贵州普定纳雍枝铅锌矿矿床成因:S和原位Pb同位素证据

通过近五年(2011~2015)勘查实现找矿重大突破的贵州普定纳雍枝铅锌矿床,位于扬子陆块西南缘,五指山背斜南东翼北中部,是黔西北铅锌成矿区的重要组成部分。矿区内已发现20余个铅锌矿体,探获铅锌金属资源储量超135万吨,是川滇黔接壤铅锌矿集区贵州境内目前已发现和探明规模最大的铅锌矿床。主矿体多呈层状、似层状、透镜状和陡倾斜脉状产出,除了陡倾斜脉状矿体产于F7断层破碎带,其余(似)层状矿体均产于下寒武统清虚洞组和上震旦统灯影组白云岩中,与围岩产状一致,层控特征明显。其矿石类型主要有块状、角砾状、细脉状和浸染状等,矿石矿物以闪锌矿为主,其次为方铅矿和黄铁矿,脉石矿物以方解石、白云石为主,含少量石英,偶见重晶石。本次研究表明,该矿床硫化物δ~(34)S_(CDT)值介于15.94‰~25.49‰之间,均值为22.41‰(n=21),其中黄铁矿δ~(34)S_(CDT)值为22.06‰,闪锌矿δ~(34)S_(CDT)值为19.37‰~25.49‰,均值为23.17‰(n=17),方铅矿δ~(34)S_(CDT)值为15.94‰~19.70‰(n=3),均值为18.23‰。各类硫化物δ~(34)S值部分重叠,总体上不具有δ~(34)S黄铁矿δ~(34)S闪锌矿δ~(34)S方铅矿的特征,暗示硫同位素在硫化物矿物间的分馏未达到平衡。此外,矿石存有少量硫酸盐矿物(重晶石),暗示成矿流体的δ~(34)S3∑S值应高于硫化物的平均δ4S值(22.41‰),接近赋矿地层中海相硫酸盐岩的δ~(34)S值(22‰~28‰)。因此,成矿流体中的还原硫最可能为海相硫酸盐岩热化学还原的产物,来源于赋矿地层中的蒸发岩。应用飞秒激光剥蚀多接收器等离子体质谱法首次获得了纳雍枝铅锌矿中方铅矿原位Pb同位素数据,结果显示Pb同位素组成非常集中(~(206)Pb/204Pb=17.828~17.860,均值17.841,~(207)Pb/204Pb=15.648~15.666,均值15.659,~(208)Pb/204Pb=37.922~37.979,均值37.960,n=32),位于上地壳平均Pb演化曲线上,表明其成矿物质具壳源特征,可能来源于基底岩石。综合矿床地质、矿物学、S和原位Pb同位素数据,本文认为纳雍枝铅锌矿床S主要来源于其赋矿地层,Pb等金属元素主要来源于基底岩石,这两组流体的混合是导致其金属硫化物沉淀成矿的重要机制,成矿流体具后生、低温热液等特征,属于密西西比河谷型(MVT)矿床,很可能形成于燕山期,与右江盆地演化有关。     

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 δ~(18)O_(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 H_2O in the hydrothermal fluids sourced from metamorphic water.Calcite samples have δ~(13)C_(PDB) values ranging from-6.2‰ to-4.1‰ and δ~(18)O_(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 δ~(34)S_(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 ~(206)Pb/~(204)Pb,~(207)Pb/~(204)Pb and ~(208)Pb/~(204)Pb 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.     

青海沱沱河地区多才玛铅锌矿床成因:原位S和Pb同位素证据

青海沱沱河地区多才玛铅锌矿床是西南三江特提斯北段新生代铅锌矿集区的典型矿床之一,本文首次应用飞秒激光剥蚀多接受器等离子体质谱法对多才玛铅锌矿床中金属硫化物的原位S和Pb同位素进行了测定。结果显示:黄铁矿、方铅矿和闪锌矿的原位S同位素的δ~(34)S_(V-CDT)值介于-26.34‰～4.24‰之间,均值-12.15‰(n=20),其中闪锌矿的δ~(34)S_(V-CDT)值介于-10.30‰～-3.52‰,均值-7.39‰(n=9);方铅矿的δ~(34)S_(V-CDT)值为-26.34‰～-11.74‰,均值-20.36‰(n=9);黄铁矿的δ~(34)S_(V-CDT)值分别为2.50‰,4.24‰。矿床δ~(34)S数据范围较宽,总体表现为富集负值硫的特征,说明有机质可能参与成矿。岩浆热液期发育的黄铁矿δ~(34)S值具有深源特征,沉积热液期发育的方铅矿和闪锌矿的δ~(34)S值表明成矿过程存在还原作用,指示盆地地层还原流体的混入,综上可认为多才玛铅锌矿床硫具有混合来源的特征。方铅矿原位Pb同位素结果为~(206)Pb/~(204)Pb=18.866～18.929,~(207)Pb/~(204)Pb=15.674～15.689,~(208)Pb/~(204)Pb=39.052～39.174。方铅矿与地层的Pb同位素组成一致,位于上地壳平均Pb演化线之上,具上地壳和地幔混合俯冲带铅的特征,表明其成矿物质的来源多样。结合矿床学、矿物学及同位素数据,本文认为多才玛铅锌矿床S元素主要来源于赋矿围岩,Pb金属元素主要来源于藏北钾质火山岩,侵入地层岩浆与盆地流体的混合是金属硫化物沉淀的重要机制。     

