铅同位素研究新进展—“双稀释剂”测定方法和“AGSO—CSIRO”模式年龄

适当的仪器质量分馏校正是提高同位素分析数据精度的关键。重新“复活”了的铅同位素“双稀释剂”测定方法可实现严格的仪器质量分别校正,以区域锆石Ｕ－Ｐｂ年龄为控制点的“ＡＧＳＯ－ＣＳＩＲＯ”铅同位素模式年龄方法可获得精度很高的定年结果,铅同位素研究的应用必将因此而得到更大的发展。     

多接收器等离子体质谱精确测定铼含量及其同位素丰度

利用多接收器等离子体质谱建立了快速精确测定铼含量及其同位素丰度的方法。溶液中加入铱元素进行铼同位素的质量分馏校正,在常规的溶液雾化进样条件下,采用同位素稀释法可准确测定纳克级的铼含量。铼标样A的自然同位素丰度的测量结果为185Re(37.437±0.008)%、187Re(62.563±0.008)%(2σ,n=5);铼稀释剂的同位素丰度测量结果为185Re(5.576±0.018)%、187Re(94.424±0.018)%(2σ,n=7);与未进行分馏校正的同位素组成的测量结果相比,精度和准确度均有提高。利用同位素稀释法测得铼标样A的浓度为(516.48±0.35)ng/g(2σ,n=5);测量精度和准确度均优于0.10%;利用反同位素稀释法对铼稀释剂B进行了详细的测量,平均测量结果为(62.74±0.26)ng/g(2σ,n=15),在分析误差范围内与其标定值完全一致;与未进行分馏校正的浓度测量结果相比,铼同位素丰度及铼含量的测量准确度均明显提高。     

激光探针等离子体质谱法（LAM—ICPMS）用于年龄锆石U—Pb定年

利用激光探针等离子体普（ＬＡＭ－ＩＣＰＭＳ）技术对中生代锆石进行了详细的２０６Ｐｂ／＾２３８定年研究。采用线扫描（Ｌｉｎｅ ｓｃａｎ）进样法减小了传统的剥深（Ｄｅｐｔｈ ｐｒｏｆｉｌｅ）进样法所引起的激光熔蚀分异效应;优化仪器参数可三ＩＣＰ－ＭＳ对Ｐｂ和Ｕ的质量歧视效应。测得了精确的＾２０６Ｐｂ／＾２３８Ｕ比值及年龄。研究结果表明,均匀颗粒锆石的＾２０６Ｐｂ／＾２３８Ｕ比值测量精度为２％～１０％,     

山西五台山地区早前寒武纪年代构造格架

根据作者等近１０多年来在五台山地区的早前寒武纪同位素的地质研究，采用单颗粒锆石Ｕ－Ｐｂ，单颗粒锆石发Ｐｂ，常规锆石Ｕ－Ｐｂ，全岩Ｐｂ－Ｐｂ，全岩Ｒｂ－Ｓｒ，全岩Ｓｍ－Ｎｄ和角闪石＾４０Ａｒ－＾３９Ａｒ等多种同位素测定方法获得的２７个数据，并以单粒颗锆石Ｕ－Ｐｂ法的９个年龄作为定年的基准，通过与其它同位素测年结果相互印证的综合研究，遂对五台山地区早前寒武纪重大地质事件年代给予了更进一步的限定，同时勾     

一件可能的Hf同位素测定标准锆石

陕西省西乡县汉南杂岩望江山岩体辉长岩中含有丰富的锆石——从600kg辉长岩样品中分选出结晶良好、内部结构简单、成因和年龄单一、Hf同位素比值均一的锆石7g,锆石粒度多为0.2-0.3mm。分别在三个不同实验室利用三种方法对该锆石样品进行了U-Pb同位素年龄测定,获得了在误差范围内完全一致的年龄：819.8 ± 2.5 Ma（LA-ICP-MS）、821.7 ± 1.7 Ma（LA-MC-ICPMS）和822.1 ± 4.5 Ma（SHRIMP）。在国内4个权威实验室对该锆石进行了Lu-Hf同位素测定,获得了在误差范围内完全一致的176Hf/177Hf同位素比值——全部421个测试点加权平均值为0.282535 ± 0.000003（2σ）。采样点岩体规模巨大,露头良好,岩石新鲜,交通方便。该锆石样品满足作为Hf同位素测定标样的各方面的指标,可能是一个比较理想的Hf 同位素测定标样。Hf同位素测定标准物质的研制,是测定获得准确可靠的Hf同位素数据的基础,具有十分重要的实用价值和科学意义。     

