogeny processes.

Genesis of the Maoping carbonate-hosted Pb–Zn deposit,northeastern Yunnan Province,China:evidences from geology and C–O–S–Pb isotopes

The Maoping Pb-Zn deposit(~3 Mt Pb+Zn reserves with grades of 12-30 wt%)is one of the largest Pb-Zn deposits in the Sichuan-Yunnan-Guizhou(SYG)metallogenic province,which has contributed a tremendous amount of lead and zinc resources for China.To obtain a further understanding of the sources of ore-forming materials and ore genesis of the deposit,S-Pb isotopes of sulfides and C-O isotopes of ore-stage calcites were systematically collected from representative orebodies at different elevations with a Finnigan MAT-253 mass spectrometer.The calcites separated from the sulfides of the NoⅠand NoⅡorebodies shared identical b13 CPDB values(-5.3 to-0.8‰)andδ18OSMOW values(+14.5 to+21.8‰)with those of the calcites in the SYG region,suggesting that CO2 in regional ore-forming fluids possibly had a homologous C-O source that originated from a ternary mixture of the dissolution of marine carbonate rocks,degassing process of the Emeishan mantle plume,and dehydroxylation of sedimentary organic matter.The No.Ⅰ-1 and No.Ⅰ-2 orebody was hosted in the same strata,but the sulfur source of No.Ⅰ-1 orebody(+13.1 to+19.0‰)with equilibrated sulfur fractionation(δ34Sspbaierite-<δ34Sgalena)and No.Ⅰ-2 orebody(+18.0 to+21.8‰)with sulfur equilibrium fractionation(δ34Sspnaierite>δ34-Sgalena)were different.They were derived from the allopatry thermochemical sulfate reduction(TSR)of overlying Carboniferous sulfates in the ore-hosting strata and local TSR of sulfates in the ore-bearing Upper Devonian Zaige Formation,respectively.The narrow and uniform Pb isotopic ratios of single galena grains collected from sulfides with 206Pb/204Pb of 18.713-18.759,207Pb/204Pb of 15.772-15.776 and 208Pb/204Pb of39.383-39.467 indicate a well-mixed metal source(s)that consist of Proterozoic Kunyang and Huili Group basement rocks and Devonian to Middle Permian ore-hosting sedimentary rocks.Besides,the late Permian Emeishan basalts are difficult to contribute metals for regional Pb-Zn mineralization despite a closely spatial relationship with the distribution of the Pb-Zn deposit.This is supported by Pb isotopic ratios plotting above the average upper crustal Pb evolution curves and staying far away from that of the agecorrected Emeishan basalts.Hence,taking into account of the similarities in tectonic setting,ore-hosting rock,ore assemblage,wall rock alteration,ore-controlling structure,and ore-forming materials and the differences in relationship with regional magmatism,fluid inclusion characteristic and ore grade between the Maoping deposit and typical MVT Pb-Zn deposit,the ore genesis of the Maoping deposit should be an MVT like Pb-Zn deposit.

Geochemical Characteristics and Sources of Ore-forming Fluids of the Mayuan Pb-Zn Deposit,Nanzheng,Shaanxi,China

The Mayuan stratabound Pb-Zn deposit in Nanzheng,Shaanxi Province,is located in the northern margin of the Yangtze Plate,in the southern margin of the Beiba Arch.The orebodies are stratiform and hosted in breciated dolostone of the Sinian Dengying Formation.The ore minerals are primarily sphalerite and galena,and the gangue minerals comprise of dolomite,quartz,barite,calcite and solid bitumen.Fluid inclusions from ore-stage quartz and calcite have homogenization tempreatures from 98 to 337℃ and salinities from 7.7 wt%to 22.2 wt%（NaCl equiv.）.The vapor phase of the inclusions is mainly composed of CH_4 with minor CO_2 and H_2S.The δD_（fluid） values of fluid inclusions in quartz and calcite display a range from-68‰ to-113‰（SMOW）,and the δ^（18）O_（fluid）values calculated from δ^（18）O_（quartz） and δ^（18）O_（calcite） values range from 4.5‰ to 16.7‰（SMOW）.These data suggest that the ore-forming fluids may have been derived from evaporitic sea water that had reacted with organic matter.The δ^（13）C_（CH4） values of CH_4 in fluid inclusions range from-37.2‰ to-21.0‰（PDB）,suggesting that the CH_4 in the ore-forming fluids was mainly derived from organic matter.This,together with the abundance of solid bitumen in the ores,suggest that organic matter played an important role in mineralization,and that the thermochemical sulfate reduction（TSR） was the main mechanism of sulfide precipitation.The Mayuan Pb-Zn deposit is a carbonate-hosted epigenetic deposit that may be classified as a Mississippi Valley type（MVT） deposit.

