REE Mineralization of Weathered Crust and Clay Sediment on Granitic Rocks in the Sanyo Belt,SW Japan and the Southern Jiangxi Province,China

Rare earth element (REE) geochemistry and mineralogy have been studied in the weathered crusts derived from the Early Yanshanian (Jurassic) biotite granites of Dabu and Dingnan, as well as in the Indosinian (Permian) muscovite–biotite granite of Aigao in southern Jiangxi province, China, and the weathered crusts and clay sediments on biotite granites in the Sanyo belt, SW Japan, that is, Okayama, Tanakami, and Naegi areas. In all of the weathered crusts, biotite and plagioclase commonly tend to decrease toward the upper part of the profile, whereas kaolinite and residual quartz and K‐feldspar increase. The weathered crusts of the Dingnan granites and some Naegi granites, which are characterized by the enrichment in light REE (LREE) in C horizons, have higher total REE (ΣREE) content than the parent REE‐enriched granites. Weathering of LREE‐bearing apatite and fluorocarbonates in the Dingnan granites and allanite and apatite in some Naegi granites may account for the leaching of LREE at the B horizons. The leached LREE must result in subsequent enrichment of LREE in the C horizons. The enrichment is probably associated with mainly adsorption onto kaolinite and partly formation of possible secondary LREE‐bearing minerals. In Japan it was found that REE mineralization occurs not in the weathered granitic crusts but in reworked clay sediments, especially kaolinite‐rich layers, derived mainly from the weathering materials of REE‐enriched granitic rocks. The clay sediments are more enriched in LREE, which likely adsorbed onto kaolinite. Concentration of heavy REE within almost all the weathered crusts and clay sediments, however, may reflect mainly residual REE‐bearing minerals such as zircon, which originated in the parent granitic rocks. The findings of the present study support the three processes for fractionation of the REE during weathering: (i) selective leaching of rocks containing both stable and unstable REE‐bearing minerals; (ii) adsorption onto clay minerals; and (iii) presence of possible secondary LREE‐bearing minerals.     

Mineralogy and geochemical behaviour during weathering of greenstone belt under tropical dry conditions in the extreme North Cameroon (Central Africa)

Mineralogy, major, trace and rare earth elements of a weathering profile developed on tertiary greenstone belt in the extreme North Cameroon are reported. The aim of which was to investigate mineralogical evolution and element mobilization and redistribution during weathering under dry tropical climate. The weathering profile consists of four main horizons: (1) a spheroidal weathering zone constituted by a corestone–shell complex, (2) a C horizon, (3) a Bw horizon and an Ah horizon. The results indicate that nontronite, a Fe-rich smectite, is the exclusive clay mineral formed in the exfoliated shells and the C horizon. It is associated with kaolinite in the upper horizons. The coexistence of these two clay minerals induced a decrease of CEC and pH which becomes neutral. The weathering index (WI) values reveal that weathering becomes more and more intensive from the corestone up to Bw horizon, which is the most weathered horizon in the weathering profile. Mass balance calculations, using Th as immobile element, indicate that Ti is quite mobile and that Al and Fe are relatively enriched at the bottom and strongly leached at the top of the profile. Alkalis and alkaline earth elements are strong leached through out the profile, except Ca which displays similar trend as Al and Fe. The same goes for LILE (Cs, Sr), TTE (Cr, Co, Ni) and HSFE (Y, Nb, Hf). In opposite, REE are depleted at the bottom and enriched in the upper horizons, with more enrichment for LREE than for HREE. It appears that weathering of greenstone belt causes a fractionation of HREE and induces a concentration of LREEs. Ce and Eu anomalies display opposite behaviour.     

