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1.
Chunying Chang Fangbai Li Chengshuai Liu Jianfeng Gao Hui Tong Manjia Chen 《中国地球化学学报》2016,35(4):329-339
Soil secondary minerals are important scavengers of rare earth elements (REEs) in soils and thus affect geochemical behavior and occurrence of REEs. The fractionation of REEs is a common geochemical phenomenon in soils but has received little attention, especially fractionation induced by secondary minerals. In this study, REEs (La to Lu and Y) associated with soil-abundant secondary minerals Fe-, Al-, and Mn-oxides in 196 soil samples were investigated to explore the fractionation and anomalies of REEs related to the minerals. The results show right-inclined chondrite-normalized REE patterns for La–Lu in soils subjected to total soil digestion and partial soil extraction. Light REEs (LREEs) enrichment features were negatively correlated with a Eu anomaly and positively correlated with a Ce anomaly. The fractionation between LREEs and heavy REEs (HREEs) was attributed to the high adsorption affinity of LREEs to secondary minerals and the preferred activation/leaching of HREEs. The substantial fractions of REEs in soils extracted by oxalate and Dithionite-Citrate-Bicarbonate buffer solutions were labile (10 %–30 %), which were similar to the mass fraction of Fe (10 %–20 %). Furthermore, Eu was found to be more mobile than the other REEs in the soils, whereas Ce was less mobile. These results add to our understanding of the distribution and geochemical behavior of REEs in soils, and also help to deduce the conditions of soil formation from REE fractionation. 相似文献
2.
对尕尔勤铜矿床花岗闪长斑岩及其锆石的稀土元素进行了分析,并对其成矿作用进行了研究。结果表明,花岗闪长斑岩稀土元素总含量变化范围不大（ΣREE=48.64×10-6~78.12×10-6）,LREE/HREE=8.67~11.68,所有样品都呈轻稀土元素相对富集、重稀土元素亏损的右倾型分配模式;δEu由弱负异常→弱正异常演化,这是因为地幔底辟作用引发地壳部分重熔形成长英质岩浆的过程中,逐步消弱了结晶分异导致的负Eu异常进而出现弱的正Eu异常。锆石具有典型的振荡环带,稀土总量较高（ΣREE=735.78×10-6~6792.10×10-6）,相对亏损轻稀土,富集重稀土,正Ce异常明显,并呈现弱的负Eu异常,这是因为在地幔流体作用下,重稀土元素及Ce较其它轻稀土元素更容易进入锆石晶格所致,Eu呈弱的负异常则是成岩后期岩体受氧化淋滤所致。综合分析,揭示出地幔流体作用导致花岗闪长斑岩具有壳幔混染甚至成矿特征,同时还能透过岩浆与围岩发生物质和能量的交换,导致变质砂岩成矿的成因机制。 相似文献
3.
The aquatic chemistry of rare earth elements in rivers and estuaries 总被引：17，自引：0，他引：17
Edward R. Sholkovitz 《Aquatic Geochemistry》1995,1(1):1-34
Laboratory experiments were carried out to determine how pH, colloids and salinity control the fractionation of rare earth elements (REEs) in river and estuarine waters. By using natural waters as the reaction media (river water from the Connecticut, Hudson and Mississippi Rivers) geochemical reactions can be studied in isolation from the large temporal and spatial variability inherent in river and estuarine chemistry. Experiments, field studies and chemical models form a consistent picture whereby REE fractionation is controlled by surface/solution reactions. The concentration and fractionation of REEs dissolved in river waters are highly pH dependent. Higher pH results in lower concentrations and more fractionated composition relative to the crustal abundance. With increasing pH the order of REE adsorption onto river particle surfaces is LREEs > MREEs > HREEs. With decreasing pH, REEs are released from surfaces in the same order. Within the dissolved (<0.22 µm) pool of river waters, Fe-organic colloids are major carriers of REEs. Filtration through filters and ultrafilters with progressively finer pore sizes results in filtrates which are lower in absolute concentrations and more fractionated. The order of fractionation with respect to shale, HREEs > MREEs > LREEs, is most pronounced in the solution pool, defined here as <5K and <50K ultrafiltrates. Colloidal particles have shale-like REE compositions and are highly LREE enriched relative to the REE composition of the dissolved and solution pools. The addition of sea water to river water causes the coagulation of colloidal REEs within the dissolved pool. Fractionation accompanies coagulation with the order of sea water-induced removal being LREEs > MREEs > HREEs. While the large scale removal of dissolved