实时在线氧校正205Pb-233U-236U稀释剂单颗粒锆石ID-TIMS U-Pb高精度年龄测定方法

单颗粒锆石化学溶蚀同位素稀释热电离质谱（CA-ID-TIMS）U-Pb法是目前精度最高的同位素地质年代学方法,由于存在²³⁶U¹⁶O¹⁸O⁺和²³⁶U¹⁸O¹⁶O⁺对²³⁸U¹⁶O₂⁺的干扰问题,目前国际上通用的U-Pb定年稀释剂是²⁰⁵Pb-²³³U-²³⁵U而不采用²⁰⁵Pb-²³³U-²³⁶U。针对该问题,本文详细探讨了热电离质谱法（TIMS）测定U同位素过程中,²³⁶U¹⁶O¹⁸O⁺和²³⁶U¹⁸O¹⁶O⁺对²³⁸U¹⁶O₂⁺的干扰对U-Pb年龄测定结果的影响程度,指出ID-TIMS U-Pb分析过程中控制²³³U-²³⁶U稀释剂的加入量,保证样品-稀释剂²³⁸U/²³⁶U混合比>0.5,²³⁶U¹⁶O¹⁸O⁺和²³⁶U¹⁸O¹⁶O⁺对²³⁸U¹⁶O₂⁺的干扰对定年结果的影响并不显著。此外,详细探讨了热电离质谱（TIMS）U、Pb同位素测定过程中二次电子倍增器（SEM）死时间的准确设定对高精度CA-ID-TIMS U-Pb定年的重要性。在此基础上,建立了在线氧校正²⁰⁵Pb-²³³U-²³⁶U稀释剂CA-ID-TIMS单颗粒锆石U-Pb年龄高精度测定方法。最后,采用所建立方法对标准锆石ZS进行了测定,获得的²⁰⁶Pb/²³⁸U年龄加权平均值为559.91±0.25Ma（2σ,仅分析误差）,与文献报道值在误差范围内一致。由于采用了²³³U-²³⁶U双稀释剂内部校正U同位素分馏效应,该标样年龄测定精度达到0.05%,优于其²⁰⁵Pb-²³⁵U单稀释剂法年龄测定结果的精度。

     

W同位素高精度负离子热电离质谱(NTIMS)测定方法

W同位素的高精度测定对于研究地球、月球和太阳系其他行星的起源和早期演化、核幔相互作用等领域具有重要意义。本文开展了负离子热电离质谱(NTIMS)高精度W同位素测定方法研究(测定WO_3~-)。采用多接收动态跳扫方式对W同位素进行测定,实时在线测定~(18)O/~(16)O,并利用实验室实时在线氧校正NTIMS Os同位素分析时获得的~(17)O/~(16)O-~(18)O/~(16)O同位素分馏趋势线计算~(17)O/~(16)O,进行氧校正计算。对多接收动态和多接收静态数据处理方式及不同的同位素分馏校正方法进行了详细对比研究。在上述工作基础上,最终建立了以~(186)W/~(184)W=0.92767进行标准化,采用多接收动态方法进行数据处理的在线氧校正W同位素NTIMS测定方法。~(182)W/~(184)W测定结果的外部精度(2RSD)可达3×10~(-6)～6×10~(-6),基本满足地球、月球和行星早期演化等W同位素研究工作的需要。     

粤北黄沙桥铀矿床花岗岩锆石U- Pb年龄、Hf同位素特征及岩石地球化学和地质意义

黄沙桥铀矿床位于诸广山岩体南部,处于城口矿集区西侧。本文针对黄沙桥铀矿床赋矿花岗岩开展了LA- ICP- MS锆石U- Pb定年、Hf同位素及地球化学组成测定,结果显示：中粗粒斑状黑云母花岗岩和中细粒斑状黑云母花岗岩年龄分别为152. 8±1. 1Ma和154. 0±1. 4Ma。元素分析结果表明：两类黑云母花岗岩均具富硅、富碱、高K2O/Na2O比值和低CaO/Na2O比值等特征,二者皆具有较一致的稀土、微量分配曲线特征;均相对富集大离子亲石元素Rb以及高场强元素Th、U、Hf,明显亏损Ba、Nb、Ti等元素;两者均具明显轻重稀土分馏特征,稀土配分曲线呈“右倾型”以及明显的Eu负异常;两类黑云母花岗岩均具有较低εHf（t）值（-15. 24～-8. 96和-13. 60～-9. 65）,二者古元古代的模式年龄为2171～1778Ma和2063～1821Ma。两类黑云母花岗岩均属于强过铝质S型花岗岩,主要由富黏土的泥质沉积岩部分熔融而来。二者均为燕山期岩浆活动的产物,是在太平洋板块俯冲导致的伸展构造背景下,由古元古代为主的地壳源区低程度部分熔融的方式形成。     

