Geochemical characteristics of porphyry copper (molybdenum) mineralization

Dealt with in this paper are some geochemical characteristics of porphyry copper mineralization, especially those observed in intrusive bodies, wall rocks, alteration zones, ores and pyrites. Ore bearing bodies have been correlated with barren ones from such aspects as major and trace elements, copper contents of biotite and pyrite, and distribution pattern of copper. In the mineralized rocks, trace elements show apparent zoning surrounding ore bodies; major and trace elements seem to show some regularities with respect to their variations in the process of alteration, and as a result each alteration zone displays its own peculiar element association. Trace elements in ores can provide information on the genetic types of ore deposits, thus of great help in distinguishing ore types, while those in pyrites may be indicative of the main mineralizing stage, providing clues for distinguishing ore-bearing from barren rocks, and of the extent of denudation of ore bodies.     

兰坪盆地白秧坪铜钴多金属矿床中钴的成矿地球化学

白秧坪铜钴多金属矿床产于下白垩统景星组陆相红色碎屑岩中，呈似层状、脉状分布于断裂带内，蚀变分带明显。研究表明：在原生矿石中钴主要赋存于独立矿物．辉砷钴矿中，同时钴可以类质同象赋存于砷黝铜矿及少量含钴黄铁矿中；在氧化矿石中，以钴华存在于矿石的表面。辉砷钴矿的成分和Co／Ni比值揭示钴的成矿作用与基性．超基性岩浆有关。矿床褪色蚀变岩、碳酸盐化蚀变岩矿石和正常岩石具有类似的稀土元素配分模式，即富集轻稀土而重稀土相对亏损、铈异常不明显而铕异常显著，但稀土元素总量、分异程度存在明显的差异。这可能与流体中带入稀土元素的方式、带入稀土的矿物类型和流体性质的差异等因素造成，反映成矿物质来源存在差异。相对正常岩石的微量元素含量，元素Cu、Co、As、Sb、Bi、Ag等在褪色蚀变岩、碳酸盐化蚀变岩和矿石中均相对富集，但在在褪色蚀变岩以亲石元素富集最明显，而在碳酸盐化蚀变岩和矿石中以显著富集亲硫元素(成矿元素)为主特征，表明在蚀变过程中，赋矿围岩本身没有为成矿作用提供主成矿元素，主成矿元素源自幔源的基性岩浆。由此认为钴的成矿作用可能主要与喜马拉雅期幔源的基性岩浆活动有关。     

The composition of magmatic Ni–Cu–(PGE) sulfide deposits in the Tati and Selebi-Phikwe belts of eastern Botswana

