扬子板块北缘马元铅锌矿床闪锌矿LA-ICP-MS微量元素特征与指示意义

马元铅锌矿床是我国近年来在扬子板块北缘探获的大型铅锌矿床,对马元铅锌矿床闪锌矿微量元素进行了高精度的LA-ICP-MS测试研究,结果表明矿床闪锌矿微量元素含量具有低Fe、Mn,高分散元素Cd、Ge、Ga,低分散元素In的特征;闪锌矿Fe、Mn含量和Ga/Ge比值特征指示了矿床成矿流体温度不高,可能为与中低温盆地流体有关的铅锌矿床;闪锌矿中分散元素In、Ge特征能有效的区分铅锌矿床的成因类型:与岩浆或火山活动有关的铅锌矿床闪锌矿具有高In或低In,低Ge的特征,而与盆地卤水有关的中低温矿床中闪锌矿则普遍富Ge贫In。依据马元铅锌矿床微量元素特征,结合矿床地质与地球化学特征,认为马元铅锌矿应属于密西西比河谷型铅锌矿床(MVT铅锌矿床)。     

阿尔金喀腊达坂铅锌矿床金属硫化物元素地球化学特征及其对成矿作用的制约

喀腊达坂铅锌矿床是近年来在阿尔金北缘红柳沟-拉配泉金铜铁多金属成矿带内发现的一处大型铅锌矿床(铅锌铜金属资源量82.88万吨,平均品位:Zn 4.14%、Pb2.52%和Cu 1.10%)。相比找矿勘查取得的重大突破,对其成矿作用的研究则显得相对薄弱,目前有关该矿床成因的认识还存在分歧。本文试图通过硫化物电子探针和LA-ICPMS微量元素分析,结合元素Mapping面分析,查明闪锌矿和方铅矿中微量元素的分布特征和赋存状态,以期为理解该矿床成因提供有益信息。分析结果显示:闪锌矿相对富Fe、Mn和Cd等元素,贫In、Sn、Ga、Cr、Ge和Co等元素,Cu和Pb的含量变化大,Fe、Mn、Cd、In、Ga和Cr在闪锌矿中以类质同象形式存在,而Cu和Pb则可能既以类质同象形式又以显微包体形式存在;方铅矿相对富Bi、Sb、Ag和Tl,贫Cd、Cu、Sn和Te为特征,其中前者以类质同象形式赋存于方铅矿中。达坂闪锌矿的颜色以红褐色、灰白色和米黄色为主,其Zn、Fe、Cd、Ga和In含量及Zn/Cd、Zn/Fe和Ga/In比值显示闪锌矿的形成温度为中温。基于闪锌矿-方铅矿共生矿物对Cd地质温度计获得的温度范围为277～321℃,平均值为290℃,亦说明达坂矿床硫化物的形成温度不高。与全球不同成因铅锌矿床的微量元素及相关比值相比,达坂铅锌矿床硫化物的微量元素组成特征与VMS型矿床(如Marketorp、Eskay Creek、澜沧老厂等)更为类似,但达坂矿床的闪锌矿中黄铜矿"病毒"结构十分发育,加之矿体变质变形特征明显。因此,本文认为达坂铅锌矿床以VMS型成因为主,但不排除后期热液对其形成有一定程度的影响。     

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。     

内蒙古浩布高铅锌矿床闪锌矿微量元素特征及其地质意义

内蒙古浩布高铅锌矿床位于大兴安岭南段黄岗-甘珠尔庙成矿带,该带是我国北方重要的铅锌多金属成矿带之一。目前,浩布高矿床闪锌矿微量元素赋存机制尚不清晰,矿床成因类型亦存在一定的争议。本研究采用激光剥蚀电感耦合等离子体质谱仪(LA-ICP-MS)原位微量元素分析手段,结合机器学习方法,对浩布高闪锌矿微量元素组成特征、赋存机制以及矿床成因类型进行了探讨。LA-ICP-MS分析结果表明,浩布高矿床中闪锌矿以富集Fe、Mn、Co、Cu、Se、Ag、Cd、In、Sn等元素,贫Ni、Ga、Ge、As、Mo、Sb、Au、Tl、Pb、Bi等元素为特征。其中,Fe、Mn、In等元素主要以类质同象的方式替代Zn赋存于闪锌矿中,Cu、Ag、Sn等元素含量变化范围较大,可能部分以微粒包裹体的形式存在。In与Cu含量具有一定的正相关,推测In在闪锌矿中富集机理可能为Cu⁺+In■³⁺2Zn²⁺。Cd与Fe含量呈一定的正相关性,而与Zn含量呈负相关性,这可能暗示在闪锌矿中Cd主要以类质同象的方式置换Zn元素而非Fe元素。通过穷举闪锌矿微量元素图解发现,...     

