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1.
Iron formations (IFs) typically contain low mass fractions of most trace elements, including the rare earth elements (REE), and few publications describe analytical methods dedicated to this matrix. In this study, we used bomb and table‐top acid dissolution procedures and ICP‐MS to determine the mass fractions of trace elements in IF reference materials FER‐1, FER‐2, FER‐3, FER‐4 and IF‐G. The full digestion of the IF samples with the bomb procedure required the addition of a small amount of water together with the acids. The results obtained by this method mostly agreed statistically with published values. The most remarkable exception was the higher values obtained for the heavy REE in FER‐3. The recoveries of the REE obtained with the table‐top procedure were slightly higher than those of the bomb digestion, except for the values of the heavy REE in FER‐3 and FER‐4, which were up to 30% lower than published values. Sintering of the samples with sodium peroxide was performed to determine the REE, but the results tended to be lower than those derived following acid digestion. On the whole, the recoveries showed dependence on the conditions of digestion, but subtle differences in trace mineral composition between samples also exerted influence on the analytical results for trace elements.  相似文献   

2.
This study reports a robust procedure that permits precise measurement of all fourteen naturally occurring rare earth element (REE) concentrations, present at ng kg?1 to sub ng kg?1 levels, in ~ 100 ml seawater. This procedure is simple and can be routinely applied to measure seawater REEs with relatively high sample throughput. The procedure involves addition of a 142Ce‐145Nd‐171Yb‐enriched spike mixture, iron co‐precipitation, REE purification with chromatographic separation and the use of a magnetic‐sector‐field ICP‐MS (Element 2) coupled with a desolvating sample introduction system (Aridus 1). Critical steps of the procedure, including co‐precipitation pH and matrix removal, have been optimised through a set of experiments described here. The accuracy of the new procedure was assessed against a gravimetric mixture of REEs, and the precision was demonstrated by repeated measurement of two well‐mixed natural seawaters. Repeated analyses of these seawater reference materials (RMs), using ~ 100 ml seawater for each aliquot, indicate precision of 3% (1s) for the REEs. Measured REE concentrations of two uncertified seawater RMs (CASS‐4 and NASS‐5) are consistent with published values, and REE concentrations of the GEOTRACES intercalibration samples show good agreement with those reported by other participant laboratories. REE concentrations for other intercalibration samples (SAFe and Arctic PS70) are also reported.  相似文献   

3.
Eleven rare earth elements (REE) have been determined in ten USGS and two CCRMP igneous rock standards using high performance ion chromatography. Duplicate analyses of two or more separately prepared aliquots of each sample were undertaken; reproducibility was better than 5% for each of the REE. In most cases, the results compare closely with published REE values for those samples for which the REE are well characterised. Where the results for individual elements are in disagreement with published data, the more erratic patterns yielded by the earlier data when plotted on chondrite-normalised REE diagrams suggest that values determined in this study are of greater accuracy.  相似文献   

4.
Various zircons of Proterozoic to Oligocene ages (1060-31 Ma) were analysed by laser ablation-inductively coupled plasma-mass spectrometry. Calibration was performed using Harvard reference zircon 91500 or Australian National University reference zircon TEMORA 1 as external calibrant. The results agree with those obtained by SIMS within 2s error. Twenty-four trace and rare earth elements (P, Ti, Cr, Y, Nb, fourteen REE, Hf, Ta, Pb, Th and U) were analysed on four fragments of zircon 91500. NIST SRM 610 was used as the reference material and 29Si was used as internal calibrant. Based on determinations of four fragments, this zircon shows significant intra-and inter-fragment variations in the range from 10% to 85% on a scale of 120 μm, with the variation of REE concentrations up to 38.7%, although the chondrite-normalised REE distributions are very similar. In contrast, the determined age values for zircon 91500 agree with TIMS data and are homogeneous within 8.7 Ma (2 s ). A two-stage ablation strategy was developed for optimising U-Pb age determinations with satisfactory trace element and REE results. The first cycle of ablation was used to collect data for age determination only, which was followed by continuous ablation on the same spot to determine REE and trace element concentrations. Based on this procedure, it was possible to measure zircon ages as low as 30.37 0.39 Ma (MSWD = 1.4; 2 s ). Other examples for older zircons are also given.  相似文献   