Distribution and fractionation of rare earth elements and Yttrium in suspended and bottom sediments of the Kali estuary,western India

Concentrations of rare earth elements (REE) and yttrium (Y), and major metals (Al, Fe and Mn) were measured in suspended particulate matter (SPM) and bottom sediments of the Kali estuary, western India, for their distribution and fractionation. The contents of SPM and metals in it were more uniform along the longitudinal transect during the monsoon. During the post- and pre-monsoons, low SPM in the upper/middle estuary coincided with high Fe and Mn and total REE (∑REE). But in the lower estuary SPM and its ∑REE content increased seaward, while Fe and Mn decreased. The Y/Ho ratios decreased seaward during the monsoon but increased during the post-monsoon. Sm/Nd ratios were more uniform along the transect during monsoon but decreased marginally seaward in other seasons. The Post-Archean Average Australian Shale (PAAS)-normalized REE patterns exhibited middle REE and heavy REE enrichment with positive Ce (\({\text{Ce}}/{\text{Ce}}^{*}\)), Eu (\({\text{Eu}}/{\text{Eu}}^{*}\)) and Y anomalies. The \({\text{Ce}}/{\text{Ce}}^{*}\) increased but \({\text{Eu}}/{\text{Eu}}^{*}\) decreased marginally seaward. The fine-grained sediments showed higher ∑REE and lower Y/Ho ratios than in coarse-grained sediments. The PAAS-normalized REE patterns of sediment were similar to that of SPM. The results revealed two processes, colloidal flocculation and coagulation of metals in the low-salinity zone and an estuarine turbidity maximum in the high salinity zone. Rare earths and yttrium (REY) in SPM and sediments primarily reflected the source rock composition than that of chemical weathering. Apart from physico-chemical processes, the mineralogy and grain size of sediments controlled the distribution and fractionation of REY in the estuary.     

Geochemical and mineralogical characteristics of recent clastic sediments from lower Godavari river: Implications of source rock weathering

The major, trace and rare earth elements geochemistry and clay mineral compositions in the river bed sediments from lower reaches of Godavari river suggest that they are derived from weathering of felsic rocks. Trace and rare earth elemental compositions indicate evidence of sedimentary sorting during transportation and deposition. Lower concentrations of transition elements, such as V, Ni and Cr imply enrichment of felsic minerals in these bed sediments. The REE pattern in lower Godavari sediments is influenced by the degree of source rock weathering. The light rare earth elements (LREE) content are indicating greater fractionation compared to the heavy rare earth elements (HREE). A striking relationship is observed between TiO₂ and gZREE content suggesting a strong control by LREE-enriched titaniferous minerals on REE chemistry. Shale-normalized REE pattern demonstrate a positive Eu anomaly, suggesting weathering of feldspar and their secondary products, which are enriched in Eu. Chondrite-normalised REE pattern is characteristic of felsic volcanic, granites and gnessic source rocks. Trace elemental compositions in sediments located near urban areas suggest influence of anthropogenic activity. Chemical Index of Alteration (CIA) is high (avg. 65.76), suggesting a moderate chemical weathering environment. X-ray diffraction analysis of clay fraction shows predominance of clay minerals that are formed because of the chemical weathering of felsic rocks.     

赣南小流域水体中稀土元素的地球化学特征

本文以赣南小流域水体为研究对象,利用VG Axiom高分辨多接受双聚焦等离子体质谱仪测定了水体中溶解态稀土元素(DREE)的含量,分析了水体中DREE的分布分异机制,并探讨了稀土元素(REE)产生分异的原因.结果表明,赣南所有的采样区水体中Ce都表现为负异常,说明其在风化壳中少活化.受自然风化作用控制为主的水体相对于页岩除Ce亏损、Eu富集外产生的分异很小,其中Eu的正异常源于Eu富集矿物的优先溶解;蒸发盐矿影响下的水体相对于自然作用为主的水体DREE没有发生明显分异;受稀土矿影响的水体中重稀土元素(HREE)富集、Eu负异常的分布模式继承了稀土矿区风化壳的特征;赣州市下游干流水体中中稀土元素(MREE)富集、Eu负异常的分布模式主要是人为影响的结果.     

