王水溶样-等离子体质谱法同时测定地质样品中砷锑铋银镉铟

采用王水溶样-等离子体质谱法测定地质样品中砷、锑、铋、银、镉、铟6个元素,探讨了测定过程中对砷、银、镉、铟干扰的消除问题。方法检出限(10SD,μg/g)分别为:砷0.2、锑0.01、铋0.005、银0.01、镉0.01、铟0.005;精密度(RSD,n=12)分别为砷1.3%~3.0%、锑0.65%~2.3%、铋1.2%~2.6%、银3.2%~6.6%、镉3.7%~8.0%、铟1.1%~5.0%;加标回收率分别为砷96.8%~106%、锑102%~108%、铋102%~106%、银99.7%~104%、镉103%~108%、铟97.9%~100%。用拟定方法测定了国家一级标准物质中砷、锑、铋、银、镉、铟,结果与标准值相符。方法适用于岩石、土壤、水系沉积物等地质样品的测定。     

氢化物发生-原子荧光光谱法测定三氧化二锑中锡

500℃时在锌粉、氯化铵存在下,锑以三氯化锑形式被挥发除去,锡与锌形成锌-锡合金留在残渣中,从而消除锑对锡的干扰。在10%(体积分数)的盐酸介质中,硼氢化钾将锡(Ⅱ)还原成四氢化锡,用氢化物发生-原子荧光光谱法测定锡的荧光强度。方法检出限为0.20 mg/kg,精密度(RSD,n=7)为3.73%,回收率为91.0%~104.5%。     

离子交换分离-石墨炉原子吸收光谱法测定高纯铟中的痕量银

银是高纯铟的常检痕量元素,由于银含量低,一般的分析方法难以达到期望的检出限。本研究样品用硝酸溶解,强酸性阳离子交换树脂分离,试液蒸发浓缩后用石墨炉原子吸收光谱法测定高纯铟中痕量银。通过溶样方法、离子交换分离条件和仪器测定条件实验,结果表明,以0.7 mol/L硝酸作为淋洗液进行分离,样品中痕量砷、铝、铁、锡及大量的铟可被分离除去;铜、镉、镁、镍、锌、铅、硅和铊不能与银分离,但对测定无影响。方法线性范围为0～50 pg,相对标准偏差(RSD,n=8)小于10%,银的检出限为0.3 pg,测定下限为0.8ng/g,比文献方法的0.02～1μg/g中最低者低2个数量级,加标回收率为93.3%～110.0%。本方法由于分离了基体铟,避免了铟对银测定的影响,兼之将试液浓缩,有效地降低了检出限,且测定时无需使用基体改进剂,成本低,灵敏度较高,适合于高纯铟中痕量银的分析。     

我国稀散金属元素铟在铅锌矿山中的分布规律与金属资源量初步估算

针对铅锌矿床MVT型(密西西比河谷型)、SEDEX型(喷流沉积型)及岩浆热液型(指与岩浆岩及火山作用有关热液矿床,包括诸如斑岩型、矽卡岩型、热液交代型矿床和陆相火山岩型矿床等)三种主要成因类型,开展稀散元素铟(In)在不同成因类型铅锌矿床中富集情况的数据资料收集统计、野外地质调查和室内研究工作,初步总结稀散金属铟(In)在铅锌矿床中的分布规律,并对赋存于我国铅锌矿山中的铟金属总量进行了估算。研究表明:铟的富集成矿具有矿床类型的专属性,主要在锡-铅锌硫化物矿床中富集,锡含量较低的各成因类型铅锌矿石中铟含量普遍不高;而含锡富铟的多金属硫化物矿床中,闪锌矿中In值远高于其他硫化物,是铟主要的寄主矿物。组合分析法计算出分布于我国铅锌矿山中的铟金属蕴藏量,表内保有储量级别为9832t,查明资源储量级别为26 115t。     

