玄武质陨石NWA8545的岩石地球化学特征以及对其母体岩浆过程的启示

NWA 8545 是一块玄武质无球粒陨石,它与碳质陨石(CC)NWA 011 成对.CC 被认为是来自于外太阳系的一类物质,由于同位素异常,它们区别于来自内太阳系的非碳质陨石(NC).NWA 011 及其成对陨石作为CC中稀有的玄武质无球粒陨石,其记录的岩浆过程可以被用来研究外太阳系早期行星母体的岩浆活动.本文利用扫描电镜、电子探针和激光剥蚀电感耦合等离子质谱仪(LA-ICP-MS)对NWA 8545 中的辉石、斜长石和陨磷钙钠石进行岩相学以及原位主微量元素的分析,并根据矿物模式丰度计算全岩稀土元素含量.电子探针结果显示NWA 8545 与 HED族陨石Eucrite(钙长辉长无球粒陨石)具有相似的主量元素特征,同时其岩相学与5 型Eucrite类似.激光微量数据表明辉石、斜长石和陨磷钙钠石的稀土元素配分都表现出略微的Ce异常,但其辉石的Ba、Sr等元素并未出现明显的富集现象,即该陨石受地球风化作用影响不明显.利用辉石和斜长石的稀土元素含量,计算平衡熔体的成分,显示其平衡熔体的成分都与全岩的成分比较接近,可以认为两者是在封闭的体系下接近同时结晶.结合变质过程和母体岩浆的成分,本文认为NWA 8545 是由其母体岩浆在经历分离结晶过程后喷发到母体行星表面冷却形成的.     

Mechanisms of weathering of meteorites recovered from hot and cold deserts and the formation of phyllosilicates

Petrographic, mineralogical and chemical analysis of naturally weathered equilibrated ordinary chondrites collected from ‘ hot’ deserts and Antarctica has revealed striking similarities and also pronounced differences in weathering between the two environments. Terrestrial weathering in all meteorites studied is dominated by oxidation and hydration of Fe,Ni metal, producing Fe-oxides and oxyhydroxides that have partially replaced the metal grains and have also occluded primary intergranular pores to form veins. Troilite weathers readily in ‘ hot’ desert environments but undergoes very little alteration under Antarctic conditions. Most of the primary porosity of ordinary chondrites has been occluded by the time that ∼ 15 to 25% of the initial Fe⁰ and Fe²⁺ has been oxidised to Fe³⁺ in both environments. Results from modelling the volume changes upon alteration of primary minerals to a range of weathering products demonstrates that the primary porosity of most meteorites is sufficient to accommodate weathering products. Dilation of primary pores and brecciation, which has been observed in parts of some meteorites, will only occur if the meteorite is especially metal-rich, or has a low primary porosity. These weathering products are absent from recent falls but have formed in a fall after ∼ 100 yr of museum storage.Cl-bearing akaganéite and hibbingite are common weathering products in Antarctic finds but occur in abundance in only one ‘ hot’ desert meteorite, Daraj 014. The majority of Fe-rich weathering products in meteorites from both environments contain low, but variable concentrations of Si, Mg and Ca. In most meteorites a proportion of these elements are inferred to be present as a very finely crystalline mineral with a ∼ 1.0-nm lattice fringe spacing; where seen within intragranular fractures this mineral has a topotactic relationship with olivine and orthopyroxene. In the heavily-weathered Antarctic finds ALHA 78045 and 77002, Si is concentrated in cronstedtite, a Fe-rich phyllosilicate. An unidentified hydrous Si-Fe-Ni-Mg mineral or gel has also partially replaced taenite in ALHA 78045. In addition to Fe-rich weathering products, ‘ hot’ desert meteorites contain sulphates, Ca-carbonate and silica, whereas such minerals are largely absent from Antarctic finds. The abundance of silicate weathering products in Antarctic meteorites is unexpected and indicates that olivine and pyroxene undergo significant chemical weathering in these environments. As preterrestrial cronstedtite is abundant in CM2 carbonaceous chondrites, the Antarctic environment may be a powerful analog for aqueous alteration in the asteroidal parent bodies of primitive meteorites.     