Geochemical and mineralogical characteristics of ion-adsorption type REE mineralization in Phuket, Thailand

Geochemical and mineralogical studies were conducted on the 12-m-thick weathering profile of the Kata Beach granite in Phuket, Thailand, in order to reveal the transport and adsorption of rare earth elements (REE) related to the ion-adsorption type mineralization. The parent rock is ilmenite-series biotite granite with transitional characteristics from I type to S type, abundant in REE (592 ppm). REE are contained dominantly in fluorocarbonate as well as in allanite, titanite, apatite, and zircon. The chondrite-normalized REE pattern of the parent granite indicates enrichment of LREE relative to HREE and no significant Ce anomaly. The upper part of the weathering profile from the surface to 4.5 m depth is mostly characterized by positive Ce anomaly, showing lower REE contents ranging from 174 to 548 ppm and lower percentages of adsorbed REE from 34% to 68% compared with the parent granite. In contrast, the lower part of the profile from 4.5 to 12 m depth is characterized by negative Ce anomaly, showing higher REE contents ranging from 578 to 1,084 ppm and higher percentages from 53% to 85%. The negative Ce anomaly and enrichment of REE in the lower part of the profile suggest that acidic soil water in an oxidizing condition in the upper part mostly immobilized Ce⁴⁺ as CeO₂ and transported REE³⁺ downward to the lower part of the profile. The transported REE³⁺ were adsorbed onto weathering products or distributed to secondary minerals such as rhabdophane. The immobilization of REE results from the increase of pH due to the contact with higher pH groundwater. Since the majority of REE in the weathered granite are present in the ion-adsorption fraction with negative Ce anomaly, the percentages of adsorbed REE are positively correlated with the whole-rock negative Ce anomaly. The result of this study suggests that the ion-adsorption type REE mineralization is identified by the occurrence of easily soluble REE fluorocarbonate and whole-rock negative Ce anomaly of weathered granite. Although fractionation of REE in weathered granite is controlled by the occurrence of REE-bearing minerals and adsorption by weathering products, the ion-adsorption fraction tends to be enriched in LREE relative to weathered granite.     

离子吸附型稀土找矿及研究新进展

21世纪以来由于稀土资源的战略地位不断提升,全球对稀土的供需变化和价格波动极为关注,并加大了稀土的勘查和开发程度。离子吸附型稀土(iRee)资源因轻重稀土元素配分齐全,且不需要通过矿物分解的方式来分离不同的稀土元素,成为近十多年全球稀土找矿和研究的热点。iRee矿产是我国的优势资源,已有40多年的开采历史,为全球稀土产业尤其是重稀土产业做出了巨大的贡献。近年来,项目组在江西、广西和云南等省区发现了一批矿产地,矿床的分布范围已从我国南方的丘陵地带扩大到高海拔(云南)和高纬度(安徽和浙江)地区,从亚热带气候扩大到热带气候,如越南、缅甸、泰国、马达加斯加及智利等国家。我们的研究继续丰富了iRee成矿“八多两高一深”的认识,即：多类型、多岩性、多期次、多层位、多模式、多标志、多因继承、多相复合,高海拔、高纬度及大深度,新矿床的发现也不断为此认识提供实例。同时,本文对亚热带和热带地区的花岗岩风化壳、华南不同岩性(花岗岩、火山岩和浅变质火山 沉积岩)以及不同稀土配分类型(LREE和HREE型)的iRee矿床进行了对比研究。目前,国内的iRee矿床无论从规模和品位,还是母岩的多样性和稀土配分的全面性都优于国外的。然而,我国长期仍无法摆脱矿山及周边环境污染和优势资源过度消耗的现状。今后,寻找经济价值大的iRee矿床是找矿的重要方向。     