We studied a number of magmatic Ni–Cu–(PGE) sulfide deposits in two distinct belts in eastern Botswana. The Tati belt contains several relatively small deposits (up to 4.5 Mt of ore at 2.05% Ni and 0.85% Cu) at Phoenix, Selkirk and Tekwane. The deposits are hosted by ca 2.7 Ga, low- to medium-grade metamorphosed gabbroic–troctolitic intrusions situated within or at the periphery of a greenstone belt. The deposits of the Selebi-Phikwe belt are larger in size (up to 31 Mt of ore grade). They are hosted by high-grade metamorphosed gabbronorites, pyroxenites and peridotites believed to be older than ca 2.0 Ga that intruded gneisses of the Central Zone of the Limpopo metamorphic belt. The composition of the sulfide mineralisation in the two belts shows systematic variation. Most of the mineralisation in the Tati belt contains 2–9% Ni and 0.05–4% Cu (Cu/Cu + Ni = 0.4–0.7), whereas most of the mineralisation in the Selebi-Phikwe belt contains 1–3% Ni and 0.1–4% Cu (Cu/Cu + Ni = 0.4–0.9). The Cu–Ni tenors of the ores in both belts are consistent with crystallization from a basaltic magma. The Tati ores contain mostly >3 ppm Pt + Pd (Pt/Pd 0.1–1), with Pd/Ir = 100–1,000, indicative of a differentiated basaltic magma that remained S-undersaturated before emplacement. Most of the Selebi-Phikwe ores have <0.5 ppm Pt + Pd (Pt/Pd < 0.1–1), with Pd/Ir = 10–500. This suggests a relatively less differentiated magma that reached S saturation before emplacement. The Tati rocks show flat mantle-normalised incompatible trace element patterns (average Th/Yb_N = 1.57), except for strong enrichments in large ion lithophile elements (Cs, Rb, Ba, U, K). Such patterns are characteristic of relatively uncontaminated oceanic arc magmas and suggest that the Tati intrusions were emplaced in a destructive plate margin setting. Most of the Selebi-Phikwe rocks (notably Dikoloti) have more fractionated trace element signatures (average Th/Yb_N = 4.22), possibly indicating digestion of upper crustal material during magma emplacement. However, as there are also samples that have oceanic arc-like signatures, an alternative possibility is that the composition of most Selebi-Phikwe rocks reflects tectonic mingling of the intrusive rocks with the country rocks. The implication is that orogenic belts may have a higher prospectivity for magmatic Ni–Cu ores than presently recognised. The trigger mechanism for sulfide saturation and segregation in all intrusions remains unclear. Whereas the host rocks to the intrusions appear to be relatively sulfur poor, addition of crustal S to the magmas is suggested by low Se/S ratios in some of the ores (notably at Selebi-Phikwe). External S sources may thus remain unidentified due to poor exposure and/or S mobility in response to metamorphism.     

四川会理小青山铜矿床地球化学特征

小青山铜矿床产于中元古界会理群小青山组中，主矿体严格受地层层位控制。通过对主要类型岩矿石（矿物）的常量、微量元素、矿物包裹体成分、稀土元素分析及不同矿物的硫、铅同位素和矿物包裹体氢氧、碳同位素测试研究，认为该矿床具有沉积、变质作用，尤其是岩浆热液叠加改造作用的特征。     

Trace metal bioaccumulation in the shells of mussels and clams at deep-sea hydrothermal vent fields

The bioaccumulation of trace metals in the carbonate shells of mussel and clams was investigated at seven hydrothermal vent fields of the Mid-Atlantic Ridge (Menez Gwen, Snake Pit, Rainbow, and Broken Spur) and the Eastern Pacific (9°N and 21°N at the East Pacific Rise and the southern trough of Guaymas Basin). Mineralogical analysis showed that the carbonate skeletons of the mytilid mussel Bathymodiolus sp. and the vesicomyid clam Calyptogena m. are composed mainly of calcite and aragonite, respectively. The first data were obtained for the content of a variety of elements in the bivalve carbonate shells from various hydrothermal vent sites. The analysis of the chemical compositions (including Fe, Mn, Zn, Cu, Cd, Pb, Ag, Ni, Cr, Co, As, Se, Sb, and Hg) of 35 shell samples and 14 water samples from the mollusk biotopes revealed the influences of environmental conditions and some biological parameters on the bioaccumulation of metals. Bivalve shells from hydrothermal fields with black smokers are enriched in Fe and Mn by a factor of 20–30 relative to the same species from the Menez Gwen low-temperature vent site. It was shown that the essential elements Fe, Mn, Ni, and Cu were more actively accumulated during the early ontogeny of the shells. The high concentration factors of most metals (n × 10²−n × 10⁴) indicate an efficient accumulation function of bivalve carbonate shells. Passive metal accumulation owing to adsorption on the shell surface was estimated to be no higher than 50% of the total amount, varying from 14% for Fe to 46% for Mn.     

