新疆伊犁河谷沙漠沉积的稀土元素特征及其环境意义

以伊犁河谷西部塔克尔莫乎尔沙漠内的可克达拉(TKP)剖面作为研究对象开展了稀土元素特征分析,结合方解石变化特征,探讨沙漠沉积稀土元素与环境变化间的关系.研究结果表明TKP剖面的稀土元素总量(不含Y)平均为130.90 μg/g,变化范围为32.88 ～ 238.58μg/g,整个剖面分配模式相似,缓右倾斜型,轻稀土适度富集,δCe,δEu和LREE/HREE比值相近,Eu中度负异常,未见明显Ce异常,指示剖面物质来源的一致性和总体干旱、半干旱的气候环境.包括Ce在内的各稀土元素、∑REE以及LREE/HREE在垂向变化上高度相关,并与方解石含量存在较好的相关关系,表明其与气候变化密切相关,在干旱区的沙漠沉积中稀土元素对古气候变化具有良好的指示作用,并据此重建了晚全新世以来伊犁河谷的气候演变过程.     

黔北务正道地区铝土矿稀土元素地球化学特征

选取新模向斜的一个钻孔剖面,对铝土矿的矿物组成及稀土元素地球化学特征进行了研究。铝土矿矿石矿物以一水硬铝石为主,另有少量一水软铝石。其次为高岭石、绿泥石等黏土矿物,以及少量重矿物。此外,在含矿岩系近底部还发现有富集Ce元素的矿物氟菱钙铈矿[Ce2Ca(CO3)3F2]。从剖面顶部至底部,铝土矿中稀土元素含量呈逐渐增加的趋势,且稀土元素参数LaN/YbN、LaN/SmN和GdN/YbN的数值均随深度逐渐增大。说明从剖面顶部至底部,稀土元素的淋滤迁出逐渐减弱,且稀土元素间存在一定的分异。稀土元素间的分异可能由不同的含稀土元素矿物抗风化淋滤差异所致。铝土矿稀土元素配分模式表现为LREE明显富集、MREE中等-弱富集、HREE相对平坦的特征,且具有明显的正Ce异常。δCe异常值随深度增加逐渐减小,接近含矿岩系底部,δCe异常值再次增大。含矿岩系上部的Ce异常是由氧化条件下Ce3+向Ce4+转变并形成方铈矿(CeO2)所致。随着深度的增加,含矿岩系的氧化性逐渐减弱,从而δCe异常值逐渐减小。接近含矿岩系底部,由于氟菱钙铈矿[Ce2Ca(CO3)3F2]的形成,导致δCe异常值再次增大。氟菱钙铈矿的沉淀可通过氟化物络合物(CeF2+或CeCO3F0)与Ca2+和HCO3-发生反应来完成。     

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。     

浙江煤山牙形石微区原位REE组成及古环境意义

本文利用激光剥蚀电感耦合等离子体质谱(LA-ICPMS),对煤山D剖面包含二叠纪-三叠纪界线层的牙形石中色变指数(CAI)较低的部分进行微区原位微量元素分析,并与利用溶解法测定的相应的沉积碳酸盐岩围岩稀土元素(REE)的组成进行了对比,探讨了它们的稀土元素组成对环境变化响应的差异及其可能的原因.结果显示,无论是稀土总量ΣREE,还是Ce异常值,牙形石的微区原位REE信息比围岩更能反映出当时的环境变化.这表明牙形石化石比围岩对环境变化更加敏感,利用牙形石微区LA-ICPMS微量元素分析的方法是可靠的.同时,牙形石的Ce异常值还能对早三叠世的环境有较好的指示意义,为二叠纪与三叠纪之交大绝灭主幕开始到早三叠世环境的剧烈变化和长期缺氧环境提供了新的证据.      

