临沧锗矿床的稀土元素地球化学研究

通过对临沧锗矿床中基底花岗岩、矿化煤以及硅质岩的稀土元素地球化学研究认为盆地基底花岗提供了形成锗矿化的锗和形成硅质岩的硅；本区陆相热水成因硅质岩的Ce异常不明显，相对富集LREE；矿化煤相对富集HREE，这可能主要与矿化煤在含锗热液的相互作用过程中，煤对重烯土的优先富集有关。     

临沧锗矿褐煤的稀土元素地球化学

采用ICP-MS测定了临沧锗矿中51件含矿煤，5件无矿煤的稀土元素和锗含量，并与含矿煤层中热水成因燧石及其底白云母花岗岩进行对比，探讨了含矿煤与无矿煤的稀土元素地球化学及其与锗超常富集的关系。得出几点初步认识（1）无矿煤和含矿煤的稀土元素主要来自基底白云母花岗岩；（2）无矿煤属正常沉积产物，含矿煤组成叠加了热水活动产物；93）形成临沧锗矿的锗可能主要由热水活动带来。     

临沧锗矿床成因初探

本文根据临沧锗矿床中富锗煤与硅质岩的空间分布规律，富锗煤中黄铁矿的硫同位素组成，锗在矿化煤层中的品位变化规律以及硅质岩的地球化学特征，探讨了分散元素锗形成独立矿床的可能机制，研究结果表明，与矿化煤层互层的硅质岩为热水沉积成因，矿化煤层中的锗主要来自形成硅质岩的热水溶液，而这种热水溶液中的锗则主要由盆地基底的富锗花岗岩所提供。     

临沧超大型锗矿床有机质与锗矿化的地球化学特征

临沧锗矿床是一产于第三系含煤岩系中的超大型矿床。矿床的最初锗源与盆地西缘的二云母花岗岩有关。主矿体产于下煤组沉积旋回的早期地层中，每一沉积阶段早期形成的褐煤和碳质泥岩中富含锗，最高含量达１４７０×１０＾－６。褐煤和碳质泥岩在矿化过程中平均富集了１６４－１６９倍。根据锗含量，褐煤和碳质泥岩可分为锗含量小于１２×１０＾－６的低锗煤（泥岩）和大于９０×１０＾－６的高锗煤（泥岩）。高锗煤中有机质富含氧官能     

一个富铜（银）矿床的成因及其形成机制的研究

铜鼓塘铜（银）矿床是一个隐伏富矿。主要形成于地洼期。具有控矿因素复杂、物质来源多，成因类型多，多期多阶段成矿等特征，应属地洼型多因复成矿床；且地洼区的地壳演化，地幔活动、矿源层（岩）的广布、叠加、改造矿化则是形成富铜（银）矿床的主要机制。     

西藏冈底岛弧带甲马铜多金属矿床成矿物质来源及成因研究

甲马铜多金属矿床位于冈底斯岛弧构造带甲马弧内沉积盆地内，它呈层状、似层状展布于该盆地中的多底沟组礁灰岩（J3d)与林布宗组砂板岩（K1l)之间的过渡带内，并严格受地层层位的控制。其含矿岩石为热水交代夕卡岩和与矿床有密切成因关系的热水沉积岩（透辉石－斜长石岩），。通过容矿岩石和矿床的同位素，稀土元素、矿物包裹体成分等示踪研究，认为矿床的成矿金属物质来自盆地基底－弧火山岩，成矿流体来自古海底热水循环系统，硫来自地层中的生物硫；水－岩反应（交代）是成矿重要机制，故该矿床系古海底热水交代成因，属与古海底热水循环系统有关的一种独特的热水交代型夕卡岩矿床。     

云南昭通临翔区大田河锗矿成因探讨

云南临翔大田河锗矿矿体呈层状、似层状、透镜状赋存于新近系中新统南林组第二段和第四段,锗矿与煤共生,其形态及产状受煤岩层控制.矿床成因类型为多渠道供源、多阶段成矿的热水沉积-改造矿床.     

