Geochemical constraints on the distribution of trace elements and volatiles in fluorapatite from the Panasqueira tin-tungsten deposit (Portugal)

A large, euhedral crystal of fluorapatite (ca. 19.5 × 20.0 mm) from the Panasqueira tin-tungsten deposit (Portugal) was investigated in terms of the distribution of trace elements by using several microanalytical techniques. The studied material represents almost pure fluorapatite with minor amounts of other cations (mainly Sr, Mn, REE and Fe), OH and Cl. Particular interest was given to the distribution of rare earth elements with respect to the crystallographic orientation. A broad range of analytical techniques were used, including optical microscopy coupled with cathodoluminescence imaging, electron probe microanalysis (EPMA), laser ablation – inductively coupled plasma mass spectrometry (LA-ICPMS), Raman microspectroscopy, and simultaneous thermal analysis coupled with mass spectrometry. The investigated crystal consists of the main crystal with a distinct core and rim (Ap_2core and Ap_2rim, respectively), which grew on a previous, euhedral crystal (Ap₁). The fluorapatite demonstrates various types of zoning: regular oscillatory, irregular, and internal sectoring, which is also reflected in trace elements concentrations. The rim Ap_2rim has lower concentrations of Mn, Sr and Fe, and significantly higher concentrations of REE compared to the core Ap_2core and older crystal Ap₁. Furthermore, the rim Ap_2rim is strongly depleted in Th, U and Pb. The entire crystal shows elevated Eu contents, expressed as a strong positive anomaly in chondrite-normalized REE patterns. With regards to the volatiles, F concentrations are constant in Ap₁, Ap_2core and Ap_2rim, whereas Cl is below the EPMA detection limit. The Ap_2rim was the only part of the investigated material containing OH and CO₃, which were observed in the Raman spectra. Furthermore, part of the crystal Ap_2core is extensively altered, likely due to fluid-induced metasomatic processes. LA-ICPMS U-Pb dating yielded highly discordant dates due to common Pb content. A lower intercept age of 297 ± 13 Ma (MSWD = 0.13) indicates the age of the fluorapatite crystallization. The overall analytical data constrain growth and post-growth processes, including crystallization of Ap₁ and Ap_2core, which both have typical hydrothermal Sn-W deposit characteristics, whereas Ap_2rim is related to a carbonate stage of the mineralization in the Panasqueira deposit.     

独居石和磷钇矿晶体结构的精确测定

本文用强功率四圆单晶衍射仪精确地修正了独居石和磷钇矿的晶体结构。独居石［Ｍｏｎａｚｉｔｅ－（Ｃｅ），ＣｅＰＯ４］属单斜晶系，ａ＝６．７８４３（１７），ｂ＝６．９８９１（１２），ｃ＝６．４５９２（１０），β＝１０３．６２６（１６）°，Ｚ＝４，空间群为Ｐ２１／ｎ。使用１１０６个［Ｆ≥３σ（Ｆ）］的独立衍射点，经多轮最小二乘法修正后，最终获得偏离因子Ｒ＝０．０６０。独居石的结构由孤立的［ＰＯ４］四面体构成，Ｃｅ位于［ＰＯ４］四面体包围之中，Ｃｅ的配位数为９，独居石的Ｃｅ—Ｏ平均键长为２．５５２，Ｐ—Ｏ平均键长为１．５２８。磷钇矿（Ｘｅｎｏｔｉｍｅ，ＹＰＯ４）属四方晶系，其晶格常数为：ａ＝６．８７９１（２４），ｃ＝６．０１４７（１９），Ｚ＝４，空间群为Ｉ４Ｉ／ａｍｄ（Ｎｏ．１４１）。使用１４２个［Ｆ≥３σ（Ｆ）］的独立衍射点，经多轮最小二乘法修正后，最终获得偏离因子Ｒ为０．０４８３。磷和氧形成四面体配位，其Ｐ—Ｏ平均键长为１．５４３；稀土钇与氧原子相连构成八次配位，其Ｙ—Ｏ平均键长为２．３３３。     

