The behaviour of trace and rare earth elements (REE) during hydrothermal alteration in the Rangan area (Central Iran)

The rhyolitic dome in the Rangan area has been subjected to hydrothermal alterations by two different systems, (1) A fossil magmatic–hydrothermal system with a powerful thermal engine of a deep monzodioritic magma, (2) An active hydrothermal system dominated by meteoric water. Based on mineralogical and geochemical studies, three different alteration facies have been identified (phyllic, advanced argillic and silicic) with notable differences in REE and other trace elements behaviour. In the phyllic alteration zone with assemblage minerals such as sericite, pyrite, quartz, kaolinite, LREE are relatively depleted whereas HREE are enriched. The advanced argillic zone is identified by the presence of alunite–jarosite and pyrophyllite as well as immobility of LREE and depletion in HREE. In the silicic zone, most of LREE are depleted but HREE patterns are unchanged compared to their fresh rock equivalents. All the REE fractionation ratios (La/Yb)_cn, (La/Sm)_cn, (Tb/Yb)_cn, (Ce/Ce¹)_cn and (Eu/Eu¹)_cn are low in the phyllic altered facies. (Eu/Eu¹)_cn in both advanced and silicic facies is low too. In all alteration zones, high field strength elements (HFSE) (e.g. Ti, Zr, Nb) are depleted whereas transition elements (e.g. V, Cr, Co, Ni, Fe) are enriched. Geochemically speaking, trace and rare earth elements behave highly selective in different facies.     

马坑铁矿床稀土元素地球化学研究

引言七十年代以来,许多研究者对马坑铁矿进行过深入的研究。关于该矿床的形成机制,特别是含矿建造中一套中一基性岩石和矿体底板岩石的成因,以及矿石的形成方式等问题,曾引起研究者们的特别关注,并开展了热烈讨论。笔者曾对该矿床的地质一地球化学特征进行了较为详细的研究,并指出它是与石炭纪海底火山活动有关的喷气-热液沉积矿床,成矿流体来源于地热对流海水与玄武岩的反应。本文是上述研究的继续和深入,目的在于为     

稀土元素在热液中的迁移与沉淀

近年来,高新技术产业的不断发展使得全球稀土资源需求不断上涨,此外稀土元素作为研究地球起源与演化等有关地球科学问题的重要工具也深受地球科学界的重视。而热水溶液体系中稀土元素迁移、富集、沉淀及分馏机制等相关理论知识的不断完善对于理解稀土成矿作用、稀土地球化学特征以及微量元素示踪等方面均具有重要意义。本文总结了近年来有关稀土元素在热液体系中迁移、沉淀以及轻、重稀土分馏的最新研究进展,对不同稀土络合物的稳定性、溶解度以及搬运稀土元素的能干性进行了阐述,最后展望了"稀土元素在热液中迁移与沉淀"研究中仍需完善及拓展的方向。     

Geochemistry of rare earth elements in the mainstream of the Yangtze River,China

Water, suspended matter, and sediment samples were taken from 8 locations along the Yangtze River in 1992. The concentration and speciation (exchangeable, bound to carbonates, bound to Fe–Mn oxides, bound to organic matter, and residual forms) of rare earth elements (La, Ce, Nd, Sm, Eu, Tb, Yb, and Lu) were determined by instrumental neutron activation analysis (INAA).The contents of the soluble fraction of REEs in the river are low, and REEs mainly reside in particulate form. In the particles, the chondrite-normalized distribution patterns show significant LREE enrichment and Eu-depletion. While normalized to shales, both sediments and suspended matter samples show relative LREE enrichment and HREE depletion. REEs are relatively enriched in fine-grained fractions of the sediments.The speciation characteristics of REEs in the sediments and suspended matter are very similar. The amount of the five forms follows the order: residual>>bound to organic matter∼bound to Fe–Mn oxides>bound to carbonates>>exchangeable. About 65 to 85% of REEs in the particles exist in the residual form, and the exchangeable form is very low. High proportions of residual REEs reveal that REEs in sediments and suspended matter are controlled by their abundances in the earth's crust. Carbonate, Fe–Mn oxide and organic fractions of REEs in sediments account for 2.4–6.9%, 5.2–11.1%, and 7.3–14.0% of the total contents respectively. They are similar to those in the suspended matter. This shows that carbonates, Fe–Mn oxides and organic matter play important roles during the particle-water interaction processes. By normalization to shales, the 3 forms of REEs follow convex shapes according to atomic number with middle REE (Sm, Eu, and Tb) enrichment, while light REE and heavy REE are depleted.     