H-O-S-Cu-Pb Isotopic Constraints on the Origin of the Nage Cu-Pb Deposit, Southeast Guizhou Province, SW China

The Nage Cu-Pb deposit,a new found ore deposit in the southeast Guizhou province,southwest China,is located on the southwestern margin of the Jiangnan Orogenic Belt.Ore bodies are hosted in slate and phyllite of Neoproterozoic Jialu and Wuye Formations,and are structurally controlled by EW-trending fault.It contains Cu and Pb metals about 0.12 million tonnes with grades of 0.2 wt% to 3.4 wt% Cu and 1.1 wt% to 9.27 wt% Pb.Massive and disseminated Cu-Pb ores from the Nage deposit occur as either veinlets or disseminations in silicified rocks.The ore minerals include chalcopyrite,galena and pyrite,and gangue minerals are quartz,sericite and chlorite.The H-O isotopic compositions of quartz,S-Cu-Pb isotopic compositions of sulfide minerals,Pb isotopic compositions of whole rocks and ores have been analyzed to trace the sources of ore-forming fluids and metals for the Nage Cu-Pb deposit.The δ65CuNBS values of chalcopyrite range from-0.09% to +0.33‰,similar to basic igneous rocks and chalcopyrite from magmatic deposits.δ65CuNBS values of chalcopyrite from the early,middle and final mineralization stages show an increasing trend due to63Cu prior migrated in gas phase when fluids exsolution from magma.δ34SCDT values of sulfide minerals range from 2.7‰ to +2.8‰,similar to mantle-derived sulfur(0±3‰).The positive correlation between δ65CuNBS and δ34SCDT values of chalcopyrite indicates that a common source of copper metal and sulfur from magma.δDH2OSMOW and δ18OH2O-SMOW values of water in fluid inclusions of quartz range from 60.7‰ to 44.4‰ and +7.9‰ to +9.0‰(T=260°C),respectively and fall in the field for magmatic and metamorphic waters,implicating that mixed sources for H2O in hydrothermal fluids.Ores and sulfide minerals have a small range of Pb isotopic compositions(208Pb/204Pb=38.152 to 38.384,207Pb/204Pb=15.656 to 17.708 and 206Pb/204Pb=17.991 to 18.049) that are close to orogenic belt and upper crust Pb evolution curve,and similar to Neoproterozoic host rocks(208Pb/204Pb=38.201 to 38.6373,207Pb/204Pb=15.648 to 15.673 and 206Pb/204Pb=17.820 to 18.258),but higher than diabase(208Pb/204Pb=37.830 to 38.012,207Pb/204Pb=15.620 to 15.635 and206Pb/204Pb=17.808 to 17.902).These results imply that the Pb metal originated mainly from host rocks.The H-O-S-Cu-Pb isotopes tegather with geology,indicating that the ore genesis of the Nage Cu-Pb deposit is post-magmatic hydrothermal type.     

Carbon-oxygen isotopic geochemistry of the Yangla Cu skarn deposit,SW China: Implications for the source and evolution of hydrothermal fluids

