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。     

高压下金属硫化物载Re能力的实验研究初探

<正>越来越多的研究结果表明,Re在不同硫化物间存在一定的分配规律。例如:辉钼矿的Re含量往往比共生的黄铁矿(Li et al.,2011)或黄铜矿(Zhu and Sun,2013)高3~5个数量级;黄铁矿的Re含量普遍比闪锌矿(Morelli et al.,2004)和方铅矿(Stein et al.,2000)高3~30倍;铅锌矿床中闪锌矿的Re含量又明显高于方铅矿(Liu et al.,2015)。这些很可能与Re在硫化物中分配系数的差异,即各硫化物载Re能力的     

柿竹园和香炉山W多金属矿床中硫化物微量元素特征:来自原位LA-ICP-MS分析

华南包括两个世界级的W矿带,分别是南岭和江南造山带W成矿带。柿竹园W多金属矿床位于南岭地区,香炉山W矿床位于江南造山带东北部。两个矽卡岩W矿床都发育硫化物成矿阶段。但硫化物和成矿元素组成存在显著的差异。前者由含Pb、Zn、Ag硫化物和黝铜矿、银黝铜矿、含Ag斜方辉铅铋矿和铁硫锡铜矿硫盐组成;后者主要为磁黄铁矿。柿竹园远接触带Pb-Zn-Ag矿脉中硫化物(闪锌矿、黄铜矿、方铅矿和磁黄铁矿)较富集B、Mn、Cr、Sb、Sn和Hg,香炉山似层状矽卡岩和硫化物-白钨矿矿体中硫化物(磁黄铁矿、黄铜矿和闪锌矿)较富集W、Se和Bi。两个矿床中黄铜矿、闪锌矿和方铅矿较富集Ag,黄铜矿、闪锌矿富集In和Sn,闪锌矿还富集Cd。两个矿床中的硫化物微量元素分析表明与矽卡岩W矿成矿相关的硫化物可载有多种微量元素。这些元素参与到硫化物中程度由多种因素控制。具体如下,硫化物中B含量高低与成矿相关岩体中B含量相关;在相对高温和还原条件下,硫化物中W含量较高;闪锌矿中Mn和Cd与Zn发生取代作用; Cr可以一定程度进入到硫化物中,并受成矿流体中Cr含量影响; Se与S发生了一定程度的取代进入硫化物,并受流体中它的含量控制; Bi在闪锌矿与黄铜矿易形成固溶体;硫化物中Sb含量受初始流体中它的含量影响,方铅矿中易包裹一定的辉锑矿(Sb_2S_3)或含Sb的硫盐矿物; Ag是否形成独立的矿物相和进入哪些硫化物中,取决于流体中Ag的初始含量和硫化物的沉淀次序;硫化物中Hg的含量受温度影响。     

新疆哈密卡拉塔格块状硫化物矿床金银赋存状态研究

新疆哈密红海黄土坡VMS矿床位于东天山卡拉塔格隆起带,是卡拉塔格矿集区内新发现的块状硫化物矿床。矿体产于卡拉塔格隆起带核部火山沉积岩建造中,具有典型的VMS型矿床“上层下脉”二元结构特征。该矿床中含金硫化物矿石主要有块状黄铁矿黄铜矿、块状黄铁矿黄铜矿闪锌矿、块状黄铁矿闪锌矿黄铜矿和块状闪锌矿。文中在对各类含金硫化物矿石进行详细的矿相学研究基础上,结合扫描电子显微镜与能谱仪联用技术(SEM/EDS),对硫化物样品中金、银的赋存状态进行研究。结果表明,4种块状硫化物中的主要矿物形成于多个期次,主要包括VMS成矿期(黄铁矿阶段、闪锌矿黄铜矿黝铜矿方铅矿阶段、石英重晶石阶段)、热液叠加期(石英黄铁矿黄铜矿闪锌矿方铅矿阶段)和表生期(铜蓝纤铁矿阶段)。矿区首次发现4颗金银金属互化物(银金矿、碲银矿),其较大的化学成分差异指示了热液环境由中酸性中性转变为更有利于Au、Ag迁移沉淀的偏碱性。后期的偏碱性热液对VMS成矿期形成矿物产生了交代作用,使得Au、Ag活化再富集。由于后期热液叠加改造,红海VMS型矿床中Au、Ag不仅赋存于VMS成矿期后期中低温闪锌矿黄铜矿阶段,也赋存于VMS成矿期早期中高温黄铁矿阶段,并贯穿整个热液叠加期。各含金矿物组合中除4颗金银金属互化物外Au多呈显微不可见状态,推测Au、Ag主要以原子或离子形式赋存于矿物晶格中或矿物空位处。     

