小秦岭东桐峪金矿床黄铁矿LA-ICP-MS微量元素特征及其成矿意义

位于华北克拉通南缘的小秦岭地区是我国仅次于胶东的大型金矿床集中区,但金矿床的成矿物质来源及成因问题一直存在较大争议.以华北南缘小秦岭矿集区东桐峪金矿床中的黄铁矿作为研究对象,在黄铁矿显微结构研究的基础上利用LA-ICP-MS对黄铁矿的微量元素进行原位分析,为进一步认识东桐峪金矿床及区内其他同类型矿床的成因提供新的资料和制约.东桐峪金矿床的黄铁矿从早到晚依次划分为3个世代(PyⅠ、PyⅡ和PyⅢ).PyⅠ主要形成于粗粒黄铁矿-石英阶段,颗粒粗大且自形程度高,呈星点状或斑点状赋存于乳白色石英脉中.PyⅡ主要形成于石英-中细粒黄铁矿阶段,呈半自形-他形结构且裂隙发育,常被晚期石英、多金属硫化物、自然金等矿物充填.PyⅢ主要形成于多金属硫化物阶段,常呈他形粒状结构与黄铜矿、方铅矿及闪锌矿等硫化物密切共生.LA-ICP-MS分析结果显示,PyⅠ中As平均含量为16.63×10-6,Au、Ag和Te含量较低且常位于检测限以下;相较而言,PyⅡ中As含量稍低,而Au、Ag和Te含量略高(其中Au含量为0.10×10-6~0.59×10-6);PyⅢ中Au、Ag和Te含量差异较大且显著升高,其中Au、Te含量最高可达35.58×10-6和79.79×10-6,而As含量较低且大部分数值低于检测限;不同世代黄铁矿的Co/Ni比值基本上都大于1,且PyⅢ的Co、Ni含量和Co/Ni比值明显低于PyⅡ和PyⅠ.以上结果表明,东桐峪金矿床的载金矿物黄铁矿中As的含量很低,金的富集与As无关;不同世代的黄铁矿中Au、Ag和Te之间存在显著且稳定的线性正相关关系,暗示金矿化与Te关系密切.另外,第3世代黄铁矿(PyⅢ)中Au、Ag及Te存在显著富集,指示Te(而不是As)在金和银的迁移、搬运、富集、沉淀等过程中具有重要作用.华北克拉通南缘小秦岭地区晚中生代大规模的金成矿作用及金矿床中普遍存在Te-Au-Ag矿物,且黄铁矿中As含量低、Te含量高等特征,暗示该区金矿床的成矿物质/成矿流体可能来自深部岩浆的脱挥发分或地幔脱气作用,而与区域变质作用的关系不大.      

Implications of pyrite geochemistry for gold mineralisation and remobilisation in the Jiaodong gold district,northeast China

The Jiaodong gold district of eastern China, the largest gold producing district in China, is located on the eastern margin of the North China Craton. It consists of three mineralisation belts: the western Zhao-Ye belt, the middle Qixia belt, and the eastern Muping–Rushan (Muru) belt. Over 85% of mineralisation is hosted in the Zhao-Ye belt, which is bordered by the mantle-tapping Tan Lu fault zone. Pyrite crystals from three deposits in the Zhao-Ye belt and three deposits in the Muru belt were studied using a combination of optical petrography, bulk pyrite geochemistry, and in-situ laser ablation ICP-MS. Results show that although mineralisation is broadly similar between the two belts, there are significant differences in ore and gangue mineral textures, pyrite geochemistry, and style of gold mineralisation.Texturally, pyrite grains from the Zhao-Ye belt are generally cubic and do not exhibit zoning. In contrast, Muru pyrite grains are more often pyritohedral, commonly exhibit well-defined concentric zoning, and display textures in ore and gangue minerals indicative of open space growth. Bulk pyrite geochemistry suggests a distinct enrichment in Pb, Bi, Au, Ag and Te in the Zhao-Ye belt, whereas the Muru belt pyrite is significantly enriched in As, Cu and Co. In situ pyrite geochemistry indicates that Au and As are variably correlated in the Zhao-Ye belt, typically only exhibiting correlation at low Au concentrations. Most gold occurs as visible electrum along pyrite fractures and grain boundaries, with a minor generation of invisible gold formed through As-facilitated uptake into pyrite. In the Muru belt, Au and As have a strong correlation and there is limited occurrence of gold particles, indicating that most gold in the Muru belt is invisible gold contained in the crystal structure of As-rich pyrite.The differences in style of gold mineralisation between the belts indicates an inherent difference in timing of gold introduction: in the Zhao-Ye belt, the visible electrum accounting for most of the gold endowment is formed post-pyrite, whereas the invisible gold in the Zhao-Ye and Muru belts is formed syn-pyrite. The heterogeneity in gold distribution in the Jiaodong district is attributed to melting of metallogenically fertile Archean crust at the base of the well-endowed Zhao-Ye belt, and the lack of a similarly fertile source region beneath the Muru belt.     