海南石碌铁矿北一南六矿体地球化学特征

北一、南六矿体是海南石碌铁矿床最主要的2个铁矿体,赋矿围岩同为二透岩,铁矿石主要为赤铁矿加少量磁铁矿.研究两矿体赋矿围岩和富铁矿石的地球化学特征,比较其物质组成差异性,可以为本矿床深部和外围找矿提供有用信息.研究表明,北一、南六2个矿体二透岩、富铁矿的主量元素、微量元素及稀土元素配分曲线差异明显;北一矿体二透岩除CaO和Co含量低于南六矿体样品外,其余氧化物及微量元素含量均高于南六矿体样品;北一矿体二透岩及富铁矿有Eu弱负异常,南六矿体二透岩及富铁矿Eu正异常;所有样品均表现Ce的弱负异常和轻稀土相对亏损、重稀土相对富集的特征.研究结果表明两矿体成矿环境或受后期热液影响不同.     

Study on the element geochemical charactersitics of the Shazi large-sized anatase ore deposit in Qinglong,Guizhou Province

The Shazi anatase ore deposit in Qinglong, Guizhou Province, is a large-sized anatase deposit that has been recently explored. The characteristics of major oxides in the ore are similar to those of modem laterite weath- ering crust and laterite in the laterite-type gold deposits in the western part of Guizhou Province. Studies on the REE characteristics of basalts and anatase ores in the study region showed that both of them do have extremely strong affinities. There are two groups of trace elements in the ores, i.e., Au-Ag-As-Sb-Hg-Tl association and Sc-TiO2-Cu-Fe-Mn association, reflecting that the formation of anatase ore is related to the formation of siliceous claystone at the early stage of eruption of the Emeishan basaltic magma. The siliceous claystones are the major country rocks for the formation of laterite-type gold ores and anatase ores. In the region anatase ores are rich in Sc and the basalts enriched in Fe, Mn, Ti and Sc are the material source of metallogenesis.     

The Sin Quyen Cu–Fe–Au–REE deposit (northern Vietnam): composition and formation conditions

The Sin Quyen Cu–Fe–Au–REE deposit is localized in the Proterozoic deposits of the Phan Xi Pang zone, northern Vietnam. The mineralization is formed by lenticular and sheet-like bodies occurring concordantly with the host rocks. Seventeen orebodies have been recognized in the deposit, which form an ore horizon up to 140 m in total thickness, about 2 km in strike, and up to 350 m in dip. The ores are of simple mineral composition: Au-rich copper and iron sulfides (chalcopyrite, pyrite, pyrrhotite) and iron oxides (magnetite, hematite). Gold and silver are distributed unevenly in the ores: Their contents vary from hundredths and tenths of ppm to 1.8 ppm. Copper sulfide ores are the main concentrator of gold and silver. All ores are characterized by high REE contents, tens and hundreds of times exceeding the element clarkes. The highest contents have been revealed for Ce and La. Orthite is the main carrier of REE. No correlation between REE and ore elements of sulfide-oxide ores has been revealed, which points to the independent formation of the mineralization. Orebodies together with the host rocks underwent metamorphism at 500–600 to 630–685 °C and 3–7 kbar. The spatial association of the mineralization with amphibolites (metamorphosed basites) and the mineral composition of ores suggest that the Sin Quyen deposit is of Cyprian volcanogenic type.     