贵州碳酸盐岩风化壳主元素、微量元素及稀土元素的地球化学特征

选取贵州高原喀斯特地区的典型碳酸盐岩原生风化剖面为研究对象,研究主元素、微量元素及稀土元素在风化壳的迁移转化及其分布规律特征,为解释碳酸盐岩风化壳元素的地球化学变化提供依据。结果显示,从上陆壳标准化蛛网图可知,Pb、Co在剖面富集,而Na、K、Cr、Rb、Sr和Ba则亏损。风化壳∑REE的变化范围为167.4~1814.2μg/g,稀土元素从剖面下部往上逐渐减少,剖面中上部LREE比HREE淋滤程度大。稀土元素球粒陨石标准化后Ce正负异常,Eu轻微负异常。以风化前缘为分界,在风化前缘以下的土层,Ce负异常,风化前缘以上的土层,Ce正异常。此外,在风化壳岩土界面附近存在一个明显且突变的碱性障,岩土界面土样的元素含量较岩粉平均增加了21倍。我们的研究显示,风化剖面主元素和微量元素的变化波动特征较为一致,说明主元素和微量元素在风化过程中的地球化学行为较为一致。铁壳层中稀土元素的含量最低,与上陆壳稀土元素十分相近,为研究上陆壳与碳酸盐岩铁壳层之间的相互联系起到了一定的借鉴作用。     

华南中-晚二叠世之交碳酸盐岩磁学特征及环境意义

磁学参数作为可靠的古气候和古环境指标, 能为全球环境变化、气候过程研究提供有价值的资料.对广西来宾铁桥剖面瓜德鲁普-乐平统界线地层进行详细岩石磁学研究, 结果表明, 铁桥剖面样品中主要磁性矿物是顺磁性矿物以及少量磁铁矿、赤铁矿.在瓜德鲁普-乐平统界线附近, 岩石磁学特征发生显著变化, 磁化率先增大再减小, 携磁矿物成分呈硬磁性矿物(赤铁矿)→软磁性矿物(磁铁矿)→硬磁性矿物(赤铁矿)的变化趋势, 这些转变仅在界线上下大约4m的岩层内完成, 与中二叠世晚期的海平面变化、古海水温度变化同步.中-晚二叠世之交碳酸盐岩磁学参数的变化显著, 反映磁性矿物在各圈层之间的运移和转换发生了转变, 这一转变起因于当时的气候环境变化.瓜德鲁普世晚期和乐平世早期, 海平面较高, 来宾地区物源少, 铁桥剖面的携磁矿物主要来自粉尘赤铁矿; 中-晚二叠世之交短暂的大规模海退作用使华南古陆面积大幅度增加, 同时陆生植物大规模灭绝, 地表侵蚀加剧, 来宾地区物源增多, 此时, 铁桥剖面的携磁矿物主要来源于河流输入的磁铁矿.      

广西来宾二叠系瓜德鲁普统-乐平统界线蓬莱滩剖面沉积微相演变及其对生物灭绝事件的响应

在中二叠世(瓜德鲁普世)末期发生了一次全球范围的生物灭绝事件,大约有34%的海洋无脊椎动物消失,同时发生了全球规模的海退事件。该事件在中国反应为东吴运动,致使华南大部分地区瓜德鲁普统—乐平统之交产生不整合。广西来宾地区位于扬子地台南缘,在中—晚二叠世时期处于滇黔桂盆地的东部。由于其独特的古地理位置,来宾地区发育了连续的中—晚二叠世海相沉积,是研究此次生物大灭绝和环境演变的绝佳位置。本文对广西来宾蓬莱滩瓜德鲁普统—乐平统(G—L)界线剖面沉积微相和生物化石进行了综合研究。研究表明,该剖面1～7层共发育5种主要的沉积微相组合,既礁基相组合、礁核相组合、覆礁相组合、礁滩相组合和深水斜坡相组合,生物礁发育于一个海退序列中。生物碎屑的丰度和类型在7a层突然急剧降低,与该剖面碳同位素的负偏和汞异常的出现一致,但实际上在这一层位只有个别牙形石和菊石消失,生物屑丰度的剧变并不能代表灭绝线,而是对海平面剧变的沉积响应。     