Crustal lineament control on mineralization in the Anarak area of Central Iran

The Anarak mining area in Iran is identified as one of the best known examples of mineralization located at the intersection of two important crustal-scale lineaments, which are the E_W striking Great Kavir fault and the NW–SE trending Urumieh-Dokhtar Magmatic Belt. The objective of this research is to investigate the role of the lineaments and their subsidiaries at Anarak area in the genesis of mineral deposits. Lineaments are long-lived features which control or affect ancient as well as young crustal sequences. Lineaments are also deep-seated, because they commonly control the emplacement of deep crustal or mantle-derived magmas. Metallogenic areas of up to ~ 1000 km² might be observed in areas where broad structural zones intersect, because they can facilitate the localization of magmatic or hydrothermal centers. The two lineaments that intersect in the Anarak area were both very active during mineralization. Therefore, it is likely that pull-apart basins or other dilatational sites at the intersection point were not preserved for substantial lengths of time, and single large magma conduits would have been divided into smaller conduits for magma penetration and hydrothermal circulation. The presence of these small conduits in addition to a small magma input could produce conditions for the circulation of mainly meteoric waters, in which the magmatism has acted as a heat source for the mineralization system. This phenomenon has led to the generation of a metallogenic area with several similar small deposits within a circular area of radius ~ 30 km centered at the intersection point. The two most famous deposits in this area are Talmessi and Meskani in which mineralization had occurred in two separate stages: first stage — fissure-filling copper sulfide mineralization associated with Eocene magmatism (veins, veinlets, and stockworks). The second is an overprinting stage which occurred after a fairly long interval which involves the formation of Ni–Co arsenides and U oxide minerals.     

Geochemistry of dissolved rare earth elements in the Equatorial Pacific Ocean

Seawater samples were collected from four locations in the Equatorial Pacific Ocean during the MR02-K06 cruise of the R/V Mirai and analyzed for dissolved rare earth elements (REEs) using inductively coupled plasma mass spectrometry. According to variations of REE concentrations and Yb/La ratios, the results show that the river input of the Papua New Guinea islands may affect the compositions of REEs in the Equatorial Pacific surface water. The Yb/La values and the REE concentrations in the waters deeper than 3,000 m in the western South Pacific and the Equatorial Pacific Oceans, which represent the characteristics of Antarctic Bottom Water (AABW), demonstrate similar variation trend with depth. This result also indicates that the REEs which originated from the South Pacific Ocean have entered the North Pacific Ocean across the equator with AABW intrusion.     

Mineral potential mapping for rare earth elements mineralization with AHP method in the Kerman-Kashmar Tectonic Zone,Central Iran

One of the major strengths of a GIS is the ability to integrate and combine multiple layers of geoscience data for producing mineral potential maps showing favorable areas for mineral exploration. Once the data is prepared properly, the GIS, jointly with other statistical and geostatistical software packages, can be used to manipulate and visualize the data in order to produce a mineral prospectivity map. Many spatial modeling techniques can be employed to produce mineral potential maps. This paper demonstrates a technique to define favorable areas for REE mineralization with AHP technique using geological, geochemical, geophysical, alteration and faults density spatial data in the Kerman-Kashmar Tectonic Zone of central Iran. The AHP is a powerful and flexible multi-criteria decision-making tool for dealing with complex problems where both qualitative and quantitative aspects need to be considered. This approach is knowledgedriven method and can be applied in other areas for conventional use in mineral exploration.     