深海沉积物中的稀土矿产资源研究进展

近年发现,太平洋和印度洋的深海盆地中存在大量富含稀土的深海沉积物。主要类型为多金属软泥、沸石黏土和远洋黏土,其中的全稀土含量(∑REY,∑REE+Y)为400×10-6~2000×10-6,最高可达6600×10-6,重稀土含量(HREE)已达到或超过中国南方离子吸附型矿床的重稀土品位两倍以上,是潜在的新型稀土资源,具有重要的经济价值。目前不少学者对富稀土的深海沉积物进行了大量地球化学及部分矿物学的工作,认为多金属软泥中的稀土元素多赋存于与海底热液作用有关的铁锰氧化物和氢氧化物中,而沸石黏土和远洋黏土中稀土元素的富集则与磷酸盐的混入密切相关,其稀土元素主要存在于与磷灰石成分相当的生物鱼骨屑中。深海黏土的北美页岩标准化稀土配分模式与海水相似,表明其中的稀土元素主要来自于海水,REY富集成矿可能主要受控于磷灰石早期成岩阶段,期间稀土元素未发生分异。尽管近些年对深海沉积物中的稀土元素研究取得了不少成果,但是,对于沉积物中的稀土富集机制及影响因素等问题仍然需要更加深入的研究。作为稀土资源大国,为了争取我国在国际海底稀土资源竞争中的话语权,维护中国的稀土利益,中国应加紧开展相关的稀土资源勘查和潜力评价。     

离子吸附型稀土矿床形成的矿物表/界面反应机制

华南离子吸附型稀土矿床提供了全球超过90%的重稀土,是我国优势的战略性关键金属矿产资源。掌握这类矿床的成矿机制和禀赋特征,可为增加稀土资源储量和高效利用稀土资源提供理论支撑。离子吸附型稀土矿床主要发育在富稀土花岗岩、浅变质岩及火山岩的风化壳中。基岩中的(含)稀土矿物是风化壳中离子态稀土的主要来源,其矿物组合很大程度上决定了稀土矿床的禀赋和分异特征。在物理-化学风化和微生物作用下,造岩矿物、含稀土矿物和稀土独立矿物逐渐溶解,使稀土元素活化和再富集。一方面,母岩风化形成的黏土矿物和铁锰氧化物具有较大的比表面积和一定的表面电荷密度,是稀土离子的主要载体;另一方面,稀土离子通过离子交换、表面吸附与络合、共沉淀,以及形成次生稀土矿物等途径富集在次生矿物表面,其富集-分异特征和赋存状态受矿物类型、pH、微生物活动等因素所控制。利用高分辨透射电镜结合选区电子衍射和电子能量损失谱,以及同步辐射X射线吸收精细结构谱,有望在原子级尺度查明稀土的微观赋存状态。未来研究需更多关注基岩中(含)稀土矿物组合及其演化路径的制约因素、微生物风化对离子吸附型稀土矿床成矿作用的约束,以及稀土元素的微观赋存状态等问题。     

浙东南离子吸附型稀土矿床成矿规律与找矿方向探讨

离子吸附型稀土矿(以下简称iRee)主要分布于我国南岭地区,浙江省虽不在南岭五省之内,但经过浙江省地勘单位三十多年的不断探索,在浙东南地区陆续发现了数个稀土矿及多个成矿远景区,填补了浙江省该类型稀土矿的找矿空白。为探究浙东南iRee矿床地质特征、成矿影响因素以及稀土元素运移、赋存规律,圈定成矿远景区,本文对区内出露的花岗斑岩型iRee,火山岩型iRee以及变质岩型iRee进行系统采样,通过岩相学、岩石地球化学等方法对各类iRee剖面进行对比研究。分析结果表明,荷地花岗斑岩的平均∑REE为271.39×10^-6,凝灰岩围岩平均∑REE为253.36×10^-6,大柘片麻岩∑REE约为517.21×10^-6,而南岭含矿岩体的平均∑REE约为289×10^-6,表明浙东南地区iRee矿床具有较好的成矿母岩条件。此外,通过对原岩中各矿物稀土元素含量的测定,查明了稀土元素主要赋存在独立的稀土矿物及少量的副矿物中,是主要的成矿物质来源;通过风化壳剖面的对比,发现稀土元素地球化学特征主要继承原岩性质,而外生作用条件使得稀土元素发生次生富集。在此工作基础上,结合前人研究成果,初步总结了区内离子吸附型稀土矿矿床成矿规律,并讨论下一步找矿方向。     