甘肃白银金属硫化物矿床及其矿区主要地质事件的同位素地质年代学研究

本文针对甘肃白银金属硫化物矿床长期争论的成矿时代问题,运用成因矿物学的方法,在对各采样点内锆石的标型特征、变生状态进行详细分类研究的基础上,采用锆石Ｕ－Ｐｂ同位素定年手段,测得成矿地代为４６４￣４４０Ｍａ,属加里东成矿期。同时结合矿区外围地层和岩体的同位素年代研究,讨论了白银地区岩浆活动及主要地质事件的演化过程。     

冰芯包裹气体的稳定同位素和气体比值的高精度测量方法与校正

冰芯包裹气的稳定同位素和气体比值不仅可用于冰芯定年,也是反演古代大气组成及气候变化的重要指标,准确重建历史时期的气候信息对包裹气体同位素组成的测量精度和准确性有很高的要求。本文系统描述了冰芯包裹气体在实验室真空管线上提取、纯化,并在同位素质谱仪上测量的流程,详细介绍了氧、氮稳定同位素及其气体比值的校正方法。冰芯包裹气的稳定同位素和气体比值易受到多种过程的干扰,如现代大气污染、质谱仪的稳定性、气体比值不同引起的质量干扰等。针对以上问题,本研究在高真空条件下处理冰芯样品,利用零点校正检测仪器的稳定性,进行化学斜率校正消除气体比值不同对同位素值造成的质量干扰,并最终将所有数据以现代空气为标样进行均一化校正。经校正后的空气标样的氧、氮同位素值(δ¹⁸O、δ¹⁵N)和气体比值(δO₂/N₂、δAr/N₂)的外部精度分别为±0.043‰、±0.044‰、±0.7‰和±0.7‰。本研究重点强调了化学斜率校正对氧、氮同位素值的影响,综合2020年1月—2022年10月期间3次离子源更换后的化学...     

锆石铀-铅定年激光剥蚀-电感耦合等离子体质谱原位微区分析进展

激光剥蚀-电感耦合等离子体质谱(LA-ICP-MS)技术是目前最常用的锆石U-Pb同位素年龄测定方法之一。该方法能够对单颗粒锆石内部年龄差异实现快速、准确的原位微区分析。文章总结了近年来激光剥蚀系统、ICP-MS技术以及LA-ICP-MS锆石U-Pb定年方法、相关应用实例研究的进展和现状。系统评述了激光发生器,剥蚀池,剥蚀参数(激光波长、脉冲宽度、剥蚀气体、孔径大小)以及四极杆和扇形磁场质谱仪对锆石U-Pb年龄数据的精度和准确度的影响。详细介绍了基于锆石年龄标准样品、标准溶液及其他标样的外标定量校准方法,单个U/Pb比值计算方法,普通铅校正方法以及同位素年龄与微量元素同时测定的方法。目前LA-ICP-MS锆石U-Pb定年技术主要应用于碎屑锆石的沉积物源区示踪和岩浆事件的年代学约束研究。     

电感耦合等离子体质谱法测量铼和锇同位素比值的质量分馏校正

用Re标准溶液测定出X Series-7电感耦合等离子体质谱(ICP-MS)检测器的死时间为43ns。由于Re和Ir的对数分馏系数线性相关,可以用Ir对Re进行在线分馏校正。利用配制的Re同位素比值标准溶液检验该方法,大多数校正值对标准值的相对偏差在±0.1%以下。ICP-MS测量时,Os的分馏系数与中位质量数成正比,采用由迭代方法得到的样品和稀释剂混合物的同位素比值(192Os/188Os)mix作为标准化值对其他Os同位素比值进行分馏校正。用已知Os同位素比值的标准溶液对该方法进行检验,结果表明,经校正后,大多数校正值与标准值的相对偏差在±0.3%以下。上述Re-Os同位素分馏校正方法将改善用ICP-MS进行Re-Os定年时的精密度和准确度。     

锆石Hf同位素组成的LAM-MC-ICPMS精确测定

在配备了NewWaveMerchantekLUV213型紫外激光探针进样系统的Isoprobe型MC—ICPMS上进行了溶液和锆石单矿物的Hf同位素比值测定，并对^176Yb和^176Lu对^176Hf的同质异位素干扰校正进行了试验。结果表明，由于自然界Lu的丰度远远小于Yb，所以^176Hf的同质异位素干扰主要来自^176Yb。当Yb／Hf较低时，可以通过同质异位素干扰校正直接难确测定出^176Hf／^177Hf比值；当Yb／Hf比值较高时，则需要进行同质异位素干扰校正和外部校正来获得难确的^176Hf／^177Hf比值。因此，用LAM—MC-ICPMS可以难确、快速地测定锆石的Hf同位素组成。     

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.     

