Trace Elements and Rare Earth Elements of Sulfide Minerals in the Tianqiao Pb-Zn Ore Deposit, Guizhou Province, China

Trace elements and rare earth elements (REE) of the sulfide minerals were determined by inductively-coupled plasma mass spectrometry. The results indicate that V, Cu, Sn, Ga, Cd, In, and Se are concentrated in sphalerite, Sb, As, Ge, and Tl are concentrated in galena, and almost all trace elements in pyrite are low. The Ga and Cd contents in the light-yellow sphalerites are higher than that in the brown and the black sphalerites. The contents of Ge, Tl, In, and Se in brown sphalerites are higher than that in light-yellow sphalerites and black sphalerites. It shows that REE concentrations are higher in pyrite than in sphalerite, and galena. In sphalerites, the REE concentration decreases from light-yellow sphalerites, brown sphalerites, to black sphalerites. The ratios of Ga/In are more than 10, and Co/Ni are less than 1 in the studied sphalerites and pyrites, respectively, indicating that the genesis of the Tianqiao Pb–Zn ore deposit might belong to sedimentary-reformed genesis associated with hydrothermal genesis. The relationship between LnGa and LnIn in sphalerite, and between LnBi and LnSb in galena, indicates that the Tianqiao Pb–Zn ore deposit might belong to sedimentary-reformed genesis. Based on the chondrite-normalized REE patterns, δEu is a negative anomaly (0.13–0.88), and δCe does not show obvious anomaly (0.88–1.31); all the samples have low total REE concentrations (<3 ppm) and a wide range of light rare earth element/high rare earth element ratios (1.12–12.35). These results indicate that the ore-forming fluids occur under a reducing environment. Comparison REE compositions and parameters of sphalerites, galenas, pyrites, ores, altered dolostone rocks, strata carbonates, and the pyrite from Lower Carboniferous Datang Formation showed that the ore-forming fluids might come from polycomponent systems, that is, different chronostratigraphic units could make an important contribution to the ore-forming fluids. Combined with the tectonic setting and previous isotopic geochemistry evidence, we conclude that the ore-deposit genesis is hydrothermal, sedimentary reformed, with multisources characteristics of ore-forming fluids.     

甘肃花牛山铅锌矿床闪锌矿LA-ICP-MS微量元素组成及其地质意义

天山—北山铅锌成矿带位于中亚造山带、塔里木板块和华北板块的交汇地带,是我国西北地区重要的金属资源产地之一。花牛山铅锌矿是天山—北山地区具典型成因意义的铅锌矿床,矿床成因机制一直存在争议。本文通过LA-ICP-MS对其闪锌矿微量组成进行分析,结果表明：该矿床闪锌矿形成于中—高温环境,以富集Fe、Mn、In、Cd、Cu等元素,贫Ga、Ge、Ni等元素为特征,其中Fe、Mn、In、Cd、Cu以类质同象的形式赋存于闪锌矿中,Ag、Pb以显微包裹体的形式赋存于闪锌矿中;其微量元素组成与岩浆热液为主导的矿床（都龙、黄岗梁、孟恩陶勒盖、赤土店）类似,除此之外,闪锌矿Tl元素质量分数以及Cd/Fe和Cd/Mn值均显示岩浆热液属性,在微量元素判别图中样品也落入岩浆热液区域。野外调研发现,矿体底部未见角砾状和网脉状矿体,矿体均发育在岩性界面及层间破碎带中。结合矿床地质特征、闪锌矿微量元素地球化学特征,认为花牛山铅锌矿床成因类型属于中高温岩浆热液型。     

内蒙古黄岗梁铁锡矿床闪锌矿LA-ICP-MS微量元素组成及其指示意义

黄岗梁铁锡矿床位于大兴安岭中南段晚古生代增生造山带。矿区内闪锌矿产于矽卡岩中,可分为浸染状和层纹状闪锌矿。本文对两种闪锌矿进行了高精度LA-ICP-MS元素含量测试,结果表明矿区两种闪锌矿具有相同成因特征,闪锌矿中Mn、Cu、As、In较富集,Ga、Ge、Cd含量较低,而As、Sn、Bi、Pb含量变化较大。Cu、Sn、Bi、Pb等元素在闪锌矿中以独立矿物赋存,Mn、Fe、Ga、Ge、Cd、In、Sb以类质同像形式赋存在闪锌矿晶格中。In/Ga、In/Ge比值较低,Zn/Cd比值为233~250,指示闪锌矿形成于中高温环境。Cd/Fe、Cd/Mn比值分别小于0.1和0.5,指示闪锌矿成因与岩浆活动有关,In Ge特征图解也指示其矽卡岩成因。通过与国内外典型矿床闪锌矿微量元素特征对比,结合矿床地质特征认为黄岗梁铁锡矿床中闪锌矿属于与燕山期岩浆作用有关的中高温矽卡型闪锌矿。     