陈家山矿煤中微量元素和稀土元素地球化学特征

通过对陈家山煤矿中下侏罗统延安组4^#主采煤层中微量元素和稀土元素的测试分析,发现煤中富集亲花岗岩的钨钼族元素W、Mo、Bi、Sn、Ba、Sr和Li,说明该区煤系形成期间的陆源碎屑主要来自花岗岩和花岗片麻岩等中、酸性岩石。4^#煤中ΣREE平均值为98.2×10^-6,稀土元素分布模式十分相似,呈左高右低的宽缓“V”型曲线,Eu负异常明显,反映出稀土元素与陆源碎屑岩关系密切,成煤期间稀土元素来源一致,陆源物质的供应相对稳定。     

白银厂铜多金属矿田微量元素和稀土元素地球化学研究

与日本黑矿及现代海底火山岩为主岩矿床相比，白银厂矿田各类矿石，尤其是块状Ｚｎ－Ｐｂ－Ｃｕ矿石具有最高的Ａｓ和Ｂｉ含量，比较高的Ｇａ、Ｃｄ和Ａｕ含量，以及较高的Ａｕ／Ａｇ和Ｃｏ／Ｎｉ比值。该矿田矿石的Ａｕ含量与闪锌矿中铁含量呈负相关关系。小铁山矿床闪锌矿与日本黑矿的闪锌矿微量元素特征很相似。矿田各类矿石ＲＥＥ型式与细碧角斑岩类岩石基体相似，这说明矿石与岩石的物质来源基本一致。研究和对比表明，火山成因     

Geochemistry of rare earth elements in bottom sediments of the Brazil Basin, Atlantic Ocean

The sedimentation and ore formation were studied in sediments from nine stations located in the 24°W profile in the Brazil Basin of the Atlantic Ocean. The sediments are represented by mio- and hemipelagic muds, which are variably enriched in hydrothermal iron and manganese oxyhydroxides. As compared to the sediments from other basins of the Atlantic Ocean, these rocks are marked by extremely high manganese contents (up to 1.33%) and maximal enrichment in Ce. It was shown that the positive Ce anomaly is related to the REE accumulation on iron oxyhydroxides. Influence of hydrothermal source leads to the decrease of Ce anomaly and LREE/HREE ratio. In the reduced sediments, preservation of positive Ce anomaly and/or its disappearance was observed after iron and manganese reduction. The REE contents were determined for the first time in the Ethmodiscus oozes of the Brazil Basin. Ore deposits of the Brazil Basin are represented by ferromanganese crust and ferromanganese nodules. Judging from the contents of iron, manganese, rare, and trace elements, these formations are ascribed to the sedimentation (hydrogenic) deposits. They are characterized by a notable positive Ce anomaly in the REE pattern. The extremely high Ce content (up to 96% of total REE) was discovered for the first time in the buried nodules (Mn/Fe = 0.88).     

相山铀矿田成矿流体特征:来自微量、稀土元素地球化学证据

相山铀矿田的成矿流体性质和来源存在争议,为进一步探讨相山铀矿田成矿流体的性质和来源,本文对相山铀矿田西部的居隆庵铀矿床和北部的沙洲铀矿床中的新鲜围岩、蚀变围岩及矿石的微量、稀土元素含量及其变化进行了研究。结果显示:在含较多热液成因萤石的居隆庵铀矿床中,从新鲜围岩到蚀变围岩到矿石,Zr、Hf含量先降低再升高;而在含少量热液萤石的沙洲铀矿床中,新鲜围岩、蚀变围岩和矿石的Zr、Hf含量基本一致。鉴于富F流体易汲取岩石中的Zr、Hf,因此,这两个矿床中不同类型样品Zr、Hf含量的不同变化趋势,可能与居隆庵铀矿床的成矿流体富F、而沙洲铀矿床的成矿流体相对贫F有关。这两个铀矿床中矿石的稀土配分曲线与其各自的新鲜及蚀变围岩的稀土配分曲线形态相似但又存在差异,说明每个矿床的新鲜围岩、蚀变围岩和矿石之间的稀土元素既具有继承性、又受到不同性质的流体的影响。居隆庵铀矿床中矿石显示Eu负异常,可能主要是继承了围岩的Eu负异常;沙洲铀矿床中矿石Eu显示弱负异常至弱正异常的特征,可能与围岩中斜长石因热液蚀变作用而释放出的Eu的进入流体有关。基于新鲜围岩、蚀变围岩及矿石的U和REE研究,推断居隆庵铀矿床成矿流体中U和REE均以F的络合物形式迁移;但沙洲铀矿床中铀矿石品位较低,可能是与流体中相对贫F有关。     