硫化物矿物对银的表面吸附作用及其成矿意义

通过硫化物矿物对银离子的吸附实验研究表明，在５０℃时，硫化物矿物对溶液中银离子的等温饱和吸附量大小顺序是：方铅矿＞黄铜矿＞辉锑矿＞闪锌矿；当温度超过７０℃时，这个顺序变为：辉锑矿＞方铅矿＞黄铜矿＞闪锌矿。这与天然多金属矿床中硫化物矿物银的含量顺序是一致的。实验证明，硫化物具有把溶液中的银富集到固体（矿物中）达１０６量级以上的能力。这些结果极好地解释了多金属矿床中银在普通硫化物中含量大小的顺序及锑和银在矿床和矿物上密切共生的关系。     

乌奴格吐山斑岩铜钼矿床中金属矿物的特征

乌奴格吐山矿床是一个大型斑岩铜钼矿床。金属矿物中以贯通性矿物黄铁矿含量最多。钼、铜、铅锌三个主要成矿阶段，黄铁矿的平均温度分别为３３１℃、２２８℃、＜２００℃。黄铁矿中Ｃｏ、Ｎｉ、Ａｓ等微量元素特征为成矿物质来源提供了重要信息。辉钼矿是唯一重要的钼矿物，主要赋存在石英－钾长石化带，以２Ｈ型为主。铜矿物有黄铜矿、锌砷黝铜矿、斑铜矿等，以黄铜矿为主，主要赋存在石英－绢云母－水白云母化带。不同世代黄铜矿微量元素的差异反映了成矿溶液的变化。方铅矿、闪锌矿主要赋存于石英－伊利石－水白云母化带。闪锌矿贫铁（ＸＦｅＳ＝４ｍｏｌ％—８ｍｏｌ％），方铅矿含Ａｇ（０．０１％—０．３５％）。     

我国一些铜镍硫化物矿床主要金属矿物的特征

镍、铜共生的铜镍硫化物矿床是镍矿也是铜矿的重要矿床类型。磁黄铁矿，镍黄铁矿、黄铜矿是这类矿床的主要金属矿物。它们的某些矿物学特征，特别是微量元素Ｃｏ／Ｎｉ比值，与其他铜矿类型明显不同，这三种矿物组成不同于任何其他铜矿类型的典型矿物共生组合， 形成特殊的海绵损铁状、球滴状构造。     

大兴安岭西坡二道河子铅锌银矿床银的赋存状态、迁移形式及沉淀机制

二道河子铅锌银多金属矿床是一个中型浅成热液矿床,它产于大兴安岭西坡得耳布干成矿带中段的晚中生代“双峰式”火山岩区。根椐野外矿脉的穿插关系和室内矿相学研究,将热液成矿期划分为四个成矿阶段,即：石英-黄铁矿阶段(Ⅰ)、石英-多金属硫化物阶段(Ⅱ)、石英-闪锌矿-方铅矿-银矿物阶段(Ⅲ)和石英-方解石-黄铁矿阶段(Ⅳ)。采用显微镜和电子探针(EPMA)微区技术对矿床中的硫化物和银矿物进行分析,结果表明,银的存在形式主要为可见银(>1μm),其次为不可见银(<1μm)。可见银主要以显微包体银和独立银矿物的形式存在,而不可见银主要呈次显微包体银和晶格银;显微(次显微)银常以浑圆状或不规则状分布在硫化物内部或硫化物和石英颗粒间隙,独立银矿物呈脉状或集合体状主要分布于方铅矿(偶见闪锌矿)脉的裂隙和边缘,晶格银赋存在方铅矿中,含量极少。结合前人研究成果,认为成矿早期(石英-黄铁矿阶段)成矿热液中的金属元素(如Ag、Cu、Fe、Pb和Zn元素等)以氯络合物形式运移,伴随着流体不混溶/沸腾作用,硫氢络合物成为主要的迁移形式。随着温度、压力的降低和大气降水的参与,成矿流体自下而上运移,并先后经历...     

内蒙某地多金属硫铁矿床中伴生金,银的赋存状态

矿床中伴生的金、银含量变化较大,银主要呈自然银和金银矿以包裹体和裂隙充填式赋存在黄铜矿中.其次呈类质同象赋存在方铅矿和闪锌矿中.金则呈次显微银金矿赋存在黄铁矿中.     