高压-超高压变质岩石中石榴石的环带和成因

在俯冲带变质过程中,石榴石是高压-超高压变质榴辉岩和片麻岩的常见变质矿物。由于石榴石具有难熔和流体中的低溶解能力的特点,通常可以很好地保存下来,并且能够保留复杂的化学成分环带,以及不同类型的矿物或流体包裹体,为解释石榴石寄主岩石经历的变质演化历史提供了重要信息。石榴子石的主微量元素成分受控于很多因素,如全岩成分、变质的温压条件、控制石榴子石形成的相关变质反应、与石榴子石共生的矿物种类和成分等。因此,在利用石榴石探讨超高压变质的演化历史时,对石榴石进行系统的主要元素、微量元素、氧同位素以及矿物包裹体分析,以及相互间的成因关系。同时,对石榴石中的锆石或独居石包裹体并进行原位U-Pb定年和微量元素分析,可以为变质石榴石的形成时代提供直接的时间制约。深入研究超高压变质岩中石榴石的生长阶段,不仅可以为含石榴石寄主岩石的变质过程提供岩石学和地球化学证据,而且对于理解石榴石的形成机制、生长规律及其变质化学动力学过程具有重要的科学意义。     

Flat rare earth element patterns as an indicator of cumulate processes in the Lesser Qinling carbonatites, China

The Lesser Qinling carbonatite dykes are mainly composed of calcites. They are characterized by unusually high heavy rare earth element concentrations (HREE; e.g. Yb > 30 ppm) and flat to weakly light rare earth element (LREE) enriched chondrite-normalized patterns (La/Yb_n = 1.0–5.5), which is in marked contrast with all other published carbonatite data. The trace element contents of calcite crystals were measured in situ by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). Some crystals show reduced LREE from core to rim, whereas their HREE compositions are relatively constant. The total REE contents and chondrite-normalized REE patterns from the cores of carbonate crystals are similar to those of the whole rock. The carbon and oxygen isotopic compositions of calcites fall within the range of primary, mantle-derived carbonatites. The initial Sr isotopic compositions (0.70480–0.70557) of calcites are consistent with an EM1 source or mixing between HIMU and EM1 mantle sources. However these sources cannot produce carbonatite parental magmas with a flat or slightly LREE enrichment pattern by low degrees of partial melting. Analyses of carbonates from other carbonatites show that carbonates have nearly flat REE pattern if they crystallize from a LREE enriched carbonatite melt. This implies that when carbonates crystallize from a carbonatite melt the calcite/melt partition coefficients (D) for HREE are much greater than the D for the LREE. The nearly flat REE patterns of the Lesser Qinling carbonatites can be explained if they are carbonate cumulates that contain little trapped carbonatite melt. Strong enrichment of HREE in the carbonatites may require their derivation by small degrees of melting from a garnet-poor source.     

In situ characterization of dolomite crystals: Evaluation of dolomitization process and its effect on zoning

Dolomitization is a dissolution–re‐precipitation process which proceeds via micrometre‐scale interface reaction horizons. However, the effect of this fundamental local medium of replacement process on precipitated dolomite crystals is rarely investigated. For this purpose, dolomite samples of Ordovician Boat Harbour Formation carbonates (Newfoundland, Canada) from Main Brook and Daniel's Harbour (about 150 km apart) were studied. The investigation used high‐resolution approaches to carry out imaging and elemental analyses of individual dolomite crystals, including scanning electron microscopy, scanning electron microscopy‐based cathodoluminescence, secondary ion mass spectrometry and electron microprobe analysis. The purpose was to better understand geochemical variations across the crystal traverses and their association with dolomite replacement processes and conditions. The scanning electron microscopy‐based cathodoluminescence‐zoning character reveals three major crystal facies. Distinctly (planar boundaries) zoned core and indistinctly zoned core are zoned dolomite crystal facies in burial dolomite from Main Brook. Relatively unzoned crystal facies was identified in that of Daniel's Harbour. Compositionally zoned dolomite crystals are characterized by decreasing Sr, Na, Y and ∑REE but increasing Mn and Fe from core to rim sections. ‘Core to rim’ zoning was not found for major (Mg and Ca) elements. The zoning exhibited by the replacive dolomite crystals is interpreted to be, principally, a result of limited exchange between solutes of the bulk pore fluid and those of dissolving precursor marine carbonate. In tandem with petrographic features, the systematic compositional zoning character demonstrates that the effectiveness of the dolomitization process grades from indistinctly zoned core to relatively unzoned crystal facies via interface reaction horizons. Homogenization of major elements of core and rim sections, seen in distinctly zoned core crystal facies and to a much greater extent in relatively unzoned crystal facies, via a secondary reaction interface, is the first recognized stage of the ‘maturation process’ followed by homogenization of the trace elements seen largely in relatively unzoned crystal facies.     