Lead Isotopic Composition and Lead Source of the Huogeqi Cu-Pb-Zn Deposit,Inner Mongolia,China

The Huogeqi orefield located on the northern side of Mt. Langshan, Inner Mongolia occurs in the Middle Proterozoic Langshan Group metamorphic rocks, and the orebodies arc stratiform. In the past twenty years, many Chinese geologists have conducted researches on the Huogeqi Cu-Pb-Zn deposit, but there has been still a controversy on its origin. Some advocate that the deposit is of sedimentary-metamorphic rcworking origin, some hold that it is of sea-floor SEDEX origin, and others have a preference for magmatic superimposition origin. The crux of the controversy is that there is no common understanding about the source of ore-forming materials. In this paper, the Pb isotopic compositions of regional Achaean-Early Proterozoic basement rocks, various types of sedimentary- metamorphic rocks and volcanic rocks in the mining district, Late Proterozoic and Hercynian magmatic rocks arc introduced and compared with the orc-lead composition, so as to constrain the source of the ore lead. The result indicates that （1） sulfides in the ores have homogeneous Pb isotopic compositions, showing a narrow variation range. Their ^206pb/^204pb ratios arc within a range of 17.027- 17.317; ^207Pb/^204pb ratios, 15.451-15.786 and ^208Pb/^204pb ratios, 36.747-37.669; （2） the Pb isotopic compositions of the regional Achaean-Early Proterozoic basement rocks arc characteristic of the old Pb isotopic composition at the early-stage evolution of the Earth, which varies over a wider range, reflecting significant differences in Pb isotopic compositions of the ores. All this indicates that the source of ore lead has no bearing on the basement rocks; （3） the sedimentary-metamorphic rocks in the mining district arc characterized by highly variable and more radiogenic Pb isotopic compositions and their Pb isotopic ratios arc obviously higher than those of ores, demonstrating that ore lead did not result from metamorphic rcworking of these rocks; （4） Pb isotopic compositions of Late Proterozoic diorite-gabbro and Hercynian granite are higher than those of ores. Meanwhile, the Pb isotopic compositions of sulfides in the small-sized strata-penetrating mineralized veinlets formed at later stages arc completely consistent with that of sulfides in stratiform-banded ores, suggesting that these veiniets arc the product of autochthonous rcworking of the stratiform-banded ores during the period of metamorphism and the late magmatic superimposition-mineralization can be excluded; （5） amphibolite, whose protolith is basic volcanic rocks, has the same Pb isotopic compositions as ores, implying that ore lead was derived probably from basic volcanism. So, the source of ore-forming materials for the Huogeqi deposit is like that of the volcanic massive sulfide （VMS） deposits. However, the orebodies do not occur directly within the volcanic rocks, and instead they overlie the volcanic rocks, showing some differences from those typical VMS-type deposits.

Characteristics of Breccias and C-O-Sr-S Isotope Geochemistry of the Duocaima Pb-Zn Deposit in Tuotuohe, Qinghai Province: Implications for the Ore-forming Process