Mobility of Rare Earth Elements in Basalt‐Derived Laterite at the Bolaven Plateau,Southern Laos

Geochemical and geochronological studies were conducted on basalts and laterites from the Bolaven Plateau in southern Laos in order to evaluate the mobility and mineralization of REE, Y and Sc during laterization. The basalts are classified into three categories: (i) small volumetric alkali basalt (eruption age: 15.7 Ma), large volumetric olivine tholeiite (1.2 Ma) and quartz tholeiite with olivine tholeiite (younger than 0.5 ± 0.2 Ma). Formation of REE minerals during laterization result in mobilization and fractionation of REE and Y in laterite profiles. Occurrence of florencite‐(Ce) in a laterite profile derived from alkali basalt immobilizes REE (particularly LREE) and this leads the laterites to be enriched in LREE relative to the parent basalt. Few positive Ce anomalies in this profile suggest that florencite‐(Ce) [(Ce)Al₃(PO₄)₂(OH)₂] formation was followed by CeO₂ precipitation due to the change of redox condition. In tholeiite‐derived laterite profiles, florencite is not recognized and REE and Y tend to be depleted relative to the parent basalts with positive Ce anomalies. This is interpreted as scavenging REE³⁺ except for Ce⁴⁺ from the laterite profile in oxidizing conditions. Sc behaves similarly to Fe during laterization and it is more abundant in the tholeiitic laterite than that in the alkali basaltic laterite. Results of sequential extraction indicate that REE of the alkali basaltic laterite are contained in residual phase, which is dominantly florencite‐(Ce), but they are rarely present in ion‐adsorption phase. It is concluded that basaltic laterites have a low potential of REE resource in terms of low REE contents and a difficulty in REE extraction.     

大冶-武山矿化夕卡岩的稀土元素地球化学研究

用ICP-MS分析了25个含矿夕卡岩样品的REE含量,其中对8个样品的石榴子石等矿物中的熔融包裹体进行了均一温度测定,还对5个夕卡岩样品石榴子石中的熔融包裹体进行了电子探针分析.在这些样品的石榴子石、辉石或方解石中都观察到熔融包裹体.夕卡岩的球粒陨石标准化REE分布模式具有两个突出特点:其一是以富集轻稀土元素(LREE)右倾为特征;其二是多数以具有Eu正异常为特征.夕卡岩球粒陨石标准化REE分布模式有三种类型:第一类型显示斜率不大的右倾直线;第二类型具有以Ce为峰值的折线的特征,即REE线段向上凸,在Ce处有一极大值(个别无峰值,LREE曲线向上凸,呈穹隆状);第三类型为过渡型REE分布模式.在当今REE资料有限的情况下,利用稀土元素地球化学特点鉴别夕卡岩成因是困难的.     

Rapid development of negative Ce anomalies in surface waters and contrasting REE patterns in groundwaters associated with Zn–Pb massive sulphide deposits

Ground and surface waters collected from two undisturbed Zn–Pb massive sulphide deposits (the Halfmile Lake and Restigouche deposits) and active mines in the Bathurst Mining Camp (BMC), NB, Canada were analysed for the rare earth elements (REE). REE contents are highly variable in waters of the BMC, with higher contents typical of waters with higher Fe and lower pH. There are significant differences between ground- and surface waters and between groundwaters from different deposits. The REE contents of surface waters are broadly similar within and between deposit areas, although there are spatial variations reflecting differences in pH and redox conditions. Surface waters are characterised by strong negative Ce anomalies ([Ce/Ce*]_NASC as low as 0.08), produced by oxidation of Ce³⁺ to Ce⁴⁺ and preferential removal of Ce⁴⁺ from solution upon leaving the shallow groundwater environment. Groundwaters and seeps typically lack significant Ce anomalies reflecting generally more reducing conditions in the subsurface environment and indicating that Ce oxidation is a rapid process in the surface waters. Deeper groundwaters at the Halfmile Lake deposit are characterised by REE patterns that are similar to the host lithologies, whereas most groundwaters at the Restigouche deposit have LREE-depleted patterns compared to NASC. Halfmile Lake deposit groundwaters have generally lower pH values, whereas Restigouche deposit groundwaters show greater heavy REE-complexation by carbonate ions. Shallow waters at the Halfmile Lake and Stratmat Main Zone deposits have unusual patterns which reflect either the adsorption of light REE onto colloids and fracture-zone minerals and/or precipitation of REE–phosphate minerals. Middle REE-enrichment is typical for ground- and surface waters and is highest for neutral pH waters. The labile portion of stream sediments are generally more middle REE-enriched than total sediment and surface waters indicating that the REE are removed from solution by adsorption to Fe- and Mn-oxyhydroxides in the order middle REE≥light REE>heavy REE.     