胶东三山岛金矿床黄铁矿原位微区微量元素特征及对矿床成因的指示

胶东地区是我国最大金成矿聚集区,其金矿床的成因长期以来一直存在很大争议,三山岛金矿床是胶东地区最大的金矿床,通过采用LA-ICP-MS分析不同阶段黄铁矿中微量元素组成,可以探讨成矿流体演化及成矿物质来源。根据野外地质特征及岩相学观察,结合SEM结构分析将三山岛金矿床的黄铁矿分为3个阶段,6个亚类,即黄铁绢英岩化带(Py1)中包裹大量绢云母和石英的Py1-a和表面光滑的Py1-b,石英—黄铁矿±菱铁矿脉(Py2)中富含矿物包裹体的Py2-a和与菱铁矿共生且表面光滑的Py2-b,石英—多金属硫化物脉(Py3)中有很多细粒多金属硫化物包裹体的Py3-a和表面光滑的Py3-b。3个阶段黄铁矿晶格中金含量均很低,大部分小于1×10^-6,金主要以可见金形式存在。从早阶段到晚阶段黄铁矿中Au与Ag,Cu,Pb,Sb有较好的正相关性,且含量有逐渐增加的趋势。最早阶段黄铁矿中Co+Ni的含量很高(最高为9268×10^-6),反映了早期黄铁矿可能来源于岩浆岩源区,后期Co/Ni值逐渐降低,暗示了成矿流体温度逐渐降低。结合地质特征和黄铁矿微量元素研究,表明三山岛金矿床成矿物质可能来源于深部岩浆热液储库,通过地震泵机制沿断裂构造多次侵位成矿。     

胶东三山岛金矿床黄铁矿显微结构和微量元素特征:对金富集机制的指示

三山岛金矿床是位于胶东金矿集区西北部的超大型破碎带蚀变岩型金矿床.该矿床细致的矿相学及元素地球化学研究尚有不足,限制了对其金富集机制及过程的理解.基于野外地质调查和室内矿相学研究将该矿床划分为4个成矿阶段:石英?绢云母?黄铁矿阶段(I)、石英?金?黄铁矿阶段(I I)、石英?金?多金属硫化物阶段(I I I)和碳酸盐?...     

西南天山阿沙哇义金矿载金矿物地球化学特征及地质意义

阿沙哇义金矿床是中国新疆西南天山目前探明的第二大金矿，是中亚造山带南缘"亚洲金腰带"的重要组成部位。野外构造调查表明，研究区在古生代期间经历了由挤压变形发展为走滑伸展两次构造作用，成矿发生在挤压变形到走滑伸展转换时期。运用矿相学、电子探针、扫描电镜及S同位素等方法确定矿床载金矿物、金的赋存状态、成矿物质来源等，结果表明:阿沙哇义金矿载金矿物主要为含砷黄铁矿、部分毒砂。含砷黄铁矿分为沉积成岩期（Py1）、成矿早期（Py2）、成矿期（Py3）；Py2、Py3富As、Te，亏S、Fe，S、As呈明显负相关；Co/Ni比值显示黄铁矿属沉积-热液成因。Au以纳米级"可见"自然金（Au0）形式存在于含砷黄铁矿中。黄铁矿、辉锑矿δ34S为9.5‰~16.3‰，显示成矿流体中硫为海相硫酸盐热化学还原产物，成矿物质来自赋矿地层。矿床属典型的中浅成造山型金矿，矿床埋藏较浅，矿区深部具有很好的找矿潜力。      