Enrichment characteristics and its geological significance of dispersed elements within sulfide minerals from the VI ore belt in the Maoping Pb-Zn deposit,Yunnan Province,ChinaSCIEI北大核心CSCD

作为华南大面积低温成矿域的重要组成部分,川滇黔铅锌矿集区是我国重要的铅锌银等资源基地之一,同时该矿集区也是Ge、Cd、Ga和In等稀散元素的超常富集区域。毛坪矿床是该矿集区内第二大铅锌矿床,累计探明铅锌金属储量超过3Mt(Pb+Zn平均品位≥18%),锗(Ge)保有储量182t。本文以新发现的Ⅵ矿带(铅锌金属已探明储量≥60万t,Pb+Zn平均品位≥20%)为研究对象,利用LA-ICPMS对主要矿石矿物闪锌矿和黄铁矿进行了微区原位微量元素组成和Mapping分析。研究结果显示Ⅵ矿带闪锌矿普遍富集Ge(最高580×10^(-6),均值81.1×10^(-6))、Cd(最高3486×10^(-6),均值1613×10^(-6))和Ga(最高190×10^(-6),均值44.4×10^(-6));黄铁矿普遍富集Mn、As、Pb、Cu、Ag和Sb。与Ⅰ和Ⅱ号矿带闪锌矿相比,Ⅵ号矿带闪锌矿更富集Ge和Ga。闪锌矿中Fe和Pb以类质同象为主,偶见黄铁矿和方铅矿显微包体;Cu、Ge、Ag和As赋存形式主要为类质同象,替代方式为Ge^(4+)+2(Cu+,Ag+,As+)↔3Zn^(2+);Cd以类质同象方式赋存为主,替代机制为Cd^(2+)↔Zn^(2+);Ga和In可能主要以类质同象方式存在。黄铁矿中Pb和Mn主要以方铅矿和碳酸盐矿物显微包体为主;Cu、As和Sb以类质同象形式存在于黄铁矿中;Ag和Zn可能以独立矿物形式赋存;Co和Ni以类质同象方式替代Fe进入黄铁矿晶格中,替代方式为Ni^(2+)+Co^(2+)↔2Fe^(2+)。毛坪矿床新发现Ⅵ矿带硫化物相比典型MVT矿床硫化物具有不同的In和Ge含量以及Cd/Fe比值,结合矿床地质特征和其他证据,表明毛坪矿床成因类型特殊,有别于经典MVT铅锌矿床,属于川滇黔型铅锌矿床。     

Cadmium isotopic constraints on metal sources in the Huize Zn-Pb deposit,SW China

The Sichuan-Yunnan-Guizhou(SYG)Zn-Pb metallogenic zone in SW China contains＞400 carbonate-hosted hydrothermal Zn-Pb deposits.Some of these,such as the Huize,Tianbaoshan,and Daliangzi deposits,are super-large deposits with significant reserves of Cd,Ge,and Ag.However,the sources of these metals remain controversial.This study investigated the Cd isotopic geochemistry of the Huize deposit,the largest Zn-Pb deposit in the SYG area.Sphalerites formed at three stages in the deposit have different colors:black or dark brown(Stage Ⅰ),red(Stage Ⅱ),and light-yellow(Stage Ⅲ).The δ114/110Cd values of the sphalerites are in the order Stage Ⅲ＜Stage Ⅰ＜Stage Ⅱ.Kinetic isotopic fractionation is likely the key factor causing the lower δ114/110Cd values in the early formed Stage Ⅰ sphalerites than in later-formed Stage Ⅱ sphalerites,with cooling of ore-forming fluids being responsible for the still lower values of the Stage Ⅲ sphalerites.In galena,the δ114/110Cd values are inversely correlated with Cd contents and tend to be higher in high-Zn galena.We speculate that Cd isotopic fractionation was significant during the precipitation of sphalerite and galena,with light Cd isotopes being enriched in galena rather than sphalerite.Comparison of the Cd isotopic signatures and Zn/Cd ratios of different endmembers suggests that the δ114/110Cd values and Zn/Cd ratios of sphalerite from the Huize deposit,as well as other large-scale deposits from the SYG area,are lie in those range of Emeishan basalts and sedimentary rocks and the mean δ114/110Cd values of these deposits show good negative correlation with 1/Cd,suggesting that the ore-forming materials of these deposits were derived from the mixing of Emeishan basalts and sed-imentary rocks.This study demonstrates that Cd isotopes can be useful proxies in elucidating ore genesis in large Zn-Pb deposits.     