river REEs in estuaries is well established, the release of dissolved REEs off river particles is a less studied process. Laboratory experiments show that there is both release and fractionation of REEs when river particles are leached with seawater. The order of sea water-induced release of dissolved REE(III) (LREEs > MREEs > HREEs) from Connecticut River particles is the same as that associated with lowering the pH and the same as that associated with colloidal particles. River waters, stripped of their colloidal particles by coagulation in estuaries, have highly evolved REE composition. That is, the solution pool of REEs in river waters are strongly HREE-enriched and are fractionated to the same extent as that of Atlantic surface seawater. This strengthens the conclusions of previous studies that the evolved REE composition of sea water is coupled to chemical weathering on the continents and reactions in estuaries. Moreover, the release of dissolved Nd from river particles to sea water may help to reconcile the incompatibility between the long oceanic residence times of Nd (7100 yr) and the inter-ocean variations of the Nd isotopic composition of sea water. Using new data on dissolved and particle phases of the Amazon and Mississippi Rivers, a comparison of field and laboratory experiments highlights key features of REE fractionation in major river systems. The dissolved pool of both rivers is highly fractionated (HREE enriched) with respect to the REE composition of their suspended particles. In addition, the dissolved pool of the Mississippi River has a large negative Ce-anomaly suggesting in-situ oxidation of Ce(III). One intriguing feature is the well developed maximum in the middle REE sector of the shale normalized patterns for the dissolved pool of Amazon River water. This feature might reflect competition between surface adsorption and solution complexation with carbonate and phosphate anions. 相似文献
4.
Khadija Semhi Osman A. E. Abdalla Salah Al Khirbash Tabisam Khan Salim Asaidi Sardar Farooq 《Arabian Journal of Geosciences》2009,2(2):143-150
Groundwater samples from six wells and various species of plants from soils developed on ophiolites were collected from an arid area (AlKhod area, Oman) and analyzed for trace elements including rare earth elements (REEs). The distribution patterns of REEs in plants indicated an enrichment in middle REEs (MREEs?=?Sm to Dy) and heavy REEs (HREEs?=?Ho to Lu), when they are normalized to the REE composition of the Post Archean Australian Shale (PAAS), with a significant negative anomaly in Ce and a positive anomaly in Eu. Compared to Oman ophiolites, the REEs in different species of plants are depleted in Ce and enriched in MREEs and slightly enriched in light REE (LREE?=?from La to Nd). Relative to PAAS, the distribution of REEs in groundwaters revealed similar patterns to the REE distribution in plants. The distribution patterns of REEs in plants relative to those in waters are nearly flat. These patterns suggest that the transfer of REEs from soil solutions to the groundwaters in Oman occurs without any significant fractionation. 相似文献
5.
Rare earth element (REE) pattern is a unique geochemical tracer and has been measured for various natural materials. Among these, the REE distribution pattern between bacteria and water exhibits anomalous enrichment in the heavy REE (HREE) part, which can act as a signature of bacteria-related materials in natural samples. In this study, the REE binding site on the cell surface of a Gram-positive bacterium (Bacillus subtilis) responsible for HREE enrichment has been identified using extended X-ray absorption fine structure (EXAFS) coupled with a study of the variation in REE distribution patterns. The EXAFS data showed that the HREEs form complexes with multiple phosphate site (including phosphoester site) with a larger coordination number (CN) at lower REE-bacteria ratios ([REE]/[bac]), while light and middle REEs form complexes to the phosphate site with a lower CN. The fraction