羌塘中部白措花岗岩岩石地球化学特征、锆石U Pb年龄和Hf同位素组成及其构造意义

本文对羌塘中部白措花岗岩的研究表明,岩体是由花岗闪长岩和二长花岗岩同时侵位的复合岩基,锆石U Pb年龄分别为213. 8±1. 3 Ma、210. 0±1. 1 Ma和208. 1±1. 4 Ma。白措花岗岩为硅过饱和的准铝质—弱过铝质岩石,Eu负异常明显,富集大离子亲石元素,亏损高场强元素,显示典型的壳源特征。εHft)为负值,主要集中于-10～-15,对应的Hf同位素二阶段模式年龄峰值为1. 78 Ga,显示源区为古元古代古老地壳;同时,花岗岩中含有大量闪长质暗色包体,表明有壳幔岩浆混合作用,推测为同时期玄武质岩浆的底侵作用,在地壳深部诱发富硅质基底岩石重熔,快速喷发形成玄武岩—流纹岩双峰式组合,而花岗岩则是由玄武质岩浆在地壳充分熔融后,岩浆沿羌塘中部已有的构造破碎带侵入形成,并且在熔融过程中有镁铁质岩浆注入少量结晶的长英质岩浆中形成暗色包体。因此,花岗岩与双峰式火山岩是同一裂陷动力机制的产物。花岗岩的侵入预示了晚三叠世羌塘盆地构造岩浆活动的结束,之上开始了羌塘侏罗纪海相盆地的沉积。     

微量地质样品铼锇含量及其同位素组成的高精度测定方法

报道了采用新型IsoProbe—T热电离质谱计测定Os含量及其同位素组成和Neptune多接收器等离子体质谱仪（MC—ICPMS）测定Re含量的分析方法。样品化学处理采用Carius管溶样、小型蒸馏法分离和微蒸馏法纯化提取Os以及阴离子树脂交换分离Re的方法。采用IsoProbe—T质谱计测定Os同位素组成具有灵敏度高和精度高的特点。对溶液标样，采用多法拉第接收器系统测定Os总量低至0．2ng的样品时，平均^192Os^16O3-离子流强度可达100mV以上并可维持约20min，其^187Os／^188Os同位素比值的测定精度可优于0．1％（1RSD）。采用所建立的化学分离流程和高精度质谱测量方法，测定了铂族元素橄榄岩标样WPR-1中Re、Os含量和Os同位素组成，测定结果与文献报道值在误差范围内吻合。     

藏南扎西康矿区流纹岩的岩石地球化学、 锆石U Pb测年和Hf同位素组成

本文对藏南扎西康铅锌锑银矿区流纹岩进行详细的岩石地球化学、锆石U Pb年代学和Hf同位素组成研究。详细的地球化学特征显示,扎西康流纹岩具有富硅（SiO2=73.37%~77.08%）、贫碱（Na2O+K2O=3.48%~3.56%）,贫Mg（MgO=0.36%~0.49%）,贫Ca（CaO=0.50%~0.66%）,强过铝质（A/CNK=2.16~2.62）, 富集Rb、Th、U、Pb等大离子亲石元素及Hf、Nd等高场强元素,并明显亏损Sr、Ti等元素。稀土总量较高（∑REE=295.71×10-6~343.82×10-6）,轻稀土富集,且轻重稀土分异明显（LREE/HREE=10.00~12.62）,弱负Eu异常（δEu=0.57~0.88）,无明显Ce异常。采用LA MC ICP MS对流纹岩锆石U Pb年龄进行测定,岩体成岩年龄为135.33±0.62Ma。锆石εHf(t)值较低,主要集中在-9.5~-24.2,显示其物源为壳源。扎西康矿区出露的流纹岩形成于早白垩世,可能是Comei—Bunury大火成岩省的一部分。     

静态测量方式的单颗粒锆石蒸发铅同位素定年方法

报道的单颗粒锆石蒸发定年方法是利用新型固体质谱计的多离子接收器配置实现的。改进的锆石蒸发^207Pb／^206Pb定年流程通过静态测量方式，在锆石蒸发过程中直接测定铅同位素比值，获得^207Pb／^206Pb年龄。应用该方法测定了元古代永宁组沉积岩的碎屑锆石，获得6颗锆石的^207Pb／^206Pb年龄值为1965—2590Ma。与传统的蒸发法流程相比，静态测量方法省时简捷，同时可以直观地观测到锆石内部的铅同位素组成变化。这些变化反映锆石结晶历史、后期事件叠加以及锆石成因等地质信息。     