岩浆-热液系统中铟的成矿作用

铟作为支撑新兴高科技产业发展的关键金属,主要应用于电子工业、半导体、焊料合金及航空航天等领域,对国家安全和经济发展至关重要.当前铟的重要来源是与花岗质岩浆有关的锡多金属矿床,其中铟的富集程度远超其他类型矿床.文章在简要概括铟矿床类型的基础上,探讨了铟在岩浆-热液系统各演化阶段的富集过程以及锡、铟同步富集的原因.在岩浆演化过程中,如果有黑云母、角闪石等铟的主要载体矿物发生分离结晶,铟的成矿潜力便会被大大削弱.当铟进入成矿流体后,铟的氯化物、氟化物和氢氧化物对铟的搬运有重要作用,流体的温度、pH值以及金属配体的种类和浓度是控制铟迁移和沉淀的重要因素.而当铟从流体中沉淀时,因四次配位的In3+与贱金属硫化物(闪锌矿、黄铜矿、黝铜矿等矿物)中四次配位的金属离子更相似,造成大量的铟以类质同象替换的方式进入硫化物而与锡发生分离;沉淀后的含铟矿物在后期地质过程中可能经历铟的重新活化、迁移和扩散等过程,导致铟再次富集.铟的富集过程与锡有关,这可能是由于铟和锡具有相似的地球化学性质,二者在表生环境中活动性弱,会滞留在经历化学风化的富黏土的沉积岩中,这样的沉积岩经变质作用会形成大量的云母类矿物,而黑云母作为铟和锡的共同载体,其在高温条件下发生分解可能是导致铟和锡在矿床中同步富集的根本原因.此外,新近在一些贫锡岩浆热液矿床中发现铟也能够超常富集,其机理尚不清楚.加强表生环境中锡与铟预富集过程的研究以及贫锡矿床中铟富集机制的研究,对查明铟-锡共生、分离机制和完善铟成矿理论至关重要.     

电感耦合等离子体发射光谱法测定锡矿中的锡

传统的极谱法、光度法或容量法来检测锡矿石中锡,其操作繁琐,工艺流程较长。现采用电感耦合等离子体发射光谱法(ICP-AES法)对锡矿石中锡进行测定,该方法简单快速,干扰少。其检出限可达0.012μg/ml,检测范围为0.003%~10%,相对误差小于5%,精密度为1.30%~2.94%。     

锡的螯合滴定

本文用巯基乙酸(TGA)或柠檬酸(Cit)定量释放Sn-EDTA中的EDTA,选择性的螯合滴定法测定样品中的Sn。大量金属离子(除Bi~(3+)外)包括Al~(3+)、Th(Ⅳ)、Zr(Ⅳ)和∑RE,均不干扰。选用二甲酚橙-溴化十六烷基吡啶(CPB)为指示剂,终点清晰、敏锐。已成功地测定高铝锡合金、锡铅镉合金、锡基合金和锡精矿中的Sn。     

灰化酸溶-电感耦合等离子体质谱法测定煤炭中的镓锗铟

准确测定煤炭中的镓、锗和铟为煤炭中稀散元素的地球化学勘查提供了重要依据,对稀散金属的综合利用具有重要的经济意义。采用现有的分析方法处理煤炭样品时,由于镓、锗和铟灰化温度不同,而锗的灰化条件严格,测定结果受灰化温度影响大,因此三元素不能同时进行前处理和测定。本文通过试验优化了煤炭中镓、锗、铟的最佳灰化温度为625℃;采用硝酸-硫酸-氢氟酸溶解灰分,8 mol/L硝酸进行复溶,避免了锗的挥发损失;通过优化仪器工作条件和干扰实验,以103Rh为内标元素,选择71Ga、74Ge和115In作为测定同位素,消除了各元素的干扰,建立了电感耦合等离子体质谱法同时测定煤炭中镓、锗和铟的分析方法。结果表明:镓、锗和铟的标准曲线线性相关系数均在0.9999以上,三元素检出限分别为0.004、0.003、0.002μg/L,精密度为1.17%~3.15%,加标回收率为96.6%~102.0%。应用本方法分析标准物质GBW07363、GBW07457和GBW07428的测定值与认定值相符。与传统的分光光度法和原子吸收光谱法比较,本方法操作更为简便快速,具有更低的测定下限,并且可以多元素同时测定。     

铟矿床时空分布、成矿背景及其成矿过程

铟是一种稀散金属元素,特殊的地球化学性质导致其难以形成独立的矿床,均以伴生矿产的形式产出于富锡岩浆热液与陆相火山-次火山热液系统,以及相对贫锡的海底(火山)热液系统。研究表明,铟矿床广泛分布于活动的大洋或大陆板块边缘,成因上主要与板块俯冲以及碰撞作用密切相关,少量与火山岩以及喷流沉积岩相关的块状硫化物矿床形成的有利构造背景则是弧后环境和裂谷环境。在不同地质历史时期,铟的巨量堆积作用主要有新第三纪、白垩纪、泥盆纪三个时期,对应的矿化类型分别以浅成低温热液-锡多金属脉型、矽卡岩型以及块状硫化物(VMS)型矿床为主,其中与铟成矿作用相关的岩浆岩多为A型或S型花岗岩。铟独立矿物目前报道约15种,主要包括自然铟、硫铟铜矿、铟石、樱井矿、羟铟石等,其中以硫铟铜矿最为广泛。绝大多数铟主要以类质同象的形式赋存于闪锌矿中,其次为黝锡矿、锌黄锡矿、黄铜矿、锡石、黝铜矿、砷黝铜矿等。富铟闪锌矿通常形成于高温热液体系,常显示阶段性富集特征,最普遍的置换机制为(Ag,Cu)~++In~(3+)2Zn~(2+)。文章指出为完善铟金属成矿理论,需进一步加强铟的成矿物质来源、铟沉淀的物理化学条件及其与主矿种成生关系的研究。     