Petrology and trace element geochemistry of Robert Massif 04261 and 04262 meteorites, the first examples of geochemically enriched lherzolitic shergottites

Shergottites sampled two distinct geochemical reservoirs on Mars. Basaltic and olivine-phyric shergottites individually sampled both geochemically enriched and depleted reservoirs, whereas lherzolitic shergottites are previously known only to exhibit a relatively limited intermediate geochemical signature that may have resulted from the mixing of the two geochemical end-member reservoirs. Here we show that recently discovered shergottites Robert Massif (RBT) 04261 and RBT 04262 are the first examples of lherzolitic shergottites originating from the enriched reservoir.RBT 04261 and RBT 04262, initially identified as olivine-phyric shergottites, are actually lherzolitic shergottites. Both meteorites exhibit nearly identical textures and mineral compositions, suggesting that they should be paired. Each consists of two distinct textures: poikilitic and non-poikilitic. The poikilitic areas are composed of pyroxene oikocrysts enclosing olivine grains; all pyroxene oikocrysts have pigeonite cores mantled by augite. The non-poikilitic areas are composed of olivine, pyroxene, maskelynite and minor amounts of merrillite, chromite and ilmenite. Olivine and pyroxene show the lowest Mg-number, and maskelynite has the lowest anorthite component among the lherzolitic shergottites. Moreover, the modal abundances of maskelynite in these two meteorites are distinctly higher than the other lherzolitic shergottites.The rare earth element (REE) budgets of RBT 04261 and RBT 04262 are dominated by merrillite. The slightly light rare earth element (LREE)-enriched pattern of this mineral is similar to that of merrillite in the geochemically enriched basaltic shergottites Shergotty and Zagami, and unlike the LREE-depleted pattern of merrillite in the other lherzolitic shergottites. The REE patterns of both high- and low-Ca pyroxenes are also similar to those in Shergotty and Zagami. The REE pattern of a melt calculated to be in equilibrium with the core of a pyroxene oikocryst is parallel to that of the RBT 04262 whole-rock as well as whole-rock compositions of other geochemically enriched basaltic shergottites. These observations imply that RBT 04262 sampled an enriched and oxidized reservoir similar to that sampled by some of the basaltic shergottites and are consistent with an oxidizing condition for the formation of RBT 04262 (log fO₂ = QFM-1.6).The petrographic and geochemical observations presented here suggest that RBT 04261 and RBT 04262 represent the most evolved magma among the lherzolitic shergottites and that this magma originated from a geochemically enriched reservoir on Mars. Based on an evaluation of the relationship between petrographic, geochemical and chronological signatures for shergottites including RBT 04261 and RBT 04262, we propose that both geochemically enriched and depleted shergottites were ejected from the same launch site on Mars.     

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.     

新疆西天山松湖铁矿床稀土和微量元素地球化学特征及其意义

松湖铁矿床位于新疆西天山阿吾拉勒成矿带中段,赋存于石炭系大哈拉军山组火山-沉积岩系中。矿体呈似层状、透镜状,主要受近EW向、NWW向高角度逆断层控制。矿石主要呈块状、条带状、团块状构造,结构主要为半自形-他形粒状;矿石矿物主要为磁铁矿,其次为赤铁矿、黄铁矿及黄铜矿,脉石矿物主要为钾长石、绿泥石、方解石、绿帘石及阳起石等。围岩蚀变发育,在垂向和水平方向上具有分带性。矿区围岩是阿吾拉勒地区早石炭世岛弧火山岩的组成部分,不同岩性具有类似的稀土元素配分模式,均为轻稀土元素富集的右倾型,发育弱的负铈异常,中到弱的负铕或正铕异常。矿石中磁铁矿的∑REE值变化于20.75×10-6~65.41×10-6,配分模式为轻稀土元素富集的右倾型,发育中到弱的负铈及负铕异常。磁铁矿与围岩的稀土元素特征表明二者具有成因联系,与岛弧火山作用有关。磁铁矿微量元素特征表明成矿物质来源于深部,磁铁矿为火山热液交代成因。结合矿床地质特征,认为松湖铁矿床为海相火山热液型矿床。     