Trace and minor elements in sphalerite from metamorphosed sulphide deposits

Sphalerite is a common sulphide and is the dominant ore mineral in Zn-Pb sulphide deposits. Precise determination of minor and trace element concentrations in sulphides, including sphalerite, by Laser-Ablation Inductively-Coupled-Plasma Mass-Spectrometry (LA-ICP-MS) is a potentially valuable petrogenetic tool. In this study, LA-ICP-MS is used to analyse 19 sphalerite samples from metamorphosed, sphalerite-bearing volcanic-associated and sedimentary exhalative massive sulphide deposits in Norway and Australia. The distributions of Mn, Fe, Co, Cu, Ga, Se, Ag, Cd, In, Sn, Sb, Hg, Tl, Pb and Bi are addressed with emphasis on how concentrations of these elements vary with metamorphic grade of the deposit and the extent of sulphide recrystallization. Results show that the concentrations of a group of trace elements which are believed to be present in sphalerite as micro- to nano-scale inclusions (Pb, Bi, and to some degree Cu and Ag) diminish with increasing metamorphic grade. This is interpreted as due to release of these elements during sphalerite recrystallization and subsequent remobilization to form discrete minerals elsewhere. The concentrations of lattice-bound elements (Mn, Fe, Cd, In and Hg) show no correlation with metamorphic grade. Primary metal sources, physico-chemical conditions during initial deposition, and element partitioning between sphalerite and co-existing sulphides are dominant in defining the concentrations of these elements and they appear to be readily re-incorporated into recrystallized sphalerite, offering potential insights into ore genesis. Given that sphalerite accommodates a variety of trace elements that can be precisely determined by contemporary microanalytical techniques, the mineral has considerable potential as a geothermometer, providing that element partitioning between sphalerite and coexisting minerals (galena, chalcopyrite etc.) can be quantified in samples for which the crystallization temperature can be independently constrained.     

贵州筲箕湾铅锌矿床硫化物中Tl-Cd-Ga富集机制及地质意义

筲箕湾铅锌矿床位于黔西北铅锌成矿区中部,为该区铅锌矿床中的又一典型代表,其金属资源量（Pb＋Zn）超过20万t。本文利用电感耦合等离子体质谱（ICP-MS）分析了不同类型矿石中原生矿石硫化物（黄铁矿、闪锌矿和方铅矿）中分散元素含量,结果显示除Cd含量较高外,Ga、In、Se、Tl和Re的富集程度均较低。不同分散元素在硫化物中表现出不同的富集规律,表现为Ga含量在闪锌矿中最高,黄铁矿次之,方铅矿最低;方铅矿中Tl含量高于闪锌矿,黄铁矿最低;Cd在闪锌矿中含量最高,方铅矿次之,黄铁矿最低;从黄铁矿→方铅矿→闪锌矿In含量依次升高;Re含量表现出在闪锌矿中最高,黄铁矿次之,方铅矿最低;Se富集程度从黄铁矿→方铅矿→闪锌矿依次升高。Ga、In和Re在不同颜色闪锌矿中富集程度相似,而Se、Cd和Tl则相对富集在棕色闪锌矿中。统计发现闪锌矿中Zn含量与Cd、Ga含量不呈类质同象的负相关特征,而其中的Fe含量与Cd、Ga含量间表现出曲线相关或负相关特征,暗示Cd、Ga可能是通过替代先进入闪锌矿中的Fe而占据其晶格,这可能是一种新的机制。闪锌矿Ga、Cd、In含量及Ga/In、Zn/Cd比值等参数,指示筲箕湾铅锌矿床形成于中-高温条件,其矿床成因类型与沉积-改造型相似。     