5.
Olivine offers huge, largely untapped, potential for improving our understanding of magmatic and metasomatic processes. In particular, a wealth of information is contained in rare earth element (REE) mass fractions, which are well studied in other minerals. However, REE data for olivine are scarce, reflecting the difficulty associated with determining mass fractions in the low ng g?1 range and with controlling the effects of LREE contamination. We report an analytical procedure for measuring REEs in olivine using laser ablation quadrupole‐ICP‐MS that achieved limits of determination (LOD) at sub‐ng g?1 levels and biases of ~ 5–10%. Empirical partition coefficients (D values) calculated using the new olivine compositions agree with experimental values, indicating that the measured REEs are structurally bound in the olivine crystal lattice, rather than residing in micro‐inclusions. We conducted an initial survey of REE contents of olivine from mantle, metamorphic, magmatic and meteorite samples. REE mass fractions vary from 0.1 to double‐digit ng g?1 levels. Heavy REEs vary from low mass fractions in meteoritic samples, through variably enriched peridotitic olivine to high mass fractions in magmatic olivines, with fayalitic olivines showing the highest levels. The variable enrichment in HREEs demonstrates that olivine REE patterns have petrological utility.  相似文献   

6.
Zircon is widely used to simulate melt generation, migration and evolution within the crust and mantle.The achievable performance of melt modelling generally depends on the availability of reliable trace element partition coefficients(D).However, a large range of D_(REE)values for zircon from natural samples and experimental studies has been reported, with values spanning up to 3 orders of magnitude.Unfortunately, a gap of knowledge on this variability is evident.In this study we model the crystallization processes of common REE-bearing minerals from granitic melts and show that the measured zircon D_(REE)would be elevated if there is crystallization of REE-enriched minerals subsequent to zircon.Nevertheless, compared to zircon D_(REE)values measured from experimental studies, this mechanism appears to have a less significant influence on those from natural granite samples since the quantity of crystallized REE-enriched minerals is very low in natural magmatic systems and/or most of them crystallize prior to zircon.Combined with recently published studies, this work supports that analysis of natural zircon/host groundmass pairs provides more robust D_(REE)values applicable to natural systems than those measured from experimental studies, which can be used to constrain the provenance of detrital zircons.  相似文献   

7.
对采自羌塘盆地那底岗日地区布曲组碳酸盐岩烃源岩进行了稀土元素地球化学研究,分析结果表明:海相碳酸盐岩烃源岩稀土总量(∑REE)最大值75.21μg/g,最小值20.58μg/g,平均值为36.67μg/g.稀土元素北美页岩标准化后具有相对富集轻稀土,亏损重稀土的特点.布曲组碳酸盐岩烃源岩Ce/Ce*值为0.83～0.9...  相似文献   

8.
Abstract. An improved alkali fusion method followed by HF-HNO3-HC1O4 treatment is performed for simultaneous determination of 23 trace elements (Sr, Y, Zr, Nb, Ba, Hf, Ta, Th, U, and REE) by ICP-MS in rock reference materials: basaltic rocks (JB-2, JB-3) and granitic rocks (JG-la, JG-2, JG-3). Our improved method offers several advantages including: (1) suppression of whitish precipitates probably composed of insoluble fluorides by addition of HCIO4, (2) simple and reliable preparation procedure, (3) instrument calibration which enables straightforward simultaneous multi-elemental analysis, and (4) the very low background levels by using pure lithium tetraborate flux. We obtained the analytical results with a reproducibility of mostly <2 % (1) for the basaltic rocks and <7 % for the granitic rocks. The higher relative standard deviation (RSD) values for granitic rocks may be attributed to sample heterogeneity of coarse-grained granitic rocks. The analytical results of the granitic rocks demonstrate that Zr and Hf abundances are consistent with the compiled values and that REE concentrations agree well with recently published data, suggesting that the Li2B4O7 fusion method applied in the present study is suitable for the analysis of the granitic rocks.  相似文献   