The Duocaima carbonate-hosted Pb-Zn deposit is a newly found large deposit in the southern area of Qinghai Province.In this paper, the characteristics, genesis, significance to Pb-Zn mineralization of the widely developed breccias, and the ore-forming process have been carefully studied based on geological documentation of drilling holes, microscopic observations of petrography and microstructure and some stable isotope measurements.Based on the compositions of the clast and matrix, the breccias can be classified into three types： limestone clasts cemented by marl; limestone clasts with fine-grained calcareous materials; and limestone clasts cemented by hydrothermal calcite.The mineralization in the first type of breccia is weak, whereas it is strong in the latter two types of breccias.According to the locations of occurrence and structural characteristics of the breccias along with the relationship between the breccias and mineralization, part of the limestone clasts that are cemented by marl and outcrop in the contact zone between the Wudaoliang Formation（Nw） and the underlying Jiushidaoban Formation（Pj） are attributed to synsedimentary fault-genetic breccia, whereas the last of the limestone clasts that are cemented by marl and developed in the Jiushidaoban Formation（Pj） are attributed to the breccia generated by karst cave collapse; the limestone clasts with fine-grained calcareous materials and the limestone clasts cemented by hydrothermal calcite are attributed to breccia formed by hydrothermal dissolution.The breccia formed by karst collapse had consistently evolved for a long period of time, while the breccias with other origins were formed around the period of mineralization（i.e., about or slightly later than 20–16 Ma）.The breccia generated by karst cave collapse and hydrothermal dissolution are somewhat related; the formation of the breccia from karst cave collapse provided open space for the later mineralization and reaction between hydrothermal fluids and host rocks, and the subsequent strong dissolution by hydrothermal fluids transformed some of the breccia formed earlier by karst cave collapse.Meanwhile, carbonate host rocks with breccias and brecciaed mineralization can be a potential sign of Mississippi Valley Type（MVT） deposits and important indicators for regional mineral exploration.The δ13CV-PDB, δ18OVSMOW, and 87Sr/86 Sr values of hydrothermal calcite in the Duocaima deposit range from 4.3‰ to 7.1‰, 14.9‰ to 20.1‰, and 0.707494 to 0.708185, respectively; the δ13CV-PDB, δ18OV-SMOW, and 87Sr/86 Sr values of the host limestones of the Jiushidaoban Formation range from 3.6‰ to 5.3‰, 18.0‰ to 20.5‰, and 0.707372 to 0.707945, respectively.The δ13CV-PDB and 87Sr/86 Sr values of hydrothermal calcite and limestone are similar, indicating single sources of C and Sr in this deposit, with the likely source being the limestone of the Jiushidaoban Formation.The minor scattering of the δ18OV-SMOW values suggests that different O isotope fluids underwent the isotope exchange reaction.The C-O-Sr isotope characteristics indicate that the host limestones experienced a dissolution and precipitation process during mineralization, which is beneficial to improving the porosity of host rocks and promoting the precipitation of metal sulfides.The δ34SV-CDT value of the breccia-type mineralization sulfides ranges from-30.4‰ to-0.3‰; that is, the δ34SV-CDT value is negative with considerable variation, illustrating that during the breccia-type mineralization process, the bacteriogenic reduction of sulfates provided the vast majority of sulfur, whereas the thermochemical reduction of sulfates was relatively unimportant.The brecciation that occurred as a result of karst cave collapse was mainly generated by the dissolution of groundwater; however, the brecciation related to hydrothermal dissolution and mineralization processes were caused by mixing of different fluids.

Geology and Isotope Geochemistry of the Yinchanggou-Qiluogou Pb-Zn Deposit,Sichuan Province,Southwest China

The Yinchanggou-Qiluogou Pb-Zn deposit,located in the western Yangtze Block,southwest China,is hosted by the Upper Sinian Dengying Formation dolostone.Ore bodies occur in the Qiluogou anticline and the NS-and NNW-trending faults.Sulfide ores mainly consist of sphalerite,pyrite,galena and calcite,with subordinate dolomite and quartz.Seventeen ore bodies have been discovered to date and they have a combined 1.0 million tons of sulfide ores with average grades of 2.27wt%Zn and 6.89wt%Pb.The δD（H2O-SMOW） and δ18O（H2O-SMOW） values of fluid inclusions in quartz and calcite samples range from-68.9‰ to-48.7‰ and 7.3‰ to 15.9‰,respectively,suggesting that H2O in the hydrothermal fluids sourced from metamorphic water.Calcite samples have δ13C（PDB） values ranging from-6.2‰ to-4.1‰ and δ18O（SMOW） values ranging from 15.1‰ to 17.4‰,indicating C and O in the hydrothermal fluids likely derived from a mixed source of metamorphic fluids and the host carbonates.The δ34S（CDT） values of sulfide minerals range from 5.5‰ to 20.3‰,suggesting that thermal chemical reduction of sulfate minerals in evaporates were the most probable source of S in the hydrothermal fluids.The 206Pb/204Pb,207Pb/204Pb and 208Pb/204Pb ratios of sulfide minerals fall in the range of 18.11 to 18.40,15.66 to 15.76 and 38.25 to 38.88,respectively.The Pb isotopic data of the studied deposit plot near the upper crust Pb evolution curve and overlap with the age-corrected Proterozoic basement rocks and the Upper Sinian Dengying Formation hosting dolostone.This indicates that the Pb originated from a mixed source of the basement metamorphic rocks and the ore-hosting carbonate rocks.The ore geology and C-H-O-S-Pb isotopic data suggest that the YinchanggouQiluogou deposit is an unusual carbonate-hosted,strata-bound and epigenetic deposit that derived ore-forming materials from a mixed source of the underlying Porterozoic basements and the Sinian hosting carbonates.