Discrimination of Pb-Zn deposit types using sphalerite geochemistry: New insights from machine learning algorithm

Due to the combined influences such as ore-forming temperature, fluid and metal sources, sphalerite tends to incorporate diverse contents of trace elements during the formation of different types of Lead-zinc (Pb-Zn) deposits. Therefore, trace elements in sphalerite have long been utilized to distinguish Pb-Zn deposit types. However, previous discriminant diagrams usually contain two or three dimensions, which are limited to revealing the complicated interrelations between trace elements of sphalerite and the types of Pb-Zn deposits. In this study, we aim to prove that the sphalerite trace elements can be used to classify the Pb-Zn deposit types and extract key factors from sphalerite trace elements that can discriminate Pb-Zn deposit types using machine learning algorithms. A dataset of nearly 3600 sphalerite spot analyses from 95 Pb-Zn deposits worldwide determined by LA-ICP-MS was compiled from peer-reviewed publications, containing 12 elements (Mn, Fe, Co, Cu, Ga, Ge, Ag, Cd, In, Sn, Sb, and Pb) from 5 types, including Sedimentary Exhalative (SEDEX), Mississippi Valley Type (MVT), Volcanic Massive Sulfide (VMS), skarn, and epithermal deposits. Random Forests (RF) is applied to the data processing and the results show that trace elements of sphalerite can successfully discriminate different types of Pb-Zn deposits except for VMS deposits, most of which are falsely distinguished as skarn and epithermal types. To further discriminate VMS deposits, future studies could focus on enlarging the capacity of VMS deposits in datasets and applying other geological factors along with sphalerite trace elements when constructing the classification model. RF’s feature importance and permutation feature importance were adopted to evaluate the element significance for classification. Besides, a visualized tool, t-distributed stochastic neighbor embedding (t-SNE), was used to verify the results of both classification and evaluation. The results presented here show that Mn, Co, and Ge display significant impacts on classification of Pb-Zn deposits and In, Ga, Sn, Cd, and Fe also have relatively important effects compared to the rest elements, confirming that Pb-Zn deposits discrimination is mainly controlled by multi-elements in sphalerite. Our study hence shows that machine learning algorithm can provide new insights into conventional geochemical analyses, inspiring future research on constructing classification models of mineral deposits using mineral geochemistry data.     

Covellite of the Semenov-2 hydrothermal field (13°31.13′ N,Mid-Atlantic Ridge): Enrichment in trace elements according to LA ICP MS analysis

As a result of LA ICP MS analysis of sulfides of the Semenov-2 hydrothermal field, it is established that covellite, which replaces Zn sulfides, is enriched in most trace elements. The Ga, Ni, and In contents in it do not vary, whereas Mn, Co, and Cd are lower than in sphalerite. The distribution of trace elements in covellite, which replaces Cu–Fe sulfides, is distinct: it is enriched in Cd, Sb, Pb, and Bi, whereas the contents of other elements are either lower or invariant. Covellite, which replaces Zn sulfides, is enriched in all trace elements relative to that replacing Cu–Fe sulfides. Enrichment of covellite in trace elements relative to primary sulfides was favored by oxidation of the hydrothermal fluid by seawater, which is similar to the processes of submarine oxidation of ancient massive sulfide deposits. Covellite is also a host to invisible gold and silver in ores of the Semenov-2 field along with toxic elements such as As, Se, Te, Tl, and Cd.     

闪锌矿LA-ICP-MS微量元素组成对西藏纳如松多铅锌矿床成矿作用的制约

西藏纳如松多铅锌矿床是冈底斯北侧Pb-Zn-Ag-Mo成矿带中规模最大且最为典型的与斑岩系统相关的铅锌矿床,发育有多种矿化样式。本次研究选取该矿床隐爆角砾岩型矿体中的闪锌矿开展LA-ICP-MS微量元素组成研究,发现其中Fe含量不高,不属于高温铁闪锌矿,以富集Cd、Mn、Co,而贫In、Ga、Ge、Se、Te为特征。闪锌矿In/Ga值、In/Ge值及Zn/Cd值指示纳如松多隐爆角砾岩型铅锌矿体形成于中低温环境,且属于热液型矿床的范畴。闪锌矿原位微量元素特征指示纳如松多铅锌矿床的形成主要受到来自于岩浆热液作用的影响和控制,成矿物质主要来自于深部斑岩岩浆系统。     