The Yangla Cu deposit is the largest Cu skarn deposit in the Jinshajiang tectonic belt. Based on the detailed observation of crosscutting relationships, three mineralization stages (i.e., pre-ore, ore and supergene) have been identified in the Yangla deposit. The pre-ore stage is dominated by prograde skarn. The ore stage is characterized by the precipitation of hydrous silicate minerals, Fe-oxides, Fe-Cu-Mo-sulfides, quartz and calcite, whose mineral assemblages were formed in the early and late sub-ore stages. The early sub-ore stage is marked by retrograde alteration with the deposition of hydrous silicate minerals (e.g., actinolite, epidote and chlorite), Fe-oxides, abundant Fe-Cu-Mo-sulfides, quartz and minor calcite. Whilst, the late sub-ore stage, associated with silicic and carbonate alteration, is represented by widespread thick quartz or calcite veins with disseminated pyrite, chalcopyrite, galena and sphalerite. We present new carbon-oxygen (C-O) isotopic compositions of the ore-hosting marble and hydrothermal calcite of this deposit. The hydrothermal calcite in the Yangla deposit was precipitated from both the early and late sub-ore stages. Calcite I from the early sub-ore stage is anhedral, and occurs as spot in the skarn or locally replaces the skarn minerals. Calcite II from the late sub-ore stage is distinguished by being coarse-grained, subhedral to euhedral and its occurrence in thick veins. Calcite I contains lower δ¹³C_PDB (−7.0‰ to −5.0‰) and δ¹⁸O_SMOW (7.2‰ to 12.7‰) than Calcite II (δ¹³C_PDB = −4.5‰ to −2.3‰; δ¹⁸O_SMOW = 10.7‰ to 19.4‰). In the δ¹³C_PDB vs. δ¹⁸O_SMOW diagram, the Calcite I and Calcite II data fall close to the igneous carbonatite field and between the fields of igneous carbonatite and marine carbonates, respectively. This suggests a dominantly magmatic origin for the early sub-ore fluids, and there might have been increasing carbonate wall rock involvement towards the late sub-ore stage. The ore-hosting marble (δ¹³C_PDB = −4.8‰ to −0.3‰; δ¹⁸O_SMOW = 10.2‰ to 23.9‰) also shows a positive δ¹³C_PDB vs. δ¹⁸O_SMOW correlation, which is interpreted to reflect the decreasing alteration intensity during the interactions between the hydrothermal fluids and ore-hosting carbonates. Simulated calculation suggests that both the Calcite I and Calcite II precipitated at 350 °C to 250 °C and 250 °C to 150 °C, respectively. We proposed that CO₂ degassing and water/rock interactions were likely the two major processes that precipitated the calcite and led to the observed C-O isotopic features of the Yangla Cu deposit.     

湘中龙山Au-Sb矿床成矿物质来源——来自S、Pb和Sr同位素证据

龙山Au-Sb矿床是湘中Au、Sb矿集区的代表性矿床,本文对其不同类型矿石、矿区围岩和区域地层进行了S、Pb、Sr同位素组成对比研究。矿石中硫化物的δ³⁴S值为-3.0‰～5.1‰,平均值2.3‰;矿区围岩的δ³⁴S值为4.0‰～5.9‰,平均值5.2‰;区域地层的δ³⁴S值为9.3‰～13.3‰,平均值11.3‰。矿石与矿区围岩、区域地层的硫同位素组成差别较大,矿石硫具岩浆来源特征。矿石中硫化物的²⁰⁶Pb/²⁰⁴Pb、²⁰⁷Pb/²⁰⁴Pb和²⁰⁸Pb/²⁰⁴Pb比值分别为16.992～18.457、15.392～15.722和37.586～38.960,矿区围岩的²⁰⁶Pb/²⁰⁴Pb、²⁰⁷Pb/²⁰⁴Pb和²⁰⁸Pb/²⁰⁴Pb比值分别为17.630～...     

四川乌斯河铅锌矿床成矿物质来源及矿床成因:来自原位S-Pb同位素证据

乌斯河铅锌矿床位于扬子板块西南缘,是川滇黔铅锌矿集区代表性大型铅锌矿床之一,估算资源量超过370万吨,Pb+Zn平均品位~15.7%。该矿床铅锌矿体主要呈层状、似层状、透镜状产于震旦系灯影组的白云岩地层中,其围岩蚀变较弱,以白云石化和方解石化为主。矿石类型主要包括块状、条带状、角砾状、脉状和浸染状等,其中矿物组成相对简单,以闪锌矿、方铅矿、白云石和方解石为主,含少量沥青和黄铁矿。该矿床地质地球化学研究程度相对较低,其成矿物质来源不清,致使该矿床存在热水沉积成因、喷流沉积-后期热液叠加改造以及MVT型等多种成因争议,难以建立统一成矿模式。本文对乌斯河铅锌矿床不同成矿阶段的硫化物（包括黄铁矿、闪锌矿和方铅矿）,开展原位硫和铅同位素地球化学研究,以查明该矿床的成矿物质来源、还原硫的形成机制和示踪成矿过程,为认识该类矿床铅锌成矿作用提供新地球化学依据。原位S同位素分析结果显示,乌斯河铅锌矿床硫化物的还原硫存在不同硫来源,成矿早阶段硫化物δ³⁴S值较低,介于+1.3‰~+14.2‰之间,暗示可能有来自于赋矿地层圈闭古油气系统中的H₂S;主成矿阶段硫化物相对富集重硫同位素,δ³⁴S值在+11.0‰~+23.3‰之间,表明其为赋矿地层的蒸发岩的热化学还原作用的产物。此外,硫化物的LA-MC-ICPMS原位Pb同位素组成分析显示,该矿床成矿金属元素主要来源于变质基底地层,水岩反应可能使赋矿地层贡献少量的成矿物质。综合矿区地质特征和已有的地球化学研究成果,本文认为乌斯河铅锌矿床属于MVT铅锌矿床,富Pb、Zn等成矿元素的流体与富H₂S的流体混合是该矿床金属硫化物沉淀的主要机制。

     

