质谱计逐级蒸发-沉积测定单颗粒锆石年龄原理及可靠性的证明——兼论锆石同位素地质年代学的适用性

讨论了锆石由于铅丢失造成自晶体表层到晶体内部放射成因207Pb/206Pb的变化趋势，热离子质谱计直进行单颗锆石石蒸发-沉积测年时，锆石在灯丝上加热蒸发和在冷灯丝上沉积时物质的分布状况，锆石中的U-Pb体系是否为封闭体系的判别标志，并对锆石年代学的适用性进行了讨论。     

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。     

质谱计蒸发-沉积测定单颗粒锆石年龄原理及讨论

本文讨论了锆石由于铅丢失造成的自晶体表层到晶体内部放射成因(~(207)Pb/~(206)Pb)_R的变化趋势;用热离子质谱计直接进行单颗粒锆石蒸发-沉积测年时,锆石在热离子质谱计灯丝上加热蒸发和在冷灯丝上沉积时物质的分布状况;锆石中的U-Pb体系是否为封闭体系的差别标志;与单颗粒锆石测年有关问题的讨论。     

用热离子发射质谱计直接测定单颗粒锆石~(207)Pb/~(206)Pb年龄

用热离子发射质谱计、双带源分层蒸发锆石并将蒸发物附着到电离带上以测定~(207)Pb/~(205)Pb值年龄。对五个锆石样品的测定结果证明,用此方法获得的~(207)Pb/~(206)Pb值年龄与用常规锆石U-Pb一致线方法获得的年龄结果相吻合。这个方法不仅对放射成因铅轻微丢失的锆石适用,对严重丢失的也得到很好的结果。     

直接蒸发单颗粒锆石测定~(207)Pb/~(206)Pb年龄的方法

在双带源热离子发射质谱计上,用Kober,B.(1987)建立的方法直接蒸发锆石测定~(207)Pb/~(206)Pb表面年龄。4件已知年龄的锆石样品测定结果表明,用该方法测定的年龄值与常规锆石U-Pb一致曲线的上交点年龄一致。使用腈基丙烯酸酯粘合剂,使得装样简单、可靠,并可增加铅离子流强度。文中首次报道了湖北广水蔡家河小河岩体、黄土寨岩体中锆石的形成年龄。     

羌塘地块南部晚白垩世火山岩离子探针测年及其对红层时代的约束

羌塘地块南部广泛出露陆相红层,1:25万区域地质调查将大部分红层划归为中新统康托组,但缺乏可靠的年代学依据。野外观测发现火山岩与红层之间存在喷发不整合接触关系,室内从火山岩选出很多岩浆锆石;应用离子探针U-Pb同位素测年方法精确测定岩浆锆石年龄,能够为研究火山喷发期次和红层形成时代提供重要依据。对羌塘地块南部红层内部粗面安山岩夹层—比洛错火山岩和扎加藏布北侧红层上覆安山岩,挑选岩浆锆石进行高精度的离子探针U-Pb同位素测年,发现比洛错粗面安山岩锆石206Pb/238U同位素年龄为(83.3±1.3)Ma,扎加藏布北侧安山岩锆石206Pb/238U同位素年龄为(75.65±0.82)Ma。这些年龄良好地揭示了晚白垩世不同期次的火山喷发时代,同时为红层形成时代和红层盆地演化提供了重要的年代学约束。根据比洛错和扎加藏布北侧火山岩的锆石U-Pb同位素测年资料,将羌塘盆地南部红层时代归属上白垩统阿布山组,这对分析羌塘地块南部油气地质构造保存条件和构造地貌演化具有重要意义。     

多离子计数器动态多接收方式锆石Pb同位素比值高精度测定方法

采用装配多离子计数器系统的TRITON Plus热电离质谱仪（thermal ionization mass spectrometer,TIMS）,建立了多离子计数器动态多接收锆石Pb同位素（以205Pb为稀释剂）测定方法.相对多离子计数器静态多接收方法,该方法完全消除了不同离子计数器间增益差异对锆石Pb同位素测定的影响.相对传统的单个二次电子倍增器（secondary electron multiplier,SEM）五次跳峰的锆石Pb同位素测定方法,该方法两次跳峰即可测定全部Pb同位素比值,Pb同位素离子流接收效率提高2.5倍,同时,降低了离子流稳定性对Pb同位素分析结果的影响.为验证方法的可靠性,对加入205Pb稀释剂的NIST981 Pb标准和标准锆石清湖（Qinghu）进行了测定.对5×10-11 g 205Pb-NIST981 Pb混标,207Pb/206Pb测定精度达到0.079%（2RSD,n=20）;对清湖标准锆石,获得的年龄结果为159.51±0.11 Ma（2SE,n=7;MSWD=1.1）,与文献报道值在误差范围内一致.      

