利用套柱法快速分离提纯Sr和Nd元素

样品放射性成因Sr-Nd同位素比值受控于源区初始同位素组成、放射性元素母体与子体相对丰度,以及衰变时间等因素。它们具有极强的示踪能力,因而在地质学领域有广泛的应用。传统的Sr-Nd同位素分析使用的是阳离子树脂,提纯Nd元素时往往涉及有机试剂以及调节pH值等操作,其分析效率较低。近年来特效树脂的出现使得分离这些元素变得简单,但是受硫酸根等因素影响,特效树脂使用次数有限。为了提高分析效率,缩短分析时间,本文开发了一种套柱法,该方法结合阳离子树脂和特效树脂,实现了Sr-Nd元素的快速分离,并且能延长特效树脂的使用寿命。实验采用阳离子树脂、Sr特效树脂和LN稀土特效树脂对玄武岩BCR-2标样进行了分析。Sr-Nd回收率均90%,BCR-2玄武岩~(87)Sr/~(86)Sr比值为0.705016±0.000016(n=36,1SD),~(143)Nd/~(144)Nd比值为0.512624±0.000012(n=39,1SD),与前人TIMS法获得的结果吻合(~(87)Sr/~(86)Sr:0.705000～0.705023;~(143)Nd/~(144)Nd:0.512630～0.512650)。最终分离提纯的溶液中~(85)Rb/~(86)Sr值小于0.01,~(147)Sm/~(144)Nd值小于0.001,表明该方法可以高效分离Rb-Sr和Sm-Nd,实现Sr、Nd同位素的准确分析。     

离子交换树脂法分离沉积物中锶和钕的影响因素研究

Sr和Nd同位素是地质学研究中经典的同位素定年和示踪体系。传统沉积物中Sr和Nd分离方法通常是利用AG50W-X8树脂分离Sr与稀土元素(REEs),再用Sr和Ln特效树脂分别对Sr和Nd纯化,但对于Fe元素含量较高的沉积物样品,该方法对REEs的洗脱率偏低,仅有50%。另外,AG50W-X8树脂高度、洗脱酸种类、Sr特效树脂淋洗酸体积以及Ln特效树脂过柱方式对Sr和Nd分离都有影响。为分析上述因素对Sr和Nd分离效果的影响,本文以水系沉积物标准物质GBW07309为例进行了研究,结果表明:(1)高含量的Fe会显著影响Sr和Nd的分离效果,而AG1-X8树脂可以有效去除Fe;(2)当AG50W-X8树脂高度为1 m L,硝酸作为洗脱酸时,Sr和REEs的分离效果较好;(3)Sr特效树脂淋洗酸中硝酸淋洗体积达到15 m L时可以有效分离Sr和Rb;(4)Ln特效树脂采用重力过柱方式时Sr和Nd分离效果较好,没有拖尾现象。本研究解决了Fe对分离Sr和Nd的干扰,K、Na、Ca、Mg、Fe、Rb、Sm去除率达到99%以上,完全满足Sr和Nd同位素分析的要求,为离子交换树脂法分离沉积物中Sr和Nd提供了较详细的前处理经验数据。     

离子交换树脂在地质样品Sr-Nd同位素测定中的应用

Rb-Sr和Sm-Nd同位素测年及同位素示踪方法在同位素地质年代学和同位素地球化学中有非常广泛的应用。目前,Rb-Sr和Sm-Nd同位素质谱测试方法通常需要对Rb、Sr和Sm、Nd进行分离纯化,因此,如何对地质样品中的Rb、Sr、Sm和Nd进行分离富集对测试结果准确与否起到至关重要的作用。离子交换分离法是SrNd同位素化学前处理阶段应用最广泛的分离方法,本文结合笔者近几年的研究工作,系统介绍离子交换树脂在Sr-Nd同位素测试中应用的发展过程和现状,重点介绍几类使用率较高的离子交换树脂(Dowex50W树脂、AG50W树脂、锶特效树脂、LN树脂、P507树脂等)的优缺点,以及各自的萃取反应机理,探索和讨论未来离子交换树脂在Sr-Nd同位素测试中应用的发展趋势。     