云南毛坪大型铅锌矿床成矿物质来源:原位S和Pb同位素制约

位于扬子板块西缘的川滇黔铅锌集区是我国重要的贱金属生产基地之一。矿集区中部的毛坪大型铅锌矿床,累计探明铅锌金属储量超过300万吨,Pb+Zn平均品位12%～30%,局部达45%,是矿集区内第二大铅锌矿床。矿体呈似层状、透镜状或脉状集中分布于猫猫山背斜NW倒转翼及其倾伏端NE向层间断裂带内。主要发育3个矿体(群),其中I号矿体(群)赋存于上泥盆统宰格组白云岩中,II号矿体(群)赋存于下石炭统摆佐组白云岩中,III号矿体(群)赋存于上石炭统威宁组白云岩中。矿石主要由闪锌矿、方铅矿和黄铁矿等矿石矿物及白云石和方解石(少量石英和重晶石)等脉石矿物组成,具有块状、浸染状或脉状构造及粒状、交代、共边、胶状、集合体或碎裂结构。可见,该矿床后生成矿特征明显。纳米离子探针(Nano SIMS)原位S同位素组成分析结果显示,细粒草莓集合体状黄铁矿和胶状闪锌矿明显亏损34S,其δ34S值变化范围为-20. 4‰～-8. 7‰之间,具有典型生物成因S特征,暗示经历了海相硫酸盐细菌还原过程(BSR);而自形粒状黄铁矿和他形粒状闪锌矿的δ34S值变化范围为22. 1‰～25. 6‰之间,明显富集重S同位素,表明经历了海相硫酸盐热化学还原过程(TSR)。由于BSR和TSR过程主要受温度控制,因此,还原态硫离子的形成最可能是原地还原的,并先经历了相对低温的BSR过程,再经历了相对高温的TSR过程。飞秒激光剥蚀多接收器等离子体质谱(fs LA-MC-ICPMS)原位Pb同位素组成分析结果显示,方铅矿的Pb同位素组成相当均一,暗示其来源单一或混合均匀,对比显示其成矿金属主要由赋矿沉积岩提供,受到一定程度的下伏基底岩石影响。此外,方铅矿的原位Pb同位素组成有随着标高增加而升高的趋势,暗示成矿流体的运移方向很可能是向上的,且随着成矿流体的演化,富放射性成因Pb的赋矿沉积岩贡献了更多的成矿金属。综上,本文认为毛坪大型铅锌矿床是流体混合作用的产物,其深部可能具有良好的找矿潜力,这是因为富含金属元素的基底岩石对深部贡献更多。     

Mineralization age and sources of ore‐forming material of the Nanmushu Zn‐Pb deposit in the Micangshan Tectonic Belt at the northern margin of the Yangtze Craton,China: Constraints from Rb‐Sr dating and Sr‐Pb isotopes

The Nanmushu Zn‐Pb deposit, hosted by the Neoproterozoic Dengying Formation dolostone, is located in the eastern part of the Micangshan tectonic belt at the northern margin of the Yangtze Craton, China. This study involves a systematic field investigation, detailed mineralogical study, and Rb‐Sr and Pb isotopic analyses of the deposit. The results of Rb‐Sr isotopic dating of coexisting sphalerite and galena yield an isochron age of 486.7 ± 3.1 Ma, indicating the deposit was formed during the Late Cambrian to Early Ordovician. This mineralization age is interpreted to be related to the timing of destruction of the paleo‐oil reservoir in the Micangshan tectonic belt. All initial ⁸⁷Sr/⁸⁶Sr ratios of sphalerite and galena (0.70955–0.71212) fall into the range of the Mesoproterozoic Huodiya Group basement rocks (0.70877–0.71997) and Dengying Formation sandstone (0.70927–0.71282), which are significantly higher than those of Cambrian Guojiaba Formation limestone (0.70750–0.70980), Cambrian Guojiaba Formation carbonaceous slate (0.70766–0.71012), and Neoproterozoic Dengying Formation dolostone (0.70835–0.70876). Such Sr isotope signatures suggest that the ore strontium was mainly derived from a mixed source, and both of the Huodiya Group basement rocks and Dengying Formation sandstone were involved in ore formation. Both sphalerite and galena are characterized by an upper‐crustal source of lead (²⁰⁶Pb/²⁰⁴Pb = 17.849–18.022, ²⁰⁷Pb/²⁰⁴Pb = 15.604–15.809, and ²⁰⁸Pb/²⁰⁴Pb = 37.735–38.402), and their Pb isotopes are higher than, but partly overlap with, those of the Huodiya Group basement rocks, but differ from those of the Guojiaba and Dengying Formations. This suggests that the lead also originated from a mixed source, and the Huodiya Group basement rocks played a significant role. The Sr and Pb isotopic results suggest that the Huodiya Group basement rocks were one of the most important sources of metallogenic material. The geological and geochemical characteristics show that the Nanmushu Zn‐Pb deposit is similar to typical Mississippi Valley type, and the fluid mixing may be a reasonable metallogenic mechanism for Nanmushu Zn‐Pb deposit.     