对于氟碳钡铈矿（Cordylite—Ce）成分与结构的质疑

本文讨论了氟碳钡铈矿的成分和结构问题。发现氟碳钡铈矿的成分、密度、折射率三者间的一致性参数很差,晶体结构与光性和空间群相矛盾,单个大阳离子的平均占有体积远大于同类矿物的平均占有体积,它的晶体结构与同类矿物不可类比。由于受当时条件的限制,在以往有关氟碳钡铈矿的成分和结构的资料中存在着一些明显的错误,有必要对其进行重新定义。其结构化学式应改为:(Na_(1-x),Ca_(0·5x))BaCe_2(CO_3)_4F。     

长江中下游典型火山盆地的水岩相互作用和金属矿床蚀变分带

长江中下游火山岩盆地中金属矿床和蚀变分带的的地球化学研究表明,它们具有内带深色蚀变带和外带浅色蚀变带,形成于600℃到100℃范围。两类蚀变带分界温度大致是300℃。大金属矿床蚀变分带剖面显示出热液系统存在有明显的温度梯度。通过与背景岩石(玄武岩石)对比研究表明,自下而上的不同蚀变岩石中主要元素含量显著变化,交代作用中的代出和代入元素在空间上是演化的。25~400℃和23MPa下矿物(钠长石、阳起石、透辉石、钙铁辉石)-H2O、岩石(玄武岩)-H2O反应的化学动力学实验表明,金属元素释放速率是温度的函数。在恒压升温过程中,从20℃到400℃,硅酸盐矿物、玄武岩中Si溶解速率不断上升;在300~350℃时,Si、Al溶解速率到最大数值。随后,温度再上升导致溶解速率下降。在300℃时,大部分矿物中Ca、Mg、Fe、Na溶解速率较高,溶液里的Ca/Si、Mg/Si、Fe/Si、Na/Si等都高于矿物中对应元素的计量比。矿物反应后的表面存在富集硅的淋失层,或有富硅铝矿物(粘土矿物)出现。在300℃时,Si溶解快于其他金属元素,溶液中金属元素与硅摩尔浓度比(Ca/Si、Mg/Si、Fe/Si、Na/Si)等都低于矿物中的计量比。矿物反应后的表面缺少硅的淋失层,或者有贫硅矿物和铁氧化物出现。作者还进行23~35MPa、20~550℃玄武岩与水反应实验。上述高温高压下矿物在水溶液中的溶解反应动力学实验和流体-玄武岩相互作用实验,对于理解金属矿床及蚀变分带形成机制提供新的依据。     

Environmental assessment of Dhaka City (Bangladesh) based on trace metal contents in road dusts

Geochemical analysis of street dusts was conducted to evaluate the environment of Dhaka City, Bangladesh. Dust samples were collected from different areas (industrial, commercial, and residential) of Dhaka City, and their major, trace and rare earth elements (REE) were determined. Samples from the commercial area had Pb concentrations double those of the industrial and residential areas. Contents of Zn, Cu, Ni, and Cr in the industrial areas were greater than those in the commercial and residential areas. The REE patterns of all dusts in Dhaka are similar and are comparable to the average upper continental crust. The condition of the Dhaka environment was compared to that in Japan and other baseline sediments using Zn–Fe₂O₃ and Pb–Fe₂O₃ diagrams. Zn–Fe₂O₃ trends for the dusts show steep inclination compared to the baseline sediment and the Japanese urban sediment trends. Dhaka lake data show enrichment of Zn over the dusts, suggestive of Zn pollution from poorly controlled industrial sources. In contrast, on the Pb–Fe₂O₃ diagram, Dhaka dusts have greater Pb contents than lake sediments, probably due to the higher traffic density in the commercial area compared to the residential area including the area around the lake. The results suggest that higher levels of Pb and Zn in street dusts in Dhaka can most likely be attributed to the anthropogenic sources like vehicle emissions to the atmosphere and a rapid development.     