9.
南方红土形成过程及其稀土元素地球化学   总被引：40，自引：3，他引：37       下载免费PDF全文
南方不同红土的化学蚀变指数(CIA),硅铝系数 、铝铁系数 硅铁铝系数 反映红土的形成经历了脱钙、脱碱基和初级脱硅富铝富铁3个主要的 风化阶段;稀土在前两个阶段中主要发生淋失,而在后一阶段中富集,其配分曲线具Eu亏损的轻稀土显著富集型特征。红土中稀土元素的赋存状态以晶格相为主,主要与基岩密切有关,而其它赋存状态则与红土化过程紧密相连。红土中可溶态稀土含量的高低是风化作用强度的有效指标。  相似文献   

10.
稀土元素(REE)的物源对比表明,苏北盆地高邮凹陷戴南组一段沉积岩的物源以其西侧张八岭隆起的元古宙浅变质岩基底为主,并与大别和苏鲁造山带的浅变质岩基底存在亲缘关系,推断研究区的母岩类型为高钾I型花岗片麻岩。而张八岭隆起的新元古代细碧—石英角斑岩和绿片岩、中生代火成岩、大别山南部大范围的榴辉岩以及宁镇山脉的中生代中酸性侵入岩对研究区的物源影响很小。在高邮凹陷内部的物源方向分析中,轻重稀土元素分馏值[(La/Yb)N]与矿物成熟度指数(MMI)形成很好的吻合,(La/Yb)N值结合稀土元素总量(∑REE)及铕异常值(δEu)可对研究区内物源方向的精确判别具有指示意义。戴南组一段沉积时期,高邮凹陷的物源主要来自4个方向:西北部柘垛低凸起方向、东部吴堡低凸起方向、南部通扬隆起方向和西南部菱塘桥低凸起方向。高邮凹陷戴南组一段的沉积相类型与REE特征的相关性分析显示,重稀土元素分馏值[(Gd/Yb)N]与沉积相间存在较为规律的变化,表现在近岸水下扇相、扇三角洲相和三角洲相随其碎屑岩的成熟度升高,(Gd/Yb)N平均值呈逐渐升高的趋势,该趋势同样表现在相同沉积相的不同沉积亚相之间,说明(Gd/Yb)N平均值可较好地反映沉积相特征。  相似文献   

11.
详细研究渤海湾盆地南堡凹陷新近系馆陶组和明化镇组泥岩的稀土元素地球化学特征。结果表明：样品稀土总量为146.2×10-6～317.1×10-6,平均值为223.3×10-6;w(LREE)/w(HREE)为8.1～14.5,平均值为11.5,相对富集LREE;Eu为明显负异常;δCe基本正常。δCe和Ceanom值的变化反映馆陶组和明化镇组为陆相沉积,水介质条件为富氧环境。稀土元素分布模式、组合特征及其与燕山褶皱带地区不同时代(期)花岗岩和中酸性火山岩稀土元素的对比结果表明：馆陶组和明化镇组地层的物源基本相同,主要来自凹陷北部燕山褶皱带地区于燕山期发育的中酸性火山岩和花岗岩体,少部分来自沉积岩。与不同构造环境杂砂岩的稀土元素特征的对比结果及δCe的特征表明南堡凹陷新近系源区属性为活动大陆边缘背景。  相似文献   