华北克拉通北部古-中元古代富碱侵入岩的Nd、Sr、Pb同位素地球化学：岩石圈地幔富集的证据

华北克拉通北部古-中元古代富碱侵入岩主要分布在燕辽三叉裂堑系和辽吉拗拉谷中及附近,为一套高碱高钾的基性-中性岩,以正长岩类为主。本文通过开展系统的 Nd、Sr、Pb 同位素研究,发现所有岩体岩石均以高负ε_(Nd)(t)为特征,ε_(Nd)(t)=-3.4～-7.5,平均值为～4.8,这与研究区古-中元古代基性-超基性岩石的 Nd 同位素特征(ε_(Nd)(t)=-4～-8) 一致,与燕辽裂堑系发育的偏碱性火山岩 Nd 同位素特征(ε_(Nd)(t)=-4.3～-8.9)也比较相似,表明它们的物质来源相似,都与富集地幔有关。Sr 同位素初始比值(~(87)St/~(86)Sr)_i比较低,主要变化在0.7028～0.7053之间,平均值为0.7041。钾长石铅同位素组成普遍较低,~(206)Pb/~(204)Pb、~(207)pb/~(204)Pb、~(208)Pb/~(204)Pb 比值变化范围(梁屯-矿洞沟岩体除外)分别为14.500～15.70l、14.887～15.150和34.178～36.537,平均值分别为14.968、14.984和35.057。在ε_(Nd)(t)-ε_(Sr)(t)图解上,所有岩体的投影点均在地幔演化趋势线附近,比较接近 EMI 型富集地幔端员,暗示它们的物质来源与 EMI 型富集地幔有关;钾长石 Pb 同位素模式图也说明这些岩体物质来源与地幔和下地壳有关。通过两端员混合模拟,揭示了岩浆演化过程中存在少量的下地壳物质混染,平均约14%左右。从2.5Ga 左右开始华北克拉通岩石圈地幔的亏损程度逐渐变小,在2.2Ga 左右局部呈现富集性特征,1.85Ga时整个岩石圈地幔已经完全转变为富集性,之后富集程度越来越高。推测早期俯冲携带的壳源物质以及后期地幔流体的交代作用可能是岩石圈地幔逐渐转变为富集性的原因。     

湖南花垣铅锌矿床成矿物质来源与成矿机制——来自S、Pb、Sr同位素的证据

湖南花垣铅锌矿床位于扬子地台东南缘,是湘西—黔东地区最典型的超大型铅锌矿床,已探明铅锌储量超过500×10~4t,其预测资源量逾1800×104t。报道了该矿床主要矿石硫化物的S、)Pb同位素研究成果,结合前人的Sr同位素数据,分析了矿床的成矿物质来源,并探讨了成矿机制。硫化物的δ~(34)S值变化范围较小,为24.5‰~34.7‰,平均值为30.2‰,硫来源于各时代碳酸盐地层中硫酸盐热化学还原作用(TSR),有机质在还原反应过程中发挥了重要作用;硫化物的~(206))Pb/~(204))Pb、~(207)Pb/~(204)Pb、~(208)Pb/~(204)Pb值分别为18.139~18.678、15.691~15.832、38.300~39.255,变化范围较小,具有上地壳来源的特点,赋矿地层下部具有高)Pb-Zn含量的地层为成矿提供了大量的金属物质;闪锌矿的~(87)Sr/~(86)Sr值变化范围为0.70915~0.70996,高于赋矿地层清虚洞组灰岩的Sr同位素比值(0.70885~0.70909),表明成矿流体可能流经围岩及基底地层,从而引起Sr同位素比值因混染作用而升高;矿石矿物的沉淀机制为2种流体的混合,即含金属物质的成矿溶液与富含有机质、硫酸盐的热水溶液在合适的部位汇合,并发生反应。     

Sources of Cretaceous Bimodal Volcanic Rocks in the Coastal Region of Southeastern China: — Constraints of the Sr content and its isotopes

Abstract Cretaceous volcanism in the coastal region of southeastern China was characteristized by occurrence of bimodal volcanics consisting of basalts and rhyolites, the geneses of which are still controversial. Based on the fact that their isotopic compositions are similar but the Sr content of the former is much higher than that of the latter, this paper discusses the respective sources of the two end-member rocks, and concludes that basalts were derived from the subduction-related enriched upper mantle wedge and their isotopic compositions had not been affected by crustal assimilation, whereas rhyolites were formed by remelting of the old metamorphic basement, but they were mixed up with the underplating basaltic magmas to various degrees so that their Sr isotopic compositions varied significantly from the sources and tended to be homogeneous to the latter.     