利用DCTA和HIBA快速有效分离Rb-Sr, Sm-Nd

Rb-Sr和Sm-Nd的有效分离是精确测定这些同位素的关键。传统的分离方法以盐酸为介质，虽然能够有效地分离这些元素，但是需要耗用大量的酸，并且无法将Sr和Ca、Mg等元素分离，对于Sm、Nd含量低的样品，回收率较低。后来有一些实验室建立了用混合的有机酸（如甲酸、乙酸、DCTA、EDTA等）来分离Sr的方法，大大减少了分离时间，减少了试剂用量，从而降低了过程空白并能够将Ca和Mg与Sr分离。本实验室在此基础上建立了一种新的Rb-Sr,Sm-Nd化学分离方法，以用于地质样品的同位素测试。该方法选用AG50W×8阳离子交换树脂，并先后采用不同的淋洗剂进行分离提纯。首先用常规方法使用盐酸作为淋洗剂将Rb-Sr和REE分开并与其他大部分元素分离，然后使用DCTA和嗜咙的混合溶液(D. P. E.）作为淋洗剂分离Rb和Sr，使用HIBA作为淋洗剂在很小体积(0.6 mI.）的阳离子交换树脂中分离Sm和Nd。使用这样的分离方法可以有效地将一些干扰离子（如Mg、Ca、Ba）和Sr分离，同时使用该分离方法可以提高分离效率，缩短分离时间，减少试剂用量，降低实验过程空白。用该方法分离国际玄武岩标样BCR-2后的Sr同位素测试结果（87Sr/86Sr= 0.705018±3)与Brian等测定的0.705024±5基本一致，Nd同位素测试结果（143 Nd/144Nd = 0.512616±9 )与本实验室以前使用HCI介质分离测定的0.512624±3基本一致，与其他研究者最近报道的BCR-1的0.512644±11和0.512650也基本一致。说明本次研究采用的新分离方法效果良好。     

树脂柱串联法分离地质样品中Sr-Nd-U

Sr、Nd、U等同位素体系被广泛应用于地球表生过程中年代测定及物源示踪等研究,高效地分离这些同位素体系,对于推广这些同位素方法的应用具有重要现实意义。若要同时分析地质样品中Sr、Nd、U三种元素的同位素,现有方法往往需要消解两份样品,一份用于Sr-Nd而另一份用于U的分离提纯。这种方法不但增加了样品用量,而且需要多次蒸干溶液转换介质,既延长了分离流程也增加了样品被污染的风险。为了提高样品利用率和分析效率,本文通过将树脂柱串联改进了分离流程,提出一种仅需消解一份样品,便可同时提取Sr、Nd、U三种元素的新方法。本方法中Sr的分离采用Sr特效树脂,包含Nd在内的稀土元素(REE)的分离采用AG50W-X8树脂,U的分离采用UTEVA特效树脂。实验中将三种树脂柱串联,采用3mol/L硝酸淋洗液淋洗,同步进行平衡树脂、上样、洗杂志,避免了蒸干操作。分离后的淋出液使用电感耦合等离子体质谱仪(ICP-MS)测试元素含量。结果表明：U的回收率接近99.9%,Sr的回收率超过90%,Nd的回收率超过80%;同时三种树脂柱串联的分离流程,主要基体元素(K、Ca、Na、Ba、Fe、Rb等)的去除率均超过9...     

Sr-Nd同位素初始比值和Nd模式年龄的误差估算

SrNd同位素参数广泛应用于岩石物质来源及其成因研究,但绝大多数研究者在应用这些参数时并未说明它们的误差大小,这种做法并不科学。作者首次利用误差传播定律推导出了有关参数的误差估算公式,这些参数包括Sr同位素的初始比值(87Sr/86Sr)t、Nd同位素的初始比值(143Nd/144Nd)t、εSr(t)、εNd(t)、Nd同位素模式年龄等。Rb、Sr含量的高低及其测定误差决定着(87Rb/86Sr)s的误差,Sm、Nd含量的高低及其测定误差决定着 (147Sm/144Nd)s的误差,(87Rb/86Sr)s的大小及其误差、(87Sr/86Sr)s误差、年龄值大小及其误差共同影响着(87Sr/86Sr)t的误差。同样,(147Sm/144Nd)s的大小及其误差、(143Nd/144Nd)s 的误差、年龄值大小及其误差共同影响着(143Nd/144Nd)t的误差。Nd同位素球粒陨石模式年龄TCHUR和单阶段亏损地幔模式年龄TDM的误差影响因素主要包括(147Sm/144Nd)s的大小、(143Nd/144Nd)s 的大小及这两个比值的误差,而Nd同位素两阶段亏损地幔模式年龄TDM2的误差除上述影响因素之外,还包括年龄值大小及其误差。通过对广西姑婆山4个花岗岩样品SrNd同位素参数及其误差的计算,作者对各个影响因素进行了详细分析,认为采用同位素稀释质谱法测试数据和高精度的年龄数据是获得理想示踪参数的保证,Rb、Sr、Sm、Nd含量沿用微量（包括稀土）元素测试结果的做法是不可取的,对高Rb样品更应该谨慎从事。建议研究者在使用SrNd同位素参数时能够估算这些参数的误差,并在文章中有所说明。     