Compositions and Pressure-Temperature Conditions of Metamorphic Fluids Overprinting the Talate VMS Pb-Zn Deposit,Southern Altay,China

The Talate Pb-Zn deposit,located in the east of the NW-SE extending Devonian Kelan volcanic-sedimentary basin of the southern Altaides,occurs in the metamorphic rock series of the upper second lithological section of the lower Devonian lower Kangbutiebao Formation（D_1k_1~2）.The Pb-Zn orebodies are stratiform and overprinted by late sulfide—quartz veins.Two distinct mineralization periods were identified：a submarine volcanic sedimentary exhalation period and a metamorphic hydrothermal mineralization period.The metamorphic overprinting period can be further divided into two stages：an early stage characterized by bedding-parallel lentoid quartz veins developed in the chlorite schist and leptite of the ore-bearing horizon,and a late stage represented by pyritechalcopyrite-quartz veins crosscutting chlorite schist and leptite or the massive Pb-Zn ores.Fluid inclusions in the early metamorphic quartz veins are mainly CO_2-H_2O-NaCI and carbonic（CO_2±CH_4±N_2） inclusions with minor aqueous inclusions.The CO_2-H_2O-NaCl inclusions have homogenization temperatures of 294-368℃,T_（m,CO2） of-62.6 to-60.5℃,T_（h,CO2） of 7.7 to 29.6℃（homogenized into liquid）,and salinities of 5.5-7.4 wt%NaCl eqv.The carbonic inclusions have T_（m,CO2）of-60.1 to-58.5℃,and T_（h,Co2） of-4.2 to 20.6℃.Fluid inclusions in late sulfide quartz veins are also dominated by CO_2-H_2O-NaCl and CO_2±CH_4 inclusions.The CO_2-H_2O-NaCl inclusions have T_（b,tot） of142 to 360℃,T_（m,CO2）of-66.0 to-56.6℃,T_（h,CO2） of-6.0 to 29.4℃（homogenized into liquid） and salinities of 2.4-16.5 wt%NaCl eqv.The carbonic inclusions have T_（m,Co2）of-61.5 to-57.3℃,and T_（h,CO2） of-27.0to 28.7℃.The aqueous inclusions（L-V） have T_（m,ice） of-9.8 to-1.3℃ and T_（h,tot） of 205 to 412℃.The P-T trapping conditions of CO_2-rich fluid inclusions（100-370 MPa,250-368℃） are comparable with the late- to post-regional metamorphism conditions.The CO_2-rich fluids,possibly derived from regional metamorphism,were involved in the reworking and metal enrichment of the primary ores.Based on these results,the Talate Pb-Zn deposit is classified as a VMS deposit modified by metamorphic fluids.The massive Pb-Zn ores with banded and breccia structures were developed in the early period of submarine volcanic sedimentary exhalation associated with an extensional subduction-related back-arc basin,and the quartz veins bearing polymetallic sulfides were formed in the late period of metamorphic hydrothermal superimposition related to the Permian-Triassic continental collision.