秦岭富水杂岩的变辉长岩中斜锆石与锆石U-Pb同位素年龄的差异及其地质意义

秦岭富水杂岩体的一些变辉长岩含有粒度较大，U、Pb含量较高的斜锆石和锆石，是U-Pb同位素测年的极好矿物。本文对秦岭富水杂岩的中粗粒角闪黑云辉长岩中的斜错石和错石分别进行了SHRIMP法和TIMS法U-Pb同位素年龄测定，获得斜锆石和锆石的U-Pb同位素年龄分别为501.4±1.2 Ma和480.0±3.4 Ma，二者相差约20 Ma；对该岩石中的斜锆石和锆石的关系及锆石的成因进行了初步研究，认为斜锆石的U-Pb同位素年龄应可解释为秦岭富水杂岩中基性岩石的形成时代，而锆石的成因比较复杂，对其U-Pb同位素年龄地质意义的合理解释需作进一步的研究。     

北京西山周口店关坻杂岩蒸发法锆石Pb-Pb年龄:太古宙成因和克拉通化事件证据

北京西山周口店地区房山岩体周围关坻杂岩的长英片麻岩和伟晶岩脉具有类似简单岩浆结晶成因锆石的蒸发法Pb-Pb年龄.伟晶岩中3个颗粒锆石的t(207Pb/206Pb)最大年龄分别为2.04,2.05,2.06 Ga,长英片麻岩中3个颗粒锆石的t(207Pb/206Pb)最大年龄分别为2.37,2.41,2.45 Ga.据此分析,关坻杂岩时代应为太古宙,经历了2.5 Ga的华北克拉通化的构造热事件,且可能保存了华北东部地块与西部地块于古元古代晚期(2.06～1.85 Ga)最终拼合为华北克拉通的年代学记录,最终拼合时间与Columbia超大陆连结过程同步.     

榍石LA-ICP-MS U-Pb定年技术研究

榍石具有较高的U含量和封闭温度,是一种重要的适用于U-Pb定年的副矿物。然而,基体效应与普通Pb校正成为制约榍石LA-ICP-MS U-Pb定年发展的主要因素。本文以~(206)Pb/~(238)U为例,采用基体归一化因子(F_(AVG))评估了锆石与榍石U-Pb定年标准的基体效应,结果显示榍石F_(AVG)几乎都大于1.20,而锆石F_(AVG)明显都小于1.20,表明锆石与榍石U-Pb定年标准存在显著的基体效应。以BLR-1榍石标准为外部校准标样,OLT1榍石获得的谐和年龄1014.9±4.8Ma(95%置信水平,n=23,MSWD=0.32)与SHRIMP谐和年龄1017.1±3.6Ma及ID-TIMS谐和年龄1014.6±1.3 Ma在误差范围内一致,同时获得~(206)Pb/~(238)U、~(207) Pb/~(235) U、~(207) Pb/~(206) Pb加权平均年龄在误差范围内与其谐和年龄一致;而以91500锆石为外部校准标样,OLT1榍石获得的~(206)Pb/~(238)U加权平均年龄为891.3±9.5 Ma(n=23,MSWD=5.3),与ID-TIMS测得的谐和年龄相比偏低约12%。经~(207)Pb法校正后,TCB榍石获得的~(206)Pb/~(238) U加权平均年龄1015.6±6.2 Ma(n=16,MSWD=0.84)与ID-TIMS谐和年龄1018.1±1.7Ma在误差范围内一致。本研究表明,采用基体匹配的榍石标准为外部标样,利用LA-ICP-MS对榍石进行U-Pb定年也能获得与ID-TIMS相一致的年龄,精度(2RSE)小于2%。     

高精度质谱计在同位素地球化学的应用前景

微量地质样品的高精度同位素比值测试已经成为地质和环境科学等领域极其重要的研究手段.新型固体热电离质谱计以其高精度和高灵敏度, 将在同位素年代学和地球化学领域有广阔的应用前景.报道采用IsoProbeT质谱计测量标准物质溶液的结果.测量锶标准物质NBS987和钕标准物质Ames分别获得平均87Sr/86Sr比值0.710 241 8±0.000 005 1和平均143Nd/144Nd比值0.512 148 4±0.000 002 9, 内部精度可达0.000 3%.微量锶标准物质(0.3~1 ng) 的同位素比值测量内部精度可以优于0.003%.结合低本底化学流程, 实现了微量地质样品的高精度同位素比值测试.这一结合将有效地促进单颗粒矿物年代学和同位素示踪在岩浆岩、变质岩、矿床、构造岩研究的应用.      