12.
Four types of apatite have been identified in the Ningwu region.The first type of apatite is widely distributed in the middle dark colored zones(i.e.iron ores) of individual deposits.The assemblage includes magnetite,apatite and actinolite(or diopside).The second type occurs within magnetite-apatite veins in the iron ores.The third type is seen in magnetite-apatite veins and (or) nodules in host rocks(i.e.gabbro-diorite porphyry or gabbro-diorite or pyroxene diorite).The fourth type occurs within apatite-pyrite-quartz veins filling fractures in the Xiangshan Group.Rare earth elements (REE) geochemistry of apatite of the four occurrences in porphyry iron deposits is presented.The REE distribution patterns of apatite are generally similar to those of apatites in the Kiruna-type iron ores,nelsonites.They are enriched in light REE,with pronounced negative Eu anomalies.The similarity of REE distribution patterns in apatites from various deposits in different locations in the world indicates a common process of formation for various ore types,e.g. immiscibility.Early magmatic apatites contain 3031.48-12080×10~(-6) REE.Later hydrothermal apatite contains 1958×10~(-6) REE,indicating that the later hydrothermal ore-forming solution contains lower REE.Although gabbro-diorite porphyry and apatite show similar REE patterns,gabbro-diorite porphyries have no europium anomalies or feeble positive or feeble negative europium anomalies, caused both by reduction environment of mantle source region and by fractionation and crystallization(immiscibility) under a high oxygen fugacity condition.Negative Eu anomalies of apatites were formed possibly due to acquisition of Eu~(2+) by earlier diopsite during ore magma cooling. The apatites in the Aoshan and Taishan iron deposits yield a narrow variation range of ~(87)Sr/~(86)Sr values from 0.7071 to 0.7073,similar to those of the volcanic and subvolcanic rocks,indicating that apatites were formed by liquid immiscibility and differentiation of intermediate and basic magmas.  相似文献   

13.
Cumulus apatite, sphene, feldspar, amphibole and biotite from the pulaskite of the Kangerdlugssuaq alkaline intrusion have been analysed for rare earth elements (REE) by instrumental neutron activation analysis. The apatite is particularly rich in REE, contains 3.6% Ce and shows a steep, light REE-enriched, chondrite-normalised pattern. The other minerals have light REE enrichment but with sphene showing a peak at Ce on a chondrite-normalised plot. REE partition coefficient values show that the light REE are preferentially accommodated by apatite relative to sphene. The differences in these coefficients result from differences in the co-ordination of the REE in the two minerals.  相似文献   

14.
Rare-earth abundances in chondritic meteorites   总被引：1，自引：0，他引：1  
Fifteen chondrites, including eight carbonaceous chondrites, have been analyzed for rare earth element (REE) abundances by isotope dilution. These analyses complement and extend earlier isotope dilution REE determinations in chondrites, performed in other laboratories, so that coverage of major chondrite classes is now complete. An examination of this body of precise and comparable REE data from individual chondrites reveals that only a small proportion of the analyses have flat, unfractionated REE patterns within experimental error. A statistical procedure is used to derive revised chondritic abundances of REE by selection of unfractionated patterns. A number of the remaining analyses show Eu anomalies and fractionated patterns consistent with magmatic fractionation as encountered in the products of planetary differentiation. However, many patterns exhibit features not readily explicable by known magmatic processes; in particular, positive Ce anomalies are often encountered. Abundance anomalies can be quantitatively determined by the use of a least-squares curve fitting procedure. The wide variety of anomalous patterns and the uncertainties in model parameters preclude detailed modeling of the origin of anomalies, but it is probable that at least some arise from fractional condensation in the solar nebula, as has been demonstrated for Allende inclusions. Elemental abundance anomalies are found in all major chondrite classes. If these anomalies are ignored, the range and nature of variation within chondrite classes are consistent with a parent body model, in which solid-liquid or solid-solid equilibria induce variations from an unfractionated bulk composition. Absolute abundances in the H, L and LL parent bodies are almost twice those of the E parent body.The persistence of anomalies in chondritic materials relatively removed from direct condensational processes implies that anomalous components are resistant to equilibration or were introduced at a late stage of chondrite formation. Large scale segregation of gas and condensate is also implied, and raises the possibility of bulk variations in REE abundances between planetary bodies.  相似文献   