豫西熊耳山地区槐树坪金矿岩石-土壤找矿指示元素的确定及其应用

槐树坪金矿床位于河南省洛阳市嵩县境内,是豫西熊耳山地区近年来新发现的大型金矿床。本次研究对槐树坪金矿区地表及井下不同类型的较新鲜围岩、蚀变岩和矿石以及地表1∶20000面积性土壤采样,分析29项微量元素,从岩石和土壤两种采样介质来确定槐树坪金矿床的地球化学找矿指示元素。一方面基于较新鲜围岩的元素含量特征确定每个微量元素在该区岩石中的异常下限,进而分别计算了蚀变岩和矿石中微量元素平均含量与异常下限的比值,即异常衬度。按照异常衬度大于1.4的标尺确定了蚀变岩与矿石中明显富集的微量元素组合。另一方面,基于Au与28项微量元素在较新鲜围岩、蚀变岩、矿石三种介质中含量关系散点图直观确定了指示金成矿的微量元素组合。综合二者确定出槐树坪金矿区岩石地球化学找矿的指示元素组合为Au、Ag、As、Sb、Hg、Sn、Mo、Bi、Cu、Pb、Zn、Cd、Nb计13项。针对地表1∶20000面积性土壤调查,采用上述岩石中异常衬度为1.4作为土壤异常下限绘制了槐树坪金矿区微量元素的地球化学异常剖析图,以槐树坪金矿区已探明鸡公山一带的主成矿段为模型确定了土壤地球化学找矿的指示元素组合为Au、Ag、As、Sb、Hg、Bi、Cu、Pb、Zn、Cd、B计11项。综合上述结果认为在找矿指示元素组合方面土壤对岩石具有明显的继承性。基于岩石与土壤介质中共同的10项找矿指示元素,构建了归一化的综合异常指标,以鸡公山矿段为标准对整个槐树坪矿区进行了综合评价,发现槐树坪矿区内马蹄沟、秦佛爷沟、姜疙瘩和天坪西4处具有类似鸡公山矿段的找矿潜力。     

矿物原位LA-ICPMS微量元素分析及其在矿床成因和预测研究中的应用进展

随着激光剥蚀电感耦合等离子质谱技术(LA-ICPMS),短波近红外光谱分析技术(SWIR)以及其它微区分析技术的飞速发展,矿物原位微量元素组成的相关研究已成为地球科学领域的热点。目前国内外的研究主要集中在利用矿物微量元素组成来反演成矿流体的性质和演化规律,示踪成矿物质的来源,约束岩石和矿床的成因,并进行成矿带的识别和矿化中心的预测,特别是近十多年,在应用矿物微量元素组成特征进行矿床预测和勘探方面取得了巨大的进展。本文简要综述了国际上该领域近年来上述有关方面的研究现状和取得的主要进展,并重点总结和论述了部分重要矿物的原位微量元素研究在成矿预测应用方面所取得的最新成果,包括:(1)通过对岩浆成因矿物,如斜长石、锆石、磷灰石和磁铁矿等元素组成研究进行成矿潜力的判别;(2)通过热液蚀变矿物,如绿帘石,绿泥石,磁铁矿和明矾石等的元素组成来预测矿化中心的方向和位置,同时进行含矿性和成矿潜力的判别。文章认为,随着微区分析技术的飞速发展,矿物原位微量元素组成的研究已成为地球科学领域特别是矿床学和勘查学的研究热点。继续加强矿物原位LA-ICPMS微量元素分析技术及相关基础研究,进一步探索和应用不同矿物微量元素组成特征来建立精确的勘探指针,有效指导深部矿床勘查,是下一步的主要发展方向。     

Volcanoplutonic association of felsic rocks in the rare-metal ore units of Transbaikalia: Geochemistry of rocks and melts, age, and P-T conditions of their crystallization