吉尔吉斯斯坦Taldybulak Levoberezhny(左岸)金矿地质特征及金属矿物学研究

Taldybulak Levoberezhny(又称左岸)矿床位于吉尔吉斯斯坦北天山东段,是区内第三大金矿(金储量130 t,平均品位6.9 g/t)。长期以来,该矿床矿物学研究薄弱,成因类型存在争议,已有观点包括斑岩型、造山型、多阶段叠加成矿等。野外地质调查及室内岩相学鉴定发现：金矿化同时受韧性剪切带和岩体控制,局部显示一定的顺层特征;常见矿石类型包括浸染细脉浸染型、石英电气石硫化物型、块状硫化物型、稀疏浸染型、方解石硫化物脉型等;相关围岩蚀变以硅化、绢云母化、电气石化、碳酸盐化最为强烈,可见绿泥石化、绿帘石化、泥化等。电子探针分析发现,左岸金矿同时发育可见金和不可见金。前者包括银金矿(w(Au)=67.90%~80.86%,w(Ag)=14.24%~30.76%)、含银自然金(w(Au)=88.95%,w(Ag)=8.09%)等,以包体金、裂隙金或粒间金形式赋存于黄铁矿中。后者可赋存于黄铁矿和黄铜矿中(w(Au)=0.16%~0.33%)。不同类型矿石中黄铁矿的形态、结构、成分存在一定差异,显示了叠加成矿的可能性。浸染状细脉浸染型矿石中黄铁矿以中粗粒(30~1 300 μm,多数>200 μm)、半自形自形立方体为主,基本无碎裂或碎裂不明显,可含有自然金、银金矿或硅酸盐包体;成分上具有中等的As(0.03%~1.72%,平均0.66%)、Co(0.06%~0.19%,平均0.13%)、Te(0.03%~0.06%,平均0.04%)含量和As/S、Fe/S、Co/As比值,基本不含Cu、Pb、Zn、Ag。石英电气石硫化物型矿石中黄铁矿多呈中粗粒(30~2 000 μm)、半自形它形粒状,往往发生碎裂,并被黄铜矿、方铅矿等矿物交代;部分颗粒可含有银金矿或硅酸盐包体;总体具有较高的As(0.05%~2.05%,平均0.97%)、Co(0.05%~0.34%,平均0.15%)含量和As/S、Fe/S比值,Co/As比值较低。块状硫化物型矿石中黄铁矿多呈半自形它形粒状产出,但粒度变化较大(250~3 000 μm或者30~300 μm);化学成分上以较高的As(0.05%~2.20%,平均1.21%)、Te(0.04%~0.09%,平均0.06%)含量,高的As/S、Fe/S比值和低的Co/As比值为特征。稀疏浸染型矿石中黄铁矿呈中粒(集中于50~200 μm)、半自形它形粒状产出,内部可含有硫化物、硅酸盐、银金矿、自然金等包体;可发生碎裂并被黄铜矿等沿裂隙充填交代;化学成分变化较大,总体具有较高的Co(0.08%~1.04%,平均0.35%)含量和Co/As比值,几乎不含Te、Cu、Zn。方解石硫化物脉型矿石中黄铁矿呈中粗粒(40~480 μm)、半自形它形粒状产出,内部往往含硅酸盐等包体;黄铁矿以显著低的As(0.04%~0.08%,平均0.06%)、Co含量(0.04%~0.20%,平均0.10%)以及As/S、Fe/S比值为特征,Co/As比值较高,且不含Zn。从上述左岸金矿的控矿构造、矿化类型、围岩蚀变以及不同类型矿石中黄铁矿形态、结构、成分的差异等4方面特征显示,左岸金矿可能存在多期次矿化、叠加成矿。     

Trace elements mineral chemistry of sulfides from the Woxi Au-Sb-W deposit,southern China

The Woxi Au-Sb-W deposit is one of the largest polymetallic ore deposits in the Xuefengshan Range, southern China, hosted in low-grade metamorphosed Neoproterozoic volcaniclastic rocks. The orebodies of the deposit are predominantly composed of banded quartz veins, which are strictly controlled by bedding and faults. Petrographic observations and geochemical results are reported on the occurrence of Au and properties of the ore-forming processes for different stages in the deposit. The veins extend vertically up to 2 km without obvious vertical metal zoning. The ore-forming process can be subdivided into four mineralization stages: Pre-ore stage; Early stage (scheelite-quartz stage); Middle stage (pyrite-stibnite-quartz stage); and Late stage (stibnite-quartz sage). Four types of pyrite (Py0, Py1, Py2, and Py3) were identified in the ores and host-rock: Py0 occurs as euhedral grains with voids in the core, ranging in size from 50 to 100 μm and formed mainly in the Pre-ore stage and Early stage; Py1 occurs as subhedral grains. Small grains (around 10 μm) of Py1 form irregularly shaped clusters of variable size ranging from tens to hundreds of μm and mainly formed in the Middle stage; Euhedral-subhedral fine-grained Py2 formed in the Late stage; Minor subhedral fine-grained Py3 was deposited in the Late-stage. Stibnite is widely distributed in the Middle and Late stage ore veins. No systemic difference was recognized in mineralogical features among stibnite formed in different stages. In addition to native gold, the lattice bound Au⁺¹ widely exists in Py1 and Py2 in the deposit, and widespread Py1 is considered as the main Au-bearing mineral with the highest Au contents. Most elements (such as Co, Ni, Cu, As, Sb, Ba, and Pb) are considered to occur as solid solution within the crystal lattice and/or invisible nanoparticles in sulfides minerals. The Co/Ni ratio of most pyrite is lower than 1, suggesting that the metals in the ore-forming fluid are sourced from sedimentary rocks. The coupled behavior between Au and As; Au and Sb suggests that the substitution of As and Sb in pyrite can enhance the incorporation of Au. Variation of trace elements in pyrites of different stages suggests some information on the mineralization processes: Large ion lithophile elements (such as Ba and Pb) are enriched in Py0 indicating that water-rock reaction occurred in the Early stage; Fine-grained Py1 with a heterogeneous distribution of elements suggests fast crystallization of pyrite in the Middle stage.     

In-situ Trace Element Analysis Characteristics of Pyrite in Sanshandao Gold Deposit in Jiaodong Peninsula: Implications for Ore Genesis