微波消解-多接收电感耦合等离子体质谱高精度测定锶钕同位素组成

应用多接收器电感耦合等离子体质谱仪(MC-ICP-MS)测定地质样品中锶、钕同位素组成时,化学前处理流程冗长、复杂,且容易出现样品未完全溶解的现象。本文采用微波消解法消解样品,在保证消解效果的前提下有效地缩短了溶样时间,在此基础上研究了锶、钕化学分离和质谱测试流程,重点考察了树脂柱的回收率和记忆效应。结果表明:树脂经10次使用后的锶、钕流程空白均低于1.0 ng,但回收率明显下降,分别由原来的98%和90%降到20%和50%,若待测样品中锶、钕含量较低,所接收的锶、钕则达不到质谱仪测试范围,因此建议锶特效树脂使用次数不超过5次,AG50W-X8稀土柱和Ln树脂使用次数不超过10次。整套流程应用于国际地质标准样品(BCR-2、W-2a、BHVO-2、AGV-2)的锶、钕分离,MC-ICP-MS所得的87Sr/86Sr、143Nd/144Nd测定值与文献报道值一致,仪器的内精度2SE(n=50)和方法的外精度2SD(n=6)均优于0.0015%,表明该流程可以满足地质样品中锶、钕同位素高精度测定的要求。     

硅酸盐中钐、钕同位素稀释测定提取方法研究

硅酸盐中Sm、Nd提取方法研究是建立Sm—Nd年代测量方法的重要环节之一。 本文从天然硅酸盐岩石中提取总稀土,然后用阳离子树脂毛细管交换柱分离Sm和Nd。稀土提取和分离效果用放射性示踪、偶氮胂Ⅲ显色和质谱鉴定。 一、总稀土提取 分析流程确定如下:200—500mg样品、氢氟     

硅酸盐中钐、钕同位素稀释测定提取方法研究

硅酸盐中sm、Nd提取方法研究是建立Sm—Nd年代测量方法的重要环节之一。本文从天然硅酸盐岩石中提取总稀土,然后用阳离子树脂毛细管交换柱分离Sm、和Nd。稀土提取和分离效果用放射性示踪、偶氮胂Ⅲ显色和质谱鉴定。一、总稀±提取分析流程确定如下:200—500mg样品、氢氟     

新疆可可托海近3号脉花岗岩成岩时代及地球化学特征研究

可可托海伟晶岩田内花岗岩类发育。本文研究的花岗岩体位于3号伟晶岩脉矿坑的东部,岩性为似斑状黑云母二长花岗岩,野外特征与矿区北部的阿拉尔花岗岩非常相似。花岗岩中锆石LA-MC-ICP-MS U-Pb测年结果表明,19个测点206Pb/238U年龄集中于399.6～409.0Ma,加权平均年龄为405.4±1.4Ma(MSDW=0.98),属于早泥盆世,比阿拉尔花岗岩的侵入时期早得多,与3号伟晶岩脉没有成因上的联系,应是区域上岩浆活动最为强烈时期的产物。岩石具有富硅(SiO2=70.69%～73.81%)、富铝(Al2O3=14.00%～15.74%)、总体髙钾(K2O/Na2O≥1),贫Fe、Mg、Ti、P特点,铝饱和指数较高(A/CNK≥1.1),属于髙钾钙碱性强过铝质花岗岩;微量元素表现出Sr、Ti、Ba、P、Nb、Ta明显的负异常和Th、U、La、Zr、Hf的正异常特征。稀土配分型式显示LREE的相对弱富集,HREE比较平坦以及Eu中等负异常。样品中87Sr/86Sr(0.72259～0.72810)、143Nd/144Nd(0.51235～0.51237)接近于陆源沉积物,Sr初始值(0.70155～0.70341)较低,f Sm/Nd(-0.32～-0.26)、Sm/Nd(0.222～0.240)比值显示分异小、较均一的Sm/Nd同位素体系;εNd(t)值变化于-3.07～-2.16,模式年龄t2DM集中在1.35Ga左右,属于中元古代。综合研究岩石中主量、微量和稀土元素、同位素特征,同时对比区域上同期岩浆活动特征,认为本文研究的花岗岩可能是在活动大陆边缘环境下,强烈的俯冲-碰撞作用导致的地壳加厚引发了深熔作用,使阿尔泰微古陆边缘内部中元古代基底部分熔融,同时有幔源物质参与;随后岩浆经过结晶分异,最终上升侵位,反映了陆缘弧花岗岩的特点。     