The results of study of chemical composition, mineral-forming medium, P-T conditions of crystallization, and the age characteristics of subvolcanic felsic rocks that are spatially associated with rare-metal granite massifs in the ore units of Transbaikalia (Sherlovaya Gora, Khangilay, Bukuka, Belukha, and Shumilovka) give grounds for defining cogenetic volcanoplutonic associations. These associations within the studied region consist of rare-metal granites, ongonites, rhyolites, ongorhyolites, and trachyrhyodacites, which have much in common, but also many differences. The common chemical features of these rocks are their peraluminium signature, low mafic index and basicity, as well as enrichment (as compared to crust) in trace lithophile elements (Li, Rb, Nb, Ta, Sn, W, and F), the low contents of Zr, REE, and Sr, and the similar distribution of trace and refractory elements. At the same time, these rocks differ in the proportions of sodium and potassium, levels of concentrations of lithophile trace and refractory elements, REE distribution patterns, P-T regimes of crystallization, and the volatile composition. The composition of melts from all types of the studied rocks and trace element distribution between melts and rocks were studied on the basis of ion-microprobe analysis of rehomogenized glasses of melt inclusions in quartz. The highest concentrations of lithophile trace elements in the melt, including Cs (up to 300 ppm), Rb (up to 1002 ppm), U (up to 42 ppm), and Th, were found in the trachyrhyodacites of the Bukuka-Belukha ore unit; in terms of Li content this melt is comparable with the Ary-Bulak ongonites (690 and 715 ppm Li, respectively), and differ by an order of magnitude in the contents of refractory and rare-earth elements (total REE 94.4 and 5.44 ppm, respectively), which is indicative of a lower differentiation degree of this melt as compared to ongonites. Potassic rhyolites are peculiar in the low content of lithophile trace elements, but residual melt reveals notable enrichment in Li (up to 130 ppm) and Nb (up to 120 ppm). The accumulation of U in the residual melt of the trachyrhyodacitic and rhyolitic magmas of Eastern Transbaikalia may indicate their high potential for postmagmatic uranium ore formation. Isotope-geochronological studies (Rb-Sr isotope system) of the Sherlovaya Gora ore unit showed that the entire complex of volcanoplutonic association (granites, ongonites, rhyolites, and ongorhyolites) formed almost simultaneously within an interval of 4 Ma: from 145.7 ± 1.3 Ma at IR_Sr = 0.70507 ± 20 and MSWD = 0.48 to 141.5 ± 1.0 Ma at IR_Sr = 0.70359 ± 63 Ma and MSWD = 0.24. A spatial association of the subvolcanic rock complex with rare-metal granite massifs, their formation within a common age interval, geochemical features, and P-T conditions of crystallization suggest that they are genetically related but were derived from variably evolved sources, which originated from a single protolith under the action of mantle plume that existed beneath Central Asia at that time (Yarmolyuk and Kovalenko, 2003).     

昆明东川区播卡金矿地球化学特征与成因

播卡金矿位于云南的东川区,由16条矿体组成。在搜集以往地质、化探资料的基础上,结合野外实地调研,研究了播卡矿区地层、岩浆岩、矿石的微量元素地球化学特征,从地球化学的角度探讨了播卡矿床的成因,依据稀土元素的分析结果研究了播卡矿床的成矿物质来源,在此基础上分析了播卡金矿的成矿过程及成矿机制。     

锗矿石和铟矿石化学成分分析标准物质研制

目前国内外没有以稀散元素锗、铟为特征元素的矿石标准物质,为了满足我国地质找矿的需求,本文采集广东省韶关凡口铅锌矿作为锗矿石候选物,广西南丹铜坑铅锌矿作为铟矿石候选物,依据国家一级标准物质技术规范,由10家实验室采用化学分析方法和现代仪器分析方法协作定值,研制了1种锗矿石标准物质(GBW07831)和1种铟矿石标准物质(GBW07833)。锗矿石标准物质定值组分为45项,铟矿石标准物质定值组分为47项,包括特征元素、共存元素、稀土元素(15项)、造岩元素和痕量元素,其中锗矿石中锗含量为21.6×10-6,铟矿石中铟含量为39.7×10-6。研制的2种标准物质丰富了我国矿石标准物质的种类,可用于锗、铟矿石化学成分分析测试的量值标准和日常质量监控。     