There are controversies about the genesis of the lode gold deposits in Jiaodong area. The Sanshandao gold deposit is the largest one in Jiaodong area. To better understand the genesis of the gold deposit, it is necessary to know the evolution of ore-forming fluid and the source of ore-forming material for the Sanshandao gold deposit. In this paper, the trace element composition of pyrite at different metallogenic stages in the Sanshandao gold deposit was analyzed by using LA-ICP-MS. Based on geological characteristics and petrography observation and SEM analysis, pyrite can be divided into three stages and six classes, including porous Py1-a and smooth Py1-b in pyrite-sericite-quartz alteration (Py1), many mineral inclusions in the Py2-a and smooth Py2-b associated with carbonate in the quartz-pyrite ± siderite veins (Py2), a lot of polymetallic sulfide inclusions hosted Py3-a and Py3-b with smooth and oscillation band in the quartz-polymetallic sulfide vein (Py3). The experimental results show that the gold content is very low in the lattice of pyrite, most of which is less than 1×10^-6, and gold mainly occurs in the form of visible gold. The contents of Au, Ag, Cu, Pb and Sb of pyrite gradually increase from early stage to late stage. The high content of Co+Ni in the earliest stage (up to 9268×10^-6) reflects that pyrite in the early stage is likely derived from magma, and the Co/Ni ratio gradually decreases, suggesting the decrease of ore forming fluid temperature. Combined with the geological observations and trace elements component of pyrite, the study shows that the genesis of the Sanshandao gold deposit is related to the evolution of magmatic hydrothermal reservoir. The ore-forming fluid is transported several times along the fault by seismic pumping.     

胶东焦家金成矿带2420~3206 m垂深金矿物和黄铁矿微量元素特征

在胶东莱州吴一村地区完成的3266.06 m深钻,是目前焦家金成矿带最深见矿钻孔,研究钻孔揭露的深部矿石中金矿物及黄铁矿微量元素特征,对探讨深部成矿作用演化具有重要意义。笔者采取深钻中2420~3206 m垂深的岩（矿）芯样品进行了详细的岩相学和矿相学研究,结合扫描电镜和电子探针微区分析,研究了矿石中金矿物的赋存状态和成分。对不同成矿阶段形成的黄铁矿进行了LA-ICPMS微量元素分析。研究结果表明,深部矿石中载金矿物主要为黄铁矿,其次为石英、黄铜矿、方铅矿,可见金主要以自然金和银金矿的形式存在,以晶隙金和裂隙金为主,其次为包体金。与浅部金矿床比较,深部金的成色较高。黄铁矿分为6种类型,第Ⅰ成矿阶段形成富Co型黄铁矿Py1,第Ⅱ成矿阶段形成富Ni型黄铁矿Py2a和Py2b,第Ⅲ成矿阶段形成富Au、As型黄铁矿Py3a和富Au、Ag、Pb、Bi型黄铁矿Py3b,第Ⅳ成矿阶段形成贫微量元素黄铁矿Py4。其中,Py1和Py2a发生强烈破碎,裂隙表面对热液中的Au络合物产生吸附作用,对金沉淀富集起重要作用。黄铁矿中Co、Ni、As等微量元素主要以类质同象形式赋存,而Au、Ag、Cu、Pb、Zn、Bi等主要以纳米级、微米级矿物包体形式赋存。Pb+Bi、Cu+Pb+Zn、Te+Bi与Au+Ag呈明显正相关,而Au与As相关性较差。黄铁矿中Co、Ni含量较低,而Au+Ag+As或Au+Ag+Pb+Bi+Cu含量较高指示成矿有利。另外,黄铁矿中Co、Ni含量较高,并且破碎强烈,成矿相关元素含量较高也指示成矿有利。     

山东莱州曲家金矿黄铁矿微量元素对成矿过程的指示

曲家金矿位于我国重要的蚀变岩型金矿矿集区之焦家金矿带的中段，矿床赋存标高为-726～-1 334 m。为研究黄铁矿的演化及其对金成矿过程的指示，运用LA-ICP-MS分析黄铁矿原位微量元素含量，结合岩相学观察和点群分析对黄铁矿进行了分类。发现黄铁矿中Co、Ni、As等微量元素主要以类质同像形式赋存，而Au、Ag、Cu、Zn、Pb、Bi等元素主要以纳米级、微米级矿物包裹体形式赋存。黄铁矿主要分为5种类型：富Co型Py1,富Ni型Py2,富Au、As型Py3,富Au、Ag、Pb、Bi型Py4及“干净”型Py5。黄铁矿微量元素特征指示成矿物质可能主要来源于前寒武纪变质基底岩石和中生代岩浆岩，少量来源于地幔，成矿热液可能属变质热液、岩浆热液和浅部大气降水的混合成因。不同类型黄铁矿反映成矿热液由富Co、Ni经富As、Au向富Pb、Bi、Au、Ag演化。Py1和Py2形成后受构造活动影响发生强烈破碎，裂隙表面对热液中金络合物增强的吸附作用促使金在裂隙中沉淀，对金的富集成矿可能起重要作用。Co、Ni含量较低，同时Au、Ag、As、Pb、Bi等元素含量较高的黄铁矿与成矿作用有密切关系。另外，黄铁矿中C...     

