次显微金在黄铁矿的毒砂中的赋存状态新探讨

重新认识了含金风黄铁矿，含金毒砂中次显微金的电子顺磁共振实验和溶解实验的结果，指出它们均不能作为存在在类质同象金的证据，含金黄铁矿和含金毒砂中的顺磁中心可能由Ａｓ，Ｓ之间的类质同象取代引起；硝酸溶解金的载体矿特后溶液中出现的Ａｕ＾３＋离子可能来自金的碲化物的微包裹体金，进而认为含金黄铁矿和含金毒砂中不可能存在类质象金。     

晶格金的电子顺磁共振研究

在国内,笔者首次采用电子顺磁共振(EPR)波谱仪研究了含金黄铁矿和含金毒砂。低温(77K)和室温(300K)下的EPR谱线都具有一个含金标型吸收峰,该峰具有各向同性的g因子,g=2.001±0.001;而不含金的黄铁矿和毒砂均无该吸收峰。这是由于在含金黄铁矿和含金毒砂中,Au~ 等不同电价的离子替换晶格中的Fe~(2 ),产生顺磁中心。故EPR波谱仪是寻找金矿的重要手段,值得推广。     

湖南黄金洞金矿床毒砂中金的赋存状态的研究

本文对湖南黄金洞金矿主要载金矿物毒砂进行了金含量、X射线衍射、电子探针、扫描和透射电镜、电子顺磁共振波谱及穆斯堡尔谱等系统分析研究.结果表明,含金毒砂在成分上及结构上都明显地偏离理想毒砂;金含量高而稳定;毒砂中的铁为F_e~(3+);金主要呈晶格金存在,以类质同象形式置换毒砂中的砷.     

毒砂中元素混入物的实际意义

毒砂(FeAs_(0.9)S_(1.1)—FeAs_(1.1)S_(0.9)含有较大量的钴(高达9％)已为人们所熟知,但毒砂含有一定数量的金则尚未引起足够的重视。事实上,大多数内生金矿床中韵毒砂都含有金,金的含量可高达400～600克/吨。据近年矿物学研究的新成果,毒砂中成类质同象代换元素混入物有钴、镍、锑、铋、硒、碲、金等多种元素。在金矿床中的毒砂内,金以类质同象方式代换铁决定了内生金矿床中毒砂含金的普遍性。据大量数据统计毒砂中的微量元素大致平均含量如下:     

金矿床中黄铁矿-毒砂-辉锑矿标型及金的赋存状态——以湖南省金矿床为例

湖南及类似地区的金矿床,金高度富集在黄铁矿、毒砂和辉锑矿中.这些载金的硫（砷）化物具有各自特征性的标型.由于黄铁矿、尤其是毒砂中的金大多属于质点小于0.1 μm的不可见金,不仅在光学显微镜下无法找到,即使利用电子探针和在高倍电镜下进行金的特征X射线扫描亦未发现金矿物富集区.由此引起了这类矿物中的金是呈超微细粒形式存在,还是以类质同像存在于其矿物晶格中的不同看法.所以,研究黄铁矿和毒砂的标型特征,查明金的赋存状态,对金的利用十分重要.经有关矿床多项实验研究及选矿试验结果,认为黄铁矿与毒砂中的不可见金,除次显微金外主要应为“纳米金”（矿物金）,而非晶格金（结构金）.     

桂东金矿黄铁矿标型特征及找矿意义

通过对桂东金矿含金和不含金黄铁矿的晶形、物理性质、晶胞参数、成分、热电性及红外吸收谱等，认为该区含金黄铁矿的标型特征在矿床成因研究和指导和矿方面有很重要意义。     

紫木凼金矿床载金矿物及金的赋存状态

紫木凼金矿床主要载金矿物为含砷黄铁矿和毒砂,氧化矿石中,金呈显微粒状自然金－显微金嵌布于褐铁矿,石英水云母,方解石的颗粒间或孔隙中,原生矿石中,金主要呈次显微粒自然金－次显微金包裹体,其次是类质同像形式赋存在含砷黄铁矿和毒砂矿物中。     