Sources of the Laoxiongdong carbonate-hosted Pb–Zn deposit in Southwest China:constraints from S–Pb–Zn isotopic compositions

The Sichuan-Yunnan-Guizhou(SYG)Pb-Zn mineral province,which has significant Pb-Zn repositories in China,is situated in the western Yangtze Block.Despite decades of research,the Pb-Zn source of deposits is still disputed between the basement rocks,sedimentary wall rocks,or the Emeishan flood basalts.The newly-discovered Laoxiongdong Pb-Zn deposit is hosted by the Late Ediacaran Dengying Formation in the SYG province.Moreover,the Laoxiongdong orebodies lie between regional deep faults and close to the Proterozoic basement and Emeishan basalts.Hence,this deposit represents a good case study on the ore-forming material source for the regional Pb-Zn mineralization.The Laoxiongdong Pb-Zn ores are massive,vein,or disseminated and have mainly sphalerite,galena,pyrite,quartz,and calcite.In this paper,we present new sulfide S-Pb-Zn isotope data of the deposit.The sulfideδ34SCDT values(+11.8 to+16.5‰)suggest that the reduced sulfur was mainly sourced from evaporites in the Late Ediacaran-Cambrian sequences.Pb isotopic ratios(206Pb/204Pb=18.004-18.107,207Pb/204Pb=15.652-15.667,and 208Pb/204Pb=38.037-38.248)suggest that the lead metal was primarily originated from the basement rocks.The sphaleriteδ66Zn values(+0.16 to+0.37‰)are also highly similar(within error)to those of basement rocks(+0.10 to+0.34‰),suggesting a basement-rocks zinc source with minor contributions from the carbonate host rocks and Emeishan flood basalts.The narrow sphalerite Zn isotopic range(0.21‰)also indicates that the Zn isotopic fractionation between the sphalerite and initial fluid was limited during the sphalerite ore precipitation.Therefore,we propose that both the Late Ediacaran Dengying Formation rocks and Proterozoic basement rocks were important ore-forming material source for the Laoxiongdong deposit,whereas the Emeishan flood basalts represent only a minor ore-material source.

A Preliminary Review on the Metallogeny of Pb-Zn Deposits in China

Lead and zinc resources are abundant in China, with the reserves of 100 million tons ranking only second in the world. There are more than 3000 lead-zinc mine areas nationwide. The classification of lead-zinc （Pb-Zn） deposits has been a highly controversial issue. From the standpoint of evaluating the potential of mineral resources, we construct a Pb-Zn deposit predictive type of classification scheme, and propose a Pb-Zn deposit comprehensive classification scheme （including 5 classes and 13 sub-types） that regards mineralization as the primary factor and the ore rock as secondary. According to the temporal and spatial distribution of Pb-Zn deposits, we conclude that a multi-period, multi-cycle orogenic environment is the most favorable for lead-zinc deposit growth, that the Proterozoic is the major eon for the growth of igneous-type deposits, the Paleozoic is an important development era for sedimentary Pb-Zn deposits, and the Mesozoic and Cenozoic are the heyday eras of magmatic type lead-zinc deposits. On this basis, we analyse the relationship between tectonic evolution and Pb-Zn metallogenic, and propose that the key factors determining geological mineralization are the metallogenic epoch of mineralization and tectonic environment, which determine the temporal and spatial distribution.

Rare earth element(REE) geochemistry of different colored fluorites from the Baoshan Cu–Pb–Zn deposit, Southern Hunan,South China

The Baoshan Cu–Pb–Zn deposit, located in the central part of the Qin–Hang belt in South China, is closely related to the granodiorite-porphyry. However, the characteristics and the source of the ore-forming fluid are still ubiquitous. According to the crosscutting relationships between veinlets and their mineral assemblages, three stages of hydrothermal mineralization in this deposit were previously distinguished. In this contribution, two different colored fluorites from the major sulfide mineralization stage are recognized:(1) green fluorites coexisting with Pb–Zn ores;and(2) violet fluorites coexisting with pyrite ores. Y/Ho ratios verify the green fluorites and violet fluorites were co-genetic. The fluorites display elevated(La/Yb)Nratios, which decrease from 1201 to 5710 for green fluorites to 689–1568 for violet fluorites, indicating that they precipitated at the early hydrothermal sulfide stage,and Pb–Zn ores crystallized earlier than pyrite ores. The similar Tb/La ratios of the fluorites also indicate that they precipitated at an early stage within a short time. From the green fluorites to violet fluorites, the total rare earth element(ΣREE)concentrationsdecreasefrom1052–1680 ppm to 148–350 ppm, indicating that the green fluorites precipitated from a more acidic fluid. The Eu/Eu*ratios increase from 0.17 to 0.30 for green fluorites to0.29–0.48 for violet fluorites, and the Ce/Ce* ratios decrease from 1.08–1.13 to 0.93–1.11, suggesting a gradual increase in oxygen fugacity(fO_(2)) and pH value of the mineralization fluid. Though the fluorites display similar REE patterns to the granodiorite-porphyry and limestone,the ΣREE concentrations of the fluorites are significantly higher than those of limestone and the granodiorite-porphyry, suggesting that an important undetected non-magmatic source is involved to provide sufficient REE for fluorites. The most plausible mechanism is fluid mixing between magma fluid and an undetected non-magmatic fluid.