安徽向山铁硫矿区硅质岩特征及成因意义

宁芜向山—皇姑山地区铁硫矿床中及附近存在大片硅质岩,属热泉沉积的硅华。其微量元素Al、Mn、Cu、Pb、Zn含量较高,且具有稀土元素总量较低,Ce明显亏损,Eu明显富集等特征。据岩石学、岩石化学特征,结合微量元素、稀土元素与同位素等综合研究表明,矿床附近硅质岩为热水成因,硅质可能来自下伏及深部地层。     

毕家山铜锌矿床有机地球化学研究（Ⅰ）：可溶有机质特征与矿床若干…

本文对毕家山铅锌矿床和围岩中可溶有机质进行了分析，研究了矿床中有机质的性质，来源和成熟度，进而探讨发矿床中有机质的原始运移形式，成矿溶液可能的成因以及矿床形成的环境。结果表明，矿床中有机质主要属水生生物和细菌成因，它起源于灰岩矿源层，其原始形式可能为腐殖酸。     

安微向心铁硫矿区硅夺特征及成因意义

宇芜向山－皇姑山地区铁硫矿床中及附近存在大片硅质岩,属热泵沉积的硅华。其微量元素Ａｌ、Ｍｎ、Ｃｕ、Ｐｂ、Ｚｎ含量较高,且具有稀土元素总量较低,Ｃｅ明显亏损,Ｅｕ明显富集等特征。据这,岩石化学特征,结合微量元素、稀土元素同位素等研究表明,矿床附近硅质岩为热水成因,硅质可能来自下伏及深部地层。     

锆石Ge含量和年龄对云南临沧锗矿床物质来源的约束

云南临沧锗矿床产在以临沧花岗岩为基底的中新世断陷盆地中。已有研究表明,成矿元素Ge来自基底花岗岩,但临沧花岗岩是复式岩基,具有多期次的岩浆活动,而Ge来自哪期岩浆活动并不清楚。文章对采自晓街、临沧、勐库和勐海的7个花岗岩样品(纵贯临沧岩基)进行了LA-ICP-MS锆石原位Ge元素含量分析和U-Pb年代学研究。研究结果表明,岩基主体岩浆活动时代与前人研究成果一致,为(215.6±2.7)Ma~(236.9±3.7)Ma,同时也有少量继承锆石(303~2533 Ma);w(Ge)在主岩浆期的锆石中为0.23×10-6~4.21×10-6,平均0.53×10-6,在继承锆石中为0.34×10-6~3.43×10-6,平均1.18×10-6;而在本次研究中新发现的年龄为106.5 Ma和87.7 Ma的年轻锆石中w(Ge)高达102×10-6。因此,推测临沧锗矿床中Ge来源于晚期岩浆或热液作用。这个结果为成矿理论的深入研究提供了新依据。     

中国锗矿成矿规律概要

锗是一种重要的稀散元素,在半导体、光电器件和其他工业领域扮演着重要角色。文章通过对已有研究成果的系统梳理,初步总结了中国锗矿的资源特征和成矿规律,并建立了成矿谱系。研究认为,中国主要的锗矿床和富锗矿床可被划分为煤层型锗矿、碳酸盐岩容矿型锗矿、岩浆热液型富锗矿床、火山岩型富锗矿床和沉积型矿产中的潜在锗资源5种类型,较为重要的类型包括煤层型和碳酸盐岩容矿型。锗成矿作用时间跨度较大,从元古代到新生代均有矿床形成,但相对集中于中生代。空间上,不同类型锗矿的分布各具特点,煤层型锗矿主要分布于大兴安岭和西南三江地区;碳酸盐岩容矿型锗矿主要分布于川滇黔地区;岩浆热液型富锗矿床、火山岩型富锗矿床主要分布于长江中下游地区和南岭地区。根据锗矿的时空分布特征及其与构造演化的关系,文章共划分出15个锗成矿带,建立了21个与锗成矿作用有关的成矿系列。     