金矿床中金与黄铁矿和毒砂的关系

卡林型金矿中的金,以肉眼,甚至在显微镜下都看不到,因而称之为“不可见金”.经过金的物相分析,发现Au与毒砂、黄铁矿有关.进一步的问题是:Au在毒砂、黄铁矿中呈何状态分布,是呈微细的独立矿物?还是类质同象?是以化学键进入毒砂、黄铁矿的晶格?还是吸附在其表面?进一步的研究表明,世界上其他类型金矿,如浊积岩型金矿、造山带内太古代绿岩带金矿、变质金矿、与火成岩有关的金矿,甚至含金的块状硫化物矿床,其中的金除了以自然金(可见金)产出外,在黄铁矿、毒砂、辉锑矿、雄黄等硫化物中还含有不可见金.从不可见金到可见金,需经过热液蚀变作用,在高As条件下,温度和硫逸度的升高,可溶出不可见金,在温度下降和还原条件下,Au以可见金形式存在于蚀变环带中.这种从不可见金到可见金的转换过程,反映了Au、As、S以及Fe等元素的地球化学特征.金矿中的黄铁矿和毒砂具有相似的结构,包括在其原始生长的晶体中含有不可见金,并且在稍后的成矿阶段内形成赋存有可见金的蚀变环带.蚀变环带以As含量高为特征,并且,后期的可见金是沿裂隙或毒砂与黄铁矿的粒间分布.可见金是热液活化了矿物内的不可见金而形成的.     

邦布造山型金矿床黄铁矿原位微量元素特征及其成矿意义数

邦布金矿床是目前在雅江缝合带研究程度最高且唯一正在开采的大型造山型金矿床.为理解邦布金矿床中金的来源及迁移沉淀机制,运用原位微区分析技术对邦布矿床中不同世代含金黄铁矿的微量元素组成进行测定.结果显示,亲铁元素Co、Ni主要以类质同象的形式进入到黄铁矿的晶格中替代Fe,As和Se呈类质同象形式替换S,Au是以纳米颗粒的形式均匀或不均匀的分布于不同产状的黄铁矿之中.邦布金矿床中的含金石英脉中三个不同世代的黄铁矿的Co/Ni比值均小于1,保存了围岩中黄铁矿的信息,显示出一种沉积或沉积改造成因.Au与As和Se具有明显的正相关关系,As和Se对Au的迁移及富集具有重要的作用.      

黄铁矿的激光拉曼谱在金矿评价中的应用

黄铁矿的拉曼光谱研究一直被人们所忽视，本文采用理论计算与实验测定相互验证的方法。求得含金黄铁矿中Ａｕ＋－［Ｓ２］２－伸缩振动的拉曼位移为３７０ｃｍ－１，弯曲振动的拉曼位移为１１１ｃｍ－１，为确定黄铁矿中晶格金的存在提供了依据。同时研究发现，含金性不同的黄铁矿，它们的拉曼特征存在显著差异：①含金性好的黄铁矿，其振动频率稍有低频方向偏移；②富金黄铁矿的拉曼强度比贫金或无金黄铁矿的拉曼强度大得多；③就小秦岭金矿床的黄铁矿而言，富金黄铁矿的ＩＰＤ＞１，贫金或无金黄铁矿的ＩＰＤ＜１；④宫金黄铁矿晶格振动的拉曼强度比其他振动的变化更为显著。此外，文中对差异产生的机理还进行了分析推导。     

Ore-microscopic and geochemical characteristics of gold-bearing sulfide minerals,El Sid Gold mine,Eastern Desert,Egypt

Gold deposits at El Sid are confined to hydrothermal quartz veins which contain pyrite, arsenopyrite, sphalerite and galena. These veins occur at the contact between granite and serpentinite and extend into the serpentinite through a thick zone of graphite schist. Gold occurs in the mineralized zone either as free gold in quartz gangue or dissolved in the sulfide minerals. Ore-microscopic study revealed that Au-bearing sulfides were deposited in two successive stages with early pyrite and arsenopyrite followed by sphalerite and galena. Gold was deposited during both stages, largely intergrown with sphalerite and filling microfractures in pyrite and arsenopyrite.Spectrochemical analyses of separated pyrite, arsenopyrite, sphalerite and galena showed that these sulfides have similar average Au contents. Pyrite is relatively depleted in Ag and Te. This suggests that native gold was deposited in the early stage of mineralization. Arsenopyrite and galena show relatively high concentrations of Te. They are also respectively rich in Au and Ag. Tellurides are, thus, expected to be deposited together with arsenopyrite and galena.     