Fractal Modeling of Sphalerite Banding in Jinding Pb-Zn Deposit, Yunnan, Southwestern China

Sphalerite banding is a common texture in Jinding （金顶） Pb-Zn deposit, Yunnan （云南）, southwestern China. The frequency distribution and irregularity of sphalerite grains observed in the bandings are characterized quantitatively by fractal models. Fractal dimensions calculated by several fractal models including box-counting model, perimeter-area （P-A） model, and number-area （N-A） model show the gradual change from outer banding to inner banding, indicating a decrease in area percentage, in irregularity, in shape and in grain size, and an increase in the numbers of grains. These results may imply an inward growth of sphalerite during mineralization, and self-organization properties are involved in the nonlinear process of mineralization.

Conditions of Ore-Mineralization and Geochemical Correlation of Rare-Elements at the Robat Pb-Zn Deposit, West of Khomein, Central Iran

The Robat geological study area is located 32 Km west-northwest of Khomein town. From the geo-structural point of view, it is in the median part of the Sanandaj-Sirjan zone [1], and from the mineralization aspect it is part of the Malayer-Esfahan Pb-Zn metallogenic belt [2]. The main hostrock of Pb-Zn ore-mineralization at the Robat deposit is the upper parts of the orbitolina-bearing limestone at its contact with the overlying unit of marl. Ore mineralization is characterized by vein-veinlet, fracture-filling and replacement textures, associated with silica, carbonate, argillic and hematitic alterations [3]. Geochemical trends of minor elements in ore represent positive correlation of Sb, Ag, Cu, Bi, Sn, Fe, U, Th, W, V, Zr and Y with Pb and Zn. Fluid inclusion study of samples indicates that primary fluid inclusions mainly consist of liquid, having an average temperature of homogeneity in the range of 160°C to 270°C, having the most frequency in the range of 180°C to 190°C at an average of 5 to 10 wt% NaCl equivalent for salinity. Based on the graph of pressure variations versus salinity (representing paleo-depth), it is understood that ore-mineralization at the Robat deposit is estimated to have formed at less than 50 bars pressure representing depths shallower than 200 m. Fluid inclusion study renders that the low salinity could be resulted from dilution by meteoric waters, also indicating that boiling could be the major mineral precipitation process. Therefore, it is concluded, based on these studies, besides field evidence, that the Robat Pb-Zn deposit shows strong affinity with MVT Pb-Zn mineralization type.

Origin of Ore-Forming Fluids of Mississippi Valley-Type (MVT) Pb-Zn Deposits in Kangdian Area, China

Analyses of fluid\|inclusion leachates from ore deposits show that Na/Br ratios are within the range of 75-358 and Cl/Br 67-394, respectively, and this variation trend coincides with the seawater evaporation trajectory on the basis of the Na/Br and Cl/Br ratios. The average Cl/Br and Na/Br ratios of mineralizing fluids are 185 and 173 respectively, which are very close to the ratios (120 and 233) of the residual evaporated seawater past the point of halite precipitation. It is suggested that the original mineralizing brine was derived from highly evaporated seawater with a high salinity. However, the inclusion fluids have absolute Na values of \{69.9\}-\{2606.2\} mmol kg\+\{-1\} and Cl values of \{106.7\}-\{1995.5\} mmol kg\+\{-1\}. Most of the values are much less than those of seawater: Na, 485 mmol kg\+\{-1\} and Cl, 566 mmol kg\+\{-1\}, respectively; the salinity measured from fluid inclusions of the deposits ranges from \{2.47 wt%\} to \{15.78 wt%\} NaCl equiv. The mineralizing brine has been diluted. The \{δ\{\}\+\{18\}O\} and δD values of ore\|forming fluids vary from \{-8.21‰\} to \{9.51‰\} and from \{-40.3‰\} to \{-94.3‰\}, respectively. The δD values of meteoric water in this region varied from \{-80‰\} to \{-100‰\} during the Jurassic. This evidenced that the ore\|forming fluids are the mixture of seawater and meteoric water. Highly evaporated seawater was responsible for leaching and extracting Pb, Zn and Fe, and mixed with and diluted by descending meteoric water, which resulted in the formation of ores.