Laser ablation coupled with ICP-MS applied to U–Pb zircon geochronology: A review of recent advances

Improvements in the technology of laser ablation and ICP-MS instruments make LA-MC-ICPMS a rapid, precise and accurate method for U–Pb zircon geochronology. In this review we describe the main stages of the evolution of this in situ approach from the early 1990s to the present time. Some key points have been progressively improved. The crater size has been reduced to achieve real in situ measurements. The laser wavelength has been reduced as well as the duration of each pulse in order to lower inter-element fractionation. The blank from the gas has to be lowered as far as possible. Double focusing instruments and magnetic field sectors allow flat-topped peaks required for precise isotope ratio measurement to be obtained. The use of a multi-ion counting system significantly improves the sensitivity of the method and the static mode of integration favours the precision of measurement of the transient signal originating from a noisy laser ablated particle beam.Combining the use of a 213 nm UV laser and a MC-ICPMS equipped with a multi-ion counting system operating in static mode, the common precisions achieved for the key ratios ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁶Pb/²³⁸U are better than 1% and 3% (2σ) respectively, including error propagation associated with standard normalization. Until now, the use of a zircon standard has remained necessary to ensure the accuracy of the calculated age. A strategy for common-Pb correction is proposed according to the age of the zircon and according to the Th/U ratio of the grains. After recording sixteen to twenty spot analyses the precision usually achieved on the age is about 1% and even significantly better for Proterozoic samples.In order to show the performance achieved by modern LA-MC-ICPMS geochronology, we tested four zircon samples covering a wide age range from 290 to 2440 Ma. These new age determinations can be compared in term of precision and accuracy since they have already been dated by reference methods (ID-TIMS and SHRIMP). Further developments in the technology of ion counters equipping modern MC-ICPMS and in laser systems will certainly be applied to a large field of geochronology studies in the near future as an alternative to SIMS for in situ age determination.     

LA-MC-ICP-MS锆石微区原位U-Pb定年技术

利用激光多接收等离子体质谱(LA-MC-ICP-MS)技术对30～1 065 Ma的系列锆石进行了详细的定年研究.包含离子计数器的多接收系统使得不同质量数的同位素信号可以同时静态接收,并且不同质量数的峰基本上都是平坦的,进而可以获得高精度的数据,均匀锆石颗粒207Pb/206Pb、206Pb/238U、207Pb/235U比值的测试精度(2σ)均为2%左右,对锆石标准的定年精度和准确度在1%(2σ)左右;不同质量数同位素信号的同时静态接收使得剥蚀时间缩短,剥蚀深度变浅,相比LA-ICP-MS方法,提高了激光剥蚀的空间分辨率.对5个锆石标准和2个实际样品的测试表明,206Pb/235U年龄测定误差在1%(2σ)以内,定年结果在误差范围内与前人报道值完全一致,测试精度达到国际同类实验室先进水平.     

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.      

Micro-Analytical Zircon and Monazite U-Pb Isotope Dating by Laser Ablation-Inductively Coupled Plasma-Quadrupole Mass Spectrometry

In this study we evaluated the capability of a 213 nm laser ablation system coupled to a quadrupole-based ICP-MS in delivering accurate and precise U-Pb ages on zircons and monazites. Four zircon samples ( ca. 50 Ma to ca. 600 Ma) and four monazite samples ( ca. 30 Ma to ca. 1390 Ma) of known ages were analysed utilising laser ablation pits with diameters of 20 μm and 60 μm. Instrument mass bias and laser induced time-dependent elemental fractionation were corrected for by calibration against a matrix-matched reference material. Tera-Wasserburg plots of the calculated U-Pb data were employed to assess, and correct for, common Pb contributions. The results indicated that the LA-ICP-MS technique employed in this study allowed precise and accurate U-Pb isotope dating of zircon and monazite on sample areas 20 μm in diameter. At this spot size, the precisions achieved for single spot ²⁰⁶Pb/²³⁸U ages, were better than 5% (2s) for monazites and zircons with ages down to 30 Ma and 50 Ma, respectively. The precisions reported are comparable to those generally reported in SIMS and LA-MC-ICP-MS U-Pb isotope determinations.     

Characterizing the U–Pb systematics of baddeleyite through chemical abrasion: application of multi-step digestion methods to baddeleyite geochronology