湘西渣滓溪钨锑矿床白钨矿的Sm-Nd和Sr同位素地球化学

渣滓溪钨锑矿床位于湘西雪峰山弧形构造带的中段,是我国典型的脉状充填型锑矿床。本文对渣滓溪矿区不同产状产出的白钨矿进行了Sm-Nd和Sr同位素研究。研究表明,渣滓溪矿区白钨矿Sm/Nd变化范围相对较宽（0.36~0.63）,143Nd/144Nd为0.51211~0.51288;在147Sm/144Nd-143Nd/144Nd图解中,该矿白钨矿样品没有明显的线性分布趋势,无法厘定出该矿的准确成矿时间。该矿白钨矿的Nd(t)明显可分为两组（-10.2~-14.7和-3.79~+0.01）,其成矿流体中的Nd主要有两个来源,一部分可能来自晚元古代地层或下伏陆壳基底的碎屑岩,另一部分很可能与冷家溪群的基性、超基性岩有关。与Nd同位素不同,渣滓溪成矿流体中Sr同位素组成均一化程度较高,该矿白钨矿87Sr/86Sr为0.7304~0.7329;该矿这种明显富放射成因87Sr的成矿热液,排除了成矿流体来自海水和赋矿围岩作为唯一矿源层的可能性,下伏陆壳的结晶基底很可能是这种高放射成因Sr的提供者。沃溪和渣滓溪矿区白钨矿Sr-Nd同位素组成的对比研究表明,两矿区的成矿物质来源有所不同,前者应来自一种更古老、更成熟、更富放射成因Sr的下伏陆壳基底。     

从废旧钴钐磁性材料中分离钴和单一镨,钕,钐的条件研究

本文用ＣＬ－Ｐ５０７萃淋树脂作为萃取色层的固定朴要研究了经Ｄ２３５阴离子树脂交换分离钴后和稀土镨钕钐的分离，对洗脱剂，洗脱条件进行了探讨，并选择出最佳分离条件。     

Crustal contamination versus enriched mantle: 143Nd/144Nd and 87Sr/86Sr evidence from the Italian volcanics

¹⁴³Nd/¹⁴⁴Nd, ⁸⁷Sr/⁸⁶Sr, and REE analyses are presented on a wide variety of Pliocene-Recent volcanic rocks from central Italy. ¹⁴³Nd/¹⁴⁴Nd varies from 0.51214–0.51289 and ⁸⁷Sr/⁸⁶Sr from 0.7255-0.7036; while the rare earth elements are characterised by light RE enrichment and a significant negative Eu anomaly. These Italian volcanics are tentatively subdivided into three zones: (1) N. Tuscany where the magmas are believed to reflect crustal anatexis. (2) A central zone in which hybrid (crust/ mantle) rocks have been recognised. (3) A southern zone, south of Rome, where mantle-derived magmas are identified which have been largely unaffected by interaction with continental crust. At Roccamonfina, in zone 3, Rb/Sr and Sm/Nd pseudo isochrons are observed but since the calculated ages are 0.5 and 2.0 b.y. respectively it is argued that a simple isochron model is not applicable and that the data are most easily explained by a recent mixing event within the upper mantle. It is envisaged that this occurred during metasomatism of the upper mantle source region by a fluid that had high ⁸⁷Sr/⁸⁶Sr and low ¹⁴³Nd/¹⁴⁴Nd and was enriched in K, Rb, and LREE's but relatively depleted in Sr²⁺ and Eu²⁺.     

Isotopic disequilibrium in ultrahigh-pressure and retrograde metamorphism of eclogite and gneiss from the Chinese Continental Scientific Drilling in the Sulu orogen, China: evidence from mineral Nd–Sr–O isotopic composition