Rare earth elements in metarhyolite dyke constraints on processes in a dynamic hydrothermal system,Um Ghannam,South Eastern Desert,Egypt

The Um Ghannam area lies within the core of Hafafit Complex, South Eastern Desert. This area is occupied mainly by granitic gneiss (orthogneiss). However, the granitic gneiss is extruded by swarm metarhyolite dykes and quartz veins. The studied metarhyolite dyke is classified into two distinctive zones. However, the intense degree of hydrothermal alteration can partition this dyke into weakly and extremely altered zones. According to the extraordinary diversity in color, this dyke is distinguished into gray to dark gray (weakly altered) and greenish (extremely altered) metarhyolite. Petrographical, mineralogical, and geochemical characteristics of the two distinctive zones are detected in a representative sample. Petrographically, the weakly altered zone is mainly represented by chloritization of primary biotite, garnet, and epidote, and argillitization of primary plagioclase. Although the extremely altered zone contains intensely altered remnants of the original rock, the extremely altered zone is distinguished by intense oxidation products (carbonate minerals and quartz, with significant amounts of secondary Cr-muscovite and hematite). The mineralogical studies are imposed on the millimeter and the micrometer scale in this important hydrogeothermal system. Except for Ca and Mg, most of the major elements are depleted at the extremely altered zone. However, the extremely altered zone is enriched in trace elements (Cr, Mn, Co, and Ni). The major elements of the extremely altered zone reflect the significant alterations (desilication, muscovitization, and carbonatization). These alteration processes have taken place in the hydrogeothermal system in the extremely altered zone. The geothermal fluid is responsible for these hydrothermal alterations. High fO₂ and high temperature are characteristic features of this fluid. Then, the high-field-strength elements such as Zr, Ti, and P are depleted as a significant hydrothermal alteration. Also, nuclear elements with the anion of (CO₃)^2? can travel as molecular complexes (carbonates), as long as the chemical and structural conditions are suitable for the movement of these elements from the metarhyolite dyke to redeposit and accumulate in another geologic formation. The rare earth elements La and Ce, as well as Yb and Lu, are partially mobilized during intensity alterations. The rare earth elements (REEs) are depleted in abundance with enrichment of CO₂ from the weakly altered zone to the extremely altered zone. The REE budget is decreased from the weakly altered zone to the extremely altered zone as 121.17 to (27.38???16.52), respectively. The significant depletion of ∑REEs is controlled by dissolution of monazite. Monazite breakdown and even apatite formation can be caused by alkaline fluid. This fluid is related to event and thermal stage. However, the negative anomaly of Eu can be noticed in all studied samples. Then, Eu anomaly may be formed from plagioclase fractionation. The weakly altered metarhyolite zone and orthogneiss have lower HREE/LREE (0.07–0.11), respectively, relative to the extremely altered metarhyolite zone (0.17???0.2). Even all studied samples at two significant zones are characterized by the enrichment of ∑LREEs relative to ∑HREEs.     