硫铟铜矿在福建紫金山铜金矿床的发现及深部找矿意义

硫铟铜矿(CuInS2)是一种罕见的铟独立矿物,在中国未曾报道过。在研究福建紫金山铜金矿床深部矿石矿物组成时,首次发现了硫铟铜矿。硫铟铜矿通常见于中高温热液矿床,紫金山铜金矿床东南矿段铜矿体中出现了硫钨锡铜矿、硫钼锡铜矿、硫铁锡铜矿、硫砷锡铜矿、锡砷硫钒铜矿、似黄锡矿、辉钼矿等高温矿物,指示紫金山矿床深部成矿温度较高,成矿流体中In、Sn、Pb、Zn、Mo、W含量较高,具有斑岩型等中高温热液成矿系统的找矿潜力。     

电感耦合等离子体质谱法测定高纯铟中铁

建立了基于碰撞/反应池（CCT）技术的电感耦合等离子体质谱法（ICP-MS）测定高纯铟中铁元素的方法。在CCT模式下,有效地消除了如⁴⁰Ar¹⁶O等多原子离子对待测元素的干扰,不分离基体就可直接测定铁。方法检出限为0.06ng/mL,精密度（RSD,n=11）<8%,回收率为94.0%～102.1%。方法与现行的国家标准分析方法相比,操作简便、高效。     

In-bearing potential of tin‒sulfide mineralization in ore deposits of the Russian Far East

The increased demand for indium has made it necessary to revise prospects of In-bearing tin ore deposits in the Russian Far East on the basis of geological data and results of recent analytical methods (X-ray fluorescence with synchrotron radiation, atomic absorption, and ICP-MS). The average In contents in ores of the Tigrinoe and Pravourmiiskoe deposits vary from 55 to 70 ppm, which allows tin ore deposits with Sn?sulfide mineralization to be considered as quite promising with respect to In production from ores of Russian deposits. By their estimated In reserves, the Tigrinoe and Pravourmiiskoe deposits may be attributed to large ore objects.     

氢化物发生原子荧光光谱法测定氢氧化铟中砷含量

文章对氢化物发生原子荧光光谱法测量氢氧化铟中砷含量的分析方法进行了研究,采用硫酸联胺把五价砷预还原成三价砷,利用三氯化砷的挥发性,经蒸馏分离砷,消除了基体铟干扰。方法线性范围为2ng/mL~70ng/mL,检测下限为2ng/mL,加标回收率为96%~113%,实际样品分析相对标准偏差为4.57%(n=5)。本方法与等离子体发射光谱法、DDTC-Ag分光光度法的分析数据吻合。     

Distribution of indium in ores of some base metal and tin–sulfide deposits in Siberia and the Russian Far East

The study of base-metal massive sulfide and tin–sulfide deposits in Siberia and the Russian Far East has revealed that the indium content in ores exceeding the average statistical value at similar deposits worldwide could be economically important. Sphalerite and chalcopyrite and chalcopyrite, bornite, and sphalerite are the major indium carriers in the base-metal massive sulfide and tin–sulfide ores, respectively. In addition, base-metal massive sulfide ores have high Cd, Ag, and Te contents, whereas tin–sulfide ores have elevated Ge, Ga, and Nb contents. This has stimulated the investment attractiveness of these deposits.     

Resource Evaluation and Some Genetic Aspects of Indium in the Japanese Ore Deposits