15.
The partitioning of rare earth elements (REE) between zircon, garnet and silicate melt was determined using synthetic compositions designed to represent partial melts formed in the lower crust during anatexis. The experiments, performed using internally heated gas pressure vessels at 7 kbar and 900–1000 °C, represent equilibrium partitioning of the middle to heavy REE between zircon and garnet during high‐grade metamorphism in the mid to lower crust. The DREE (zircon/garnet) values show a clear partitioning signature close to unity from Gd to Lu. Because the light REE have low concentrations in both minerals, values are calculated from strain modelling of the middle to heavy REE experimental data; these results show that zircon is favoured over garnet by up to two orders of magnitude. The resulting general concave‐up shape to the partitioning pattern across the REE reflects the preferential incorporation of middle REE into garnet, with DGd (zircon/garnet) ranging from 0.7 to 1.1, DHo (zircon/garnet) from 0.4 to 0.7 and DLu (zircon/garnet) from 0.6 to 1.3. There is no significant temperature dependence in the zircon–garnet REE partitioning at 7 kbar and 900–1000 °C, suggesting that these values can be applied to the interpretation of zircon–garnet equilibrium and timing relationships in the ultrahigh‐T metamorphism of low‐Ca pelitic and aluminous granulites.  相似文献   

16.
Twenty-one surficial sand samples from the Altar Desert coastal and desert dune systems were analysed for rare earth elements (REE) content. This was done to observe the provenance signatures for four strategic dune localities near the Colorado River Delta, the El Pinacate dune fields, and the beaches of the north of the Gulf of California in the state of Sonora, Mexico. Our goals are to show which mechanisms (i.e., aeolian, marine) exert more influence on the composition of the Altar Desert dune sands. This study also shows the usefulness of REE spatial distribution to determine the relative mobility of the sand. Some sand samples from the dune systems in San Luis Río Colorado (SLRC), Golfo de Santa Clara (GSC), and Puerto Peñasco (PP) displayed dissimilar REE concentrations with respect to the rest of the sand samples from the same sites. These differences can be related to short aeolian transport distance in the sands with high REE concentrations and long aeolian transport distance in the sands with low REE concentrations. Besides, high REE concentration in the sands might be due to their closeness to the Colorado River Delta sediments and to recycled sands derived from granitic rocks. In contrast, all the sand samples from the El Pinacate (EP) site have similar REE concentration values, suggesting that the El Pinacate dune sands are influenced by more selective aeolian processes and less diverse heavy mineral content. The Altar Desert dune sands are derived from granitic sources eroded by the Colorado River. Our results also indicate that the Altar Desert dune sands are low in heavy mineral content (with the exception of Fe and Ti bearing minerals) and enriched in carbonates with phosphates (especially at the PP site) yielding poor correlations between REE and major element concentrations. The REE geographical distribution values in the Altar Desert dune sands indicate that light and heavy REE concentration values are related to aeolian transport, maturity of the sands, their low weathering rates, proximity of the source rocks, and the biogenic debris input from beach sands into the dune.  相似文献   

17.
The Lower Eocene Celtek Formation is located in the Sorgun district of thecity of Yozgat in Turkey.In the study area,Paleozoic,Campanian-Maastrichtian,Eocene,Miocene and Quaternary units are exposed.The Celtek Formation is noteworthy with its coal and oil shale deposits.Samples were collected from one exposure(YCOSK)and two boreholes(SJ and C boreholes)at the facility operated by the Yeni Celtek Coal Management.Concentrations of REE in oil shales from these localities were determined using the ICP-MS technique.REE and total organic carbon(TOC)values of a total of 32 samples were compared with normalized REE contents of various environments.TOC contents of the samples ranged from 1.37wt%to 11.8wt%(mean 4.96wt%).The averages of all samples for the all normalized values show similar patterns.Normalized REE patterns are represented by the enrichment in the order of LREE>MREE>HREE and display negative Ce and positive Eu anomalies.ΣREE vs.TOC were compared.ΣREE vs.TOC showed a weak positive correlation,whereasΣLREE vs.(M+HREE)andΣLREE vs.ΣREE were positively correlated.Regarding tectonic provenance characteristics,the Celtek Formation oil shales were formed in microenvironments with physicochemical conditions changing in character from oxic to euxinic,representing a transitional terrestrial–marine environment.  相似文献   