Genesis of the Bianjiadayuan Pb-Zn polymetallic deposit,Inner Mongolia,China:Constraints from in-situ sulfur isotope and trace element geochemistry of pyrite

The Southern Great Xing'an Range(S(GXR)which forms part of the eastern segment of the Central Asian Orogenic Belt(CAOB)is known as one of the most important Cu-Mo-Pb-Zn-Ag-Au metallogenic belts in China,hosting a number of porphyry Mo(Cu),skarn Fe(Sn),epithermal Au-Ag,and hydrothermal veintype Ag-Pb-Zn ore deposits.Here we investigate the Bianjiadayuan hydrothermal vein-type Ag-Pb-Zn ore deposit in the southern part of the SGXR.Porphyry Sn± Cu± Mo mineralization is also developed to the west of the Ag-Pb-Zn veins in the ore field.We identify a five-stage mineralization process based on field and petrologic studies including(i)the early porphyry mineralization stage,(ii)main porphyry mineralization stage,(iii)transition mineralization stage,(iv)vein-type mineralization stage and(v)late mineralization stage.Pyrite is the predominant sulfide mineral in all stages except in the late mineralization stage,and we identify corresponding four types of pyrites:Pyl is medium-grained subhedral to euhedral occurring in the early barren quartz vein;Py2 is medium-to fine-grained euhedral pyrite mainly coexisting with molybdenite,chalcopyrite,minor sphalerite and galena;Py3 is fine-grained,subhedral to irregular pyrite and displays cataclastic textures with micro-fractures;Py4 occurs as euhedral microcrystals and forms irregularly shaped aggregate with sphalerite and galena.LA-ICP-MS trace element analyses of pyrite show that Cu,Pb,Zn,Ag,Sn,Cd and Sb are partitioned into pyrite as structurally bound metals or mineral micro/nano-inclusions,whereas Co,Ni,As and Se enter the lattice via isomorphism in all types of pyrite.The Cu,Zn,Ag,Cd concentrations gradually increase from Pyl to Py4,which we correlate with cooling and mixing of ore-forming fluid with meteoric water.Py2 contains the highest contents of Co,Ni,Se,Te and Bi,suggesting high temperature conditions for the porphyry mineralization stage.Ratios of Co/Ni(0.03-10.79,average 2.13)and sulphur isotope composition of sulfide indicate typical hydrothermal origin for pyrites.The δ~(34)S_(cDT) values of Pyl(0.42‰-1.61‰,average1.16‰),Py2(-1.23‰to 0.82‰,average 0.35‰),Py3(—0.36‰to 2.47‰average 0.97‰).Py4(2.51‰--3.72‰,average 3.06‰),and other sulfides are consistent with those of typical porphyry deposit(-5‰to 5‰),indicating that the Pb-Zn polymetallic mineralization in the Bianjiadayuan deposit is genetically linked to the Yanshanian(Jurassic-Cretaceous)magmatic-hydrothermal events.Variations of δ~(34) S values are ascribed to the changes in physical and chemical conditions during the evolution and migration of the ore-forming fluid.We propose that the high Sn content of pyrite in the Bianjiadayuan hydrothermal vein-type Pb-Zn polymetallic deposit can be used as a possible pathfinder to prospect for Sn mineralization in the surrounding area or deeper level of the ore field in this region.     

黔东南坑头金矿床热液蚀变特征及成矿过程研究

黔东南金成矿区位于江南造山带金成矿省的西南端,成矿条件优越。坑头金矿床是黔东南金成矿区的一个中型矿床,在其深部找矿中,发现除石英脉型矿体外,还存在蚀变岩型矿体。然而,这种蚀变岩型矿体的构造形态、蚀变类型、与石英脉型矿体之间关系和金的赋存状态尚不清楚。本研究与当前的勘查工作紧密结合,围绕石英脉型矿体和新发现的蚀变岩型矿体为研究切入点,借助微区分析技术(扫描电镜和电子探针)进行系统的“流体- 蚀变- 成矿”研究。蚀变矿物金红石矿物化学显示为热液成因,具有典型造山型金矿床的金红石标型特征。围岩的沉积- 成岩过程(包括低级变质作用过程),主要形成了草莓状黄铁矿和含铁碳酸盐岩,为后期含金硫化物(黄铁矿和毒砂)的形成提供物质基础(如Fe)。金的成矿富集过程主要经历了绢云母+毒砂+黄铁矿+石英(Ser+Apy+Py+Qtz)阶段、黄铁矿+毒砂+石英(Py+Apy+Qtz)阶段和自然金+石英(Au0+Qtz)阶段。在Ser+Apy+Py+Qtz阶段,主要表现为含矿流体与围岩的初级交代,形成大量浸染状黄铁矿+毒砂的硫化带;Py+Apy+Qtz阶段主要为流体沿着剪切带再交代,形成蚀变岩型矿体;Au0+Qtz阶段主要表现为含金石英大脉的形成。金的赋存状态研究显示,蚀变岩矿体中Au以他形显微- 次显微自然金赋存在蚀变岩硫化物裂隙中,或以化学结合态方式赋存在黄铁矿和毒砂中(后者占主导)。在晚期Au0+Qtz阶段,自然金呈自形、粗粒(~0. 5 mm)赋存在石英脉中。综合研究认为,多期构造(流体)交代导致的溶解- 再沉淀可能是坑头金富集成矿主要原因之一。     