Negative cerium anomalies in the saprolite zone of serpentinite lateritic profiles in the Lomié ultramafic complex,South-East Cameroon

Strong negative cerium anomalies are developed in the saprolite zone of two serpentinite lateritic profiles in the Mada region of the Kongo–Nkamouma massif in the Lomié ultramafic complex (South-East Cameroon).The total lanthanide contents increase strongly from the parent rock (1.328 ppm) to the weathered materials (ranging from 74.32 to 742.18 ppm); the highest value is observed in the black nodules from the western weathering profile and the lowest one in the top of the clayey surface soil from the same profile. The lanthanide contents, except cerium, are highest in the saprolite and decrease along the profile. The light REE contents are very high compared to those of the heavy REE (LREE/HREE ranging from 3.21 to 44.37). The lanthanides normalized with respect to the parent rock reveal: (i) strong negative Ce anomalies with [Ce/Ce¹] ranging from 0.006 to 0.680 in the saprolite zone; (ii) strong positive Ce anomalies with [Ce/Ce¹] ranging from 1.23 to 23.96 from the top of the saprolite to the clayey surface horizon; (iii) positive Eu anomalies with [Eu/Eu¹] ranging from 2.09 to 2.41 in all the weathered materials.Mass balance evaluation shows that, except cerium, lanthanides have been highly accumulated in the saprolite zone and moderately concentrated in the upper part of both profiles. Cerium has been highly accumulated in the nodules of the West Mada profile. The presence of negative Ce anomalies is confirmed by its low degree of accumulation whereas the positive ones are related to its high degree of accumulation.     

Rare-earth element mobility during ore-forming hydrothermal alteration: A case study of Dongping gold deposit Hebei Province,China

REE mobility during hydrothermal ore-forming processes has been extensively investigated in recent years and the potential of REE to provide information about ore forming processes has commonly been recognized.The Dongping gold deposit,which is located in northwestern Hebei Province,China,occurring in the inner contact zone of the Shuiquangou syenite complex,is spatially,and probably genetically,related to the syenite,the deposit was formed under the moderate to high temperature(220℃ to 320℃),weakly acidic to weakly alkaline,rather high fo2(lgfo2=-30～-34)environment.The REE study of the host rocks,altered wall rocks,ores and gangue minerals from the deposit suggests that the REEs have been mobilized and differentiated during K-feldspathization and silicification.The extremely altered syenite enveloping auriferous quartz vein shows positive Ce anomaly and larger LREE/HREE ratio than that of the unaltered syenite.The REE concentrations and patterns of the ores are determined by the ore types and mineral assemblages,LREE/HREE ratios in the gangue quartz and hydrothermal Kfeldspars are relatively low.The most significant observation is that the gangue quartz shows significant positive Eu anomaly,whereas the hydrothermal K-feldspars show less significant or no positive Eu anomaly at all relative to the primary feldspar in the unaltered syenite. It is evident that the REEs are mobile during K-feldspathization and silicification in the ore forming process.Weak to moderate K-feldspathization caused REE mobility without apparent differentiation with the exception of extreme K-feldspathization and silicification which resulted in significant depletion of HREE and Eu and relative enrichment of Ce.The REE,Y,U,Th and Au contents of the syenite decrease as the degrees of K-feldspathization and silicification of the rocks increase towards the auriferous quartz veins.As the ores were deposited under a rather oxidized environment,Ce^4 predominated over Ce^3 .The precipitation of the former in the form of CeO2 or absorpted onto the secondary mineral assemblage resulted in the inconsistent removal of the REE and the relative Ce enrichment in the strongly altered rocks.in contrast,Eu was present mainly in a low valence state (Eu^2 ).The geochemical differences from the other REE^3 and much less sites in the secondary minerals to accommodate the Eu released form the original minerals resulted in the enrichment of Eu in the fluids.The mobility and differentiation of REE and the coherent mobilities of Y,U,Th and Au also support the argument that the syenite is one of the source rocks for gold mineralization.The REE contents and patterns of the altered rocks enveloping the auriferous quartz vein could be used as a guide for locating ore veins in mineral exploration.     