Geochemistry of trace and rare earth elements during weathering of black shale profiles in Northeast Chongqing,Southwestern China: Their mobilization,redistribution, and fractionation

In this study, the mobilization, redistribution, and fractionation of trace and rare earth elements (REE) during chemical weathering in mid-ridge (A), near mountaintop (B), and valley (C) profiles (weak, weak to moderate, and moderate to intense chemical weathering stage, respectively), are characterized. Among the trace elements, U and V were depleted in the regolith in all three profiles, Sr, Nb, Ta, Zr, and Hf displayed slight gains or losses, and Th, Rb, Cs, and Sc remained immobile. Mn, Ba, Zn, Cu, and Cr were enriched at the regolith in profiles A and B, but depleted in profile C. Mn, Pb, and Co were also depleted in the saprock and fractured shale zones in profiles A and B and enriched in profile C. REEs were enriched in the regolith and depleted at the saprock zone in profiles A and B and depleted along profile C. Mobility of trace and REEs increased with increasing weathering intensity. Normalized REE patterns based on the parent shale revealed light REE (LREE) enrichment, middle REE (MREE), and heavy REE (HREE) depletion patterns. LREEs were less mobile compared with MREEs and HREEs, and this differentiation increased with increasing weathering degree. Positive Ce anomalies were higher in profile C than in profiles A and B. The Ce fractionated from other REE showed that Ce changed from trivalent to tetravalent (as CeO₂) under oxidizing conditions. Minimal REE fractionation was observed in the saprock zone in profiles A and B. In contrast, more intense weathering in profile C resulted in preferential retention of LREE (especially Ce), leading to considerable LREE/MREE and LREE/HREE fractionation. (La/Yb)_N and (La/Sm)_N ratios displayed maximum values in the saprock zone within low pH values. Findings demonstrate that acidic solutions can mobilize REEs and result in leaching of REEs out of the highly acidic portions of the saprock material and transport downward into fractured shale. The overall behavior of elements in the three profiles suggests that solution pH, as well as the presence of primary and secondary minerals, play important roles in the mobilization and redistribution of trace elements and REEs during black shale chemical weathering.     

赣南新元古代变质岩稀土矿物及其地球化学特征

近年来赣南地区首次报道了变质岩离子吸附型稀土矿床的发现,为离子吸附型稀土的找矿提供了新思路。赣南地区新元古代变质岩大面积分布,风化壳也广泛发育。文章对30件稀土元素含量(300×10~(-6))高的变质岩矿物样品进行了详细的电子探针分析,旨在查明赣南新元古代不同类型变质岩中的稀土矿物种类及特征,探讨其成因、对全岩稀土元素含量的贡献以及离子吸附型稀土元素的成矿潜力。研究表明,区域上变质岩可大致分为6类,分别是变质凝灰岩类、板岩类、千枚岩类、片岩类、变砂岩类和变粒岩类,不同类型变质岩的稀土矿物组合不同,除了普遍存在的、难风化的独居石、磷钇矿和锆石外,部分岩性中出现易风化的褐帘石、含稀土元素绿泥石和含稀土元素金红石,及表生的水磷酸盐和磷铝酸盐等矿物。这些富稀土矿物贡献了全岩中大部分稀土元素,且部分矿物成因与后期流体作用相关,为成矿提供了良好的条件。文章总结分析认为,赣南地区广泛分布的变质岩中,片岩类、变砂岩类和变质凝灰岩类均具有相对易风化的稀土矿物组合,尤其变质凝灰岩类和变砂岩类,能为离子吸附型稀土成矿提供充足的物质来源,具有可观的离子吸附型稀土成矿潜力。     