藏南白垩纪缺氧与富氧沉积的稀土元素地球化学特征

研究了藏南Cenomanian-Turonian界线缺氧沉积和Santonian-Campanian富氧沉积的稀土元素特征,重点探讨古海洋氧化还原条件变化与稀土元素地球化学之间的关系。结果表明,缺氧事件层ΣREE增加30%,Ce和Eu含量分别增加40%和114%;富氧沉积层ΣREE明显增加,其中以Eu含量增加107%最为明显,Ce增幅最小,表现为相对亏损。缺氧沉积稀土元素分布型式为Ce和Eu富集的右倾型,富氧沉积分布型式以Ce亏损和Eu富集为特征。Ce异常显示缺氧事件期间为稳定而持续的低溶解氧还原条件,而富氧事件由古海洋瞬间的氧化事件和逐渐趋于正常状态的氧化条件两个阶段组成。     

云南白牛厂银多金属矿床成矿作用特征的稀土元素地球化学约束

为了研究白牛厂银多金属矿床成矿作用特征,对矿区岩浆岩、围岩和矿石的稀土元素进行了ICP-MS分析测试。花岗岩稀土元素组成表现了较强的Eu负异常和弱的Ce负异常。围岩稀土元素特征表现出一定程度的热水沉积成因。矿石的稀土元素组成大致可分为两组：一组矿石表现为Eu正异常或无异常和Ce负异常,反映喷流沉积稀土元素组成特征,主要是距离花岗岩体较远的白羊矿段,指示成矿热液为温度较高（＆gt;250℃）、相对还原的流体,另外,Eu正异常和Ce负异常同时出现,说明矿石沉淀时较高温度的流体与少量的海水发生了对流混合;另一组矿石表现出与岩浆岩一致的球粒陨石标准化稀土配分模式,显示岩浆热液叠加改造成因,主要是距离花岗岩体较近的穿心洞矿段和对门山矿段。两组矿石稀土元素组成特征总体来说随着花岗岩体距离的变化而变化。根据岩浆岩、围岩和矿石的稀土元素组成特征,白牛厂银多金属矿床由喷流沉积形成主矿体,燕山期花岗质岩浆活动对矿体部分叠加改造。     

江西乐平早二叠世地层

江西乐平早二叠世地层朱相水（江西师范大学地理系，江西南昌，３３００２７）关键词地层，早二叠世，栖霞期，乐平，江西实测剖面位于江西乐平沿沟煤矿矿区东隅，３ｋｍ无甲村附近，早Ｍ叠世地层发育于象鼻山与鲤鱼山之间。剖面系笔者与乐平矿务局沿沟煤矿的姚克敏、徐光...     

稀土元素：海相硅岩沉积环境的有效指标

世界范围内海水的REE研究表明,不同环境海水的REE有一定的差异.海相硅质沉积也显示出与周围海水相似的REE特征,其中最明显的是Ce异常。对已知沉积环境的硅岩所作REE研究说明,利用硅岩的REE特征可以帮助判别海相沉积环境。江西南部寒武—奥陶系中广泛产出厚层的层状硅岩,根据Ce的异常,推测此区硅岩形成于大陆边缘—大洋盆地的过渡地区。     

中国南方二叠-三叠系界线及其附近粘土层稀土元素地球化学研究

本文对广泛发育于中国南方,连续的二叠-三叠系海相界线及其附近粘土层(蒙脱石—伊利石粘土岩)进行了稀土元素地豫化学的研究。查明了REE分布特征;REE沿粘土层垂向上的变化,比较了界线粘土与非界线粘土在REE分布上的差异。讨论了界线粘土的成因,根据稀土模式所作的综合分析,提出了由中酸性山火山岩和代表冲击溅射产物的上部地壳物质组合的混合新模式。     

Colloidal Control on the Distribution of Rare Earth Elements in Shallow Groundwaters