福建尤溪丁家山矿区闪锌矿中微量元素及其对晶体结构影响研究

应用矿相显微镜、显微电子能谱分析、粉晶X射线衍射等分析手段,研究了丁家山闪锌矿中微量元素的存在状态和富集特征。通过闪锌矿晶体化学式的对比,研究发现闪锌矿可以分为两个世代,它们的成矿温度存在明显差异。通过微量元素比值推断该矿床为高中温内生矿床,并经受过后期改造。闪锌矿受类质同象离子置换的影响,其晶胞参数与微量元素含量关系密切。同时在该矿区首次发现了白钨矿。     

四川盆地Guadalupian统碳酸盐岩稀土元素和碳-锶同位素特征及地质意义

Guadalupian(瓜德鲁普世)晚期是地球演化史中的重要转折期,海退事件、大规模火山作用引起的生物多样性危机,是全球地质灾变的重要组成部分,在扬子克拉通Guadalupian统碳酸盐岩地层中留下了清晰的时空印迹。本文以四川盆地坡渡剖面茅口组顶部的碳酸盐岩地层为研究对象,通过系统的碳、锶同位素、稀土元素测试分析以及生物地层研究,揭示了Guadalupian时期海退事件、峨眉山玄武岩喷发事件的发生与演化过程,并进一步分析了其与生物危机的耦合关系。研究发现,海退事件始于Jinogondolella postserrata带,海平面降低导致陆源物质供给量增加,引起~(87)Sr/~(86)Sr升高、δ~(13)Ccarb负偏、稀土总量上升以及Y/Ho比值降低;峨眉山玄武岩喷发开始于J. altudaensis带,火山作用过程中释放的富~(12)C的CO_2冲击了碳循环系统,大量幔源物质输入到海洋,引起了海水碳酸盐~(87)Sr/~(86)Sr、δ~(13)Ccarb同步负偏移,以及稀土总量与配分模式的急剧改变。Guadalupian时期频繁的水体深度变化,是对峨眉山地幔柱活动的响应。频繁的海退事件造成浅水生物栖息地的不断锐减,持续的火山作用导致大量CO_2、SO2、Cl2等有毒气体的释放,触发了生物多样性危机由浅水逐步扩大到深海。     

碱熔共沉淀-电感耦合等离子体质谱法测定橄榄岩中的稀土元素

橄榄岩的稀土元素特征对研究岩石成因、岩浆作用过程具有重要的意义。橄榄岩中的稀土元素含量低(∑REEs=0.1~1μg/g),且存在镁、铁等基体元素的干扰,难以准确测定。前人通常利用高压密闭酸溶-离子交换法处理样品,将稀土元素与镁、铁等基体元素分离,达到了预富集的效果,但耗时长(消解时间接近7天)、操作步骤繁多,不利于大批量样品的分析。本文建立了过氧化钠碱熔、Fe(OH)_3和Mg(OH)_2共沉淀的样品前处理方法,通过离心使溶液与沉淀分离,从而实现了稀土元素与镁、铁等基体元素的快速分离,再采用电感耦合等离子体质谱法测定稀土元素含量。方法检出限为0.17~2.18 ng/g,加标回收率为95%~101%,国家标准物质(GBW07101和GBW07102)的测定值与标准值的相对误差小于20%,相对标准偏差(RSD,n=11)小于10%。该方法既减少了分步沉淀过程中带来的损失,也缩短了分析周期(消解时间仅需一天),操作简便,分析效率高。     

氟碳铈钡矿Ba3Ce2(CO3)5F2晶体结构重测

氟碳铈钡矿Ba₃Ce₂(CO₃)₅F₂的晶体结构原先被描述为Cm和P2空间群,经单晶X射线衍射方法重测为C2/m空间群;采用2339个独立反射,151个可变参数,R=0.034,R_w=0.05.经检测,未发现明显违反C心布拉维格子的反射;误差允许范围内位移椭球体与所定空间群相容。结构中的原子排列与化合物Ba₃La₂(CO₃)₅F₂相似,可被描述为平行于(102)层间有序结构,层与层之间通过碳酸根相联结。     