四川稀土精矿的稀土元素和微量元素地球化学特征及开发利用意义

产自广东省梅州市玉水铜矿的景文矿,属于含水、重稀土-矾-铝硅酸盐矿物(简写为HREE-V-铝硅酸盐矿物),其化学结构式为Y₂Al₂V₂⁴⁺(SiO₄)₂O₄(OH)₄,该矿物在全球属首次发现,暂未开展相关研究。相对于含轻稀土矿物,含重稀土矿物在电子探针分析过程中,当被高压电子束轰击时,被激发出来的特征X射线线系繁多,线系之间分布更加密集,彼此之间相互重叠的现象也更为严重,要获得理想数据的难度很大,是亟待解决和突破的技术难题。本文对该矿物进行了精细的电子探针定量分析,获得理想的化学成分数据,为新矿物命名提供了理论数据技术支撑。通过对实验方法的探索和总结获得以下结果：①利用15kV加速电压、100nA束流对试样进行全元素扫描,以此确定出17种元素;②在定量分析过程中,对重叠峰进行了剥离;③利用仪器软件中的Zoom-Peak ID程序,选择出17种元素的分析线系、精确的峰位及上下背景值;④选取合适的标样及测试时间等定量分析条件,最终获得理想的定量分析结果(平均总量97.41wt%)。上述四条也是确保获得理想定量分析数据的关键因素。

     

Geochemistry of rare earth elements in micro-and macronodules from the pacific bioproductive zone

Concentrations and compositions of rare earth elements (REE) in three micronodule fractions (50–250, 250–500, and >500 μm), coexisting macronodules, and host sediments are examined. The samples were collected from three sites (Guatemala Basin, Peru Basin, and northern equatorial Pacific) located in elevated bioproductivity zones of the surficial water. The influence of micronodule size is dominant for REE compositions and subordinate for REE concentrations. For example, the Ce concentration inversely correlates with the micronodule fraction dimension and drops to the lowest value in macronodules and host sediments. The Ce decrease is generally accompanied by the Mn/Fe increase in micro- and macronodules. Hence, the role of diagenetic source of material directly correlates with the micronodule dimension. The contribution of diagenetic source is maximal for macronodules. The REE signature distinctions of micronodules and macronodules can be attributed to variations of hydrogenic iron oxyhydroxides and diagenetic (hydrothermal) iron hydroxophosphates that are the major REE carriers in ferromanganese ore deposits. The relationship and general trend in the chemistry of coexisting macronodules suggest that they can represent products of the initial stage of nodule formation.     

辽宁四道沟热液金矿床中石英的稀土元素的特征及意义

本文用ＩＣＰ－ＭＳ测定了辽宁四道沟金矿矿脉中石英及其中流体包裹体中的稀土元素含量,发现石英的稀土元素配分模式类似于其中流体包裹体的稀土元素配分模式,推断石英中的稀土元素主要赋存于注流体包裹体中,流体包裹体中的稀土元素了石英的稀土元素配分模式,原生包裹中的流体是和石英同源的,其稀土元素指示的是石英形成过程中流体的信息。而次生包裹体中的流体是石英形成后的流体活动产物,其稀土元素指示的是后期流体活动的信     

Geochemistry of the rare earth elements in ferromanganese nodules from DOMES Site A,northern equatorial Pacific

The distribution of rare earth elements (REE) in ferromanganese nodules from DOMES Site A has been determined by instrumental neutron activation methods. The concentrations of the REE vary markedly. Low concentrations characterize samples from a depression (the valley), in which Quaternary sediments are thin or absent; high concentrations are found in samples from the surrounding abyssal hills (the highlands) where the Quaternary sediment section is relatively thick. Moreover, the valley nodules are strongly depleted in the light trivalent REE (LREE) and Ce compared with nodules from the highlands, some of the former showing negative Ce anomalies.The REE abundances in the nodules are strongly influenced by the REE abundances in coexisting bottom water. Some controls on the REE chemistry of bottom waters include: a) the more effective removal of the LREE relative to the HREE from seawater because of the greater degree of complexation of the latter elements with seawater ligands, b) the very efficient oxidative scavenging of Ce on particle surfaces in seawater, and c) the strong depletion of both Ce and the LREE in, or a larger benthic flux of the HREE into, the Antarctic Bottom Water (AABW) which flows through the valley. The distinctive REE chemistry of valley nodules is a function of their growth from geochemically evolved AABW. In contrast, the REE chemistry of highland nodules indicates growth from a local, less evolved seawater source.