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。     

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.     

黔东柏松铅锌矿床闪锌矿LA-ICP-MS微量元素组成特征及其地质意义

黔东柏松铅锌矿床位于扬子板块东南缘的湘西–黔东成矿带。与该成矿带内其他铅锌矿床相比,柏松铅锌矿床地质地球化学研究程度较低,矿床成因类型以及Cd、Ge、Ga等关键金属元素在闪锌矿中的赋存状态尚不清楚。本文通过LA-ICP-MS对该矿床闪锌矿微量元素组成进行分析,结果显示:柏松铅锌矿床中闪锌矿富集Cd、Fe、Ge、Pb,亏损V、Co、Ni、Cu、Te、Bi等元素。结合闪锌矿微量元素含量和Zn/Cd、Zn/Fe值特征,认为该矿床形成温度较低,根据Fe、Ga、Ge、Mn和In估算其成矿温度在75～135℃之间。闪锌矿中Fe与Cd具有较明显的负相关性,表明它们主要以类质同象的形式赋存于闪锌矿中,替代机制为:Zn²⁺?Fe²⁺、Zn²⁺?Cd²⁺,而Ge主要的替代机制为2Zn²⁺?Ge⁴⁺+□(□为晶体空位),Ga与Cu替代机制为2Zn²⁺?Ga³⁺+Cu⁺,In与Cu可能存在(Cu⁺     

豫西熊耳山蒿坪沟Ag-Au-Pb-Zn多金属矿床闪锌矿矿物学和微量元素组成特征及其成矿启示

蒿坪沟银金铅锌多金属矿床是豫西熊耳山地区重要的铅锌多金属矿床之一,矿体主要赋存在蚀变破碎带和断裂带内,成矿与区内岩浆活动关系密切。目前该矿床的研究集中于同位素地球化学、成矿时代和成矿物质来源等方面,但从矿物角度示踪成矿过程的报道较少。本文以矿石中不同世代闪锌矿为研究对象,开展电子探针和LA-ICP-MS原位主微量元素分析,查明不同世代闪锌矿的矿物学和微量元素组成特征,以反演矿床成矿物理化学条件进而约束矿床成因类型。结果表明,该矿床中闪锌矿主要存在两个世代：第一世代闪锌矿(Sp1)呈黑褐色或浅褐色,常与黄铁矿和黄铜矿共生,相对富集Fe、Mn、Cd、Cu和In;第二世代闪锌矿(Sp2)呈黄褐色或暗褐色,与大量方铅矿共生,裂隙被它形黄铁矿和碳酸盐充填,相对富集Co、Ge、Sn和Pb。闪锌矿中主要富集的元素为Fe、Co和In,其中Fe、Mn、Cd、Co和In等元素基本是以类质同象的形式赋存在闪锌矿的矿物晶格中,而Ag、Sb、Cu和Pb可能是以子矿物或显微包裹体的形式赋存。此外,Zn/Cd、Zn/Fe和Ga/In比值以及Fe温度计指示闪锌矿形成于中低温(沉淀时流体温度为229～259℃)和低硫逸...     