内蒙古别鲁乌图铜多金属矿床锆石U-Pb年龄和S、Pb同位素特征及其地质意义

为了明确内蒙古别鲁乌图铜多金属矿床的成矿年龄与矿床成因,对该矿床中与成矿关系密切的流纹岩进行了锆石U-Pb年龄以及主要金属硫化物的S、Pb同位素测试。其中流纹岩的锆石²⁰⁶Pb/²³⁸U加权平均年龄为(271.7±1.6) Ma(MSWD=1.02),显示成矿作用发生于二叠纪。金属硫化物的S同位素分析结果显示δ³⁴S_V-CDT值分布在-0.6‰～1.0‰之间,平均为0.49‰,变化范围较窄,显示S的来源单一;Pb同位素组成比较集中,²⁰⁶Pb/²⁰⁴Pb为18.207～18.674,²⁰⁷Pb/²⁰⁴Pb为15.620～15.699,²⁰⁸Pb/²⁰⁴Pb为38.144～38.790,具有壳幔混源的特征。S、Pb同位素特征均指示成矿物质主要来源于岩浆热液。结合区域地质、矿床地质、空间分带等特征以及S、Pb同位素组成可知,别鲁乌图铜多金属矿床为VHMS型矿床,形成于二叠纪...     

冀北东猴顶A型花岗岩成因：岩石地球化学、锆石 U Pb年代学及Sr—Nd—Pb—Hf同位素制约

本文对河北丰宁地区前人所定的东猴顶正长斑岩和石英正长斑岩进行了岩石学、锆石U Pb年代学、元素地球化学以及Sr—Nd—Pb—Hf同位素分析。LA MC ICP MS锆石U Pb测年和岩石学显示东猴顶岩体为早白垩世（~129Ma）钾长花岗斑岩,而非前人认为的侏罗纪—白垩纪正长斑岩和石英正长斑岩。东猴顶岩体具有高硅（6907%~7300%）、富碱（Na2O+K2O：900%~1056%）和FeO（全铁）/MgO比值大的特征,属高钾钙碱性系列;岩石富集轻稀土,负铕异常明显（δEu：025~041）,相对富集K、Rb等大离子亲石元素和Zr、Hf、Th、U、Y等高场强元素,亏损Ca、Ba、Sr、P、Ti、Cr、Ni、Co等元素,Ga/Al比值高,具A型花岗岩特征,可能形成于伸展环境构造体制。岩体n（87Sr)/n(86Sr）i=070815~071197,εNd（t）值为-132~-168,对应的二阶段模式年龄（T2DM）为20~23Ga;全岩n(206Pb)/n(204Pb)i=16745~16765,n(207Pb)/n(204Pb)i=15372~15394,n(208Pb)/n(204Pb)i=37706~37794;锆石Hf同位素组成为εHf（t）值=-207 ~ -92,二阶段模式年龄（TDMC）为19~26 Ga。同位素特征表明岩体源岩可能主要来自壳源物质。考虑到华北克拉通东部地壳生长的主要时期为新太古代,因此,东猴顶岩体的岩浆来源于太古代地壳物质和部分亏损地幔物质的混合源区,是华北克拉通北缘中生代岩石圈强烈减薄、地壳伸展作用的结果。     

延边地区明月沟组安山岩的形成时代与岩石成因:锆石U-Pb年代学、地球化学及Hf同位素证据

为确定延边地区明月沟组火山岩的形成时代、成因及构造背景,对明月沟组中的安山岩开展了岩石学、SIMS锆石U-Pb年代学、岩石地球化学及锆石Hf同位素特征研究。结果表明:明月沟组安山岩中的锆石为岩浆成因锆石。代表安山岩形成时代的两件样品中锆石的~(206)Pb/~(238)U加权平均年龄分别为(111±4)Ma(n=6,MSWD=3.2)和(113±3)Ma(n=6,MSWD=1.4),属早白垩世晚期。岩石地球化学特征上,明月沟组安山岩相对富钠,属高钾钙碱性系列,具有明显富集大离子亲石元素(K、Ba)和轻稀土元素,亏损重稀土元素和Ta、Nb等高场强元素的特征,结合其Hf同位素组成特征,暗示明月沟组安山岩的源岩应为受俯冲板片流体成份参与的亏损地幔。结合区域构造演化背景,明月沟组安山岩的形成应与早白垩世古太平洋板块向欧亚大陆板块的斜向俯冲作用相关。     

