A Review of Progress in Microbeam Lu-Hf Isotopic Analysis on Minerals
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摘要:
矿物微区Lu-Hf同位素分析技术为了解岩浆活动和变质反应的微观过程以及示踪沉积物源信息提供了重要手段，极大地促进了岩石地球化学等领域学科发展。本文评价了176Yb和176Lu同质异位素、稀土元素氧化物以及富Ta基体等对微区Hf同位素测量精度和准确度的影响方式、校正策略和应对方案，总结了针对锆石、斜锆石、钙钛锆石、钛锆钍矿、异性石、金红石、锡石和铌铁矿等富铪矿物的微区Lu-Hf同位素分析方法、适用对象以及相关标样特征。富镥矿物的微钻/微锯Lu-Hf同位素等时线定年具有高精度的特点，可精确限定多期造山作用和矿物生长持续时间等。利用激光剥蚀电感耦合等离子体三重四极杆串级质谱(LA-ICP-Q-MS/MS)可以实现对石榴石等富镥矿物微米尺度高空间分辨率的微区Lu-Hf单点/等时线定年。该方法依赖Hf与NH3的碰撞反应实现Lu和Hf的在线分离，达到同步测量176Lu/177Hf和176Hf/177Hf比值的目的。新一代带碰撞/反应池的多接收串级磁式质谱具有高稳定性和高灵敏度特性，可在消除多离子(团)干扰的同时实现高精度Hf同位素分析，是未来微区Lu-Hf同位素分析发展的重要方向。
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关键词:
- Lu-Hf同位素 /
- LA-MC-ICPMS /
- 锆石 /
- 石榴石 /
- 微区分析
要点(1) 评述了消除微区Lu-Hf同位素分析离子(团)干扰和基体元素拖尾效应的策略。
(2) 归纳了通过外标和稳定同位素比值监控富铪矿物微区Lu-Hf同位素分析准确性的办法。
(3) 总结了依赖碰撞反应实现富镥矿物微区Lu-Hf同位素定年的方法及改进方向。
HIGHLIGHTS(1) The strategies to eliminate the interference of ions (clusters) and the tailing effect of matrix elements during microbeam Lu-Hf isotopic analysis are reviewed.
(2) Two ways to monitor the accuracy of microbeam Lu-Hf isotopic analysis on hafnium-rich minerals, including external standards and internal stable isotope ratios, are summarized.
(3) The collision reaction methods for microbeam Lu-Hf isotope dating on lutetium-rich minerals are introduced and new development directions are discussed.
Abstract:BACKGROUNDMircobeam Lu-Hf isotopic analysis on minerals provides an important means to understand the microscopic process of magmatic activity and metamorphic reaction and to trace provenance of sediment, which greatly promotes the development of petrogeochemistry. Many methods were provided to obtain accurate and precise microbeam Lu-Hf isotopic data, and many mineral standards for microbeam Lu-Hf isotopic analysis were developed.
OBJECTIVESTo review and understand the microbeam methods for Lu-Hf isotopic analysis.
METHODSSystematic compilations of published data of standards and discussion on the different methods for microbeam Lu-Hf isotopic analysis.
RESULTSThe development history of microbeam Lu-Hf isotopic analysis in the past 30 years is reviewed, and the influence of 176Yb and 176Lu isobars, REE oxides, and Ta-rich matrices on the precision and accuracy of Hf isotope measurement is systematically evaluated as well as the different correction strategies and programs provided in previous studies. In addition, a comprehensive compilation of the different Yb and Lu isotopic compositions reported in references and the different methods of microbeam Lu-Hf isotopic analyses on various Hf-rich minerals such as zircon, baddeleyite, zirconolite, zirkelite, calzirtite, eudialyte, rutile, cassiterite, and columbite-group minerals is made. The micro-drill/micro-saw sampling Lu-Hf isotopic analysis of Lu-rich minerals has played an important role in revealing the multi-stage orogenic process and the duration of mineral growth. The advent of laser ablation inductively coupled plasma triple quadrupole mass spectrometry (LA-ICP-Q-MS/MS) has increased the spatial resolution of Lu-Hf single-spot/isochron dating analysis of Lu-rich minerals to the micrometer scale. This method relies on the collision reaction of Hf and NH3 to realize the online separation of Hf from Lu, and achieves the purpose of synchronous measurement of 176Lu/177Hf and 176Hf/177Hf ratios, which is introduced in detail.
CONCLUSIONSThe new generation of tandem multi-collector sector field mass spectrometer with collision/reaction cell has high stability and sensitivity, which can be used to determine online separation of Hf from REEs, produce high-precision Hf isotope measurements for high Yb/Hf or Ta-rich minerals under high spatial resolution conditions, and significantly improve the precision and accuracy of microbeam Lu-Hf isotopic analysis. This deserves extensive attention in the future.