Crystal growth and the formation of chemical zoning in garnets

A crystal growth model is developed which generalizes the Rayleigh fractionation process. The new growth model allows some insight into the interpretation of nonequilibrium behavior of minerals, primarily the chemical zoning profiles exhibited by metamorphic minerals. A nonlinear equilibrium term for exchange of constituents between a growing mineral and a reservoir is initially incorporated into the usual isothermal fractionation model. Criteria are established to decide when a simple distribution term is sufficient to describe the growth and exchange process. The model is then extended to allow for temperature changes during a cooling or heating event. Finally, an exact solution is obtained for the temperature dependent case incorporating a time dependent growth rate. The growth models are successfully used to obtain growth rates of 0.01 to 0.09 cm/million year and describe the magnesium and iron zoning profiles of garnets from Phillipston, Massachusetts. The generalized model confirms the development of zoning during the retrograde growth of garnet in the late stages of the Acadian orogeny.     

Concentrations of rare earth elements in topsoil from East China

Fifty topsoil samples collected from 12 different regions of East China have been analyzed for rare earth elements (REEs). The average REE concentrations of the 50 topsoil samples are much higher than world average and are characterized by LREE-enrichment, HREE-depletion, Eu-depletion and Ce-enrichment. However, the REE concentration is not strongly affected by the climate of the sampling site; it is controlled mainly by parent materials. The plot of Ce/Eu against Eu/Sm is proved to be useful to distinguish different parent materials of topsoil. Each element in the 50 topsoil has a good correlation with its neighboring element. Seven of the 13 values are above 0.987.     

Patterns of rare earth and other trace elements in Paleogene and Miocene clayey sediments from the Mondego platform (Central Portugal)

In the present study the origin of clay deposits occurring in an inland platform, in central Portugal, was investigated by their mineralogical and chemical composition. The clay deposits, exploited for ceramic industry are composed of silt-clay facies, the Monteira Member and the Arroça Member, which are assigned to the Coja Formation (Paleogene) and the Campelo Formation (Miocene), respectively. These clayey facies show almost compositional homogeneity, especially concerning texture. The mineralogical composition of the Monteira Member displays slightly higher content in smectite and interstratified clay minerals, which is supported by the chemical composition of samples analyzed. Both members present similar REE patterns, displaying an intense weathering record and little variation in the source area composition. Minor element geochemistry suggests low content in heavy minerals and transition metals. REE patterns and ratios of geochemical parameters support the dominant metasedimentary provenance, with a granite source contribution and also mature recycled sediments of continental origin. The study results’ suggest that the clays of these two members have the same source in terms of lithology and recycled sediments from the Hesperian massif. During the deposition of the Arroça Member, a major remobilization of the Monteira Member is suggested, explaining the geochemical similarity of both facies.     

Monazite behaviour and age significance in poly-metamorphic high-grade terrains: A case study from the western Musgrave Block, central Australia

Integrated, in situ textural, chemical and electron microprobe age analysis of monazite grains in a migmatitic metapelitic gneiss from the western Musgrave Block, central Australia has identified evidence for multiple events of growth and recrystallisation during poly-metamorphism in the Mesoproterozoic. Garnet + sillimanite-bearing metapelite underwent partial melting and segregation to palaeosome and leucosome during metamorphism between 1330 and 1296 Ma, with monazite grains in leucosome recording crystallisation at 1300 Ma. Monazite breakdown during melting is inferred to have occurred in the palaeosome. During a subsequent granulite facies event at 1200 Ma, deformation and metamorphism of leucosome and palaeosome resulted in partial disturbance of ages and potential minor growth on 1300 Ma monazite in leucosome. Growth of new, high-Y (+HREE) monazite in palaeosome domains occurred during garnet breakdown in the presence of sillimanite to cordierite and spinel, as a result of post-peak isothermal decompression. Diffusive enrichment of resorbed garnet rims in Y + HREE suggests garnet breakdown occurred slower than volume diffusion of REE. Monazite in both palaeosome and leucosome were subsequently partially to penetratively recrystallised during a retrogression event that is suggested to have occurred at 1150–1130 Ma. The intensity of recrystallisation and disturbance of ages appears linked to proximity to retrogressed garnet porphyroblasts and their occurrence in the relatively reactive or ‘fertile’ local environments provided by the palaeosome/mesosome volumes, which caused localised changes in retrogressive fluids towards compositions more aggressive to monazite. Like reaction textures, it is apparent that domainal equilibrium and reaction may control or at least strongly influence monazite REE and U–Th–Pb chemistry and hence ages.     