Geochronological framework and Pb, Sr isotope geochemistry of the Qingchengzi Pb–Zn–Ag–Au orefield, Northeastern China

The Qingchengzi orefield in northeastern China, is a concentration of several Pb–Zn, Ag, and Au ore deposits. A combination of geochronological and Pb, Sr isotopic investigations was conducted. Zircon SHRIMP U–Pb ages of 225.3 ± 1.8 Ma and 184.5 ± 1.6 Ma were obtained for the Xinling and Yaojiagou granites, respectively. By step-dissolution Rb–Sr dating, ages of 221 ± 12 Ma and 138.7 ± 4.1 Ma were obtained for the sphalerite of the Zhenzigou Zn–Pb deposit and pyrargyrite of the Ag ore in the Gaojiabaozi Ag deposit, respectively. Pb isotopic ratios of the Ag ore at Gaojiabaozi (²⁰⁶Pb/²⁰⁴Pb = 18.38 to 18.53) are higher than those of the Pb–Zn ores (²⁰⁶Pb/²⁰⁴Pb = 17.66 to 17.96; Chen et al. [Chen, J.F., Yu, G., Xue, C.J., Qian, H., He, J.F., Xing, Z., Zhang, X., 2005. Pb isotope geochemistry of lead, zinc, gold and silver deposit clustered region, Liaodong rift zone, northeastern China. Science in China Series D 48, 467–476.]). Triassic granites show low Pb isotopic ratios (²⁰⁶Pb/²⁰⁴Pb = 17.12 to 17.41, ²⁰⁷Pb/²⁰⁴Pb = 15.47 to 15.54, ²⁰⁸Pb/²⁰⁴Pb = 37.51 to 37.89) and metamorphic rocks of the Liaohe Group have high ratios (²⁰⁶Pb/²⁰⁴Pb = 18.20 to 24.28 and 18.32 to 20.06, ²⁰⁷Pb/²⁰⁴Pb = 15.69 to 16.44 and 15.66 to 15.98, ²⁰⁸Pb/²⁰⁴Pb = 37.29 to 38.61 and 38.69 to 40.00 for the marble of the Dashiqiao Formation and schist of the Gaixian Formation, respectively).Magmatic activities at Qingchengzi and in adjacent regions took place in three stages, and each contained several magmatic pulses: ca. 220 to 225 Ma and 211 to 216 Ma in the Triassic; 179 to 185 Ma, 163 to 168 Ma, 155 Ma and 149 Ma in the Jurassic, as well as ca. 140 to 130 Ma in the Early Cretaceous. The Triassic magmatism was part of the Triassic magmatic belt along the northern margin of the North China Craton produced in a post-collisional extensional setting, and granites in it formed by crustal melting induced by mantle magma. The Jurassic and Early Cretaceous magmatism was related to the lithospheric delamination in eastern China. The Triassic is the most important metallogenic stage at Qingchengzi. The Pb–Zn deposits, the Pb–Zn–Ag ore at Gaojiabaozi, and the gold deposits were all formed in this stage. They are temporally and spatially associated with the Triassic magmatic activity. Mineralization is very weak in the Jurassic. Ag ore at Gaojiabaozi was formed in the Early Cretaceous, which is suggested by the young Rb–Sr isochron age, field relations, and significantly different Pb isotopic ratios between the Pb–Zn–Ag and Ag ores. Pb isotopic compositions of the Pb–Zn ores suggest binary mixing for the source of the deposits. The magmatic end-member is the Triassic granites and the other metamorphic rocks of the Liaohe Group. Slightly different proportions of the two end-members, or an involvement of materials from hidden Cretaceous granites with slightly different Pb isotopic ratios, is postulated to interpret the difference of Pb isotopic compositions between the Pb–Zn–(Ag) and Ag ores. Sr isotopic ratios support this conclusion. At the western part of the Qingchengzi orefield, hydrothermal fluid driven by the heat provided by the now exposed Triassic granites deposited ore-forming materials in the low and middle horizons of the marbles of the Dashiqiao Formation near the intrusions to form mesothermal Zn–Pb deposits. In the eastern part, hydrothermal fluids associated with deep, hidden Triassic intrusions moved upward along a regional fault over a long distance and then deposited the ore-forming materials to form epithermal Au and Pb–Zn–Ag ores. Young magmatic activities are all represented by dykes across the entire orefield, suggesting that the corresponding main intrusion bodies are situated in the deep part of the crust. Among these, only intrusions with age of ca. 140 Ma might have released sufficient amounts of fluid to be responsible for the formation of the Ag ore at Gaojiabaozi.Our age results support previous conclusions that sphalerite can provide a reliable Rb–Sr age as long as the fluid inclusion phase is effectively separated from the “sulfide” phase. Our work suggests that the separation can be achieved by a step-resolution technique. Moreover, we suggest that pyrargyrite is a promising mineral for Rb–Sr isochron dating.     