准格尔煤田西南部煤层夹矸及顶底板稀土元素地球化学特征及地质意义

准格尔煤田含煤岩系高岭岩资源丰富,高铝矿物来源备受关注。采用高分辨率电感耦合等离子质谱等技术对石炭-二叠系太原组6号和山西组4号煤夹矸及顶底板中的稀土元素进行分析,并探讨了其物质来源。结果表明,6号煤夹矸及顶底板中稀土元素总量（ΣREY）均值为167.69μg/g,接近上地壳ΣREY值（168.4μg/g）;4号煤夹矸及顶底板中ΣREY均值为210.22μg/g,高于上地壳的ΣREY值。4号煤夹矸及顶底板中轻稀土含量均值与6号煤相当,中稀土和重稀土含量均值为6号煤两倍以上。6号煤夹矸及顶底板分层样中δCe为0.82～0.94,δEu为0.53～0.87;4号煤中δCe为0.88～0.98,δEu为0.74～0.97;均为Ce、Eu负异常。6号煤层夹矸及顶底板稀土元素主要来源于盆地北西侧阴山地区元古界花岗岩和北东侧下古生界沉积岩。4号煤层夹矸及顶底板稀土元素物源主要为盆地北侧阴山地区下古生界和元古界的沉积岩和火成岩系。     

Partitioning of rare earth elements, yttrium, and some major elements among source rocks, liquid and vapor of Larderello-Travale geothermal field, Tuscany (Central Italy)

Rare earth elements (REE), yttrium and some major element concentrations have been measured in the high-enthalpy fluids (HEF) of several geothermal wells and the fluid′s source rocks in the Larderello-Travale area (Tuscany/Central Italy). The REE and Y abundances in the HEF range from 0.1 to about 10 pmol/kg and are slightly higher in the HEF originating from evaporite/carbonate sequences (Calcare Cavernoso) than in those from phyllites. The resulting REY distribution factors between HEF and source rocks, ^appKdsource-rockHEF defined as the ratios of REY/Ca in both phases, range from <0.01 to 0.03 and 0.03 to 0.1 for phyllites and evaporite-limestone sequences (Calcare Cavernoso), respectively. REE+Y are more retained by the source rocks than Ca. HEF show no inherited and, with exception of a small Y anomaly, no acquired anomalies. This indicates a static equilibrium between HEF and the source rocks. The absence of any Eu anomalies points to temperatures less than 250°C in the source region. The small negative Y anomalies are the result of Y depletion in the rock fractions taking part in the water-rock interaction.Due to depressurization of the HEF to about 120°C and 2 bars, a liquid and a vapor phase is produced, which were sampled for the determination of the REE+Y partitioning between the two phases. The apparent partition factors between vapor and liquid ^appDliquidvapor of REE+Y range between 0.05 to 0.2 and about 3 for HEF originating from the phyllites and evaporites/carbonates, respectively. Among all ionic species determined, only NH₄⁺ has an apparent partition factor ^appDliquidvapor above one. In general, REY partition more easily into the vapor phase than the earth alkaline and alkaline elements. No significant correlation of REE+Y in the vapor phase with any of the determined ionic species could be detected. This probably points to the dominant presence of ion pairing such as REY(OH)₃^o or REYO(OH)^o.     

Trace element and isotopic evidence for REE migration and fractionation in salts next to a basalt dyke

Neodymium and Sr isotopic compositions and the rare earth elements (REE) distribution patterns have been determined in salts adjacent to a basaltic dyke along 2 parallel horizontal profiles. The salts, originally consisting of carnallite (KMgCl₃ · 6H₂O), have been transformed during basalt intrusion mainly into halite (NaCl) and sylvite (KCl) by fluids saturated in NaCl. The Sr isotope data suggests that much more fluid penetrated the upper than the lower horizon. The Nd isotope data shows that in the upper horizon, where fluid flow was stronger, Nd is essentially derived from the basalt. In contrast, in the lower horizon a strong salt Nd component is present.The REE data document in both horizons is a strong depletion of Ce, Pr, Nd, Sm and Eu with increasing distance from the basalt. This depletion of the light rare earths (LREE) is stronger in the upper horizon where fluid flow was stronger. The authors suggest that this REE fractionation is more likely due to precipitation of LREE-enriched accessory minerals such as apatite, than to differential REE solubility caused by selective REE complexation. This finding is of interest for REE behaviour in brines in general, and for the behaviour of radioactive REE and actinides in a salt repository for high-level nuclear waste in particular.     