闽中梅仙丁家山铅锌矿床硫化物微量元素地球化学特征及其成矿意义

梅仙丁家山铅锌矿床是闽中新元古代马面山群中多个大中型铅锌多金属矿床的典型代表.本文以丁家山铅锌矿床两类矿石(含磁黄铁矿矿石和含磁铁矿矿石)内的闪锌矿和黄铁矿为研究对象,通过电子探针及LA-ICP-MS微量元素分析技术,揭示二者的微量元素组成和赋存状态,探讨成矿温度及矿床成因方面的重要信息.分析结果显示:闪锌矿内Fe、Mn、Cd、Cu、In、Pb、Bi元素较为富集,两类矿石内的闪锌矿除Fe元素含量相差较大以外(平均值分别为9.3％和1.7％),其他元素含量并无明显差异;电子探针面扫描和LA-ICP-MS剥蚀图像显示元素Mn、Cd、In以类质同象形式存在,而Fe、Cu、Pb、Bi则有类质同象和显微包体2种存在形式.黄铁矿微量元素含量整体较低,元素Co、Ni、Pb、Bi相对富集,Ni、Mn主要以类质同象形式存在,Cu、Co有类质同象替换和显微包体2种形式,Pb、Bi主要以方铅矿包体形式存在.两类矿石中的闪锌矿Zn/Cd比值分别在120～150之间和93～210之间,均指示中温成矿条件.两类闪锌矿内Fe、Cd、Mn元素含量特征与典型矽卡岩型矿床内的闪锌矿相吻合;矿床内硫化物硫同位素组成揭示成矿物质来自于岩浆岩.上述证据共同支持梅仙丁家山铅锌矿矿床属矽卡岩型矿床.     

闽中丁家山铅锌多金属矿区闪锌矿中Fe、Cd、Mn元素赋存特征及其地质意义

闪锌矿内Fe、Cd、Mn等元素含量不但影响闪锌矿的晶胞参数,而且蕴藏着丰富的矿床成因信息。闽中梅仙矿田丁家山铅锌矿区存在磁铁矿型和磁黄铁矿型两类矿石。本文通过X射线原位衍射和电子探针分析分别对两类矿石中闪锌矿的晶胞参数和Zn、Fe、Cd、Mn元素含量进行了测试,结果表明,闪锌矿晶胞参数具有磁黄铁矿型矿石磁铁矿型矿石理论值的特征,引起晶胞参数差异的主要原因是闪锌矿内Fe、Mn元素的含量。此外,两类矿石闪锌矿内Fe元素含量差距悬殊,Zn、Fe、Cd元素之间的替代关系和替代强度差异明显,结合研究区地质特征,认为这两类矿石可能是两次不同成矿作用的产物。     

Effect of bacterial activity on trace metals release from oxidation of sphalerite at low pH (<3) and implications for AMD environment

A series of experiments was conducted to better understand the bacterial influence on the release of trace metals during oxidation of sphalerite mineral and element cycles in acid mine drainage (AMD) systems. Batch experiments were carried out as biotic and abiotic control at pH 3. Acidithiobacillus ferrooxidans, sulfur and Fe(II) oxidizer, was used in the biotic sphalerite experiment. The abiotic control experiment was run without adding the bacteria. The release behavior of six trace metals (As, Cd, Co, Pb, Cu and Mn), Fe and Zn were determined during the period of 54 days. Compared to the abiotic experiments, enhanced oxidation of sphalerite by bacteria produced high sulfate (~2,000 mg/L) and Fe_tot (139 mg/L) along with the low pH (<2.3). Consistent with this, the concentration of trace metals (As, Cd, Co, Pb, Cu and Mn) was significantly higher in the biotic experiments than those in the abiotic experiments. Results indicate that the distributions of Co and Cd in both biotic and abiotic experiments are directly related to the sphalerite dissolution whereas Pb, Cu distribution shows no strong relation to sphalerite dissolution especially in the abiotic experiments. Pb distribution in the solution appears to be controlled by pH-dependent solubility. Approximately 80% of the trace metals were removed from the solution at the end of the biotic experiments along with biologically induced Fe precipitation. Experimental results showed that bacteria play major role not only in the release of trace metal from sphalerite but also in controlling concentration of the metals in the solution by producing Fe-oxyhydroxides. The study suggest that in order to develop an effective rehabilitation strategy for AMD, it is necessary to understand bio/geochemical processes governing mobilization and deposition of trace metals in the environment.     