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Keywords:
- Lu-Hf isotope /
- LA-MC-ICPMS /
- zircon /
- garnet /
- microbeam analysis
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铬(Cr)是一种常见的变价金属元素，在自然界中广泛分布于各类岩石、土壤、水体和生物体中。+3价铬是一种人体必需的微量元素，而易溶于水的+6价铬则被列为对人体危害最大的8种化学物质之一，也是国际公认的3种致癌金属元素之一。在一些地生环境中，铬会过度富集，从而造成严重的环境污染和生态健康问题。因为+6价铬的强活动性，地表环境中铬的形态转化、迁移、富集与毒性已受到环境科学研究领域内诸多学者的广泛关注[1-3]，特别是在现代环境中的铬污染研究方面，依据各种氧化还原反应得到的铬同位素分馏系数，铬同位素可用于指示地下水中有毒的+6价铬还原为无毒的+3价铬的程度[1]。在天体化学研究中，由于53Mn(半衰期仅为3.7±0.4Ma)可较快地衰变为53Cr，53Mn-53Cr体系可用为研究早期太阳系演化的天文计时器[4-5]。由于铬同位素在氧化-还原反应中会发生显著的分馏，铬稳定同位素体系已逐渐发展为示踪古海洋与大气氧水平的代用指标[2]。此外，铬同位素已被用来示踪成矿物质来源[6]以及地外撞击和行星演化等[7]过程。总的来说，由于近年来铬分析技术和分馏机理研究的不断完善，铬稳定同位素已成为地学与环境科学领域的一个前沿研究方向。
铬同位素应用研究的急剧拓展，亟需发展高精度的铬同位素分析技术。受限于早期测试技术的相对落后，观察到自然界铬同位素的组成变化与≥0.5‰的测试精度几乎在同一个数量级，因而难以揭示其同位素组成的真实变化及其蕴含的科学意义。直到1999年，伊利诺伊大学香槟分校地质系的Johnson教授首先在VG54普通型热电离质谱仪(TIMS)上成功开发了测试精度达到0.2‰的铬同位素双稀释剂分析方法后，他们据此观察到Cr6+还原Cr3+过程中铬同位素会产生明显的分馏。后来随着多接收器电感耦合等离子体质谱(MC-ICP-MS)和多接收器热电离质谱(MC-TIMS)的发展，更高精度的铬稳定同位素分析技术(≤0.08‰)逐渐成为现实。为获得高精度的铬同位素数据，前期的化学分离纯化、测试中的干扰扣除和质量歧视校正，特别是纯化过程中Fe、Ti和V的去除至关重要。由此，本文阐述了当前铬同位素常用的化学分离纯化方法和主要仪器分析技术，同时对目前主流的质量歧视校正方法进行了讨论，旨在为进一步促进铬同位素在地球与环境科学领域的应用和发展提供技术支撑。
1. 铬的基本地球化学性质
铬在周期表中位于第4周期第6B族，是一种氧化还原敏感元素。岩石中铬主要以Cr(Ⅲ)的形式存在，土壤与水体中则主要以Cr(Ⅵ)和Cr(Ⅲ)的形式共同存在。在低氧逸度和pH≤4时，铬以Cr3+和Cr(OH)2+为主；高氧逸度时主要以H2CrO40-CrO42-(随pH变化)和Cr2O72-(酸性)的形式出现。在pH为6~12时，可以以Cr(OH)3或Cr2O3的方式形成沉淀；pH≥12时，则以CrO42-的形式为主。弱中性至碱性条件下有Fe3+出现时，可形成CrxFe1-x(OH)3矿物。在金属离子如Pb2+、Sr2+、Ba2+等存在的情况下，Cr(Ⅲ)或Cr(Ⅵ)能够形成难溶解的亚铬酸或铬酸盐的沉淀。在现代大气氧的浓度和地表环境中，铬往往以CrO42-的形式发生迁移。如果存在Fe2+/Fe3+、Mn2+/Mn4+、S2-/SO42-等氧化还原对，以及低分子的有机质(如抗坏血酸、富里酸、胡敏酸等)时，Cr(Ⅵ)能够发生还原，以Cr(OH)3或Cr2O3的形式沉淀[8-9]。Cr(Ⅲ)在二氧化锰存在的环境中较易发生氧化，形成较易迁移的CrO42-。所以，铬形态的稳定和转化与环境的Eh和pH条件变化密切相关(图 1)。对于铬稳定同位素体系而言，Cr(Ⅲ)与Cr(Ⅵ)间的氧化还原过程是导致铬同位素分馏的主要因素[10]。此外，无论是Cr(Ⅲ)还是Cr(Ⅵ)阴离子团，均存在吸附和络合现象，如被黏土矿物吸附或与有机质络合等[11-13]，这些过程也能够导致不同程度的铬同位素分馏[14]。因此，不同形态的铬具有明显差异的地球化学行为，既影响着环境中铬的毒性、迁移和循环过程，也制约着各种地球化学过程中铬同位素的分馏[15-16]。
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2. 铬同位素组成的表达