桂东北铅锌矿床银的富集规律

作者对桂东北地区铅锌矿床中银的产出特征和富集规律进行了阐述。银主要以首次发现的含银硫盐矿物（深红银矿、银黝铜矿和含银锌黝铜矿等）产出，其次呈杂质元素分散在金属硫化物中，银的含量按方铅矿、黄铜矿、闪锌矿、黄铁矿的顺序依次降低，矿体从上向下具Ｃｕ、Ｐｂ（Ａｇ），Ｚｎ→Ｐｂ，Ｚｎ→Ｚｎ的垂向变化规律，银主要富集于上部，并与方铅矿、黄铜矿紧密伴生。     

大兴安岭南段主要金属矿物的成分标型特征

内蒙古东部的黄岗-甘珠尔庙矿带是地处大兴安岭南段的锡乡金属矿带。矿带中各矿床的磁铁矿、锡石、方铅矿、闪锌矿的主元素和微量元素数据表明,这些矿床是属与燕山期岩浆活动有关的矽卡岩型、热液型、斑岩型和云英岩型矿床;其成矿金属组分中的铁来源于区域晚古生代海相中-基性火山岩,部分铅锌来源于区域二叠纪地槽沉积物。研究还表明,与燕山期偏碱性花岗岩有关的锡钨矿床和与燕山期中酸性花岗岩类有关的铅锌矿床其方铅矿、闪锌矿的微量元素含量及比值存在明显的差别。     

Geochemical Peculiarities of Galena and Sphalerite from Polymetallic Deposits of the Dal’negorskii Ore Region (Primorsky Krai,Russia)

New data on the composition of the major minerals from the skarn and vein polymetallic deposits of the Dal’negorskii ore region are reported. Analysis of galena and sphalerite was carried out by the X-ray fluorescent energy-dispersive method of synchrotron radiation for the first time. It is shown that the minor elements in major minerals of different deposits are typomorphic. Among these elements are Fe, Cu, Ni, Cd, Ag, Sn, and Sb, as well as In in sphalerite and Te in galena. The high concentrations of Ag, Cu, Te, Cd, and In in the extracted minerals indicate the complex character of mineralization. The compositional patterns of ore minerals characterize the sequence of mineral formation from the skarn to vein ores, and the sequence of deposits from the mesothermal to epithermal conditions. This provides geochemical evidence for the stage model of the formation of mineralization in the Dal’negorskii ore region.     

四川石棉金矿床中的黝铜矿族矿物

四川石棉西部碳酸盐岩系中的金矿床产于泥盆系中统,受层间蚀变破碎带控制。其中分布有为数较多的黟同矿族矿物,与黄铁矿、黄铜矿、方铅矿、闪锌矿和Ａｕ－Ａｇ系列矿物共同组成矿石的矿物组合和Ａｕ－Ｃｕ－Ａｇ－Ｐｂ－Ａｓ－Ｓｂ－Ｂｉ的元素组合。电子探针分析表明黝铜矿族矿物有同铜矿、黝铜矿、砷黝铜矿和锌砷黝铜帮等,其中,Ｆｅ－Ｚｎ、ＡｓＳｂ之间分别呈完全类质同象。在垂向上,黝铜矿的成分自上而下由富锌锑向富铁砷演     

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。     

Distribution Patterns of Ag in Hydrothermal Precipitates from the Okinawa Trough

The Okinawa Trough is characterized by enrichment of Ag in hydrothermal precipitates; however, the distribution of this enrichment remains poorly constrained. This study presents the results of a field-emission scanning electron microscopy and electron-microprobe analysis based mineralogical and geochemical investigation of the spatial distribution of Ag within Ag-rich sulfide samples from the Okinawa Trough. The tetrahedrite, covellite, and galena in these samples contain high concentrations of Ag(average values of 1.60, 0.78, and 0.23 wt%, respectively) and also various Ag sulfosalts. Examination of the Ag budget of these samples indicates that most of the Ag is hosted by tetrahedrite followed by galena. The Ag within tetrahedrite is incorporated by substitution into the Cu site, whereas galena becomes Ag-enriched by the coupled incorporation of monovalent Ag, Tl, and Cu, and trivalent Sb and Bi into Pb lattice sites. Tetrahedrite and galena containing higher concentrations of Sb favor increased Ag substitution. Four sets of Ag host minerals are identified with distinct ore formation temperatures. Tetrahedrite and galena concentrate the majority of Ag at medium temperatures(150–300°C). Other Ag host minerals concentrate only minor or trace amounts of Ag, including massive sphalerite, chalcopyrite, and pyrite at high temperatures(300°C), colloform pyrite and sphalerite at low temperatures(150°C), and Ag-sulfosalts at even lower temperatures(100°C).     