Abstract. There have been two primary sources for industrial indium; one from massive sulfides, while the other is dissemination-veins and skarns, related to felsic igneous rocks. The latter group of the In-bearing deposits is abundant in the Japanese Islands. Indium occurs as In-minerals such as sakuraiite, roquesite, laforetite and many unidentified minerals, but the majority is contained as an impurity in sphalerite, and tin and copper sulfides. Average grades of the ores from which indium has been extracted vary from a few ppm (e.g., Kosaka mine) to more than 300 ppm (Toyoha mine). The amount of indium in all the major basemetal deposits is estimated by analyzing representative samples. The main indium deposits are subvolcanic and tin-poly-metallic vein types. The largest one is Toyoha mine (4,700 tons hi) and the Ashio mine (ca. 1,200 tons In) was found to be the second largest. Many small occurrences, were recognized in the Miocene magnetite-series belt, besides the classic occurrences in the ilmenite-series granitic terrains of SW Japan, including the Ikuno and Akenobe tin(-tungsten) polymetallic veins, located in the northern margin of the late Cretaceous Sanyo ilmenite-series province. Magnetite-series magmas with deep source are necessary to concentrate sulfur in the magma chamber but sedimentary source rocks and their reducing agents are needed to collect and to precipitate indium. The Japanese islands are essentially accretionary terrains intruded by various deep oxidized magmas; thus forming magnetite/ilmenite-series paired belts, which are sometimes mixed. This unique geologic setting may be the most fundamental reason why indium is rich in vein-type deposits of the Japanese Island arcs.     

火焰发射光谱法测定锂辉石中锂

样品用氢氟酸-高氯酸混合酸消解处理,用火焰原子发射法测定锂辉石中的锂含量。结果显示,在1%(体积分数)的硝酸介质中,空气压力0.3 MPa、乙炔流量1.2 L/min的条件下测定,100倍量的钾、钠、钙、钡、锶等共存元素不干扰测定。方法回收率为94.0%~106.0%,精密度(RSD)小于2%(n=10)。     

New data on distribution of indium in ore deposits of Central Kazakhstan

Iron, tin, tungsten, copper, and polymetallic deposits are examined and the paper investigates the mineral distribution of indium in mineral deposits in central Kazakhstan. Indium is a relatively rare element; of the 18 formations examined only five revealed high concentrations of indium. Economic accumulations were discovered only in Early and Late Variscan skarnitic formations with lead-zinc, copper, and bismuth mineralizations. Among the hypogene minerals, indium was found in sulfides, and silicates. Among supergene minerals indium was found only in oxides, carbonates, and silicates. Sphalerites are the principal collector of indium. No connection between the enrichment in indium and the typomorphic peculiarities of different varieties of sphalerites could be established. In mineral deposits with higher indium concentration, a paragenetic connection of this element with tin is noticeable. Regular enrichment of sphalerites in indium would admit as most probable an isomorphous replacement of zinc and bivalent iron by indium. — A.W. Bellais     

In, Sn, Pb and Zn Contents and Their Relationships in Ore-forming Fluids from Some In-rich and In-poor Deposits in China

All the indium-rich deposits with indium contents in ores more than 100×10- 6 seems to be of cassiterite-sulfide deposits or Sn-bearing Pb-Zn deposits, e.g., in the Dachang Sn deposit in Guangxi, the Dulong Sn-Zn deposit in Yunnan, and the Meng'entaolegai Ag-Pb-Zn deposit in Inner Mongolia, the indium contents in ores range from 98×10-6 to 236×10-6 and show a good positive correlation with contents of zinc and tin, and their correlation coefficients are 0.8781 and 0.7430, respectively. The indium contents from such Sn-poor deposits as the Fozichong Pb-Zn deposit in Guangxi and the Huanren Pb-Zn deposit in Liaoning are generally lower than 10×10-6, i.e., whether tin is present or not in a deposit implies the enrichment extent of indium in ores. Whether the In enrichment itself in the ore -forming fluids or the ore-forming conditions has actually caused the enrichment/depletion of indium in the deposits? After studying the fluid inclusions in quartz crystallized at the main stage of mineralization of several In-rich and In-poor deposits in China, this paper analyzed the contents and studied the variation trend of In, Sn, Pb and Zn in the ore-forming fluids. The results show that the contents of lead and zinc in the ore-forming fluids of In-rich and -poor deposits are at the same level, and the lead contents range from 22×10-6 to 81×10-6 and zinc from 164×10-6 to 309×10-6, while the contents of indium and tin in the ore-forming fluids of In-rich deposits are far higher than those of In-poor deposits, with a difference of 1-2 orders of magnitude. Indium and tin contents in ore-forming fluid of In-rich deposits are 1.9×10-6-4.1×10-6 and 7×100-6-55×10-6, and there is a very good positive correlation between the two elements, with a correlation coefficient of 0.9552. Indium and tin contents in ore-forming fluid of In-poor deposits are 0.03×10-6-0.09×10-6 and 0.4×10-6--2.0×10-6, respectively, and there is no apparent correlation between them. This indicates, on one hand, that In-rich ore-forming fluids are the material basis for the formation of In-rich deposits, and, on the other hand, tin probably played a very important role in the transport and enrichment of indium.