coordinated to carboxylate increased for all REEs with increasing [REE]/[bac] ratio. On the other hand, the enrichment of HREE in the REE distribution patterns of the bacteria was less marked with increasing [REE]/[bac] ratio. This result is consistent with the EXAFS data, because the REE pattern of surface complex with multiple phosphate in a reference material exhibits a monotonous increase for heavier REE, while phosphate surface complex with a low CN and a carboxylate site reach a maximum around Sm and Eu. Based on these results, it is clear that the REE are primarily bound to the phosphate site and subsequently to the carboxylate site on the bacterial cell surface.Regarding the pH dependence in the range (3 < pH < 7), both the EXAFS and REE pattern data indicate that the fraction of REE-carboxylate increased as the pH increases. The results above obtained for B. subtilis were also valid for Escherichia coli, a Gram-negative bacterium, showing that similar phosphate and carboxylate sites are also available in the cell walls of E. coli, or other Gram negative bacteria. In all our results, the variation in REE patterns correlated with the binding site indicated by EXAFS, showing that the REE pattern itself reflects the binding site of the REE at the bacterial surface for various parameters (pH and [REE]/[bac] ratio). Thus, the REE patterns can be used to estimate the binding sites for lower [REE]/[bac] ratios where spectroscopic techniques cannot be applied.The average bond length between the REE and oxygen was compared for various REE sorbed on bacteria, showing that the bond length for HREE (Er to Lu) was much shorter than those extrapolated from the trend between La and Dy, because of the selective binding of the HREE as the multiple phosphate surface complexes. Our results are consistent with the selective enrichment of the HREE at the bacterial cell surfaces, considering that chemical species with a shorter bond length are more stable. Thus, it is clear that the HREE enrichment at the bacterial cell surfaces is caused by the formation of the multiple phosphate surface complexes. Based on these results, it is suggested that materials having such phosphate sites such as bacteria and bacteria-related materials can induce anomalous HREE enrichment in natural systems. 相似文献
6.
We sampled two box-core sediments from the slope of the eastern South Korea Plateau (SKP) in the East Sea (Sea of Japan) at water depths of 1400 and 1700 m. Two chemical fractions of extractable (hydroxylamine/acetic acid) and residual rare earth elements (REEs) together with Al, Ca, Fe, Mg, Mn, P, S, As, Mo, and U were analyzed to assess the post-depositional redistribution of REEs. Extractable Fe and Mn are noticeably abundant in the oxic topmost sediment layer (<3 cm). However, some trace elements (e.g., S, As, Mo, U) are more abundant at depth, where redox conditions are different. Analysis of upper continental crust (UCC)-normalized (La/Gd)UCC, (La/Yb)UCC, and (Ce/Ce*)UCC revealed that the extractable REE is characterized by middle REE (MREE) enrichment and a positive cerium (Ce) anomaly, different from the case of the residual fraction which shows slight enrichment in light REEs (LREEs) with no Ce anomaly. The extractable MREEs seem to have been incorporated into high-Mg calcite during reductive dissolution of Fe oxyhydroxides. In the top sediment layer, the positive Ce anomaly is attributed to Ce oxide, which can be mobilized in deeper oxygen-poor environments and redistributed in the sediment column. In addition, differential concentrations of Ce and other LREEs in pore water appear to result in variable (Ce/Ce*)UCC ratios in the extractable fraction at depth. 相似文献
7.
对大同盆地典型高砷地下水开展了稀土元素地球化学研究.研究表明: 高砷地下水具有低∑REE含量及富集重稀土(HREEs)特征.地下水中低含量∑REE与含水层沉积物中Fe-Mn氧化物/氢氧化物对REEs的吸附有关.地下水中重稀土元素相对于轻稀土元素的富集可能是吸附作用和碳酸根离子同REEs发生络合作用的共同结果.采用平均大陆上地壳标准化的地下水稀土元素分布表现出显著的Ce及Eu正异常.地下水Ce/Ce*值及Eu含量与Fe+Mn具有显著相关性, 表明铁锰氧化物还原性溶解是控制Ce/Ce*值及Eu含量特征的主要因素.Ce/Ce*值及Eu含量与As浓度的关系表明, Ce异常及Eu含量特征能对地下水中As的富集进行有效指示. 相似文献
8.