A 7-year monitoring period of rare earth element (REE) concentrations and REE pattern shapes was carried out in well water samples from a 450 m long transect setup in the Kervidy/Coët-Dan experimental catchment, France. The new dataset confirms systematic, topography-related REE signatures and REE concentrations variability but challenges the validity of a groundwater mixing hypothesis. Most likely, this is due to REE preferential adsorption upon mixing. However, the coupled mixing–adsorption mechanism still fails to explain the strong spatial variation in negative Ce anomaly amplitude. A third mechanism—namely, the input into the aquifer of REE-rich, Ce anomaly free, organic colloids—is required to account for this variation. Ultrafiltration results and speciation calculations made using Model VI agree with this interpretation. Indeed, the data reveal that Ce anomaly amplitude downslope decrease corresponds to REE speciation change, downhill groundwaters REE being mainly bound to organic colloids. Water table depth monitoring shows that the colloid source is located in the uppermost, organic-rich soil horizons, and that the colloid input occurs mainly when water table rises in response to rainfall events. It appears that the colloids amount that reaches groundwater increases downhill as the distance between soil organic-rich horizons and water table decreases. Topography is, therefore, the ultimate key factor that controls Ce anomaly spatial variability in these shallow groundwaters. Finally, the <0.2 μm REE fraction ultimately comes from two solid sources in these groundwaters: one located in the deep basement schist; another located in the upper, organic-rich soil horizon.     

扬子东南大陆边缘晚前寒武纪古海洋演化的稀土元素记录

本文采用中子活化方法分析了晚震旦～早寒武纪１９件样品的稀土元素组成,发现硅质岩石ＲＥＥ配分形式有着复杂的变化,初步可以划分为五种类型,包括“台地型”、“红海型”、“海水型”及两种特殊的配分形式。剖面上Ｃｅ异常由小到大的演变反映了古海洋底层水由缺氧环境向氧化条件的逐渐转化。正Ｅｕ异常的出现代表了热水沉积事件的存在。     

Chemico-mineralogical attributes of clays from the late Cretaceous–early Palaeogene succession of the Um Sohryngkew river section of Meghalaya,India: Palaeoenvironmental inferences and the K/Pg boundary

A continuous shallow marine 10 m thick succession within the Langpar Formation in the Um Sohryngkew river section of Meghalaya, containing late Maastrichtian through early Danian planktonic foraminiferal zones – CF4, CF3, CF2, CF1, P0, Pα and P1a and the K/Pg boundary (between CF1 and P0) that makes unique of its kind. The section has been re-studied and sampled for clay mineralogy to understand the palaeoenvironmental conditions prevalent in the region and to assess the K/Pg transition. The relative abundances of the clay mineral phases permitted a threefold sub-division of the studied section with a illite, illite/ smectite dominated lower part, illite, kaolinite and abundance of montmorillonite dominated middle part and kaolinite–montmorillonite dominated upper part. Enriched HREEs in the lower part of the succession suggest variations in the pH of alteration solutions. Most of the samples show positive cerium (δCe) and europium (δEu) anomalies, the former reflecting oxidizing conditions at the time of clay formation. Illite dominated clays present a positive Eu anomaly, formed at relatively higher temperatures than the clays with less illite and without Eu anomalies, whereas clays occurring in the lower and upper parts exhibit a prominent negative Eu anomaly. Shifts in the redox condition found in this section are more or less similar to the foraminiferal changes and Au, Pt, Pd anomalies. Clay mineralogical attributes and REE patterns, comparable to those of the known K/Pg boundaries, appeared within the CF3 and CF2 zones in the Um Sohryngkew river section. The sample at the boundary between CF3 and CF2 is marked by a negative <delta>Ce anomaly, high La/Yb and TOC values, suggesting that sea level rise during the upper part of CF3 was caused by tectonism rather than warming. The similar characteristics of clay minerals and REE patterns, attributed to the initiation of tectonic events during the CF3 zone, indicate environmental changes that affected the shelf area and the provenance of these sediments.     