扬子板块周缘MVT型铅锌矿床闪锌矿微量元素组成特征与指示意义:LA-ICPMS研究

扬子板块周缘铅锌多金属成矿带内分布着数以百计的沉积岩容矿型铅锌矿床,它们不仅是我国主要的铅锌矿产地,同时也是重要的稀散元素(Ge、Ga等)生产基地。本次研究采用LA-ICPMS技术分别测定了扬子板块西南缘的会泽铅锌矿床、金沙厂铅锌矿床、大梁子铅锌矿床,扬子板块北缘的马元铅锌矿床以及扬子板块东南缘的凤凰茶田锌(铅)汞矿床中闪锌矿的微量元素组成,以揭示闪锌矿中微量元素(稀散元素)的富集规律和赋存状态,并为矿床成因类型的厘定及稀散元素矿产资源综合利用提供更多依据。LA-ICPMS微量元素测定结果显示闪锌矿中不同微量元素(稀散元素)分布不均匀,但这些矿床中闪锌矿总体以富集稀散元素Ge、Ga、Cd,贫In、Se、Tl、Te为特征,其Fe、Mn含量要明显低于与岩浆热液有关的高温闪锌矿,指示了扬子板块周缘铅锌矿床可能形成于中-低温成矿流体,而与岩浆热液无直接的成因联系,此外这些矿床中闪锌矿富Ge贫In的特征与其他的密西西比河谷型铅锌矿床(MVT)一致。同时,本次研究综合分析了闪锌矿中不同微量元素(稀散元素)之间的相关关系,并与闪锌矿微量元素LA-ICPMS时间分辨率特征相结合,研究表明:这些铅锌矿床中稀散元素Ge可能主要通过3Zn2+?Ge4++2(Cu+,Ag+)和2Zn2+?Ge4++□(晶体空位)的替代方式进入闪锌矿,Ga在闪锌矿中富集机理主要为2Zn2+?(Cu,Ag)++(Ga,As,Sb)3+。此外,为进一步揭示不同成因类型铅锌矿床中稀散元素的富集规律,本文还系统对比了全球范围内不同类型铅锌矿床闪锌矿的稀散元素(均为LA-ICPMS数据)组成特征,并初步探讨了造成不同成因闪锌矿中稀散元素(Ge、Ga和In)差异性富集的主要控制因素,研究表明:(1) Ge在中低温盆地卤水成矿系统(MVT和SEDEX矿床)和岩浆-火山热液成矿系统(浅成脉状铅锌矿床和VMS矿床)形成的闪锌矿中均可能富集成矿,但中低温浅成脉状矿床中Ge的富集程度要明显高于高温脉状矿床,指示了成矿温度是控制闪锌矿中Ge富集的一个重要因素。(2)铅锌矿床闪锌矿中In主要为岩浆来源,In倾向于在成矿温度较高的岩浆及火山热液成因铅锌矿床中富集成矿,而壳源的MVT和SEDEX型铅锌矿床中闪锌矿均贫In。可见除形成温度外,成矿物质来源是决定闪锌矿是否富In的关键因素。(3)除矽卡岩型铅锌矿床外,其他不同成因类型、不同形成温度的铅锌矿床中闪锌矿均可能富Ga。矽卡岩型铅锌矿床闪锌矿具有明显的贫Ga、Ge的特征,这可能是由于矽卡岩化过程中稀散元素Ga、Ge大量进入早期矽卡岩矿物,进而导致了成矿流体以及随后形成的闪锌矿中Ga、Ge的贫化。综上所述,闪锌矿中稀散元素富集与否和富集程度受成矿物质来源、成矿流体性质以及流体演化过程等多因素的综合控制。(4)扬子板块周缘铅锌矿床闪锌矿的微量元素(稀散元素)组成特征指示了它们形成于中低温成矿环境,稀散元素的富集规律与其它MVT型铅锌矿床类似。     

藏南扎西康矿床闪锌矿微量元素地球化学特征及地质意义北大核心CSCD

为进一步探讨扎西康矿床的成因,用电感耦合等离子体质谱仪(ICP-MS)对矿床中的闪锌矿进行了稀土、微量元素分析。结果表明,闪锌矿的稀土总量较低,轻稀土富集,重稀土亏损,轻重稀土分馏明显,稀土元素配分模型总体呈明显右倾,有明显负Eu异常和弱负Ce异常;微量元素相对富集Fe、Mn、Cd、Cu等,贫In、Ga、Ge、Tl等元素,Sn、Pb、Ag含量变化较大,与岩浆热液成因的闪锌矿相似,同时闪锌矿的ln Ga-ln In、Zn/Cd-Se/Te-Ga/In等成因判别图解中也清晰显示其为岩浆热液成因,说明扎西康锌多金属矿床可能与深部岩浆热液活动有关。     