18.
Rare Earth Element (REE) concentrations in agricultural soil obtained from the Mobile Metal Ion (MMI®) weak extraction technique are compared with soil total concentrations (sodium peroxide fusion followed by acid dissolution) for 118 and 174 agricultural soil samples from Italy and Sweden, respectively. Spatial distribution maps and statistics for both analytical techniques are compared between the two national datasets. In spite of similarity of REE concentration in two countries, the median values of REE is higher than Italy but extreme concentration of REE in Italy is due to young volcanic activities. Extractability of REEs is significantly higher in Swedish soils than in Italian soils. Heavy Rare Earth Element (HREE) in Sweden show higher concentrations compared to Italy in MMI® extraction data where correlate with REE mineralisation. Principal Component Analysis (PCA) is used to elucidate correlations and anomalies in the REE distribution. Results show that there is a clear correlation between REE anomalies and natural factors such as lithology of the underlying bedrock, the presence of mineralisations, pH of soils, climate and precipitation. According to the PCA results, anomalous behaviour of Eu, Ce, Tb and Gd can be explained by the dominant mineralogy of the parent material and the variable affinity of REEs to bind to clay minerals and clay-size particles.  相似文献   

19.
洪瑾  甘成势  刘洁 《地学前缘》2019,26(4):45-54
地学共享数据库(如GEOROC、PetDB等)可为地球科学研究提供重要基础数据。然而,这些数据库均存在一个明显缺陷:样品的9种主量元素(SiO2、TiO2、Al2O3、CaO、MgO、MnO、K2O、Na2O和P2O5)均有准确数据,但稀土元素(rare earth elements,REE)数据大量缺失。鉴于REE在地球化学领域的重要作用,我们尝试为数据库缺失的REE值提供一个补全方案,即利用机器学习中的随机森林方法实现由9种主量元素预测REE值。以洋岛玄武岩(ocean island basalt,OIB)为例,把从GEOROC库中搜集到的1 283组OIB数据按8∶2的比例分为两组,其中80%的数据作为训练数据集用于建模,20%的数据作为测试数据集验证模型。比较了随机森林和多元线性回归方法对相同数据进行建模和预测的效果差异,发现无论是回归建模还是预测,随机森林方法都优于多元线性回归,且随着输入参数与输出参数之间关系的复杂化,这种优势更加明显。随机森林对测试数据集的预测效果整体较好,只是随着REE原子序数的增大,预测效果逐渐减弱。这一方面可能是因为原子序数大的REE与主量元素的关系更弱;另一方面可能是由于原子序数大的REE与主量元素的关系更加复杂。其次,随机森林方法预测的REE配分曲线与实际配分曲线吻合度较高,且预测所得配分曲线的区分能力较强,能够反映实际配分曲线之间的相对差异,这一点对推断地球化学过程尤为重要。随机森林方法随着训练数据的增多,其建立的模型也将越稳定,预测结果也会更精确。因此,随着数据库的不断完善,对数据库中REE值的预测也将更为可信、可行。  相似文献   

20.
Our current lack of understanding of the partitioning behavior of Sc, Y and the REE (rare-earth elements) can be attributed directly to the lack of a sufficiently large or chemically diverse experimental data set. To address this problem, we conducted a series of experiments using several different natural composition lavas, doped with the elements of interest, as starting compositions. Microprobe analyses of orthopyroxene, pigeonite, olivine, magnetite, ilmenite and co-existing glasses in the experimental charges were used to calculate expressions that describe REE partitioning as a function of a variety of system parameters. Using expressions that represent mineral-melt reactions (versus element ratio distribution coefficients) it is possible to calculate terms that express low-Ca pyroxene-melt partitioning behavior and are independent of both pyroxene and melt composition. Compositional variations suggest that Sc substitution in olivine involves either a paired substitution with Al or, more commonly, with vacancies. The partitioning of Sc is dependent both on melt composition and temperature. Our experimentally determined olivine-melt REE Ds (partition coefficients) are similar to, but slightly higher than those reported by McKay (1986) and support their conclusions that olivines are strongly LREE depleted. Y and REE mineral/melt partition coefficients for magnetite range from 0.003 for La to 0.02 for Lu. Ilmenite partition coefficients range from 0.007 for La to 0.029 for Lu. These experimental values are two orders of magnitude lower than many of the published values determined by phenocryst/matrix separation techniques.  相似文献   

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