桂西南早-中三叠世东平-足荣大型锰矿床地球化学、年代学及成因研究

广西东平-足荣大型锰矿床位于桂西南锰矿带上,是广西重要的锰矿富集区。其含矿地层为三叠系北泗组,是一套以硅-泥-灰为主浅海台盆相含锰碳酸盐岩沉积,含锰矿物主要为钙菱锰矿、锰方解石和锰白云石。本文对矿区锰矿层顶部的沉凝灰岩及含锰岩系开展了详细的岩石学、岩石地球化学和锆石U-Pb年代学研究,进而对锰矿成矿时代、成因、沉积环境、沉凝灰岩源区和大地构造背景进行了探讨。锆石SHRIMP U-Pb定年结果显示,3件沉凝灰岩样品的锆石呈自形-半自形板柱状,发育良好的岩浆锆石振荡环带结构。~(206) Pb/~(238)U年龄加权平均值分别为250.8±2.1Ma(MSWD=0.98)、250.6±2.2Ma(MSWD=0.49)和243.6±2.3Ma(MSWD=0.44)。进一步限定了"东平"式锰矿的成矿时代为早-中三叠世(不晚于241～246Ma的范围内)。沉凝灰岩的构造环境判别图解及微量、稀土元素特征显示其岩浆可能形成于与俯冲消减作用相关的碰撞-弧相关或活动大陆边缘相关背景,推测东平-足荣锰矿的形成可能受到广西凭祥-东兴火山作用的影响。含锰岩系的U、V和Mo元素含量及U/Th、V/Cr、V/(V+Ni)、Ni/Co 比值显示东平-足荣锰矿形成于氧化-次氧化的沉积环境。logU-logTh、Fe/Ti-Al/(Al+Fe+Mn)图解及微量元素Ba含量、Ba/Sr值均指示成矿作用受到热水作用的影响。综合矿床地质研究,东平-足荣锰矿形成于弧后盆地拉张构造背景中,锰成矿受同期火山及海底热液作用影响,水体沉积环境为氧化-次氧化条件。     

Petrophysical zoning of the Natalka ore field

The petrophysical properties of 1168 rock and ore samples collected across the sections of the Natalka ore field have been determined. 235 of them were prepared as thin and polished sections and studied by geological-mineralogical methods. The general two-level petrophysical zoning of the ore field was established and substantiated. Its relations with ore areas, the interzonal space, altered wall rocks, and the mineral composition were determined. Both levels of the revealed petrophysical zoning are traced in the ore field over 4 km along the strike and 800 m down the dip. The subvertical conductivity zone (confined to the Omchak ore cluster) has spatial-genetic relations with the petrophysical changes, which reflect the established mineralogical composition and structure of the metasomatites and ores.     

Associations of trace elements in the sulfides of black smokers from the Broken Spur,Menez Gwen,and Snake Pit hydrothermal fields

Thorough processing of a huge amount of analytical data from Electron-Probe Microanalyses (EPMA) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) allowed us to define several trace-element associations in sulfides from three hydrothermal vent fields at the Mid-Atlantic Ridge (Broken Spur, Menez Gwen, and Snake Pit). The presence of such association may indicate the occurrence of certain mineral phases at the micro- and/or nano-scales.     

Major and Trace Elements of Magnetite from the Qimantag Metallogenic Belt: Insights into Evolution of Ore–forming Fluids

Magnetite, as a genetic indicator of ores, has been studied in various deposits in the world. In this paper, we present textural and compositional data of magnetite from the Qimantag metallogenic belt of the Kunlun Orogenic Belt in China, to provide a better understanding of the formation mechanism and genesis of the metallogenic belt and to shed light on analytical protocols for the in situ chemical analysis of magnetite. Magnetite samples from various occurrences, including the ore–related granitoid pluton, mineralised endoskarn and vein–type iron ores hosted in marine carbonate intruded by the pluton, were examined using scanning electron microscopy and analysed for major and trace elements using electron microprobe and laser ablation–inductively coupled plasma–mass spectrometry. The field and microscope observation reveals that early–stage magnetite from the Hutouya and Kendekeke deposits occurs as massive or banded assemblages, whereas late–stage magnetite is disseminated or scattered in the ores. Early–stage magnetite contains high contents of Ti, V, Ga, Al and low in Mg and Mn. In contrast, late–stage magnetite is high in Mg, Mn and low in Ti, V, Ga, Al. Most magnetite grains from the Qimantag metallogenic belt deposits except the Kendekeke deposit plot in the " Skarn " field in the Ca+Al+Mn vs Ti+V diagram, far from typical magmatic Fe deposits such as the Damiao and Panzhihua deposits. According to the(Mg O+Mn O)–Ti O2–Al2O3 diagram, magnetite grains from the Kaerqueka and Galingge deposits and the No.7 ore body of the Hutouya deposit show typical characteristics of skarn magnetite, whereas magnetite grains from the Kendekeke deposit and the No.2 ore body of the Hutouya deposit show continuous elemental variation from magmatic type to skarn type. This compositional contrast indicates that chemical composition of magnetite is largely controlled by the compositions of magmatic fluids and host rocks of the ores that have reacted with the fluids. Moreover, a combination of petrography and magnetite geochemistry indicates that the formation of those ore deposits in the Qimantag metallogenic belt involved a magmatic–hydrothermal process.     