Development of a Matrix‐Matched Sphalerite Reference Material (MUL‐ZnS‐1) for Calibration of In Situ Trace Element Measurements by Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry

Sphalerite (ZnS) is an abundant ore mineral and an important carrier of elements such as Ge, Ga and In used in high‐technology applications. In situ measurements of trace elements in natural sphalerite samples using LA‐ICP‐MS are hampered by a lack of homogenous matrix‐matched sulfide reference materials available for calibration. The preparation of the MUL‐ZnS1 calibration material containing the trace elements V, Cr, Mn, Co, Ni, Cu, Ga, Ge, As, Se, Mo, Ag, Cd, In, Sn, Sb, Tl and Pb besides Zn, Fe and S is reported. Commercially available ZnS, FeS, CdS products were used as the major components, whereas the trace elements were added by doping with single‐element ICP‐MS standard solutions and natural mineral powders. The resulting powder mixture was pressed to pellets and sintered at 400 °C for 100 h using argon as an inert gas. To confirm the homogeneity of major and trace element distributions within the MUL‐ZnS1 calibration material, measurements were performed using EPMA, solution ICP‐MS, ICP‐OES and LA‐ICP‐MS. The results show that MUL‐ZnS‐1 is an appropriate material for calibrating trace element determination in sphalerite using LA‐ICP‐MS.     

湖南栗山铅锌铜多金属矿床闪锌矿微量元素特征及成矿指示意义

位于江南造山带中段的湘东北地区是我国华南重要的金铅锌铜钴多金属矿产地之一,栗山铅锌铜多金属矿床是该区近年来找矿勘查新发现的一大型矿床。该矿床位于晚侏罗世—早白垩世幕阜山岩体南缘,矿体主要赋存于岩体及其与地层接触带的构造破碎带内,空间上与岩体关系密切,然而目前关于该矿床的研究十分薄弱。本文采用电子探针和激光剥蚀电感耦合等离子质谱仪开展了闪锌矿的原位微区微量元素分析。微量元素组成分析结果表明,闪锌矿以富集Co、Ga而贫Fe、Cd、Ge为特征,其中Fe、Mn、Cd、Co、Ga等元素以类质同象形式产出,而Cu、Pb、Ag和Sn等元素则还以包裹体形式赋存于闪锌矿中。根据不同微量元素间的相关关系,认为闪锌矿中可能存在Zn²⁺↔Fe²⁺、4 Zn²⁺↔2 Fe²⁺+Ge⁴⁺+□(其中□表示空位)、3 Zn²⁺↔2 Cu⁺+Ge⁴⁺、2 Zn²⁺↔Ag⁺+Sb³⁺等简单和复杂替代关系。闪锌矿的Zn/Fe、Ga/Ge、Ge/In、Ga/In比值和Fe温度计等指示闪锌矿形成于中低温(240~250 ℃)、低硫逸度(lgf(S₂)=-13.3~-9.6)环境。栗山矿区闪锌矿的微量元素组成特征有别于金顶砂岩型、SEDEX型、VMS型、MVT型和夕卡岩型铅锌矿,结合低的Cd/Fe(0.03~0.14,平均0.06)、Cd/Mn(1.54~6.30,平均2.91)比值和Ge含量,暗示该矿床成矿作用与岩浆活动有关。综合矿区地质特征和区域构造-岩浆演化,认为该矿床是在太平洋板块俯冲后撤引起的伸展构造背景下形成的与燕山期幕阜山岩体有关的中低温岩浆热液充填交代型矿床。该类型矿床闪锌矿具有鲜明的微量元素组成特征,可为判别具相似地质特征的矿床成因提供借鉴。     

新疆小热泉子铜(锌)矿床硫化物显微结构及稀土、微量元素研究

新疆小热泉子铜(锌)矿床位于大南湖晚古生代岛弧带内,矿体主要赋存于一套凝灰质火山碎屑沉积岩中,矿石类型主要为块状黄铜矿矿石、闪锌矿矿石和脉状硫化物矿石。硫化物的显微结构研究表明,黄铁矿主要发生脆型变形,形成碎裂结构、细粒化结构、充填交代结构、"布丁"结构以及变斑晶结构,黄铜矿和闪锌矿发生塑性变形,黄铜矿表现为"S型"面理结构以及在闪锌矿中呈团斑状结构,电子探针结果表明黄铜矿发生明显的活化迁移富集作用。硫化物的稀土微量元素研究表明,闪锌矿中Mn、Ga、As等元素含量很低,Ga/In<<1,Ge/In多数小于1,174相似文献   