On the geological availability of germanium

Based on a detailed statistical analysis of chemical data published in the scientific literature, estimates were made of the minimum amounts of recoverable Ge contained within sulphidic zinc ores and coals, given current processing technologies. It is expected that at least 119 kt (～7 kt in zinc ores and ～112 kt in coal) of recoverable germanium exist within proven reserves (at present stage of knowledge) at grades in excess of 100 ppm in sphalerite and 200 ppm in coal, while at least 440 kt (～50 kt in zinc ores and ～390 kt in coal) should become recoverable in the future, being associated to coal reserves at 8–200 ppm Ge and zinc resources containing in excess of 100 ppm Ge in sphalerite. Mississippi Valley Type (MVT) deposits are expected to be the most important hosts of germanium-rich sphalerite, while both brown and hard coals are expected to be equally important as hosts of germanium. The approach taken in this publication shows that reliable minimum estimates for the availability of by-product metals lacking suitable reserve/resource data may be attained by using robust statistical methods and geochemical data published in the scientific literature     

临沧锗矿床的微量元素地球化学

采用ICP-MS测定了临沧锗矿中51个含矿煤、5个无矿煤、9个硅质岩样品的微量元素含量,并与基底二云母花岗岩进行对比,探讨了含矿煤与无矿煤的微量元素地球化学及其与锗超常富集的关系,得出几点认识: a 含矿煤、无矿煤和硅质岩中的大多数微量元素来自基底的二云母花岗岩; b 热水携带了成矿所必需的锗; c Nb可作为锗矿化的指示元素      

锗的地球化学及资源储备展望

锗是众多高新技术领域的重要原材料,随着无人驾驶、5G、太阳能电池和催化剂等产业的飞速发展,锗在中国及全球未来需求量将十分巨大,在国民经济建设中具有重要地位,许多国家将其作为国家重要战略资源进行严格控制、管理和储备,因此,锗资源的地质勘探和战略储备是今后国家持续发展的重要需要。文章总结了锗的地球化学性质、晶体化学及矿物学、地球化学行为控制因素、全球富锗矿床类型等,根据我国锗资源特征,结合"川滇黔铅锌矿集区"内多数矿床中锗超常富集普遍现象,提出该区可作为中国锗资源战略储备基地,具有巨大潜在经济价值。开展"川滇黔铅锌矿集区"锗超常富集机理研究,不仅可以补充和完善锗地球化学行为的科学内容,提供认识该区铅锌成矿作用的重要地球化学信息,更重要的是为地质勘探的深入和综合利用该区锗资源提供科学依据,从而为建立中国锗资源战略储备基地提供实际地质地球化学支撑。虽然中国是全球最大的锗生产国和出口国,但其产品多为初级产品,加强锗产品深加工研发不仅具有广阔的前景,也将是中国锗资源综合利用发展趋势。     

临沧超大型锗矿床的沉积环境、成岩过程和热液作用与锗的富集

临沧超大型锗矿庆的形成与其沉积、成岩和热液作用有密切联系。详细研究了矿床煤岩产出特征、煤岩组成、无机矿物、微量元素、腐殖体反射率,认为该矿床中的锗主要源于盆地西缘的白云母花岗岩的风化作用。在沉积作用阶段,锗被湖水中的低等生物和腐殖酸富集,为形成矿化煤打下基础。临沧褐煤经历了泥炭化阶段、早期成岩阶段和热液改造阶段。泥炭化阶段,沉积物中锗被凝胶体吸附和配合。早期成岩阶段,与腐残酸结合的锗,在碱性还原条     

Experimental study of germanium adsorption on goethite and germanium coprecipitation with iron hydroxide: X-ray absorption fine structure and macroscopic characterization