渝东南地区石牛栏组稀土元素地球化学特征及地质意义

渝东南地区的下志留统石牛栏组作为重要的油气储集层,研究其古环境变化、物质来源及物源区构造背景具有重要意义。本文采用稀土元素总量w(ΣREE)、REE配分模式、以及w(ΣLREE)/w(ΣHREE)、w(La)_N/w(Yb)_N、w(Ce)_N/w(Yb)_N、w(La)_N/w(Sm)_N、w(Gd)_N/w(Yb)_N、δEu、δCe、Ce_(anom)等特征值研究方法,对渝东南下志留统石牛栏组典型剖面的稀土元素特征及古海洋环境和物源进行深入研究。结果表明:石牛栏组灰岩稀土元素总量略低于大陆地壳平均值,轻稀土较为富集,重稀土亏损,铕明显负异常,铈负异常较微弱。w(ΣREE)证实了石牛栏组的沉积水体由浅缓慢变深再急剧变浅的变化过程。Eu负异常、Ce负异常和C_(eanom)值均揭示石牛栏组沉积时期海水具有弱还原性。REE的分异程度反映了石牛栏组从沉积早期到沉积晚期,沉积速率总体降低。稀土元素的比值特征及w(ΣREE)—w(La)/w(Yb)图解表明其物源源自雪峰山隆起,源岩主要为沉积岩。     

Rare Earth Elements Composition and Constraint on the Genesis of the Polymetallic Crusts and Nodules in the South China Sea

The rare earth elements(REE) composition of the polymetallic crusts and nodules obtained from the South China Sea(SCS) were analyzed through inductively coupled plasma mass spectrometry.Results revealed great differences in the REE abundances(∑REE) of the SCS polymetallic crusts and nodules; the crusts show the highest ∑REE, whereas the nodules exhibit the lowest ∑REE. The similarity in their NASC-normalized patterns, the enriched light REE(LREE), the markedly positive Ce anomaly(δCe), and the non-or weakly positive Eu anomaly(δEu), suggest that the polymetallic crusts and nodules are of hydrogenetic origin. Moreover, the REE contents and their relevant parameters are quite different among the various layers of the crusts and nodules, which probably results from the different marginal sea environments and mineral assemblages of the samples. The growth profiles of the SCS polymetallic crusts and nodules reveal the tendency ∑REE and δCe to slightly increase from the outer to the inner layers, suggesting that the growth environments of these samples changed smoothly from an oxidizing to a relatively reducing environment; in addition, the crust ST1 may have experienced a regressive event(sea-level change) during its growth, although the REE composition of the seawater remained relatively stable. On the basis of the regional ∑REE distribution in the SCS crusts and nodules,the samples collected near the northern margin were influenced by terrigenous material more strongly compared with the other samples, and the REE contents are relatively low. Therefore, the special geotectonic environment is a significant factor influencing the abundance of elements, including REE and other trace elements. Compared with the oceanic seamount crusts and deep-sea nodules from other oceans,the SCS polymetallic crusts and nodules exhibit special REE compositions and shale-normalized patterns, implying that the samples are of marginal sea-type Fe-Mn sedimentary deposits, which are strongly affected by the epicontinental environment, and that they grew in a more oxidative seawater environment. This analysis indicates that the oxidized seawater environment and the special nano property of their Fe-Mn minerals enrich the REE adsorption.     

Rare Earth Elements in Egyptian Phosphorites

Egyptian phosphorites from Abu Tartur(Western Desert),El Mahamide mine(Nile Valley) and Rabah mne(Eastern Desert)show variable degrees of relative REE enrichment.Black plateau phosphorites of Abu Tartur are substantially enriched in REE as compared to the Red Sea and Nile Valley phosphorites.P-rich organic matter from the Abu Tartur and Rabah mines recorded negative Ce and positive Eu anomalies.Positive Eu anomaly reveals an anoxic event prior to the phase of Late Cretaceous phosphate formation.Ce is a redox indicator.Mixing of sea water and upwelling during the Late Cretaceous was responsible for the recording of positive Eu and negative Ce anomalies in the Egyptian phosphorites.     

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.