Rare earth elements (REE) of dissolved and suspended loads in the Xijiang River, South China 总被引：4，自引：0，他引：4
The Xijiang River is the main channel of the Zhujiang (Pearl River), the second largest river in China in terms of water discharge, and flows through one of the largest carbonate provinces in the world. The rare earth element (REE) concentrations of the dissolved load and the suspended particulate matter (SPM) load were measured in the Xijiang River system during the high-flow season. The low dissolved REE concentration in the Xijiang River is attributed to the interaction of high pH and low DOC concentration. The PAAS-normalized REE patterns for the dissolved load show some common features: negative Ce anomaly, progressively heavy REE (HREE) enrichment relative to light REE (LREE). Similar to the world’s major rivers the absolute concentration of the dissolved REE in the Xijiang River are mainly pH controlled. The degree of REE partitioning between the dissolved load and SPM load is also strongly pH dependent. The negative Ce anomaly is progressively developed with increasing pH, being consistent with the oxidation of Ce (III) to Ce (IV) in the alkaline river waters, and the lack of Ce anomalies in several DOC-rich waters is presumably due to both Ce (III) and Ce (IV) being strongly bound by organic matter. The PAAS-normalized REE patterns for the dissolved load and the SPM load in rivers draining the carbonate rock area exhibit middle REE (MREE) enrichment and a distinct maximum at Eu, indicating the preferential dissolution of phosphatic minerals during weathering of host lithologies. Compared to the Xijiang River waters, the MREE enrichment with a maximum at Eu disappeared and light REE were more depleted in the South China Sea (SCS) waters, suggesting that the REE sourced from the Xijiang River must be further fractionated and modified on entering the SCS. The river fluxes of individual dissolved REE introduced by the Xijiang River into the SCS vary from 0.04 to 4.36 × 104 mol a−1. 相似文献
9.
研究风化壳中纳米微粒的稀土元素特征,对于从微观层面揭示我国华南风化壳型稀土矿床成因具有重要意义。以广西平南富稀土花岗岩风化壳剖面(ΣREEmax含量1 201 ×10-6)为典型案例,采用物理方法(超纯水,MQW)和化学方法(Na4P2O7, TSPP)两种技术手段,提取了花岗岩风化产物中的纳米微粒(1~100 nm)。进而采用中空纤维流场流分离-电感耦合等离子质谱仪联用技术(HF5-ICP-MS),对纳米微粒进行了连续分离和表征,同步获得了不同粒径纳米微粒中REE的含量特征。结果指示,化学提取剂TSPP能有效打破花岗岩风化产物中的大颗粒团聚体,它对纳米微粒的提取效率比物理提取方法高102~103倍。在TSPP提取的纳米微粒悬浮液中,REE含量(ΣREETSPP含量)最高可占到风化产物全岩REE总量(ΣREE含量)的80.5 %。纳米微粒主要分布于2~5 nm和10~30 nm两个粒径区间,另有少量粒径为30~80 nm的纳米微粒出现。其中,在2~5 nm微粒中,REE峰位与有机质大分子峰位对应,指示二者在离子键合作用下形成了聚合体。而在10~30 nm微粒中,REE峰位与Al元素峰位相对应,指示REE被黏土矿物纳米微粒吸附或离子交换。此外,本研究还发现轻稀土(LREE)与重稀土(HREE)在纳米微粒中的分布并不一致。其中以La、Ce、Pr和Nd为代表的LREE元素集中出现在2~5 nm和10~30 nm的纳米微粒中,而以Tb和Lu为代表的HREE元素除了在上述两个粒径的纳米微粒中有含量显示外,还分布于30~80 nm的纳米微粒中,指示了花岗岩风化产物中可能存在着相对独立的、与有机质和黏土矿物无直接关联的重稀土纳米微粒矿物。上述发现为进一步认识风化壳型稀土矿床中稀土元素的赋存状态和富集分异过程提供了新的启示。 相似文献
10.
《Applied Geochemistry》1998,13(4):451-462
Water, suspended matter, and sediment samples were taken from 8 locations along the Yangtze River in 1992. The concentration and speciation (exchangeable, bound to carbonates, bound to Fe–Mn oxides, bound to organic matter, and residual forms) of rare earth elements (La, Ce, Nd, Sm, Eu, Tb, Yb, and Lu) were determined by instrumental neutron activation analysis (INAA).The contents of the soluble fraction of REEs in the river are low, and REEs mainly reside in particulate form. In the particles, the chondrite-normalized distribution patterns show significant LREE enrichment and Eu-depletion. While normalized to shales, both sediments and suspended matter samples show relative LREE enrichment and HREE depletion. REEs are relatively enriched in fine-grained fractions of the sediments.The speciation characteristics of REEs in the sediments and suspended matter are very similar. The amount of the five forms follows the order: residual>>bound to organic matter∼bound to Fe–Mn oxides>bound to carbonates>>exchangeable. About 65 to 85% of REEs in the particles exist in the residual form, and the exchangeable form is very low. High proportions of residual REEs reveal that REEs in sediments and suspended matter are controlled by their abundances in the earth's crust. Carbonate, Fe–Mn oxide and organic fractions of REEs in sediments account for 2.4–6.9%, 5.2–11.1%, and 7.3–14.0% of the total contents respectively. They are similar to those in the suspended matter. This shows that carbonates, Fe–Mn oxides and organic matter play important roles during the particle-water interaction processes. By normalization to shales, the 3 forms of REEs follow convex shapes according to atomic number with middle REE (Sm, Eu, and Tb) enrichment, while light REE and heavy REE are depleted. 相似文献
11.