陕西镇安丘岭卡林型金矿金的赋存状态和富集机理

丘岭金矿床是西秦岭地区重要的卡林型金矿之一, 金矿化赋存于上泥盆统南阳山组和下石炭统袁家沟组地层中, 容矿岩石的岩性为钙质粉砂岩、粉砂质页岩和泥质灰岩.金矿石中主要金属矿物为黄铁矿和毒砂, 非金属矿物则以石英、方解石和绢云母为主.通过对矿石矿物黄铁矿和毒砂的扫描电镜-能谱分析、电子探针分析和激光剥蚀电感耦合等离子体质谱分析, 对丘岭金矿床金的赋存形式和富集机理进行了较为详细的研究.结果表明, 丘岭金矿床中金主要以次显微不可见金的形式存在, 其次为显微可见金.次显微金包括: (1)固溶体金(Au+), 主要存在于环带状细粒黄铁矿的含砷增生边区域和毒砂中, 少量存在于环带状黄铁矿的核部不含砷区域; (2)纳米级自然金颗粒(Au0), 存在于粗晶黄铁矿中.环带状细粒黄铁矿核部的次显微金可能主要以胶体吸附的形式存在, 暗示容矿岩石在沉积成岩过程中有金的初步富集, 而环带状黄铁矿幔部和毒砂中的Au则主要来源于成矿流体, 以S和As的络合物形式搬运.显微可见金主要分布在细粒黄铁矿的晶体边缘和热液蚀变绢云母、石英及方解石中, 粒径通常小于3~5 μm, 其形成可能与成矿流体中金的局部过饱和及成矿流体对细粒黄铁矿和毒砂中次显微金的活化和再次富集有关.      

硫化物中不可见金的研究现状

近年来,不可见金的研究,运用高分辩透射镜和离子探针等综合测试方法取得了很大突破。不可见金,指的是硫化物中以超显微包裹体或固熔体形式存在的超显微金、次显微金。金质点上限近来Cook等定为0.1μm。由加拿大、希腊、美国等一些金矿床研究表明,硫化物中不可见金主要见于卡林金矿床以及热液、块状硫化物及矽卡岩型矿床中,其形成多与载体矿物黄铁矿、毒砂相关,并往往优先富集于毒砂中,如卡林金矿床黄铁矿金含金量为数十至数n×10-n×100×10-6,而毒砂中则高达近一倍。不可见金的研究,在当前无论对其矿石加工工艺研究,还是对找矿工作,都具有重要意义。     

金矿床中毒砂标型特征及金的赋存状态——以湖南金矿床为例

湖南含砷金矿资源储量大,分布广,类型多.矿床中的砷矿物主要为毒砂,几乎所有金矿床中的毒砂都含Au（一般120×10-6~250×10-6）,且比共生的黄铁矿含Au量高2~5倍,甚至1个数量级以上.毒砂中金的分布率高达64.3%~94.05%.毒砂的生成期有早、晚2期.化学成分为富S亏As型,并以富含微量元素Sb（Se）、Ni、Co而贫Mn及晶胞参数a0值增大等为标型特征.大多数含Au毒砂均含有相当数量的“不可见金”,即使利用电子探针也难以发现.初步认为毒砂中的“不可见金”多呈纳米级微细粒状存在.     

Metamorphic Rock-hosted Disseminated Gold Deposits—A Case Study of the Xiaotongjiapuzi Gold Deposit of Eastern Liaoning

The Xiaotongjiapuzi gold deposit occurs in a Palaeoproterozoic rift accretionary terrane in eastern Liaoning and is hosted by a carbonate formation of the Dashiqiao Formation, Liaohe Group. The metamorphic grade of the host rock is low amphibolite-high greenschist facies. Gold, which is mainly invisible, is distributed in pyrite and arsenopyrite. The grains of Au-bearing sulphide minerals are fine, ranging from 0.0 n to 1 mm. The wall-rock alterations are characterized by low-temperature silification, hydro-sericitization, sericitization and carbonatization. The homogenization temperatures of the fluid inclusions in quartz closely associated with gold mineralization range from 140 to 240° C. The metallogenic age represented by the Ar-Ar isotopic age of sericite is 167 Ma. Comparisons and studies show that the Xiaotongjiapuzi gold deposit can be classified as the submicron-sized disseminated deposit (analogous to the Carlin-type) hosted in metamorphic rocks.     