藏南查拉普金矿床载金矿物特征与金的赋存状态

黄铁矿和毒砂是卡林型和造山型金矿床重要的载金矿物。文章通过电子探针(EPMA)分析研究了藏南查拉普金矿床不同类型黄铁矿和毒砂中Au、As、S、Fe等元素的含量变化和分布规律,发现不同阶段的黄铁矿具有不同的结构特征和元素组成特点。沉积成岩期黄铁矿(Py1)主要呈草莓状、胶状,常构成环带状黄铁矿的核心,其中金的含量最高,显示了金在沉积成岩期的大量富集。热液期早阶段黄铁矿(Py2)主要呈自形-半自形的立方体,与Py1元素(S、Fe、As)组成相近,显示了一定的继承演化关系。热液期主阶段黄铁矿(Py3)与毒砂共生,多呈自形-半自形的五角十二面体、立方体,常包裹早期的黄铁矿形成环带结构。Py3中As的含量明显升高,其增加量近似等于S的减少量,说明As主要进入黄铁矿晶格替代了S的位置。各个阶段的黄铁矿和毒砂中Au的分布在EPMA微束的分辨率下均显示是不均匀的,Au在Py1和大部分Py2中主要以纳米级自然金(Au0)的形式存在;而在Py3中主要以(Au+)的形式存在,少部分以纳米级自然金(Au0)形式存在。Py1的结构及元素组成与典型卡林型金矿和造山型金矿沉积成岩期黄铁矿的特点相似,而Py3的大量发育则符合卡林型金矿的特征。     

Gold and sulphide minerals in Tertiary quartz pebble conglomerate gold placers, Southland, New Zealand

Auriferous quartz pebble conglomerates (QPC) formed during Tertiary sedimentary recycling in the Waimumu district, Southland, New Zealand. These sediments contain fine-grained gold of detrital origin with abundant surface textures and gold-forms associated with authigenic gold remobilisation. Most authigenic gold contains no detectable silver and occurs as overgrowths on detrital Au–Ag and Au–Ag–Hg alloys that contain up to 13 wt.% Ag, and 9 wt.% Hg. Fine-grained Au–Ag and Au–Ag–Hg alloys are compositionally heterogeneous, exhibiting both well-defined silver-depleted and silver-enriched rims. Rare coarse Au–Ag alloy is intergrown with quartz and is homogenous. Discrete grains of authigenic, porous, sheet-like gold occur in carbonaceous mudstone within a QPC sequence. Some QPC contain abundant sulphide minerals. Some of these sulphides (pyrite and arsenopyrite) are of long-distance detrital origin, presumably from the Otago Schist, whereas the bulk of the sulphide suite is marcasite of variably transported diagenetic origin, derived from the erosion of QPC and underlying Tertiary sediments. There has also been authigenic deposition of sulphide minerals in the QPC themselves. These diagenetic sulphides include framboidal and anhedral marcasite, and framboidal and euhedral pyrite. Sulphur isotope data for the sulphide minerals range from − 45‰ to + 18‰ (relative to VCDT). Sulphur isotope data for euhedral detrital pyrite and arsenopyrite range from − 9‰ to − 1‰ and are most likely derived from the Otago Schist to the north. Both framboidal and anhedral marcasite have lower values (< − 20‰) reflecting microbial sulphate reduction as a source for the precursor hydrogen sulphide. Anhedral marcasite contains elevated concentrations of Ni, Co, As and Cr, commonly with compositional banding of these metals.Both the gold and diagenetic sulphides from the Belle-Brook QPC are compositionally similar to gold and sulphides from Archaean QPC. Porous, sheet-like authigenic gold is morphologically similar to gold associated with carbonaceous material in the Witwatersrand. In addition, Southland marcasite textures resemble the rounded and banded pyrite in Witwatersrand QPC placers. There is abundant evidence from these Tertiary QPC in southern New Zealand for sedimentary transport of sulphide minerals and post-depositional sulphide mineralisation in the surficial environment despite an oxygen-rich atmosphere. These young deposits thus provide an example of authigenic gold and sulphide textures formed during diagenesis in unmetamorphosed placers. Many of these textures are similar to those commonly ascribed to metamorphic processes in Archaean auriferous QPC.     

胶东乳山金矿床成矿过程:周期性压力波动诱发的流体不混溶

位于胶东东部苏鲁地体内的乳山金矿曾是我国单脉金储量最大的矿床,其主矿脉为一具有复杂内部结构的富金石英脉,形成于包含周期性流体活动的增量增长过程。该矿床成矿流体演化、精细成矿过程和金沉淀机制仍缺乏有效制约。本研究在详细结构构造观察基础上,在代表单次成矿流体活动的同一石英层内识别出分别代表三个连续成矿阶段的三类黄铁矿,开展激光剥蚀-电感耦合等离子质谱原位微量元素测试。结果显示不同阶段黄铁矿微量元素成分基本一致,Co、Ni、As等元素因成矿流体间歇性压力波动而周期性地以不同含量进入黄铁矿,形成这些元素的韵律成分环带。Au等其他微量元素在不同阶段黄铁矿内均匀分布,其分布行为受压力波动影响较小。间歇性压力波动和由此引发的周期性流体不混溶使乳白色粗粒石英和黄铁矿、烟灰色中细粒他形石英和黄铁矿依次大规模沉淀,金银碲化物、银金矿、自然金和方铅矿、闪锌矿、黄铜矿等硫化物随后在愈加富Au、Ag、Te、Pb、Zn和Cu等的流体中近于同时沉淀。在此过程中成矿流体虽整体表现为还原性,但其还原性随着压力波动而不断递减氧化性持续增加;流体碲逸度早期保持稳定,后期则大幅上升。金以可见金形式充填先成黄铁矿裂隙或沿黄铁矿边缘分布,周期性流体压力波动引发的间歇性流体不混溶导致H_2S、CO_2和CH_4等气体大规模逸出,金硫络合物失稳分解,金被吸附至黄铁矿内水力致裂形成的裂隙面发生沉淀。排除了先成黄铁矿内不可见金再活化为可见金的可能性,认为周期性流体压力波动引起的流体不混溶是引发乳山金矿床可见金高效沉淀的关键机制。     