Trace element composition of silicate minerals in the porphyritic and nonporphyritic chondrules of Elenovka (L5) and Knyahinya (L/Ll5) meteorites

The results of SIMS and EPMA studies on the silicate minerals and bulk compositions (SEM-EDS) of porphyritic and nonporphyritic chondrules from Elenovka and Knyahinya meteorites are reported. The trace element composition of silicate minerals (olivine, low-Са pyroxene) in equilibrated ordinary chondrites (EOC) has not been affected considerably by thermal metamorphism on the chondritic parent bodies. Therefore, equilibrated chondrites can be used for chondrule-forming processes studies. Low-Са pyroxene in nonporphyritic chondrules contains higher REE, Ba, Sr concentrations than that in porphyritic chondrules at similar trace element concentrations in the olivine of chondrules. The data obtained indicate that the formation of non-porphyritic chondrules was triggered by an increase in the cooling rate of chondrules upon the formation of pyroxene, rather than a difference in the initial conditions of chondrule formation. Higher refractory incompatible element (Nb, LREE) concentrations in the olivine of chondrules than those in the olivine of the matrix and contrasting trace element (Zr, Sr, Cr, REE) concentrations in the low-Са pyroxene of the chondrules and the matrix suggest that the matrix and chondrules of the meteorites formed in one reservoir under different physico-chemical conditions (density, redox state, rotation speed, homogeneity, temperature, shocks, electrical discharge, etc.).     

碳酸盐岩红色风化壳Ce异常特征及形成机理

Ce在贵州碳酸盐岩红色风化壳剖面上部表现为正异常,在底部稀土超常富集层显示强烈亏损。通过对Ce的质量迁移系数的计算,结合相态分析和水化学分析结果,对碳酸盐岩红色风化壳中“的异常行为进行系统的分析后发现：在剖面上部,Ce^3＋氧化水解,水解产物主要与铁锰氧化物共沉淀,少量的与粘土矿物结合,使得ce保留而相对显示正异常;在剖面底部,Ce负异常一方面来源于对基岩负异常的继承;更重要的是,Ce较其他轻稀土稳定,发生迁移富集的量远远小于La,Nd等轻稀土元素,导致Ce在底部富集时相对于其他轻稀土元素发生强烈亏损。而Ce与HCO3^-络合迁出并不是导致碳酸盐岩红色风化壳中强烈Ce负异常的主要原因。     

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.     

Behaviour of REE and mass balance calculations in a lateritic profile over chlorite schists in South Cameroon

An in situ weathering profile overlying chlorite schists in the Mbalmayo-Bengbis formations (South Cameroon) was chosen for the study of the behaviour of REE and the evaluation of geochemical mass balance. After physical and mineralogical studies, the chlorite schists and the undisturbed weathered materials were chemically analyzed for major elements (X-ray fluorescence and titrimetry) and REE (ICP-MS). The behaviour of the REE in the Mbalmayo weathering system was established in comparison with the REE of the reference parent rock. Mass balance calculations were applied to both major elements and REE. The mineralogy of the materials was determined with the aid of a Philips 1720, diffractometer. The chlorite schists of the Mbalmayo sector show low REE contents (Σ=153.44 ppm). These rocks are relatively rich in LREE (about 125 times the chondritic value) and relatively poor in HREE (about 20 times the chondritic value). The REE diagram normalized to chondrites shows a slightly split graph ((La/Yb)_N=6.18) with marked enrichment in LREE (LREE/HREE=9.50) in relation to HREE. Moreover, these spectra do not present any Ce anomaly, but a slightly positive Eu anomaly. The imperfectly evolved profile, whose materials are genetically linked, shows an atypical behaviour of REE. In effect, the LREE are more mobile than the HREE during weathering ((La/Yb)NASC<1) with weak Ce anomalies. This has been rarely reported in lateritic profiles characterized by higher HREE mobility than LREE during weathering processes with high Ce anomalies. This is either due to the difference in the stability of REE-bearing minerals, or to the weak acidic to basic pH conditions (6.70<pH<7.80), or even due to the average evolution of the weathering materials. The pathway of the REE along the profile is as follows: (1) leaching in the saprolites and summit of the profile, except for Ce, which precipitates very weakly in the nodular materials and the coarse saprolite materials, (2) at the base of the profile, solutions come in contact with chlorite schist formations, at this level, the pH increases (pH=7.79), HREE and a part of LREE partially void of Ce precipitate and (3) the other part of LREE precipitates further up in the profile. The geochemical mass balance calculations reveal that these elements are leached in the same phases as the relatively high Si, Al, K and Fe²⁺ contents.     