“寨背式”离子吸附型稀土矿床多类型稀土矿化及其成因 总被引：1，自引：0，他引：1
赣南寨背离子吸附型稀土矿床产于寨背复式花岗岩体的风化壳中,自20世纪80年代发现以来一直以轻稀土型开采,近年在轻稀土型花岗岩风化壳中发现了重稀土矿。为了探讨轻稀土型花岗岩风化过程中重稀土元素的迁移、分馏和富集机制,本文选择了区内三个具有代表性的风化壳钻孔(ZK1、ZK2和ZK4)对其进行了全相和离子交换相稀土元素地球化学研究。结果显示：钻孔ZK4中离子交换相稀土含量介于14.90×10-6～835.8×10-6之间,并富集轻稀土(LREE/HREE=2.28～10.78);钻孔ZK1中离子交换相稀土含量达1470×10-6(9件样品均值),具有从轻稀土型向重稀土型过渡的配分特征(LREE/HREE=1.30～1.65),并且剖面自上而下显示轻、重稀土逐渐富集的趋势;钻孔ZK2中离子交换相稀土含量为492.4×10-6(8件样品均值),自上而下稀土配分类型从轻稀土型过渡至重稀土型(LREE/HREE=0.43～2.25),且轻稀土富集在全风化层上部而重稀土则富集在下部。三个钻孔的Nb/Ta和Zr/Hf... 相似文献
12.
Veronique Kamgang Kabeyene Beyala Estelle Ndome Effoudou Priso Georges Emmanuel Ekodeck 《Chemie der Erde / Geochemistry》2009,69(1):61-13
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. 相似文献
13.
PENG Jun YI Haisheng XIA Wenjie Postdoctoral Researchers Flow Station of SW China Petroleum Institute Institute of Sedimentary Geology Chengdu University of Technology Chengdu E-mail.tjc@cdit.edu.cn Institute of Sedimentary Geology Chengdu University of Technology Chengdu 《《地质学报》英文版》2000,74(1):46-53
In the Hunan-Guizhou-Guangxi area there have developed very thick bedded siliceous rocks of the late Sinian. The rocks have a fairly pure composition, with an average content of siliceous minerals exceeding 95%. They are relatively rich in Fe and Mn, and poor in Al, Ti and Mg. The Fe/Ti, (Fe+Mn)/Ti, Al/(Al+Fe+Mn) and U/Th ratios and the Al-Fe-Mn and Fe-Mn-(Ni+Co+Cu)×10 triangle diagrams all show that they are hydrothermal sedimentary siliceous rocks. In the rocks the total amount of REEs is low, the δCe shows an obvious negative anomaly and the 8Eu a weak anomaly, and LREE>HREE, all indicating that they are products of hydrothermal processes. The δ30Si and δ18O values, as well as the formation temperature of the rocks all clearly show that the silica forming the rocks comes from hot water. Besides, analyses of the depositional environment of the rocks using the MnO/TiO2 ratio and the δCe and δ30Si values yield the same conclusion that they are formed in environments from continental marginal slope 相似文献
14.