MC-ICP-MS高精度测定Pb同位素比值

多接收器等离子体质谱是近年发展起来的高精度同位素分析手段之一，通过用等离子体质谱测量Pb国际标准物质NBS981和NBS982,显示出多接收器等离子体质谱分析Pb同位素的优势。利用205Tl/203Tl进行作为内标，可以实现Pb同位素的质量分馏校正，极大地提高了Pb同位素分析的重现性。相比较热电离质谱，该方法精度更高，样品的用量更少，测试时间更短，多接收器等离子体质谱测定Pb同位素技术有良好的应用前景。     

高精度测量岩石样品Ce同位素组成的TIMS方法

介绍了对岩石样品的Ce同位素组成进行高精度测量的TIMS方法.采用α-羟基异丁酸(α-HIBA) 离子交换法分离和纯化岩石样品中的La、Ce元素, Ce同位素组成和La、Ce含量测定在Triton热电离质谱仪上完成.质谱标样JMC304的138Ce/142Ce比值统计值为0.0225762±0.0000015, 与大部分文献值一致.应用该方法对USGS玄武岩标样BCR-2和峨眉山玄武岩EQB的138Ce/142Ce比值和La、Ce含量进行了分析, 其结果分别为: 0.0225572±0.0000010、25.2±0.3μg/g、55.8±0.9μg/g和0.0225755±0.0000003、54.2±0.4μg/g、117.4±1.3μg/g.BCR-2的La、Ce含量测定结果与其证书值在误差范围内一致, 其分析精度为0.001%~0.005%.所有样品的140Ce/142Ce比值测定结果统计值为7.9439±0.0002, 介于文献最低值7.941与最高值7.947之间, 可能代表了该比值的最佳估计值.      

Chemical Separation of Tungsten and Other Trace Elements for TIMS Isotope Ratio Measurements Using Organic Acids

One requirement for isotope ratio measurement results with small measurement uncertainties is that the element of interest is effectively separated from the sample matrix. Efficient chemical separation of W from matrix components, especially Ti, can be challenging, particularly for large test portion masses (> 1 g). We present a new W separation procedure that takes advantage of the distinct complexation behaviour of Ti and W with citrate ligand in a moderately low pH, oxidising solution. This preparation procedure can reduce the Ti/W ratio of large (4–10 g) basaltic (i.e., high‐matrix) test portions by a factor of 10⁵, relative to their original compositions, in a two‐step separation procedure. The procedure additionally provides a separate, well‐purified Mo fraction. We show that optimal separation requires precise selection of reagent concentrations and sample load. The procedure was employed to determine the μ¹⁸²W composition of BHVO‐2 as ?6.7 ± 4.2 (2 standard deviation, 2s). The principles derived from this method may prove useful for chemical separation of other elements used for geochemical and cosmochemical applications given an appropriate selection of organic acid. Future successful applications of this method may reveal that the use of organic acids as procedural reagents is a currently under‐utilised tool for efficient chemical separation protocols.     

Evaluation of the Residual Mass Fractionation in High-Precision Cr Isotopic Analysis with TIMS

The Cr isotope ratios of terrestrial and extra-terrestrial materials are emerging as one of the most important tracers in geosciences. Previous studies on Cr isotopic measurements using TIMS have found that there is residual Cr isotopic fractionation between the mass-fractionation-corrected ⁵³Cr/⁵²Cr and ⁵⁴Cr/⁵²Cr ratios, which may cause an offset of obtained ratios from the reference values. The residual fractionation was thought to be caused by the evaporation of Cr-oxide species during thermal ionisation, but the mechanism by which this residual fractionation could be reduced remained unclear. Here we revisit the issue of residual fractionation and propose that this problem can be alleviated by utilising W filaments instead of conventionally used Re filaments for Cr ionisation. Using W filaments, the formation of CrO⁺ was suppressed during heating as the filament temperature was ~ 100 °C lower than when Re filaments were used. In repeated measurement of a carbonaceous chondrite, the intermediate precisions of ⁵³Cr/⁵²Cr and ⁵⁴Cr/⁵²Cr ratios in the W filament runs were two to three times better than those of the Re filament runs. Therefore, the new finding of this study will be of key importance for future studies of Cr isotopes for terrestrial and extra-terrestrial materials.     