Trace and minor elements in sphalerite: A LA-ICPMS study

Sphalerite is an important host mineral for a wide range of minor and trace elements. We have used laser-ablation inductively coupled mass spectroscopy (LA-ICPMS) techniques to investigate the distribution of Ag, As, Bi, Cd, Co, Cu, Fe, Ga, Ge, In, Mn, Mo, Ni, Pb, Sb, Se, Sn and Tl in samples from 26 ore deposits, including specimens with wt.% levels of Mn, Cd, In, Sn and Hg. This technique provides accurate trace element data, confirming that Cd, Co, Ga, Ge, In, Mn, Sn, As and Tl are present in solid solution. The concentrations of most elements vary over several orders of magnitude between deposits and in some cases between single samples from a given deposit. Sphalerite is characterized by a specific range of Cd (typically 0.2-1.0 wt.%) in each deposit. Higher Cd concentrations are rare; spot analyses on samples from skarn at Baisoara (Romania) show up to 13.2 wt.% (Cd²⁺ ↔ Zn²⁺ substitution). The LA-ICPMS technique also allows for identification of other elements, notably Pb, Sb and Bi, mostly as micro-inclusions of minerals carrying those elements, and not as solid solution. Silver may occur both as solid solution and as micro-inclusions. Sphalerite can also incorporate minor amounts of As and Se, and possibly Au (e.g., Magura epithermal Au, Romania). Manganese enrichment (up to ∼4 wt.%) does not appear to enhance incorporation of other elements. Sphalerite from Toyoha (Japan) features superimposed zoning. Indium-sphalerite (up to 6.7 wt.% In) coexists with Sn-sphalerite (up to 2.3 wt.%). Indium concentration correlates with Cu, corroborating coupled (Cu⁺In³⁺) ↔ 2Zn²⁺ substitution. Tin, however, correlates with Ag, suggesting (2Ag⁺Sn⁴⁺) ↔ 3Zn²⁺ coupled substitution. Germanium-bearing sphalerite from Tres Marias (Mexico) contains several hundred ppm Ge, correlating with Fe. We see no evidence of coupled substitution for incorporation of Ge. Accordingly, we postulate that Ge may be present as Ge²⁺ rather than Ge⁴⁺. Trace element concentrations in different deposit types vary because fractionation of a given element into sphalerite is influenced by crystallization temperature, metal source and the amount of sphalerite in the ore. Epithermal and some skarn deposits have higher concentrations of most elements in solid solution. The presence of discrete minerals containing In, Ga, Ge, etc. also contribute to the observed variance in measured concentrations within sphalerite.     

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。     

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.     

云南都龙超大型锡锌多金属矿床中闪锌矿微量及稀土元素地球化学特征

云南马关都龙锡锌多金属矿床位于滇东南老君山锡锌钨多金属成矿区南部,是我国三大锡石硫化物矿床之一,目前对其矿床成因认识存在较大分歧。本文采用ICP-MS对都龙矿床中闪锌矿微量元素及稀土元素组成进行分析,以探讨该矿床成矿作用,为甄别已有成因观点提供证据。结果表明,矿床中闪锌矿以富集Fe、Mn、In、Co、Sn和贫Cd、Ga、Ge、Ni等元素为特征,成矿温度属于中—高温,其微量元素组成与白牛厂矿床(与燕山晚期花岗岩有关的矽卡岩型矿床)中的闪锌矿非常相似,和远源矽卡岩型铅锌矿床(核桃坪和芦子园)中闪锌矿存在一定差异,明显有别于喷流沉积型铅锌矿床(云南澜沧老厂和广东大宝山)中闪锌矿。此外,该矿床闪锌矿稀土配分模式多为轻稀土元素富集中等的向右倾斜曲线,以LREE/HREE值高、Eu负异常明显和Ce异常不明显为特征,与矿区燕山晚期隐伏花岗岩稀土元素特征基本一致,成矿物质来源以矿区燕山晚期隐伏花岗岩为主。结合近期矿山开采和地质勘探所揭露的矿化和矽卡岩蚀变的垂向分带等矿床地质特征,认为云南马关都龙锡锌多金属矿床属于与燕山晚期花岗岩有关的矽卡岩型多金属矿床,其中层状矽卡岩的形成应为成矿流体顺层交代的结果,矿化类型和围岩蚀变的分带与隐伏岩体的距离有关。     

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.     