为探讨下扬子地区二叠系硅质岩的硅质来源和形成背景,以巢湖地区二叠纪栖霞组和孤峰组硅质岩为研究对象,收集了前人大量有关栖霞组和孤峰组的研究成果和数据,并对采自栖霞组和孤峰组硅质岩样品进行了主量元素、微量元素、稀土元素测试。栖霞组、孤峰组硅质岩样品测试结果显示,硅质岩的稀土元素经北美页岩标准化后的配分曲线近似平坦型向左倾斜,有弱Ce负异常,且HREE弱富集,反映了热水沉积硅质岩的特征。研究区硅质岩样品的Al Fe Mn三角图中,样品投点分布较广,即Al比值变化范围较大,认为是岩浆在喷发过程中受硅-铝质陆壳混染作用的结果。结合沉积环境判别指标分析认为：栖霞组硅质岩沉积时期其沉积环境主要为大陆边缘环境;孤峰组硅质岩沉积时期其沉积环境为大陆边缘-海盆过渡环境。从栖霞组到孤峰组沉积时期,海侵规模不断变大,水体变深,海盆面积扩大,研究区在不同时期沉积环境存在差异。研究区栖霞组、孤峰组硅质岩的沉积与大陆边缘裂陷活动紧密相关。 相似文献
15.
Rare earth element studies of surficial sediments from the southwestern Carlsberg Ridge,Indian Ocean
The rare earth element (REE) contents of sixteen surficial calcareous sediments from the southwestern Carlsberg Ridge, Indian
Ocean, have been determined. The total REE vary from 35 ppm to 126 ppm and are inversely related to the calcium carbonate
content. REEs show a strong positive correlation with Al + Fe + K + Mg + Na (r
2= 0.98) and Mn + Fe + Cu + Ni (r
2= 0.86) suggesting that the REE is associated with a combined phase of clays (mainly illite) and Mn-Fe oxyhydroxides. The
aeolian input into these sediments is suggested from the weak positive Eu/Eu* anomaly. Shale-normalized (NASC) pattern along
with La(n)/Yb(n) ratio suggest enrichment of heavy REE (HREE) relative to the light REE (LREE) with a negative Ce/Ce* anomaly implying retention
of a bottom water REE pattern.
An erratum to this article is available at . 相似文献
16.
The distribution and content of rare-earth elements (REEs) were determined in two radish species, the cultivated Raphanus sativus and the wild Raphanus raphanistrum, that were grown under laboratory-controlled conditions, in three substrates consisting of illite for one and two smectite substrates for the others, with the two smectite substrates being characterised by different porosities. The plants were split into leaves and stems + roots for analysis. The results indicate that both species take up systematically higher amounts of REEs when grown in the illite substrate, even considering that the smectite equivalent contains about three times more REEs. The REE uptake is also more plant species than mineral composition dependent: R. raphanistrum takes up 3.5–6.7 times more REEs than R. sativus, depending on the substrate, its porosity and the considered plant segments. Increased substrate porosity favours the take up of the REEs, but no specific uptake is observed in leaves relative to that in the combined stems and roots. The transfer of the REEs from minerals to plant organs does not appear to induce systematically identical patterns: (1) in the case of R. sativus, a positive Eu anomaly is visible in all patterns from both segment groups grown in both substrates. When grown in illite, the heavy REEs are also enriched in the stems and roots, which has not been observed in any other organ or in the other substrate and (2) in the case of R. raphanistrum, a very significant positive Gd anomaly, which is not expected to fractionate relative to the other REEs as do Ce and Eu, is observed in all segments of the plants grown in both substrates. A slight negative Ce anomaly is also visible in some of the REE patterns, suggesting some changes in the oxidation–reduction conditions in the substrates near the roots during plant growth. The comparison of the REE patterns from leaves relative to those of the roots + stems shows that those of R. raphanistrum grown in illite provide a spectrum that is very specific with significant deficits in La, Ce, Gd, Tm, Yb and Lu in the leaves. In the other cases, the patterns do not outline significant differences except for R. sativus grown in illite, in which the leaves are enriched in light and medium REEs from La to Gd relative to the stems + roots. 相似文献