Diffusion rates of Sr and O in minerals are often comparable while Nd has a lower diffusion rate during thermal overprint(s); thus, the O isotope systems between metamorphic minerals can serve as an indicator to evaluate whether equilibrium of Rb–Sr and Sm–Nd systems has been preserved in the metamorphic minerals that experienced retrograde metamorphism. This study presents a combination of investigation on Sm–Nd, Rb–Sr, and O isotopic compositions of minerals separated from ultrahigh-pressure eclogite and gneiss that were collected from the main hole of the Chinese Continental Scientific Drilling project located in the Sulu orogen, eastern China. Oxygen isotopic compositions of minerals from gneiss and eclogite yield two temperature groups of 620–740 and 460–590°C, representing diffusion cessation of isotopic exchange during the eclogite-facies recrystallization and later amphibolite-facies retrograde overprint. Rb–Sr mineral regressions of two eclogite samples give consistent Triassic ages of 244 Ma, corresponding to eclogite-facies metamorphism, while the same minerals do not yield meaningful Sm–Nd isochron ages. This phenomenon likely suggests that Rb–Sr isotopic equilibrium was achieved during eclogite-facies metamorphism and preserved during late amphibolite-facies retrogression. In contrast, Sm–Nd isotopic equilibrium between the minerals of eclogite was not achieved under UHP metamorphic conditions. Regressions of epidote and biotite of one gneiss sample give a Triassic Sm–Nd age of 243 ± 34 Ma, corresponding to the time of the eclogite-facies metamorphism, and a Jurassic mineral Rb–Sr age of 187.5 ± 1.8 Ma. These results imply that fluids have played an important role to achievement of the Sm–Nd isotopic equilibrium during eclogite-facies metamorphism and re-equilibration of the Rb–Sr isotopic system during later retrograde overprint.     

Phlogopite in the generation of olivine-melilitites from Namaqualand, South Africa and implications for element fractionation processes in the upper mantle

Major and trace element and Sr, Nd and Pb isotope analyses are presented for thirteen olivine-melilitites from Namaqualand, South Africa. Major element variations are consistent with derivation from carbonated garnet-peridotite at depths of at least 100 km and trace element abundances indicate melt fractions of 4%. Ubiquitous negative K anomalies and low, buffered K₂O concentrations are interpreted to reflect the effect of residual phlogopite during melting. It is suggested that phlogopite stability and low melt potassium saturation concentrations are enhanced by high CO₂/(CO₂ + H₂O) conditions. Residual phlogopite can also account for low measured Rb/Sr, Ba/Sr and Th/U ratios in the melilitites. REE abundances are controlled by residual garnet and hence Sm/Nd ratios are low (0.13–0.18). U/Pb ratios vary from 0.05 to 5 and are a function of Pb concentration which is in turn controlled by residual Pb-rich phase (probably sulphide). Nd and Sr isotopes are comparable with OIB from St. Helena, although two samples extend to higher ⁸⁷Sr/⁸⁶Sr ratios. Present day Pb isotopes are much more variable and partly reflect radiogenic growth since emplacement as a result of the highly variable U/Pb ratios.

Many of the trace element characteristics of the melilitites are distinct from those of within-plate potassic magmas despite both being derived from phlogopite-bearing, enriched mantle source regions. This can be attributed to the depth at which source enrichment occurred and the subsequent control exerted by phlogopite and carbonate during melting. In contrast to melilitites, potassic magmas are derived from shallower depths under low CO₂/(CO₂ + H₂O) conditions and at higher temperatures at which phlogopite melts more readily.

The incompatible element ratios of the melilitites are also similar to those both observed in HIMU ocean island basalts (OIB) and inferred for HIMU OIB source regions from isotope variations (viz, low Sm/Nd, Rb/Sr, K/Nb, Th/U and high U/Pb and Ce/Pb). It is suggested that HIMU OIB's may be derived from sources that have been subject to enrichment by a melt generated in the presence of residual phlogopite.     

Precise Determination of Sm and Nd Concentrations and Nd Isotopic Compositions in Highly Depleted Ultramafic Reference Materials

In this study, a high‐precision method for the determination of Sm and Nd concentrations and Nd isotopic composition in highly depleted ultramafic rocks without a preconcentration step is presented. The samples were first digested using the conventional HF + HNO₃ + HClO₄ method, followed by the complete digestion of chromite in the samples using HClO₄ at 190–200 °C and then complete dissolution of fluoride formed during the HF decomposition step using H₃BO₃. These steps ensured the complete digestion of the ultramafic rocks. The rare earth elements (REEs) were separated from the sample matrix using conventional cation‐exchange chromatography; subsequently, Sm and Nd were separated using the LN columns. Neodymium isotopes were determined as NdO⁺, whereas Sm isotopes were measured as Sm⁺, both with very high sensitivity using single W filaments with TaF₅ as an ion emitter. Several highly depleted ultramafic rock reference materials including USGS DTS‐1, DTS‐2, DTS‐2b, PCC‐1 and GSJ JP‐1, which contain extremely low amounts of Sm and Nd (down to sub ng g^?1 level), were analysed, and high‐precision Sm and Nd concentration and Nd isotope data were obtained. This is the first report of the Sm‐Nd isotopic compositions of these ultramafic rock reference materials except for PCC‐1.