Distribution and existing forms of trace elements from Maliping Pb-Zn deposit in northeastern Yunnan,China : A LA-ICPMS studyEI北大核心CSCD

The Sichuan-Yunnan-Guizhou (SYG) Pb-Zn metallogenic province, located in southwestern margin of the Yangtze Block, is an important part of the large-scale low-temperature metallogenic domain in southwestern China. The Maliping Pb-Zn deposit, situated in the central part of Zhaotong-Qujing metallogenic belt, was found in northeastern Yunnan Province recently. The orebody is hosted in Late Cambrian Yuhucun Formation, occurring as stratabound, tense and venis. The mineral assemblage of the Maliping deposit is relatively simple. The main sulfide minerals are sphalerite and galena with minor pyrite. Gangue minerals include mainly dolomite, calcite, quartz and barite. LA-ICPMS spots and mapping analysis for the different sulfides from Maliping Pb-Zn deposit, and the distribution and existing forms of germanium, cadmium, indium and other trace elements were investigated. The results show that different sulfides are characterized by different contents of trace elements. Mn, Cu, Sn, Cd, In and Ge are mainly enriched in sphalerite, while galena from this deposit is enrichment of Ag, Sb and Se, and pyrite is characterized by enrichment of As, Co and Ni. Comparing with the content of dispersed elements in different sulfides, the results indicate that sphalerite is the primary carrier mineral of Ge, In and Cd. Cd, Ge, In, Mn, As, Sb and Ag occur as isomorphous substitution in the sphalerite, and Cu mostly exists in sphalerite as isomorphism but part of Cu occurs as micro-inclusions (chalcopyrite) in sphalerite. Considered the distinct positive relationship between Cu and Ge, the results imply that the substitution mechanism of Ge and Cu is possibly 3Zn(2+) <-> Ge4+ + 2Cu(+). Additionally, sphalerite from Maliping Pb-Zn deposit is characterized by enrichment of Cd, Ge and depleted in Mn, Fe, Co and Sn which coincides with the feature of MVT Pb-Zn deposit and differs from the sedimentary-exhalative deposit and magmatic-hydrothermal deposit. On account of the geological features, other geochemical researches and its ore-forming temperature belonging to low temperature, it is suggested that the Maliping deposit belongs to an MVT Pb-Zn deposit. Notably, we imply that ore-forming fluid extracted indium of magmatic and volcaniclastic rocks from the metamorphic basement, resulting in the enrichment of indium in sphalerite from the deposit.     

云南澜沧老厂铅锌多金属矿床闪锌矿微量元素组成

云南澜沧老厂是三江成矿带南段最重要铅锌多金属矿床之一,通过LA-ICPMS和ICP-MS微量元素组成分析结果表明,矿床中闪锌矿属于铁闪锌矿,形成于中温环境,以富Fe、Mn、Cd和In等元素为特征,其中Fe、Mn、Cd、In等元素以类质同象形式赋存于闪锌矿中,而Pb、Cu 、Sn和Bi等元素含量变化范围较大,以显微包裹体(方铅矿和黄铜矿等)赋存于闪锌矿中。本矿床闪锌矿中Fe和Mn等微量元素组成与VMS矿床类似,但In和Cd的异常富集可能暗示其独特的成矿机制。总体而言,其闪锌矿微量元素组成特征和与燕山-喜山期花岗岩叠加改造作用有关的喷流沉积铅锌矿床(如云南白牛厂和广东大宝山)相似,而明显不同与矽卡岩型矿床(如核桃坪与鲁子园),更不同于MVT型铅锌矿床(牛角塘、会泽和勐兴)和金顶铅锌矿床。结合矿床产出地质特征,笔者认为云南澜沧老厂铅锌多金属矿区经历了古、中、新特提斯期不同程度的拉张与闭合发展演化,使矿床多期同位叠加成矿特征明显,其闪锌矿微量元素组成具喷流沉积成因特征,深部喜山期花岗斑岩与铅锌成矿作用关系不大,但在其侵入过程中叠加改造作用使闪锌矿等硫化物组合及其微量元素组成发生一定程度变化(如局部富集Sn和Sb等元素)。此外,两种测试方法结果对比可以看出,在硫化物单矿物微量元素分析中,LA-ICPMS相对于ICP-MS分析具有更高精度,不仅可以进行硫化物原位分析,并能即时了解微量元素在硫化物中赋存状态,而且克服了ICP-MS分析中由于单矿物选样不纯致使测试误差大等弱点。     