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碳酸盐岩是地球表层岩石圈的重要组成部分,其化学组成可提供沉积环境与海洋水体演化等信息,然而,前人对碳酸盐岩中稀土等元素的分布与变化特征关注不足。本文选择穿越中国东部6个一级大地构造单元的3条地球化学走廊带,系统采集了582件碳酸盐岩地层样品,并准确分析了包括稀土元素(REE)在内的81项指标的含量。结果表明,中国东部地球化学走廊带碳酸盐岩稀土元素(REE＋Y)总量为(0.59～183)×10-6,均值为24.0×10-6,纯净碳酸盐岩(CMC含量≥99％)均值为4.80×10-6。PAAS标准化后其显示具有轻稀土相对于中稀土和重稀土略亏损、δEu轻微正异常、δCe中度负异常等特征。白云岩中稀土含量、LREE/HREE值一般低于石灰岩;砂泥质含量相近时,前中生代各时代碳酸盐岩稀土分布模式相差不大,各构造单元稀土分布特征基本相似;与其他时代相比,中生代及中新元古代碳酸盐岩具有相对较平坦的稀土分布模式。研究表明,碳酸盐岩中稀土分布受碎屑物质影响明显,表现为稀土元素含量与碳酸根负相关,与碎屑物质相关元素(Si、Ti、Rb、Cs、Th、Zr等)、黏土相关元素(Al、Fe、K等)等正相关。成岩过程及白云化过程对较纯净碳酸盐岩中稀土分布特征影响不明显。我国古生代纯净碳酸盐岩分布模式受控于海相环境,其分布模式与现今海水相近;中生代纯净石灰岩受到陆相或海陆交互相的影响,具有较平坦的稀土分布模式。氧化还原条件对δCe的影响较δEu更为明显,δCe值受海相环境控制,极端正异常值(δCe＞1.3)受到还原环境或/和热液影响。若假定海水中REE自中元古代至今无太大变化,各时代稀土元素分配系数均值介于103.55～102.39,分配系数差异是造成碳酸盐岩中轻稀土亏损、Ce负异常及Y正异常的主要原因。微生物(席)可富集稀土等金属元素并改变沉积环境,这可能是造成中新元古界碳酸盐岩较平坦的稀土分布模式的主要原因。 相似文献
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《Chemie der Erde / Geochemistry》2015,75(3):403-417
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. 相似文献
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Differential Fractionation of Rare Earth Elements in Oxidized and Reduced Granitic Rocks: Implication for Heavy Rare Earth Enriched Ion Adsorption Mineralization 
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下载免费PDF全文 Ion adsorption rare earth element (REE) deposits in southern China are the exclusive source of heavy REEs (HREEs) in the world, and this HREE‐enriched character of the deposits is inherited from the REE compositions of the underlying granitic rocks. Such HREE‐enriched rocks form from heavy fractionation of reduced granitic magmas. We explore why reduced granitic magmas are enriched in HREEs during the fractionation, based on the REE geochemistry of granitic rocks and abundance of REEs in their constituent minerals in the southwestern Japan arc of Cretaceous to Paleogene age. The compilation of the whole rock geochemistry and REE compositions of the granitic rocks of the Sanin (oxidized), Sanyo (reduced) and Ryoke (reduced) belts in the southwestern Japan arc indicates that: (i) light REEs (LREEs) decease with fractionation of the granitoids in the Sanin belt but this trend is not clear in the granitoids in the Sanyo belt and LREEs rather increase in the Ryoke granitoids; (ii) Eu decreases with fractionation in all the belts; and (iii) HREEs slightly, but steadily decrease in the Sanin belt but enrich significantly in the Sanyo and Ryoke belts with fractionation. Analytical results of REE concentrations by scanning electron microscope with energy dispersive X‐ray spectroscope and laser ablation‐inductively coupled plasma mass spectrometer in the constituent minerals in a granodiorite sample from the Sanin belt show a moderate concentration of REEs in hornblende (577 ppm) in addition to high concentrations in allanite (~20 %), britholite (~30 %), primary titanite (8922 ppm), apatite (4062 ppm), and zircon (1693 ppm). Because primary titanite and allanite are commonly present in the oxidized granitoids but not in the reduced ones, the REE depletion in the fractionated, oxidized granites is attributed to the crystallization of these minerals. In contrast, scarcity of these minerals in the reduced granitoids enriches REEs, in particular HREEs in the fractionated magmas, which finally precipitate REEs in the granites and pegmatites. Both positive, but different correlation ratios between the Nb and Dy concentrations in the granitoids of the Sanin and Sanyo‐Ryoke belts suggest that columbite–pyrochlore‐group and fergusonite‐group minerals are the major HREE host in the oxidized and reduced granites, respectively. 相似文献