Constraints of Sr isotopic compositions of apatite and carbonates on the origin of Fe and Cu mineralizing fluids in the Lala Fe-Cu-(Mo,LREE) deposit,SW China

Numerous Fe-Cu deposits with mineralization styles similar to iron oxide-copper gold (IOCG) deposits form the Kangdian Fe-Cu metallogenic province, southwestern (SW) China. As one of the largest deposits in the region, the ~ 1.0 Ga Lala Fe-Cu deposit is hosted in a Paleoproterozoic volcanic-sedimentary succession named the Hekou Group which is alternately intruded by ~ 1.0 Ga doleritic plutons. This deposit has a paragenetic sequence evolving from Stage I of Na-alteration to Stage II of Fe mineralization, and finally to Stage III of Cu-(Mo, REE) mineralization, coeval with mafic-felsic intra-plate magmatism in the region. This study conducted in-situ Sr isotopic analyses on apatite and carbonate, aiming to resolve the long controversial issue regarding the origin of the Fe and Cu mineralizing fluids in the deposit. Apatite of Stage II has ⁸⁷Sr/⁸⁶Sr ratios varying from 0.71380 to 0.72733, much higher than those of synchronous igneous rocks in the region (0.7074 to 0.7091), but similar to the Paleoproterozoic host rocks (0.71368 to 0.71837 at ~ 1.0 Ga). This similarity indicates that radiogenic Sr of the Fe mineralizing fluid was dominantly sourced from the host rocks. Apatite and calcites of Stage III have ⁸⁷Sr/⁸⁶Sr ratios (0.75758–0.79293) much higher than apatite of Stage II and the host rocks but similar to the Archean basement rocks (as high as 0.80 at ~ 1.0 Ga) beneath the cover of the Yangtze Block, suggesting that the highly radiogenic Sr isotopic composition of the Cu mineralizing fluid was mainly inherited from the old basement rocks. In combination with previous C-O-S isotopic data indicating a magma-hydrothermal origin, it was suggested that the Fe mineralizing fluid was exsolved from a mafic magma that generated the ~ 1.0 Ga doleritic plutons, and inherited radiogenic Sr from the host rocks during fluid-rock interaction. By contrast, the Cu mineralizing fluid might have been sourced from another pulse of magmatic, Cu-Mo-REE- and CO₂-rich fluid which have once interacted with Archean basement rocks prior to mineralization. The source of such a Cu-Mo-REE-rich fluid was not well constrained in current study but was inferred to be exsolved from a hidden felsic magma. We propose that intrusions of the bimodal magmas in Kangdian are responsible for regional hydrothermal circulation which led to Fe-Cu-(Mo, REE) mineralization in the Kangdian province.     

C, O, S and Sr isotope studies on the genesis of Fe-carbonate and barite mineralizations in the Attepe iron district (Adana, Southern Turkey)

The Attepe district consists of Precambrian, Lower–Middle Cambrian, Upper Cambrian–Lower Ordovician and Mesozoic formations. It contains several iron deposits and occurrences. Three types of iron-mineralizations can be distinguished in the area; (i) Sedimentary Fe-sulfide in Precambrian bituminous metapelitic rocks, and Fe-oxides in Precambrian metasandstones (SISO), (ii) vein-type Fe-carbonate and oxides composed of mainly siderite, ankerite and hematite including barite in Lower–Middle Cambrian metacarbonates of the Çaltepe Formation (HICO), (iii) karstic Fe-oxides and hydroxides essentially in the Lower–Middle Cambrian metacarbonates and the unweathered Fe-carbonates (KIO). The latter type is more widespread and located at the upper parts of the most important mineable iron deposits like Attepe deposit.

Oxygen-, carbon-, sulfur- and strontium-isotope studies have been performed on siderites and barites in the vein-type ores, and on calcites in the recrystallized Çaltepe Limestones to investigate the sources and formation mechanism of primary ore-forming constituents. The δ¹³C values of siderites and calcites in limestones of the Çaltepe Formation range from −10.10‰ to −8.20‰, and from −0.8‰ to 2.30‰. Both carbonate minerals show δ¹⁸O values between 17.50–18.30‰ and 16.20–23.00‰, respectively. The δ¹³C and δ¹⁸O isotopic variations do not indicate any direct or linear relations between siderites and limestones. However, it is possible that the carbon and oxygen isotopic compositions of carbonate minerals could be changed to some extent, when limestones were subjected to hydrothermal processes or thermal alterations during metamorphism.

The isotopic values of barites display 32.40–38.30‰ for δ³⁴S and 12.20–14.70‰ for δ¹⁸O. The strontium isotope ratios (0.717169–0.718601) of barites and the sulfur isotope compositions of barites and pyrites suggest that there are no direct linkages of ore-forming compounds neither with a magmatic source nor with sedimentary pyrite formations in the Precambrian bituminous shales of the Attepe formation.

According to the field observations and the stable isotope data, siderites and ankerites should be formed by interaction between iron-rich hydrothermal fluids and Çaltepe limestones, whereas isotope ratios of barites indicate that they were formed by mixing of sulfur-rich meteoric waters and deeply circulated hydrothermal solutions.     