Study on the Cu–As–Sb–Ag–Bi–Pb–Te Sulfosalt Minerals from the Hydrothermal System of Southwestern Hokkaido,Japan

Shin‐Otoyo, Suttsu, Teine, Date, Chitose, and Koryu are sites rich in precious and base metal Miocene–Pleistocene epithermal deposits, and located in southwestern Hokkaido, Japan. The deposits are predominantly hosted by the Green Tuff Formation of Middle Miocene age. Ore petrographic study of these deposits shows the occurrence of variable quantities of Cu–As–Sb–Ag–Bi–Pb–Te sulfosalt minerals. Determination of mineralogical and chemical compositions of the sulfosalt minerals was undertaken to elucidate the time and spatial changes of the sulfide‐sulfosalt minerals. Various types of sulfosalt minerals identified from gold–silver and base metal quartz–sulfide veins represented some sulfosalt mineralization phases, such as the Cu–Fe–Sn–S phase of mawsonite and stannite; Cu–(As,Sb)–S phase of tetrahedrite–tennantite and luzonite–famatinite series minerals; (Cu,Ag)–Bi–Pb–S phase of emplectite, pavonite, friedrichite, aikinite, and lillianite–gustavite series minerals; (Ag,Cu)–(As,Sb)–S phase of proustite–pyrargyrite and pearceite–polybasite series minerals; and Bi–Te–S phase of tetradymite and kawazulite minerals. There are some trends in the paragenetic sequence of sulfosalt mineralization in southwestern Hokkaido (in complete or partial) as follows: sulfide → Cu–Fe–Sn–S → (Cu,Ag)–Bi–Pb–S → (Bi–Te–S) → Cu–(As,Sb)–S → ([Ag,Cu]–[As,Sb]–S). The formation of sulfosalt minerals is characterized by the introduction of some elements such as Sn, Bi, and Te at an earlier stage and an increase or decrease of some elements such as As and Sb, followed by the introduction of Ag at the later stage of ore mineral paragenesis sequence. Mineral composition of the Chitose and Koryu deposits are slightly different from those of Shin‐Otoyo, Suttsu, Teine, and Date due to their lack of Sn (tin) and Bi (bismuth) mineralization. The variable concentrations and relationships are not simply with redistributed trace elements from the original sulfide minerals of chalcopyrite, pyrite, galena, and sphalerite. Some heavier elements were also introduced during the replacement reaction, which is consistent with the occurrence of their associated minerals.     

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.     

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。     

Ore and Skarn Mineralogy of the Yamato Mine,Yamaguchi Prefecture,Japan, with Emphasis on Silver‐, Bismuth‐, Cobalt‐, and Tin‐bearing Sulfides

Assemblages and chemical compositions of ore minerals from the Yamato mine, Yamaguchi Prefecture, Japan, were investigated in detail to clarify its characteristics as a skarn deposit. Special attention was paid to silver‐, bismuth‐, cobalt‐, and tin‐bearing sulfide minerals and native gold at the mine, which are described here for the first time. Samples of arsenopyrite‐dominant massive ore, and garnet‐rich, clinopyroxene‐garnet‐rich, and wollastonite‐bearing skarn ores were collected from the mine dump. Arsenopyrite is the most abundant ore mineral (>80 vol.%) in the massive ore, in association with both As‐poor/free and As‐bearing pyrite. The major ore minerals in the skarn specimens are pyrite, pyrrhotite, arsenopyrite, chalcopyrite, galena, and sphalerite, along with minor argentite, Ag‐Pb‐Bi sulfate, matildite, bismuthinite, native bismuth, molybdenite, scheelite, stannite, stannoidite, cassiterite, cobaltite, gersdorffite, and Co‐rich violarite. In addition, native gold is observed in the interstices of gangue minerals. Based on the mineral assemblages and textures of the specimens examined, the major ore minerals formed in the early stage of mineralization, and the Bi‐, Ag‐, Co‐, Ni‐, As‐ and Sn‐mineralization occurred in the middle stage. Native gold was deposited in the late stage. The estimated formation temperature of the middle mineralization stage was 312±5 °C, according to iron and zinc partitioning between stannite and coexisting sphalerite. The mineralogical properties and mineralization process of the Yamato mine are consistent with those of common skarn‐ and vein‐type ore deposits associated with ilmenite‐series granitoids in the San‐yo and San‐in districts.