Metamorphic Rock-hosted Disseminated Gold Deposits--A Case Study of the Xiaotongjiapuzi Gold Deposit of Eastern Liaoning

The Xiaotongjiapuzi gold deposit occurs in a Palaeoproterozoic rift accretionary terrane in eastern Liaoning and is hosted by a carbonate formation of the Dashiqiao Formation, Liaohe Group. The metamorphic grade of the host rock is low amphibolite-high greenschist facies. Gold, which is mainly invisible, is distributed in pyrite and arsenopyrite. The grains of Au-bearing sulphide minerals are fine, ranging from 0.0 n to 1 mm. The wall-rock alterations are characterized by low-temperature silification, hydro-sericitization, sericitization and carbonatization. The homogenization temperatures of the fluid inclusions in quartz closely associated with gold mineralization range from 140 to 240° C. The metallogenic age represented by the Ar-Ar isotopic age of sericite is 167 Ma. Comparisons and studies show that the Xiaotongjiapuzi gold deposit can be classified as the submicron-sized disseminated deposit (analogous to the Carlin-type) hosted in metamorphic rocks.     

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.     

Mineralogy of the Boroo Gold Deposit in the North Khentei Gold Belt,Central Northern Mongolia

Mineral assemblages and chemical compositions of ore minerals from the Boroo gold deposit in the North Khentei gold belt of Mongolia were studied to characterize the gold mineralization, and to clarify crystallization processes of the ore minerals. The gold deposit consists of low‐grade disseminated and stockwork ores in granite, metasedimentary rocks and diorite dikes. Moderate to high‐grade auriferous quartz vein ores are present in the above lithological units. The ore grades of the former range from about 1 to 3 g/t, and those of the latter from 5 to 10 g/t, or more than 10 g/t Au. The main sulfide minerals in the ores are pyrite and arsenopyrite, both of which are divisible into two different stages (pyrite‐I and pyrite‐II; arsenopyrite‐I and arsenopyrite‐II). Sphalerite, galena, chalcopyrite, and tetrahedrite are minor associated minerals, with trace amounts of bournonite, boulangerite, geerite, alloclasite, native gold, and electrum. The ore minerals in the both types of ores are variable in distribution, abundance and grain size. Four modes of gold occurrence are recognized: (i) “invisible” gold in pyrite and arsenopyrite in the disseminated and stockwork ores, and in auriferous quartz vein ores; (ii) microscopic native gold, 3 to 100 µm in diameter, that occurs as fine grains or as an interstitial phase in sulfides in the disseminated and stockwork ores, and in auriferous quartz vein ores; (iii) visible native gold, up to 1 cm in diameter, in the auriferous quartz vein ores; and (iv) electrum in the auriferous quartz vein ores. The gold mineralization of the disseminated and stockwork ores consists of four stages characterized by the mineral assemblages of: (i) pyrite‐I + arsenopyrite‐I; (ii) pyrite‐II + arsenopyrite‐II; (iii) sphalerite + galena + chalcopyrite + tetrahedrite + bournonite + boulangerite + alloclasite + native gold; and (iv) native gold. In the auriferous quartz vein ores, five mineralization stages are defined by the following mineral assemblages: (i) pyrite‐I; (ii) pyrite‐II + arsenopyrite; (iii) sphalerite + galena + chalcopyrite; (iv) Ag‐rich tetrahedrite‐tennantite + bournonite + geerite + native gold; and (v) electrum. The As–Au relations in pyrite‐II and arsenopyrite suggest that gold detected as invisible gold is mostly attributed to Au⁺¹ in those minerals. By applying the arsenopyrite geothermometer to arsenopyrite‐II in the disseminated and stockwork ores, crystallization temperature and logfs₂ are estimated to be 365 to 300 °C and –7.5 to –10.1, respectively.