热电离质谱铀系法测定碳酸盐标样

用高精度热电离质谱（ＴＩＭＳ）铀系法测定碳酸盐标样的年龄,测定结果与α谱仪铀系法进行比较,铀含量和年龄值均吻合。方法对Ｕ的回收率可达９５％,Ｔｈ为９２％。ＴＩＭＳ铀系法具有样品用量少、测试时间短、精度高的优点。     

High Precision Determination of 48Ca/42Ca Ratio by TIMS for Ca Isotope Fractionation Studies

For studies of mass-dependent fractionation of calcium isotopes in natural materials, the ⁴⁸Ca/⁴²Ca ratio is a superior choice to the conventionally measured ⁴⁴Ca/⁴⁰Ca ratio for two important reasons. These are (1) mass-dependent fractionation can be determined free from the effects of inherited or ingrown radiogenic ⁴⁰Ca and (2) this ratio increases the spread of measured isotopic masses by 50%, resulting in statistically better resolution of fractionation, assuming similar precision. A third, though strictly technical, advantage is the inherent ability of a mass spectrometer to measure ratios close to unity (⁴⁸Ca/⁴²Ca) more precisely than very small or large ratios (⁴⁴Ca/⁴⁰Ca). However, because of the very low natural abundance of both ⁴⁸Ca and ⁴²Ca, their ratio has been very difficult to measure, the only attempt so far being on a high mass resolution MC-ICP-MS with a precision of 0.33%. We report here determination of the ⁴⁸Ca/⁴²Ca ratio by the more commonly available and user-friendly multi-collector TIMS using a ⁴³Ca-⁴⁶Ca double-spike, with a significantly better precision of 0.18% (2s). The ⁴⁸Ca/⁴⁰Ca or ⁴⁴Ca/⁴⁰Ca ratio can also be measured in the same mass spectrometer run to provide complementary information on any radiogenic component.     

High-Precision Direct Determination of the ~(87)Sr/~(86)Sr Isotope Ratio of Bottled Sr-Rich Natural Mineral Drinking Water Using MC-ICP-MS

Strontium has four naturally occurring stable isotopes,84Sr,86Sr,87Sr,and 88Sr,with abundances of 0.56,9.87,approximately 7.04,and 82.53 atomic %,respectively.The 87Sr/86Sr isotope ratio is variable due to the addition of radiogenic 87Sr produced by the beta decay of 87Rb with a half-life of 4.88 ± 0.05 Ga.Thus,     

A Preliminary Appraisal of Seven Natural Zircon Reference Materials for In Situ Hf Isotope Determination

There is a growing need for new zircon reference materials for in situ Hf-isotope analysis by laser ablation-multicollector inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS). In this contribution we document the results of a preliminary investigation of seven natural zircons, conducted in order to test their suitability in this regard. Solution MC-ICP-MS data on separated Lu and Hf fractions provided reference compositional data while the results of ca. 750 in situ LA-MC-ICP-MS analyses allowed assessment of potential micrometre-scale heterogeneity. On the basis of these analyses and additional relevant considerations such as availability, size and (Lu)Yb/Hf ratio, we suggest that, of the currently available zircons, Temora-2 and Mud Tank are most likely to provide robust reference materials for Hf isotope determinations both at the present time and into the future. The former has the advantage of also being well-characterised for U-Th-Pb systematics and suitable for in situ age determination, while the latter is the most readily available and is of very large grain size. Additional materials such as BR266, and 91500, although limited in supply, show more consistent Lu/Hf ratios and are thus of use in monitoring elemental fractionation during ICP-MS analysis.     

直接熔融热电离质谱法测定硼硅玻璃中硼同位素比值

硼硅玻璃是目前压水堆应用最多的可燃毒物材料,产品中硼同位素组成的准确测定对燃耗预估及产品质量判定具有重要意义。文章基于直接熔融热电离质谱法,首先探讨了硅元素对硼酸中硼同位素测量结果的影响,结果表明:Si/B质量比小于9时,硅对NIST 951a硼酸标准物质测量结果无显著干扰,采用直接熔融热电离质谱法测定核电用硼硅玻璃中硼同位素比值具有可行性;随后,详细分析了Na/B摩尔比、甘露醇和石墨加入量3个参数对测试结果的影响,得到的最佳参数为Na/B摩尔比9、加入甘露醇及3μL石墨发射剂;最后,采用优化测试参数,对实际硼硅玻璃样品进行了测试,并以NIST 951a硼酸标准物质为外标对测量结果进行分馏校正,结果发现分馏校正后样品的不确定度来源主要是标准物质。研究成果可满足硼硅玻璃的燃耗预估及产品质量的快速判定需要。