滇西陇川营盘山离子吸附型稀土矿稀土元素分布特征

滇西陇川地区广泛分布着白垩纪至古近纪中酸性花岗岩,以邦棍尖山为代表的岩体花岗岩稀土含量较高,经复杂的风化淋滤作用,岩体中的稀土元素在风化壳中迁移、富集成矿,陇川营盘山稀土矿即为近年新发现的该类型矿产地之一。为研究新发现的营盘山稀土矿稀土元素分布特征、富集规律及稀土配分特征,利用电感耦合等离子体质谱仪(ICP-MS)分析成矿母岩及其风化壳不同风化程度样品稀土分量,结果表明:风化壳各层位稀土元素分布特征相比母岩具有明显的继承性,随风化程度升高,轻重稀土分馏程度升高,轻稀土在全风化层上部相对富集,且随风化程度升高轻稀土富集程度升高,而重稀土的富集程度则逐渐减弱,Gd是风化壳富集能力最强的元素,Dy富集能力最弱,Ce富集在近地表,重稀土具有更强的向下迁移能力。同时,研究发现该稀土矿床的稀土配分特征为低钇、铕,富镧、铈、钕。     

华南花岗岩风化壳中稀土元素地球化学及矿石性质研究

华南稀土花岗岩风化壳主要可分为腐值层、全风化层和半风化层。在岩石的风化淋滤过程中，稀土以水合或羟基水合离子吸附在全风化层中的主要矿物埃洛石和高岭石等粘土矿物上。这些层状粘土矿物具有取代结构和断面余键两个吸附活性中心。量子化学计算表明两个吸附活性中心对不同稀土的吸附能力为：Ｌａ＾３＋〉Ｃｅ＾３＋〉Ｐｒ＾３＋〉Ｎｄ＾３＋〉Ｓｍ＾３＋〉Ｅｕ＾３＋〉Ｇｄ＾３＋〉Ｔｂ＾３＋〉Ｄｙ＾３＋〉Ｈｏ＾３＋〉Ｙ＾３＋     

皖南姚村岩体花岗岩风化壳稀土元素赋存特征

皖南地区花岗岩风化壳中稀土元素普遍富集，局部已成为矿床，其中，郎溪县姚村岩体风化壳富集程度较高。LA- ICP- MS锆石U- Pb定年表明，姚村花岗岩体的形成年龄为127. 9±1. 4 Ma，属于皖南地区燕山期晚期岩浆作用的产物。风化壳可细分为残坡积层（A）、强半风化层（C1）、过渡层（C2）、弱半风化层（C3）和基岩（D） 5层。稀土总量在纵向剖面上呈“波浪式”分布，各层稀土分布型式表现出对原岩的继承性。风化壳稀土配分型式与基岩一致， 富集LREE，轻重稀土分馏明显\[(La/Yb)N=15. 6\]，但总含量明显更高。基岩∑REE为338×10-6，半风化层∑REE最高达642×10-6，富集约两倍。风化壳物质由风化残余主矿物（石英、钾长石、斜长石、黑云母）、黏土矿物（高岭石、埃洛石、伊利石、三水铝石等）和副矿物（锆石、磷灰石、榍石等）等组成。黏土矿物以伊利石含量最高，指示风化壳发育不成熟。REE与埃洛石含量明显正相关，与其他黏土矿物关系不明显。（含）稀土矿物（尤其是榍石）对风化壳中稀土元素的贡献量超过 50%，其次为斜长石，是风化壳中REE的重要来源。     