Partitioning of trace elements in co-crystallized sphalerite–galena–chalcopyrite hydrothermal ores

There is an abundance of published trace element data for sphalerite, galena and chalcopyrite in natural systems, yet for a co-crystallized assemblage comprising these base metal sulphides, there is no detailed understanding of the preferred host of many trace elements. Laser-ablation inductively-coupled plasma mass spectrometry trace element maps and spot analyses were generated on 17 assemblages containing co-crystallized sphalerite and/or galena and/or chalcopyrite from 9 different ore deposits. These deposits are representative of different ore types, geologic environments and physiochemical conditions of ore formation, as well as superimposed syn-metamorphic remobilisation and recrystallization. The primary factors that control the preferred base metal sulphide host of Mn, Fe, Co, Cu, Zn, Ga, As, Se, Ag, Cd, In, Sb, Te, Tl and Bi are element oxidation state, ionic radius of the substituting element, element availability and the maximum trace element budget that a given sulphide mineral can accommodate. Temperature, pressure, redox conditions at time of crystallization and metal source, do not generally appear to influence the preferred base metal sulphide host of all the trace elements. Exceptions are Ga, In and Sn recrystallized at high metamorphic grades, when the preferred host of Ga and Sn usually becomes chalcopyrite. In more typical lower temperature ores, the preferred host of Ga is sphalerite. Indium concentrations also increase in chalcopyrite during recrystallization. At lower temperatures the partitioning behaviour of Sn remains poorly constrained and shows little predictable pattern among the data here. The results obtained may be used as a tool to assess co-crystallization. If trace element distributions in a given base metal sulphide assemblage match those reported here, and assuming those distributions have not been significantly altered post (re-) crystallization, then it may be suggestive of a co-crystallized assemblage. Such information provides a foundation for novel attempts to develop trace element-in-sulphide geothermometers.     

滇东北麻栗坪铅锌矿床微量元素分布与赋存状态:LA-ICPMS研究

位于扬子板块西南缘的"川滇黔接壤铅锌矿集区"是我国西南大面积低温成矿域的重要组成部分,麻栗坪铅锌矿床位于该矿集区昭通-曲靖成矿带中段,是近年来滇东北地区新发现的铅锌矿床。本文以麻栗坪铅锌矿不同硫化物为研究对象,通过LA-ICPMS原位点测试和元素Mapping分析,尝试揭示该矿床中Ge、Cd和In等微量元素在不同硫化物中分布规律与赋存状态。本次研究发现,麻栗坪矿床不同硫化物中富集的微量元素明显不同,闪锌矿主要富集Mn、Cu、Sn、Cd、In和Ge,而方铅矿主要富集Ag、Sb和Se,黄铁矿则富集As、Co和Ni。闪锌矿是分散元素Ge、In和Cd的主要载体矿物,且Cd、Ge、In、Mn、As、Sb和Ag以类质同象形式赋存于闪锌矿中;而Cu则主要以类质同象形式存在,部分Cu以黄铜矿的显微包裹体形式赋存于闪锌矿中,其中以类质同象赋存于闪锌矿中Cu和Ge呈现明显的相关性,可能暗示其与Zn的置换方式为:3Zn2+Ge4++2Cu+。总体上,该矿床闪锌矿以富集Cd、Ge,贫Fe、Mn、Co、Sn为特征,这些微量元素组成与典型MVT型矿床基本一致,明显有别于喷流沉积和岩浆热液型矿床,而与中低温条件下形成的闪锌矿微量元素组成相似。结合该矿床后生成矿特征明显等地质地球化学研究成果,我们认为该矿床应属于MVT型铅锌矿床。值得注意的是,该矿床闪锌矿相对富集In,可能暗示其形成具有特殊性,这可能与其成矿流体在长距离运移过程中所流经地层有关,该类流体活化萃取了基底地层的中-酸性岩浆岩或火山碎屑岩中的In,致使矿床中闪锌矿相对富集In。