贵州务川大竹园铝土矿床伴生镓富集规律及沉积环境特征

通过对贵州务川大竹园铝土矿床的研究,发现矿床中伴生镓的含量普遍超过了工业综合利用的最低指标。Ga在含铝岩系中均有不同程度的分布,Ga与TiO₂、Cr、Zr、Sn呈中等正相关关系,说明Ga可能赋存于含TiO₂、Cr、Zr、Sn的矿物中; Ga与Al₂O₃呈弱正相关关系,说明Ga可能以类质同象的形式存在于Al的化合物中。Sr/Ba=1.09~19.69>1,表明铝土矿形成于海相沉积环境; Th/U=1.72~12.31,表明铝土矿可能风化作用不彻底; Ga/Al=0.45~1.84,表明成矿介质酸碱度的变化幅度较小。从含矿岩系矿物组合中含黄铁矿、高岭石等矿物可以推断介质为酸性的可能性较大; 稀土元素(rare earth element, REE)球粒陨石标准化分布曲线向右倾斜,轻稀土元素(LREE)富集,重稀土元素(HREE)亏损,δCe显示为弱正异常,Ce/Ce^*=1.17~10.17>1,表明铝土矿形成于富氧的沉积环境,δEu显示为负异常,进一步表明成矿是以氧化环境为主。综合分析认为大竹园铝土矿床形成于以海相沉积作用为主的富氧的沉积环境。     

Rare earth element variations resulting from inversion of pigeonite and subsolidus reequilibration in lunar ferroan anorthosites

We present results of a secondary ion mass spectrometry study of the rare earth elements (REEs) in the minerals of two samples of lunar ferroan anorthosite, and the results are applicable to studies of REEs in all igneous rocks, no matter what their planet of origin. Our pyroxene analyses are used to determine solid-solid REE distribution coefficients (D = C_REE in low-Ca pyroxene/C_REE in augite) in orthopyroxene-augite pairs derived by inversion of pigeonite. Our data and predictions from crystal-chemical considerations indicate that as primary pigeonite inverts to orthopyroxene plus augite and subsolidus reequilibration proceeds, the solid-solid Ds for orthopyroxene-augite pairs progressively decrease for all REEs; the decrease is greatest for the LREEs. The REE pattern of solid-solid Ds for inversion-derived pyroxene pairs is close to a straight line for Sm-Lu and turns upward for REEs lighter than Sm; the shape of this pattern is predicted by the shapes of the REE patterns for the individual minerals.Equilibrium liquids calculated for one sample from the compositions of primary phases, using measured or experimentally determined solid-liquid Ds, have chondrite-normalized REE patterns that are very slightly enriched in LREEs. The plagioclase equilibrium liquid is overall less rich in REEs than pyroxene equilibrium liquids, and the discrepancy probably arises because the calculated plagioclase equilibrium liquid represents a liquid earlier in the fractionation sequence than the pyroxene equilibrium liquids. “Equilibrium” liquids calculated from the compositions of inversion-derived pyroxenes or orthopyroxene derived by reaction of olivine are LREE depleted (in some cases substantially) in comparison with equilibrium liquids calculated from the compositions of primary phases. These discrepancies arise because the inversion-derived and reaction-derived pyroxenes did not crystallize directly from liquid, and the use of solid-liquid Ds is inappropriate. The LREE depletion of the calculated liquids is a relic of formation of these phases from primary LREE-depleted minerals. Thus, if one attempts to calculate the compositions of equilibrium liquids from pyroxene compositions, it is important to establish that the pyroxenes are primary. In addition, our data suggest that experimental studies have underestimated solid-liquid Ds for REEs in pigeonite and that REE contents of liquids calculated using these Ds are overestimates.Our results have implications for Sm-Nd age studies. Our work shows that if pigeonite inversion and/or subsolidus reequilibration between augite and orthopyroxene occurred significantly after crystallization, and if pyroxene separates isolated for Sm-Nd studies do not have the bulk composition of the primary pyroxenes, then the Sm-Nd isochron age and ε_Nd will be in error.     