皖南姚村岩体花岗岩风化壳稀土元素赋存特征

皖南地区花岗岩风化壳中稀土元素普遍富集，局部已成为矿床，其中，郎溪县姚村岩体风化壳富集程度较高。LA- ICP- MS锆石U- Pb定年表明，姚村花岗岩体的形成年龄为127.9±1.4 Ma，属于皖南地区燕山期晚期岩浆作用的产物。风化壳可细分为残坡积层（A）、强半风化层（C1）、过渡层（C2）、弱风化层（C3）和基岩（D）五层。稀土总量在纵向剖面上呈“波浪式”分布，各层稀土分布型式表现出对原岩的继承性。风化壳稀土配分型式与基岩一致， 富集LREE，轻重稀土分馏明显(La/Yb)N=15.6），但总含量明显更高。基岩∑REE为338×10-6，半风化层∑REE最高达642×10-6，富集约两倍。风化壳物质由风化残余主矿物（石英、钾长石、斜长石、黑云母）、黏土矿物（高岭石、埃洛石、伊利石、三水铝石等）和副矿物（锆石、磷灰石、榍石等）等组成。黏土矿物以伊利石含量最高，指示风化壳发育不成熟。REE与埃洛石含量明显正相关，与其他黏土矿物关系不明显。（含）稀土矿物（尤其是榍石）对风化壳中稀土元素的贡献量超过百分之五十，其次为斜长石，是风化壳中REE的重要来源。     

Rare earth elements, yttrium and H, O, C, Sr, Nd and Pb isotope studies in mineral waters and corresponding rocks from NW-Bohemia, Czech Republic

The sparkling waters from the area of Kyselka near Karlovy Vary at the western slope of the Doupovske hory, Bohemia (Czech Republic), and CO₂-poor waters from two underground boreholes at Jachymov, Krusne hory, Bohemia, have been studied with the aim of characterizing the distribution of rare earth elements, yttrium, and H, O, C, Sr, Nd, Pb isotopes during the low-temperature alteration processes of the host rocks. Additionally, leaching experiments were performed at pH 3 on the granitic and basaltic host rocks from Kyselka and the granite of Jachymov. All REE patterns of the granite- and the basalt-derived waters from the Kyselka area are different from those of their source rocks and the leachates of the latter. This elucidates the inhomogeneous distribution of REE and Y among the solid phases in the altered magmatic rocks. The Eu and Ce anomalies in granite-derived waters are inherited, the Y anomaly is achieved by fluid migration. Yttrium is always preferentially leached by mineral waters, whereas Y/Ho ratios of rocks and their leachates are very similar. The REE abundances in waters from the wells in Jachymov are derived from rocks intensely leached and depleted in easily soluble REE-bearing minerals, whereas the granites and basalts from Kyselka still contain soluble, REE-bearing minerals. A comparison of REE/Ca patterns of the experimental leachates with those of the mineral waters elucidate the high retention of REE in rocks during water–rock interaction. In strongly altered rocks Sr isotope ratios of mineral waters and rocks differ widely, whereas the corresponding Nd isotope ratios are very similar. ²⁰⁷Pb/²⁰⁸Pb, ²⁰⁶Pb/²⁰⁸Pb and ²⁰⁶Pb/²⁰⁷Pb ratios in mineral waters are independent from U/Th ratios in the rocks. ²⁰⁶Pb/²⁰⁸Pb and ²⁰⁶Pb/²⁰⁷Pb are lower in mineral waters than in their source rocks and their leachates, which indicates that Pb is primarily derived from solid phases that do not contain significant contents of leachable U and Th. Thus, mineral waters, although CO₂ rich, only interact with surface films on minerals and not with the bulk of the minerals as in the leaching experiments.Calculation of mixing ratios of waters from the granitic and basaltic sources of the waters from the Kyselka area yield about 40% of water from the underlying granite in water recovered from the basalt, whereas the granite-derived water is mixed with only about 5% of the water from the basalt.