Multi-stage pyrite and hydrothermal mineral assemblage of the Hatu gold district (west Junggar,Xinjiang, NW China): Implications for metallogenic evolution

The Hatu, Qi-III, and Qi-V gold deposits in the Hatu–Baobei volcanic–sedimentary basin (west Junggar, Xinjiang) represent the proximal, middle, and distal parts of the Hatu gold district, respectively. Orebodies of these deposits mainly consist of Au-bearing quartz veins and altered host rocks with disseminated sulfide minerals. Six types of pyrite in these mines are studied here to illustrate ore-formation processes. Sedimentary pyrite, including framboidal and fine-grained pyrite, occurs in mudstone-bearing sedimentary rocks or altered volcanic–sedimentary rocks. Framboidal pyrite formed during redox changes in sedimentary layers. Hydrothermal pyrite contains five subgroups, from Py1 to Py5. Porous Py1 formed prior to gold mineralization, and is overgrown by Py2 that contains inclusions of sulfide minerals and native gold. Coarser Py3 coexists with arsenopyrite and native gold, and contains the greatest As concentrations. Gold and antimony are also preferentially concentrated in arsenian Py2 and Py3. The Au–As-deficient Py4 and Py5 formed during the post-ore process. There is a negative correlation between the As and S contents in Py1, Py2, and Py3, implying the substitution of sulfur by arsenic. Gold precipitated under relatively reducing condition in framboid- and graphite-bearing tuffaceous rocks. Cesium, Rb, Sr, La, Ce, Au, As, Sb, Cu, and Pb are concentrated in altered host rocks. The Au-bearing quartz veins and disseminated sulfide mineral orebodies were formed via a co-genetic hydrothermal fluid and formed during different stages. The variation of fO₂ during fluid/rock interactions, and crystallization of arsenian pyrite were major factors that controlled gold precipitation.     

四川木里梭罗沟金矿床载金黄铁矿原位微量元素特征

甘孜–理塘缝合带是四川重要的金矿带之一。梭罗沟大型金矿床是该带上的典型矿床,但其矿床成因仍存在争议。为了准确厘定其矿床成因,本文对梭罗沟金矿床中的它形和自形（五角十二面体）的载金黄铁矿进行了LA-ICP-MS原位微量元素分析。结果显示梭罗沟它形黄铁矿元素含量变化较小,较为集中,而自形黄铁矿具有明显的核–幔–边结构,元素含量变化范围较大。总体上,两种黄铁矿中Au与As均具有明显的正相关性,但Au与FeS₂和Co/Ni值具有负相关性。它形黄铁矿和自形黄铁矿的Co/Ni值分别为0.2和57.1,两者都具有较高的Au和较低的Ag含量;这表明它形黄铁矿主体来源于沉积作用,受后期成矿热液改造,而自形黄铁矿属于热液成因。梭罗沟金矿床成矿过程为火山–沉积岩中的Au在变质热液作用下再活化富集的结果,属于典型的造山型金矿床。     

Fluid source and physicochemical conditions of the polymetallic mineralization in Gawuch Formation,Kohistan Island Arc,NW Pakistan