Sources of stream sediments in the granulite terrain of the Walawe Ganga Basin,Sri Lanka,indicated by rare earth element geochemistry

Thirty-eight samples of stream sediments draining high-grade metamorphic rocks in the Walawe Ganga (river) Basin, Sri Lanka, were analysed for their REE contents, together with samples of metamorphic suites from the source region. The metamorphic rocks are enriched in light REE (LREE) compared to heavy REE (HREE) and are characterised by high La/Lu ratios and negative Eu anomalies. The chondrite-normalised patterns for these granulite-grade rocks are similar to that of the average post-Archaean upper crust, but they are slightly enriched with La and Ce. The REE contents of the <63-μm fraction of the stream sediments are similar to the probable source rocks, but the other grain size fractions show more enriched patterns. The <63-μm stream sediments fraction contains lower total REE, more pronouncd negative Eu anomalies, higher Eu_N/Sm_N and lower La _N/Lu_N ratios relative to other fractions. The lower La _N/Lu_N ratio is related to the depletion of heavy minerals in the <63-μm fraction. The 63–125-μm and 125–177-μm grain size fractions of sediments are particularly enriched in LREE (average ΣLREE=2990 μg/g and 3410 μg/g, respectively). The total HREE contents are surprisingly uniform in all size fractions. However, the REE contents in the Walawe Ganga sediments are not comparable with those of the granulite-grade rocks from the source region of the sediments. The enrichment of REE is accounted for by the presence of REE containing accessory mineral phases such as zircon, monazite, apatite and garnet. These minerals are derived from an unknown source, presumably from scattered bodies of granitic pegmatites.     

Mineral geochemistry of the Sangan skarn deposit,NE Iran: Implication for the evolution of hydrothermal fluid

The Sangan iron skarn deposit is located in the Sabzevar-Dorouneh Magmatic Belt of northeastern Iran. The skarn contains zoned garnet, clinopyroxene and magnetite. Cores and rims of zoned garnets are generally homogeneous, having a relatively high ΣREE, low ΣLREE/ΣHREE ratios, and positive Eu anomalies. The cores of the zoned clinopyroxenes are exceptionally HREE-rich, with relatively high ΣREE and HREE/LREE ratios, as well as positive Eu anomalies. Clinopyroxene rims are LREE-rich, with relatively low ΣREE contents and HREE/LREE ratios, and do not have Eu anomalies. Magnetite grains are enriched in LREEs in comparison with the HREEs and lack Eu anomalies. Variations of fluid composition and physicochemical conditions rather than YAG-type substitution mechanism are considered to have major control on incorporating trace elements, including REE, into the skarn mineral assemblage. Based on baro-acoustic decrepitation analysis, the calc-silicate and magnetite dominant stages were formed at similar temperatures, around 350–400 °C. In the Sangan skarns, hydrothermal fluids shifted from near-neutral pH, reduced conditions with relatively high ΣREE, low LREE/HREE ratios, and U-rich characteristics towards acidic, oxidized conditions with relatively low ΣREE, high LREE/HREE ratios, and U-poor characteristics.     