铼-锇同位素测年法研究综述

Re-Os同位素测年的最合适的对象为辉钼矿,定年是基于放射性的187Re通过β衰变成为187Os而引起锇同位素异常来计算地质年代的。在目前的测试研究中,较常用的方案为Carius管溶样法-蒸馏分离Os-萃取分离Re-TJA PQ ExCell ICPMS测定同位素比值。在我国有许多成功用Re-Os同位素测定钼矿床成矿年龄的范例,对认识矿床特征及成因、总结区域的成矿演化规律、解决相关地质问题具有重要的理论意义,而且对于指导矿床的预测和勘查具有很高科学价值。     

Lead Isotopic Composition in Biogenic Certified Reference Materials Determined by Different ICP‐based Mass Spectrometric Techniques

This work presents data for the radiogenic Pb isotopic ratios (²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁶Pb) in nine biogenic certified reference materials (NIST SRM 1515, 1566b, 1570a, 1573a, 1575a; BCR 100, BCR 101, BCR 670 and IAEA 359), which are suitable for analytical quality control in environmental research. The results were obtained using three different types of ICP‐based mass spectrometer (quadrupole‐based/magnetic sector field single‐collector ICP‐MS instruments and a multi‐collector ICP‐MS) and applying different mass bias correction procedures (calibrator‐sample bracketing and external Tl normalisation) with and without Pb separation from the matrix using ion exchange chromatography. In the majority of the samples, the measurements from all three of the ICP‐MS instruments were in agreement within ± 0.1%, despite the lower analytical precision of the single‐collector ICP‐MS instruments. We demonstrate that the presence of the sample matrix did not significantly influence the Pb isotopic ratios measured by magnetic sector field ICP‐MS, whereas the use of the two different mass bias corrections resulted in a systematic difference of 0.09% for the ²⁰⁸Pb/²⁰⁶Pb ratio.     

Multi-collector ICP-MS Analysis of Pb Isotope Ratios in Rocks: Data, Procedure and Caution

The authors measured Pb isotope compositions of seven USGS rock reference standards, i.e. AGV-1, AGV-2, BHVO-1, BHVO-2, BCR-2, BER-1/1 and W-2, together with NBS 981 using a micromass isoprobe multi-collector inductively-coupled plasma mass spectrometer (MC-ICP-MS) at the University of Queensland. 203Tl-205Tl isotopes were used as an internal standard to correct for mass-dependant isotopic fractionation. The results for both NBS 981 and USGS rock standards AGV-1 and BHVO-1 are comparable to or better than double- and triple-spike TIMS (thermal ionization mass spectrometry) data in precision. The data for BHVO-2 and, to a lesser extent, AGV-2 and BCR-2 are reproducibly higher for 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb than double-spike TIMS data in the literature. The authors also obtained the Pb isotope data for BIR-1/1 and W-2, which may be used as reference values in future studies. It is found that linear correction for Pb isotopic fractionation is adequate with the results identical to those corre     

The typing of Au and base-metal occurrences by plasma/mass spectrometry: initial results

This paper discusses the application of the newly developed ELAN 250 I.C.P./mass spectrometer to exploration geochemistry. This instrument combines an inductively coupled plasma with a quadrupole mass spectrometer. The combination of these two existing technologies makes it possible for the first time to perform stable-isotope and elemental analysis rapidly and concurrently.Particular attention is paid to the use of lead isotopes to type Au and base-metal occurrences. Data are presented on galena samples obtained from the Geological Survey of Canada and the Royal Ontario Museum. Consideration is also given to the potential usefulness of Pb isotopes and trace-element data to type mineral occurrences and to identify new ones.     

Concurrent Determination of U‐Pb Age and REE Mass Fractions of Zircon by High Mass Resolution SIMS

A combined geochronological and geochemical investigation for the same domain of zircon provides valuable information on timing and genesis, particularly in the case of multi‐growth metamorphic zircon. A high spatial resolution concurrent analytical method for zircon U‐Pb age and rare earth element content was successfully achieved in this study, using a multi‐collector secondary ion mass spectrometer (SIMS) at a ~ 8 μm diameter scale. Special instrument parameters were employed, including a high mass resolution of approximately 15000 applied to replace the previous energy filter method, and a dynamic multi‐collector mode used to reduce the measurement time to 18 min per analysis. Six zircon reference materials yielded precise and accurate ²⁰⁶Pb/²³⁸U ages, which are comparable to those obtained by the ordinary mono‐collector method, but with 2–3 times higher spatial resolution. All zircon grains measured in this study showed enriched heavy‐REE (HREE) contents consistent with previously reported values determined by LA and solution ICP‐MS methods. The light‐REE (LREE) mass fractions measured using both SIMS and LA‐ICP‐MS methods in this study, although with quite different volume, show consistent results within uncertainties.