The Cu-Sb-Pb polymetallic vein deposit is hosted by metavolcanics rocks of the Gawuch Formation at the Kaldom Gol area of the northwest Kohistan arc terrain in northern Pakistan. The mineralization is closely associated with the dioritic to granodioritic rocks of the Lowari pluton, which was intruded into the Gawuch metavolcanics. Details of ore characterization and processes of ore genesis of this evidently hydrothermal mineralization are not well documented. Integrating petrographic, mineral-chemical and isotopic investigations, this study aims to comprehend the source of hydrothermal fluids, geochemical evolution, mineral inclusions and physicochemical conditions of the Cu-Sb-Pb polymetallic vein deposit in Gawuch metavolcanics in the Kohistan arc terrain in northern Pakistan. The mineralization is distinguished into three types of ore-gangue associations: Type Ia, Type Ib, and Type II. The textural study revealed two pyrite generations: (i) Py1 displaying euhedral to subhedral habits and containing scarce inclusions, and (ii) Py2 occurring as anhedral grains hosting abundant inclusions. Type Ia is characterized by Py1 associated with abundant quartz (Qz) showing comb texture, sericite (Ser), and minor chlorite (Chl). Type Ib comprises Qz + Ser + Chl and Py2, chalcopyrite (Ccp), and magnetite (Mag). Type II is represented by mosaic quartz, rhombic adularia, and bladed calcite, and the ore minerals fahlore and galena. Alteration zones composed of Qz-Ser ± Chl and Qz-Ser-Chl, surround Type I (a, b) and Type II veins, respectively. Fahlore and galena mostly replace pyrite of Type Ia and chalcopyrite of Type Ib. In addition, malachite, azurite, hematite and covellite occur as secondary (supergene) minerals. The Co/Ni ratios (>1) of Kaldom Gol pyrites suggest that the ore-forming fluids were hydrothermal in origin and Py1 and Py2 solidified at 221–304 °C and 225–261 °C, respectively. The LA-ICP-MS time-resolved depth profiles confirm the existence of sphalerite, and chalcopyrite inclusions in pyrite (Py1 and Py2) and millerite, bravoite, vaesite, Au-tellurides, native Au and galena inclusions in chalcopyrite and fahlore. Sulfur isotope compositions of pyrites (δ³⁴S = Py1, −0.58 to +2 ‰; δ³⁴S = Py2, −0.24 to +2.04 ‰) indicate that the ore-forming fluids were derived from magmatic source (s). The mineral assemblage, hydrothermal alterations, textures, temperature and δ³⁴S of pyrites suggest that the Cu-Sb-Pb polymetallic mineralization at Kaldom Gol represents an intermediate-sulfidation type of epithermal deposit.     

阳山金矿带金的赋存状态及其对成矿过程的指示意义

阳山金矿带是西秦岭金矿带已探明金储量最大的独立金矿区,其矿化样式主要为微细浸染状矿化,其次为石英脉型矿化,可见金与“不可见金”均有发育,该金矿带是研究造山型金矿金赋存状态的理想地区,其研究成果对理解金成矿作用和过程以及指导选矿工艺具有重要意义。论文在翔实的野外地质调查和显微观察基础上,将成矿期划分为早阶段(黄铁矿石英)、主阶段(黄铁矿毒砂绢云母石英)和晚阶段(辉锑矿石英方解石),综合应用电子探针、激光剥蚀电感耦合等离子体质谱、电感耦合等离子质谱仪、高分辨率透射电镜、X射线粉晶衍射等技术,剖析阳山金矿带不同成矿阶段金的赋存状态,进而探讨其对成矿过程的指示意义。研究表明：成矿早、主阶段以微细浸染状硫化物矿化为主,金主要以晶格金的形式赋存于黄铁矿和毒砂中;而成矿晚阶段以脉状矿化为主,金主要以自然金的形式存在。金的赋存状态的变化,指示从成矿早阶段到晚阶段,成矿温度、压力逐渐降低,成矿流体成分由富As流体演化为相对贫As且富Sb的流体。     

LA-ICP-MS trace element analysis of pyrite from the Xiaoqinling gold district, China: Implications for ore genesis

The Xiaoqinling district, the second largest gold producing district in China, is located on the southern margin of the North China Craton. It consists of three ore belts, namely, the northern ore belt, the middle ore belt and the southern ore belt. Pyrite from the Dahu gold deposit in the northern ore belt and Wenyu and Yinxin gold deposits in the southern ore belt were investigated using a combination of ore microscopy and in-situ laser-ablation inductively-coupled plasma-mass spectrometry (LA-ICP-MS). A range of trace elements was analyzed, including Au, Te, Ag, Pb, Bi, Cu, Co, Ni, Zn, Mo, Hg, As and Si. The results show that there are no systematic differences between the trace element compositions of pyrite in the three deposits from different ore belts. In general, Au concentrations in pyrite are low (from < 0.01 ppm to 2.2 ppm) but Ni concentrations are rather high (up to 8425 ppm). A four-stage mineralization process is indicated by microscopic and field observations and this can be related to the systematic trace element differences between distinct generations of pyrite. Stage I precedes the main gold mineralization stage; pyrite of this stage has the lowest Au concentrations. Stages II and III contributed most of the gold to the ore-forming system. The corresponding pyrite yielded the highest concentrations of Au and Ni. Our microscopic observations suggest that pyrite in the main gold mineralization stage precipitated simultaneously with molybdenite that has been previously dated as Indosinian (~ 218 Ma by Re–Os molybdenite dating), indicating the Indosinian as the main gold mineralization stage. The Indosinian mineralization age and the geological and geochemical features of these gold deposits (e.g., low salinity, CO₂-rich ore fluids; spatial association with large-scale compressional structures of the Qinling orogen; δ¹⁸O and δD data suggestive of mixing between metamorphic and meteoric waters; δ³⁴S and Pb-isotopic data that point to a mixed crustal-mantle source) all point to typical orogenic-type gold deposits. High Ni concentrations (up to 8425 ppm) of pyrite possibly linked to deep-seated mafic/ultramafic metamorphic rocks provide further evidence on the orogenic gold deposit affinity, but against the model of a granitic derivation of the mineralizing fluid as previously suggested by some workers. Generally low Au concentration in pyrite is also consistent with those from worldwide orogenic gold deposits. Therefore, the gold mineralization in the Xiaoqinling district is described as orogenic type, and is probably related to Indosinian collision between the North China Craton and the Yangtze Craton.