REE and actinide microdistribution in Sahara 97072 and ALHA77295 EH3 chondrites: A combined cosmochemical and petrologic investigation

We report the results of rare earth elements (REEs) and U-Th inventory of individual minerals (oldhamite, enstatite and niningerite) in two of the most unequilibrated and primitive EH3 known so far, ALHA77295 and Sahara 97072. Under the highly reducing condition that prevailed during the formation of enstatite chondrites, REEs are mainly chalcophile and concentrated in oldhamite. The study is guided by detailed petrographic investigations of the individual minerals in chondrules, complex sulfide-metal clasts and enstatite-dominated matrices.We developed two textural parameters in order to resolve the evolution of oldhamite condensates and their residence in the solar gas prior to their accretion in the individual objects or in matrices and relate these textural features to the measured REE patterns of the individual oldhamite crystals. These textural parameters are the crystal habit of oldhamite grains (idiomorphic or anhedral) and their host assemblages. REE concentrations were measured by SIMS and LA-ICPMS.Oldhamite grains display REE enrichments (10-100 × CI). Four types of REE patterns are encountered in oldhamite in ALHA77295. In general the REE distributions cannot be assigned to a specific oldhamite-bearing assemblage. The most represented REE pattern is characterized by both slight to large positive Eu and Yb anomalies and is enriched in light REEs relative to heavy REEs. This pattern is present in 97% of oldhamite in Sahara 97072, suggesting a different source region in the reduced part of the nebula or different parental EH asteroids for the two EH3 chondrites. Different parental asteroids are also supported by MgS-FeS zoning profiles in niningerite grains adjacent to troilite revealing both normal and reverse zoning trends and different MnS contents. The observed homogeneity of REE distribution in oldhamite grains in Sahara 97072 is not related to the mild metamorphic event identified in this meteorite that caused breakdown of the major K- and Rb-bearing sulfide (djerfisherite).REE concentrations in enstatite range between 0.2 and 8 × CI. Hence, enstatite is an important REE host next to oldhamite. Most patterns are characterized by negative Eu and Yb anomalies. Niningerites are negligible contributors to bulk EH3 REE inventory. Average positive Eu and Yb anomalies observed in most oldhamite are complimentary to the negative ones in enstatite thus explaining the flat patterns of the bulk meteorites. The condensation calculations based on cosmic abundances predict that the first oldhamite condensates should have flat REE patterns with Eu and Yb depletions since Eu and Yb condense at lower temperature than other REE. However, this pattern is seen in enstatite. Our findings are at odds with the predicted negative Eu and Yb anomalies in oldhamite earliest condensates from a closed system in a reduced solar source. Our petrographic, mineral chemistry and REE abundances of oldhamite, enstatite and niningerite discards an origin of oldhamite by impact melting (Rubin et al., 2009).Our results do not support in first order the scenario of the incorporation of REE in the Earth’s core to explain ¹⁴²Nd excess in terrestrial samples relative to chondrites because oldhamite is the major REE carrier phase and has super-chondritic Sm/Nd ratios.     

Petrological and geochemical characteristics of Zhaibei granites in Nanling region,Southeast China: Implications for REE mineralization

Mineralization with ion adsorption rare earth elements (REEs) in the weathering profile of granitoid rocks from Nanling region of Southeast China is an important REE resource, especially for heavy REE (HREE) and Y. However, the Jurassic granites in Zhaibei which host the ion adsorption light REE (LREE) ores are rare. It is of peraluminous and high K calc-alkaline composition, which has similar geochemical features of high K₂O + Na₂O and Zr + Nb + Ce + Y contents and Ga/Al ratio to A-type granite. Based on the chemical discrimination criteria of Eby [Geology 20 (1992) 641], the Zhaibei granite belongs to A1-type and has similar source to ocean island basalts. The rock is enriched in LREE and contains abundant REE minerals including LREE-phosphates and halides. Minor LREE was also determined in the feldspar and biotite, which shows negligible and negative Eu anomalies, respectively. This indicates that the Zhaibei granite was generated by extreme differentiation of basaltic parent magmas. In contrast, granites associated with ion adsorption HREE ores contain amounts of HREE minerals, and show similar geochemical characteristics with fractionated felsic granites. Note that most Jurassic granitoids in the Nanling region contain no REE minerals and cannot produce REE mineralization. They belong to unfractionated M-, I- and S-type granites. Therefore, accumulation of REE in the weathering profile is controlled by primary REE mineral compositions in the granitoids. Intense fractional crystallization plays a role on REE enrichment in the Nanling granitoid rocks.