Adsorption of germanium on goethite was studied at 25 °C in batch reactors as a function of pH (1-12), germanium concentration in solution (10⁻⁷ to 0.002 M) and solid/solution ratio (1.8-17 g/L). The maximal surface site density determined via Ge adsorption experiments at pH from 6 to 10 is equal to 2.5 ± 0.1 μmol/m². The percentage of adsorbed Ge increases with pH at pH < 9, reaches a maximum at pH ∼ 9 and slightly decreases when pH is further increased to 11. These results allowed generation of a 2-pK Surface Complexation Model (SCM) which implies a constant capacitance of the electric double layer and postulates the presence of two Ge complexes, and , at the goethite-solution interface. Coprecipitation of Ge with iron oxy(hydr)oxides formed during Fe(II) oxidation by atmospheric oxygen or by Fe(III) hydrolysis in neutral solutions led to high Ge incorporations in solid with maximal Ge/Fe molar ratio close to 0.5. The molar Ge/Fe ratio in precipitated solid is proportional to that in the initial solution according to the equation (Ge/Fe)_solid = k × (Ge/Fe)_solution with 0.7 ? k ? 1.0. The structure of adsorbed and coprecipitated Ge complexes was further characterized using XAFS spectroscopy. In agreement with previous data on oxyanions adsorption on goethite, bi-dentate bi-nuclear surface complexes composed of tetrahedrally coordinated Ge attached to the corners of two adjacent Fe octahedra represent the dominant contribution to the EXAFS signal. Coprecipitated samples with Ge/Fe molar ratios >0.1, and samples not aged in solution (<1 day) having intermediate Ge/Fe ratios (0.01-0.1) show 4 ± 0.3 oxygen atoms at 1.76 ± 0.01 Å around Ge. Samples less concentrated in Ge (0.001 < Ge/Fe < 0.10) and aged longer times in solution (up to 280 days) exhibit a splitting of the first atomic shell with Ge in both tetrahedral (R = 1.77 ± 0.02 Å) and octahedral (R = 1.92 ± 0.03 Å) coordination with oxygen. In these samples, octahedrally coordinated Ge accounts for up to ∼20% of the total Ge. For the least concentrated samples (Ge/Fe < 0.001-0.0001) containing lepidocrocite, 30-50% of total co-precipitated germanium substitutes for Fe in octahedral sites with the next-nearest environment dominated by edge-sharing GeO₆-FeO₆ linkages (R_Ge-Fe ∼ 3.06 Å). It follows from the results of our study that the largest structural change of Ge (from tetrahedral to octahedral environment) occurs during its coprecipitation with Fe hydroxide at Ge/Fe molar ratio ?0.0001. These conditions are likely to be met in many superficial aquatic environments at the contact of anoxic groundwaters with surficial oxygenated solutions. Adsorption and coprecipitation of Ge with solid Fe oxy(hydr)oxides and organo-mineral colloids and its consequence for Ge/Si fractionation and Ge geochemical cycle are discussed.     

Geochemical behavior of inorganic germanium in an unperturbed estuary

Eleven monthly estuarine profiles of dissolved inorganic germanium (Ge_i) and silica (Si) in a natural, pristine river/bay system demonstrate that Ge-removal and -input parallel the seasonal silica cycle, reflecting Ge-uptake by and -dissolution from diatoms. The Ge/Si atom ratio of the river is 0.6 ± 0.15 × 10^?6, which is near the average value for continental granites and for uncontaminated, remote, natural rivers (0.7 ± 0.3 × 10^?6). The $\text{Ge}\text{Si}$ ratio escaping this estuary to the ocean is 0.8 × 10^?6, reflecting some estuarine enhancement of the fluvial Ge-flux, probably due to release of Ge_i from fluvial particulates. Nevertheless, the post-estuarine $\text{Ge}\text{Si}$ ratio is not significantly different from the continental crustal ratio but is very different from the ratio in sea-floor hot springs and mid-ocean ridge hydrothermal plumes (4 ± 2 × 10^?6) and in oceanic basalts (2.6 × 10^?6). Thus natural estuarine processes do not obscure the contrasting $\text{Ge}\text{Si}$ signatures entering the ocean from dissolution of continental and sea-floor silicates.     

非传统稳定同位素锗的测试进展及其地质应用

Ge具有亲硫、亲铁、亲石和亲有机质的特性,被广泛应用于矿床学、环境科学等学科。然而,由于测试技术和手段的限制,Ge同位素在地球科学中的应用还很有限,但已显示出较好的应用潜力。本文在综合前人研究成果的基础上,结合笔者最新的研究工作,对Ge同位素的测试技术和手段等方面做了较全面的总结,内容包括Ge同位素化学前处理方法的研究进展、Ge同位素测试过程中仪器产生的质量歧视的校正方法。同时,亦对自然界样品中Ge同位素的组成、Ge同位素分馏机制及应用等方面做了评述。