U–Pb baddeleyite geochronology has become a major tool for dating mafic rocks, especially dikes associated with Large Igneous Provinces. However, in many cases, post-crystallization Pb-loss and intergrowth of baddeleyite and zircon limit the precision and/or accuracy of crystallization ages. We present results from multi-step digestion experiments designed to understand and reduce these effects. Experiments were carried out on Neoproterozoic baddeleyites with zircon inter- and over-growths from the Gannakouriep dike swarm, Namibia, and on fragments of a large Paleoproterozoic baddeleyite from the Phalaborwa carbonatite, South Africa. Multi-step digestion experiments on annealed Phalaborwa baddeleyite were designed to test whether the recently developed chemical abrasion technique for U–Pb zircon geochronology can be applied to baddeleyite. The experiments generated complex results—individual digestion steps were both normally and reversely discordant suggesting that U and Pb were decoupled in the multi-step digestions—and indicate that the current form of multi-step chemical abrasion is not an effective method for reducing the impact of Pb-loss in baddeleyite. A separate set of experiments on the Gannakouriep baddeleyite focused on isolating the zircon and baddeleyite components in composite grains. Conventional single-step digestion experiments for this sample resulted in a discordant suite of analyses with significant scatter attributed to inter- and over-grown zircon and highlight the difficulty of obtaining precise and accurate ages from composite grains. To isolate the baddeleyite and zircon in these grains, a two-step HCl–HF chemical abrasion procedure for annealed grains was developed. This technique was successful at selectively dissolving the baddeleyite and zircon components. Secondary zircon inter- and over-growths of baddeleyite can occur in samples affected by low-temperature alteration to granulite facies metamorphism, and the new HCl–HF chemical abrasion procedure provides a method for resolving both the igneous and metamorphic history of these composite grains.     

Laser ablation coupled with ICP-MS applied to U–Pb zircon geochronology: A review of recent advances

Improvements in the technology of laser ablation and ICP-MS instruments make LA-MC-ICPMS a rapid, precise and accurate method for U–Pb zircon geochronology. In this review we describe the main stages of the evolution of this in situ approach from the early 1990s to the present time. Some key points have been progressively improved. The crater size has been reduced to achieve real in situ measurements. The laser wavelength has been reduced as well as the duration of each pulse in order to lower inter-element fractionation. The blank from the gas has to be lowered as far as possible. Double focusing instruments and magnetic field sectors allow flat-topped peaks required for precise isotope ratio measurement to be obtained. The use of a multi-ion counting system significantly improves the sensitivity of the method and the static mode of integration favours the precision of measurement of the transient signal originating from a noisy laser ablated particle beam.Combining the use of a 213 nm UV laser and a MC-ICPMS equipped with a multi-ion counting system operating in static mode, the common precisions achieved for the key ratios ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁶Pb/²³⁸U are better than 1% and 3% (2σ) respectively, including error propagation associated with standard normalization. Until now, the use of a zircon standard has remained necessary to ensure the accuracy of the calculated age. A strategy for common-Pb correction is proposed according to the age of the zircon and according to the Th/U ratio of the grains. After recording sixteen to twenty spot analyses the precision usually achieved on the age is about 1% and even significantly better for Proterozoic samples.In order to show the performance achieved by modern LA-MC-ICPMS geochronology, we tested four zircon samples covering a wide age range from 290 to 2440 Ma. These new age determinations can be compared in term of precision and accuracy since they have already been dated by reference methods (ID-TIMS and SHRIMP). Further developments in the technology of ion counters equipping modern MC-ICPMS and in laser systems will certainly be applied to a large field of geochronology studies in the near future as an alternative to SIMS for in situ age determination.     

连山关-高家沟花岗岩体LA—ICP—MS锆石U—Pb年龄及其地质意义

笔者采用颗粒锆石LA—ICP—MS法获得了连山关-高家沟花岗岩体U—Pb不一致线上交点年龄为2198±31．5Ma和2162±31Ma。通过与辽东地区U—Pb法、Sm—Nd法和颗粒锆石年龄比对,揭示了辽东地区广泛发育的一期古元古代花岗岩浆事件的精确年代。根据岩石地球化学特征和岩体与地层接触关系,笔者认为该期花岗岩是在拉伸状态下早期基底岩石重熔的产物。年代学资料表明,连山关-高家沟岩体为壳源岩浆多次重熔侵位的花岗杂岩体。     

青岛榴辉岩及胶南群片麻岩的锆石U-Pb 年龄——胶南群中晋宁期岩浆事件的证据

研究表明，苏鲁地体是扬子与华北陆-陆碰撞造山带的一部分（东段）。其主要变质岩系——胶南群，是扬子陆块北缘俯冲陆壳的基底。在已有的文献中，人们均将胶南群划为早、中元古代地体。组成胶南群的主要岩石是长英质片麻岩，在其中间包含有少量斜长角闪岩、大理岩、超镁铁岩和榴辉岩。大量的Sm-Nd 及 40Ar/39Ar 同位素定年已证明了，胶南群在三叠纪时，经历了与华北和扬子陆块碰撞有关的高压或超高压变质作用，原岩的时代缺乏可靠的年龄测定，被认为是早、中元古代岩石。然而最近我们对青岛附近仰口的退变质榴辉岩及胶南群片麻岩的     

锆石裂变径迹年龄和逐层蒸发法铅年龄测定对比研究

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