Geological significance of nickeliferous minerals in the Fule Pb–Zn deposit, Yunnan Province, China

The Fule Pb–Zn deposit is located in the Sichuan–Yunnan–Guizhou Province, and it is an important and giant low temperature metallogenic domain in China.In our research area, the Pb–Zn deposits are mainly hosted in the Permian Yangxin Formation and are composed of dolostone and limestone. The distance between the ore bodies and the Permian Emeishan basalt ranged from 50 to160 m. In this study, the nickel rich minerals, including vaesite, polydymite and millerite, were reported for the first time in the Fule deposit. These minerals occurred as xenomorphic mineral aggregate and were sporadically distributed in the sphalerite–galena–calcite vein, which is the main ore type in the deposit. Our study indicated that the paragenetic sequence of minerals in the Fule deposit is the following order: polydymite → vaesite→ millerite → sphalerite → galena → tetrahedrite(tennantite).The geological occurrence characteristics of those nickeliferous minerals suggested that the Permian Emeishan basalt is a possible barrier layer of Pb–Zn ore-forming fluid, and it is an important source for the Ni and part of the Cu in the deposit. The Sichuan–Yunnan–Guizhou Pb–Zn mineralization province is a world-class production base of Pb and Zn, in which the Permian Emeishan basalt and Pb–Zn deposits have uniformly spatial distribution, but the relationship of mineralization between them is still under debate. This report provides new evidence forunderstanding the relationship between Pb–Zn mineralization and Permian Emeishan basalt in the Sichuan–Yunnan–Guizhou Pb–Zn mineralization province.

Discovery of Wolitu Pb-Zn deposit through geochemical prospecting under loess cover in Inner Mongolia, China

We report the finding of the Wolitu Pb-Zn deposit in Inner Mongolia, China, through a series of geochemical surveys. The Wolitu area, located in the loess-cover area in the Hure Banner, Tongliao City,Inner Mongolia, and neighboring the Horqin Sandy Land to the north, had no previous history of Pb-Zn mining or record of Pb-Zn mineralization. Our study identified a large Pb-Zn anomaly with potential zones of mineralization by stream sediment survey. Random rock sampling reveals limonitization at sporadic outcrops in the gullies. The high concentrations of Pb in the residual debris provided guidelines to fix the position for exploratory trench. Oxidized concealed orebodies were identified by trenching.Blind orebodies in veins hosted within the structural zone between slates and marbles of the upper Carboniferous Shizuizi Formation and the Permian granite were discovered by drilling. It is computed that the ore reserve may reach up to 540,000 tones with Pb grade of 1.27% and Zn of 1.9%. This case study is an excellent example for identifying potential polymetallic deposits in loess covered terrains using geochemical exploration.

MANTLE SOURCE NATURE OF ORE FLUIDS FOR THE JINDING Pb-Zn DEPOSIT, LANPING, YUNNAN

Geological setting\;Jinding superlarge Pb\|Zn deposit lies in the Lanping basin between the Lancangjiang fracture zone and the Jinshajiang\|Ailaoshan fracture zone. The Lanping basin is a Meso\|Cenozoic rifting basin whose basement consists of the Paleozoic strata. Mesozoic paralic and continental sediments with a thickness of about 20000m deposited in the basin. In the Paleocene, gypsum\|salt\|bearing strata with a thickness of more than 1000m accumulated. In the Cenozoic, collision of the Indian plate with the Eurasian plate resulted in strong folding and napping and subsequent extensions in the Oligocene and Pliocene. The extensions were responsible for alkaline magmatic intrusion in the centre and alkaline magmatic extrusion in the east.Faulting is well developed. N\|S\|trending Bijiang fault with a length of 120km links with the Jinshajiang fracture zone in the north and with the Lancangjiang fracture zone in the south, controlling on the Cenozoic Lanping rifting basin and acting as passage\|way for ore fluids.