Geochemical Fingerprint and Iron Ore Potential of the Siliceous Itabirite from Palaeoproterozoic Nyong Series,Zambi Area,Southwestern Cameroon

The study area forms part of an emerging iron ore province of southern Cameroon. Geochemistry analyses reveal that the siliceous itabirite has a very simple chemical composition, with Fe₂O₃ and SiO₂ representing more than 96 wt.% of the average composition; suggesting chemical precipitates of silica and iron. Low Al₂O₃ and TiO₂ concentrations and a weak positive correlation between them point to a minor detrital component in the precipitated marine sediments. The Si/Al ratio (average 52.7) indicates the hydrothermal origin of the studied itabirite. The Al–Si discrimination diagram supports this interpretation through the plot of all data in the hydrothermal field. The studied samples have low iron content (about 39.32% Fe), high gangue content (40.97% SiO₂ and 1.3 % Al₂O₃) and low concentration of the deleterious elements (0.16 % P and < 0.01% S). The main gangue mineral is silica which can be efficiently removed from iron ores during preparation of raw materials for the blast furnace process. According to commercial standards for crude iron ores, it may be concluded that the Zambi iron ores are a low‐grade magnetic ore that can be profitably exploited for the production of iron for steel production.     

Controls on the fractionation of isovalent trace elements in magmatic and aqueous systems: evidence from Y/Ho,Zr/Hf,and lanthanide tetrad effect