40Ar/39Ar dating,fluid inclusions and S–Pb isotope systematics of the Shabaosi gold deposit,Heilongjiang Province,China

The Shabaosi deposit is the only large lode gold deposit in the northern Great Xing'an Range. The gold ore bodies are hosted by sandstone and siltstone of the Middle Jurassic Ershi'erzhan Formation, and are controlled by three N–S‐trending altered fracture zones. The gold ore bodies are composed of auriferous quartz veinlets and altered rocks. Fluid inclusion studies indicate that the ore‐forming fluids belong to a H₂O–NaCl–CO₂–CH₄ system, with salinities between 0.83 and 8.28 wt% NaCl eq., and homogenization temperatures ranging from 180 to 320 °C. The δ³⁴S values of sulphides show a large variation from −16.9‰ to 8.5‰. The Pb isotope compositions of sulphides are characterized by a narrow range of ratios: 18.289 to 18.517 for ²⁰⁶Pb/²⁰⁴Pb, 15.548 to 15.625 for ²⁰⁷Pb/²⁰⁴Pb, and 38.149 to 38.509 for ²⁰⁸Pb/²⁰⁴Pb. The μ values range from 9.36 to 9.51. These results suggest that the ore‐forming fluids/materials were mainly of magmatic hydrothermal origin, derived from magmas produced by partial melting of the lower crust. The ⁴⁰Ar/³⁹Ar age of auriferous quartz veinlets from the Shabaosi gold deposit is about 130 Ma. The Shabaosi gold deposit has counterparts in similar orogenic gold deposits, and was formed during the post‐collisional setting of the Mongolia–Okhotsk Orogen. Copyright © 2014 John Wiley & Sons, Ltd.     

Hydrochemical and isotope characteristics of spring water and travertine in the Baishuitai area (SW China) and their meaning for paleoenvironmental reconstruction

A method of combining hydrochemical data logging and in situ titrating with measurement of stable carbon and oxygen isotopes was used to reveal the hydrochemical and isotopic characteristics in the Baishuitai travertine scenic area of SW China. It was found that the travertine-forming springs have a very high concentration of calcium and bicarbonate, and accordingly very high CO₂ partial pressures, which are not likely to be produced by biological activity in soil alone. Further analysis of the stable carbon isotopes of the springs shows that the high pressure of CO₂ is mainly related to an endogenic CO₂ source. That means the Baishuitai travertine is endogenic in origin. This is contrast to the commonly accepted saying that the travertine deposition in this study simply is a product of warm and humid conditions in a karst ecological environment. Rapid CO₂ degassing from the water is triggered by the much higher partial pressures in water than that of the surrounding air. Consequently, as the waters flow downstream of the spring the pH increases, the waters become supersaturated with respect to calcite, and travertine is deposited. The preferential release of ¹²CO₂ to the atmosphere results in a progressive increase of travertine ¹³C downstream. This is concluded with a preliminary discussion of variation in travertine-forming water temperatures, according to differences in stable oxygen isotopic compositions of the travertine formed in different epochs at Baishuitai. It was found that the change in water temperature is as high as 13 °C, i.e., from 23 °C at about 2500 years b.p., to 10 °C at present. This may mainly reflect that the effect of geothermal source on water temperature is decreasing. The problems involved in paleoenvironmental reconstruction with endogene travertine are also discussed. They are the impacts of "dead carbon" in radiocarbon dating and the enrichment in ¹³C of travertine by endogenic CO₂ and degassing of CO₂ from water, which has to be considered in paleovegetation reconstruction when using ¹³C data of the endogene carbonate deposits.     

Genesis of Pb–Zn Mineralization Beneath the Xiangshan Uranium Orefield,South China: Constraints from H–O–S–Pb Isotopes and Rb–Sr Dating

The volcanic‐hosted Xiangshan uranium orefield is the largest uranium deposit in South China. Recent exploration has discovered extensive Pb–Zn mineralization beneath the uranium orebodies. Detailed geological investigation reveals that the major metallic minerals include pyrite, sphalerite, galena, and chalcopyrite, whilst the major non‐metallic minerals include quartz, sericite, and calcite. New δ¹⁸O_fluid and δD_fluid data indicate that the ore‐forming fluids were mainly derived from magmatic, and the sulfide δ³⁴S values (2.2–6.9‰) suggest a dominantly magmatic sulfur source. The Pb isotope compositions are homogeneous (²⁰⁶Pb/²⁰⁴Pb = 18.120–18.233, ²⁰⁷Pb/²⁰⁴Pb = 15.575–15.698, and ²⁰⁸Pb/²⁰⁴Pb = 37.047–38.446). The ⁸⁷Sr/⁸⁶Sr ratios of sulfide minerals range from 0.7197 to 0.7204, which is much higher than volcanic rocks and fall into the range of metamorphic basement. Lead and strontium isotopic compositions indicate that the metallogenic materials probably were derived from metamorphic basement. Pyrite Rb–Sr dating of the ores yielded 131.3 ± 4.0 Ma, indicating that the Pb–Zn mineralization occurred in the Early Cretaceous.