Ore Genesis for Stratiform Ore Bodies of the Dongfengnanshan Copper Polymetallic Deposit in the Yanbian Area, NE China：Constraints from LA-ICP-MS in situ Trace Elements and Sulfide S–Pb Isotopes

The Dongfengnanshan Cu polymetallic deposit is one representative deposit of the Tianbaoshan ore district in the Yanbian area, northeast(NE) China. There occur two types of ore bodies in this deposit, the stratiform ore bodies and veintype ones, controlled by the Early Permian strata and the Late Hercynian diorite intrusion, respectively. Due to the ambiguous genetic type of the stratiform ore bodies, there has been controversy on the relationship between them and veintype ore bodies. To determine the genetic type of stratiform ore bodies, laser ablation inductively coupled plasma mass spectrometry(LA-ICP-MS) in situ trace elements and S–Pb isotope analysis have been carried on the sulfides in the stratiform ore bodies. Compared with that in skarn, Mississippi Valley-type(MVT), and epithermal deposits, sphalerite samples in the stratiform ore bodies of the Dongfengnanshan deposit are significantly enriched in Fe, Mn, and In, while depleted in Ga, Ge, and Cd, which is similar to the sphalerite in volcanic-associated massive sulfide(VMS) deposits. Co/Ni ratio of pyrrhotites in the stratiform ore bodies is similar to that in VMS-type deposits. The concentrations of Zn and Cd of chalcopyrites are similar to those of recrystallized VMS-type deposits. These characteristics also reflect the intermediate ore-forming temperature of the stratiform ore bodies in this deposit. Sulfur isotope compositions of sulfides are similar to those of VMS-type deposits, reflecting that sulfur originated from the Permian Miaoling Formation. Lead isotope compositions indicate mixed-source for lead. Moreover, the comparison of the Dongfengnanshan stratiform ore bodies with some VMStype deposits in China and abroad, on the trace elements and S–Pb isotope characteristics of the sulfides reveals that the stratiform ore bodies of the Dongfengnanshan deposit belong to the VMS-type, and have closely genetic relationship with the early Permian marine volcanic sedimentary rocks.     

大兴安岭北段岔路口斑岩Mo-热液脉状Zn-Pb成矿系统硫化物微量元素的分布、起源及其勘探指示

岔路口斑岩Mo-Zn-Pb矿床位于大兴安岭北段,是近年来新发现的超大型斑岩-热液脉状Mo-Zn-Pb成矿系统,脉状Zn-Pb矿化直接叠置在斑岩Mo矿化顶部。本文挑选岔路口斑岩型矿化及热液脉型矿化的黄铁矿、闪锌矿、方铅矿,通过EMPA、ICP-MS等多种方法分析硫化物的主微量元素组成,发现岔路口各阶段硫化物均富集Mo元素,相比于斑岩型矿化各阶段中的黄铁矿,Zn、Pb、Mn、Cd、Ga、Ag、Bi等元素在铅锌矿阶段内相对富集;相比于过渡阶段,铅锌阶段闪锌矿中Mo、Co元素及方铅矿中的Bi、Cd和Ag元素含量下降。微量元素在不同阶段内的变化可能是流体降温和天水混合的结果。黄铁矿的稀土总量与成矿岩体最接近,且与成矿岩体和围岩有相似的稀土配分模式,并有较明显的Eu负异常;黄铁矿宽广的Y/Ho比值(25.0~39.0)与成矿岩体的Y/Ho比值范围(27.4~38.7)最接近,同时包括了围岩相对较窄的Y/Ho比值(25.7~31.3),这表明成矿物质主要与成矿岩体同源,可能加入了一定量的围岩物质,岔路口硫化物富Mo的特征受控于深部斑岩Mo矿化岩浆-热液系统。对比东秦岭-大别W-Mo-Pb-Zn矿集区的远源热液脉状Pb-Zn矿床,岔路口浅部近源脉状矿化中的黄铁矿具有更高含量Mo/Ag-Bi/Sb比值和Mo/Pb-Sn/Sb比值,因此浅部硫化物的高Mo含量以及黄铁矿中相关元素比值的高值,可为脉状Zn-Pb矿化附近隐伏斑岩钼矿化的勘探提供新线索。此外,与其他热液脉状和斑岩型矿床相比,岔路口矿床硫化物更富集中高温元素;且综合分析多类矿床的硫化物的微量元素后,本文还初步查明不同矿床类型硫化物富集的微量元素,这一尝试可为矿床成因的判断提供新的思路。