 The parameters which control the behaviour of isovalent trace elements in magmatic and aqueous systems have been investigated by studying the distribution of yttrium, rare-earth elements (REEs), zirconium, and hafnium. If a geochemical system is characterized by CHArge-and-RAdius-Controlled (CHARAC) trace element behaviour, elements of similar charge and radius, such as the Y-Ho and Zr-Hf twin pairs, should display extremely coherent behaviour, and retain their respective chondritic ratio. Moreover, normalized patterns of REE(III) should be smooth functions of ionic radius and atomic number. Basic to intermediate igneous rocks show Y/Ho and Zr/Hf ratios which are close to the chondritic ratios, indicating CHARAC behaviour of these elements in pure silicate melts. In contrast, aqueous solutions and their precipitates show non-chondritic Y/Ho and Zr/Hf ratios. An important process that causes trace element fractionation in aqueous media is chemical complexation. The complexation behaviour of a trace element, however, does not exclusively depend on its ionic charge and radius, but is additionally controlled by its electron configuration and by the type of complexing ligand, since the latter two determine the character of the chemical bonding (covalent vs electrostatic) in the various complexes. Hence, in contrast to pure melt systems, aqueous systems are characterized by non-CHARAC trace element behaviour, and electron structure must be considered as an important additional parameter. Unlike other magmatic rocks, highly evolved magmas rich in components such as H₂O, Li, B, F, P, and/or Cl often show non-chondritic Y/Ho and Zr/Hf ratios, and “irregular” REE patterns which are sub-divided into four concave-upward segments referred to as “tetrads”. The combination of non-chondritic Y/Ho and Zr/Hf ratios and lanthanide tetrad effect, which cannot be adequately modelled with current mineral/melt partition coefficients which are smooth functions of ionic radius, reveals that non-CHARAC trace element behaviour prevails in highly evolved magmatic systems. The behaviour of high field strength elements in this environment is distinctly different from that in basic to intermediate magmas (i.e. pure silicate melts), but closely resembles trace element behaviour in aqueous media. “Anomalous” behaviour of Y and REEs, and of Zr and Hf, which are hosted by different minerals, and the fact that these minerals show “anomalous” trace element distributions only if they crystallized from highly evolved magmas, indicate that non-CHARAC behaviour is a reflection of specific physicochemical properties of the magma. This supports models which suggest that high-silica magmatic systems which are rich in H₂O, Li, B, F, P, and/or Cl, are transitional between pure silicate melts and hydrothermal fluids. In such a transitional system non-CHARAC behaviour of high field strength elements may be due to chemical complexation with a wide variety of ligands such as non-bridging oxygen, F, B, P, etc., leading to absolute and relative mineral/melt or mineral/aqueous-fluid partition coefficients that are extremely sensitive to the composition and structure of this magma. Hence, any petrogenetic modelling of such magmatic rocks, which utilizes partition coefficients that have not been determined for the specific igneous suite under investigation, may be questionable. But Y/Ho and Zr/Hf ratios provide information on whether or not the evolution of felsic igneous rocks can be quantitatively modelled: samples showing non-chondritic Y/Ho and Zr/Hf ratios or even the lanthanide tetrad effect should not be considered for modelling. However, the most important result of this study is that Y/Ho and Zr/Hf ratios may be used to verify whether Y, REEs, Zr, and Hf in rocks or minerals have been deposited from or modified by silicate melts or aqueous fluids. Received: 4 September 1995 / Accepted: 30 October 1995     

内蒙古二道河子铅锌矿成因研究

基于矿床地质调查,并通过岩矿石地球化学和锆石U-Pb测年研究,探讨了二道河子铅锌矿床成因。该矿床赋存于中侏罗统塔木兰沟组中,受北西向断裂-裂隙构造控制,矿体多呈脉状,围岩以火山岩为主,夹有砾岩。据常量、微量、稀土元素和Pb、Sr、Nd同位素测试结果:火山熔岩中SiO2质量分数为48.01%～56.44%,岩屑晶屑凝灰岩中为69.09%～71.73%。前者稀土总量高于后者,两者稀土配分型式相似,均显弱负铕异常;而前者Pb、Zn、Cu等成矿元素的含量却远低于后者。火山岩富集Rb、U、Th等大离子亲石元素,Sr普遍亏损,相对亏损Nb、Ta以及Ti等高场强元素。火山岩ISr=0.704 925～0.706 632,εNd(t)=0.5～2.0,εSr(t)=8.5～32.8,tDM=619～730Ma。火山岩和矿石的Pb同位素组成十分接近,206Pb/204Pb=18.130～18.475,207Pb/204Pb=15.526～15.567,208 Pb/204 Pb=38.078～38.286,μ值为9.32～9.40。矿床主要围岩岩屑晶屑凝灰岩的SHRIMP锆石U-Pb年龄为(164.2±2.3)Ma,这表明火山岩为混有壳源物质的幔源岩浆形成。火山活动分为2期:早期表现为中(基)性火山喷发;晚期岩浆活动发生于中侏罗世晚期,形成酸性火山碎屑岩。成矿物质由与火山岩有关的岩浆系统提供,富集于晚期岩浆中。与成矿有关的侵入岩可能是晚期岩浆作用形成的次火山岩。矿床可能是岩浆分异的含矿热液沿火山岩中的断裂、裂隙充填交代形成,成矿时代为中侏罗世晚期—晚侏罗世。