Upper Maastrichtian shallow marine environments and neoselachian assemblages in North Iberian palaeomargin (Castilian Ramp,Spain)

Upper Maastrichtian deposits formed in a nearshore subtidal environment within the Valdenoceda Formation (Castilian Ramp, North Iberian margin) are described together with two recently found selachian assemblages. Rare earth element concentrations (REE) have been used to assess the degree of taphonomic mixing and reworking, observing that it is minor or non-existent, and differences in degree of preservation and ecologic mixing can be explained by biostratinomic processes. The patterns of REE also helped to obtain a better understanding of the depositional environment, including the diagenetic history from burial to final degree of bone preservation.The fossil assemblages here described are close to that of the late Maastrichtian of Albaina (in the enclave of Condado de Treviño, Burgos), both in the Basque-Cantabrian Region, but their age may be slightly older (early late Maastrichtian). In total, the new assemblages consist of 17 taxa, assigned to 11 genera of shallow-water dwellers combined with individuals from the outer shelf. They represent cosmopolitan taxa (Squalicorax pristodontus, Serratolamna serrata and Rhombodus binkhorsti) together with local species (Rhinobatos echavei, Rhinobatos ibericus). Although there are not significant differences between Albaina and Quintanilla la Ojada faunas, the new assemblages add interesting taphonomic and geochemical information to the few existing uppermost Cretaceous deposits with fossil sharks in southwestern Europe.     

Heavy metals and rare earth elements (REEs) in soil from the Nam Co Basin,Tibetan Plateau

Twenty-eight soil samples collected from the Nam Co Basin, Tibetan Plateau, have been analyzed for heavy metals (Cd, Cr, Ni, Cu, Zn, Pb and Mn), arsenic (As) and rare earth elements (REEs). In addition, for establishing the basic physio-chemical characteristics of the soil, pH, total organic concentration, electrical conductivity, and effective cation exchange capacity were measured. The results indicate that soil in the Nam Co Basin is still at an early alkaline weathering stage (pH = 7.94). Mean concentrations of heavy metals and As decreased as follows: Mn > Cr > Zn > Pb > Ni > Cu > As > Cd. The values of Cd, Cr, As, Pb and REEs in soil from the Nam Co Basin are higher relative to averaged background values over China. The chondrite-normalized diagrams of REEs suggest high REE(ΣLa → Eu)—enrichment, HREE(ΣGd → Lu)—depletion and Eu—depletion. Vertical profiles indicate that both heavy metals (except As) and REEs primarily exist in the surface soil. However, heavy metals and REEs vary in the surface soil between the southern and the northern bank of Nam Co. These differences are controlled mainly by parent materials.     

西藏知不拉铜多金属矿床地质、石榴子石分带特征及其地质意义

西藏知不拉铜多金属床是冈底斯成矿带东段典型的矽卡岩矿床,石榴子石是矿区最主要的矽卡岩矿物,其颗粒间的空隙是金属矿物的主要赋存部位。本文通过详细的钻孔编录,结合岩矿鉴定及电子探针分析,划分出两种不同类型的石榴子环带,并在垂向上具有明显的分带:产于顶板凝灰岩中的石榴子石以钙铁榴石为主,环带中心颜色深,向外逐渐变浅,由纯钙铁榴石过渡到钙铝榴石;而位于底板大理岩附近石榴子石多以钙铝榴石为主,从环带核部向外颜色变深,化学组成由钙铝榴石向钙铁榴石变化,其它化学成分变化不大。反映该区上下两套不同性质围岩在石榴子石形成过程中所起的作用不同,其中上部凝灰岩主要提供了Fe,底部大理岩则是Ca的来源,热液流体贡献Si、Al及部分Fe,并随着环境和物质成分改变导致环带外侧具有不同于核部的变化趋势。这很好地解释了石榴子石矽卡岩在空间上具有上部为钙铁榴石、向下逐渐过渡到钙铝榴石的空间分带。石榴子石特征及分带显示了其属热液接触交代成因,这为矿床类型的确定提供了依据,也为在该区域内寻找类似矿床指明了方向。