自然界中铬有4种稳定同位素，分别是50Cr(4.35%)、52Cr(83.79%)、53Cr(9.50%)和54Cr(2.36%)[17]。由于50Cr和54Cr都存在同质异位素50Ti、50V和54Fe等的干扰，且52Cr丰度相对较高，一般使用δ53/52Cr比值表示铬同位素的组成。目前，国际上多采用NIST SRM979和NIST SRM3112a作为铬同位素标准物质，但前者使用更为广泛，后者使用较少。对于这两种标准，可以按照公式δ53/52CrA/B=δ53/52CrA/X+δ53/52CrX/B+(δ53/52Cr A/X×δ53/52Cr X/B/1000)进行转换(A代表样品，X代表NIST 3112a，B代表NIST 979)，或按照δ53/52CrNIST 979≈δ53/52CrNIST 3112a+0.07的近似计算即可。对于自然样品，铬同位素组成的表示方式通常有两种，一种是以δ53/52Cr表示的千分分馏(公式1)，另一种是以ε53/52Cr表示的万分分馏(公式2)[18-21]。其表达式如下：
${\delta ^{53 - 52}}{\rm{Cr = }}\left[ {\frac{{{{\left( {^{53}{\rm{Cr}}{{\rm{/}}^{52}}{\rm{Cr}}} \right)}_{{\rm{样品}}}}}}{{{{\left( {^{53/52}{\rm{Cr}}} \right)}_{{\rm{NIST\;979}}}}}} - 1} \right] \times 1000 $
(1) ${\varepsilon ^{53 - 52}}{\rm{Cr = }}\left[ {\frac{{{{\left( {^{53}{\rm{Cr}}{{\rm{/}}^{52}}{\rm{Cr}}} \right)}_{{\rm{样品}}}}}}{{{{\left( {^{53/52}{\rm{Cr}}} \right)}_{{\rm{NIST\;979}}}}}} - 1} \right] \times 10000 $
(2) 一般而言，地球环境和地质样品中因铬同位素存在相对较大的分馏，常用δ值表示。而对于地外样品，特别是对于太阳系早期形成物质如陨石中的铬同位素，常用ε值表示。
3. 自然样品中铬的分离纯化技术
一般而言，进行任何同位素分析都要经过严格的化学分离纯化，这是获取高精度金属同位素比值的重要前提，铬也一样。在地表土壤和地下水中，铬的价态主要以+6价为主；在陨石、岩石和沉积物中，铬主要以+3价为主。铬的化学分离纯化就是利用不同形态铬的差异行为通过离子交换树脂来实现。近年来文献中有关铬分离纯化方法的对比见表 1，下面也将当前比较流行的三种分离纯化流程进行对比综述。
表 1 铬的分离纯化方法对比Table 1. Comparison of the chemical methods for separating Cr参考文献 发表时间 树脂柱 过柱次数 洗脱剂 样品类型 样品浓度
(μg/g)铬回收率
(%)总空白
(ng)Lugmair等[5] 1998 Mitsubishi
AG-X8 (200~400目)2 1mol/L盐酸
1.8mol/L盐酸陨石 20.8 ≈70 几个ng Ball等[18] 2000 AG1-X8
AG50W-X82 2mol/L硝酸
5mol/L硝酸自然水 / / / Ellis等[1] 2002 AG1-X8
AG1-X82 0.1mol/L盐酸
0.1mol/L盐酸地下水 0.13 / / Frei等[19] 2005 AG1-X8
AG1-X8
AG50W-X8
AG1-X84 6mol/L盐酸
4mol/L硝酸
5mol/L硝酸
0.1mol/L盐酸BIF铁矿石 / 95~99 0.7~2.3 Trinquier等[22] 2008 AG50W-X8 (200~400目)
AG50W-X8 (200~400目)2 1mol/L盐酸
2mol/L盐酸玄武岩、铅锌矿和白云岩等 18 >80 4 Schoenberg等[23] 2008 AG1-X8 (200~400目) 1 2mol/L硝酸 玄武岩、页岩和超基性岩 52.96 80~90 < 20 Yamakawa等[24] 2009 AG1-X8 (200~400目)
AG50W-X8 (200~400目)
AG50W-X8 (200~400目)3 6mol/L盐酸
1mol/L盐酸
1.8mol/L盐酸玄武岩 439 86~90 1 Qin等[25] 2010 AG50W-X8 (200~400目)
AG1-X8 (100-200目)
AG50W-X8 (200~400目)3 4mol/L硝酸
6mol/L盐酸
2mol/L盐酸陨石 27 80 < 100 Døssing等[26] 2011 AG1-X8 (100-200目)
AG1-X8 (100-200目)2 6mol/L盐酸
6mol/L盐酸河水 0.08 >95 5~10 Moynier等[6] 2011 AG50W-X8 (200~400目)
AG50W-X8 (200~400目)
AG50W-X8 (200~400目)3 1mol/L盐酸
1mol/L盐酸
硝酸/氢氟酸/盐酸陨石 / >90 < 1 Bonnand等[27] 2011 AG50W-X8 (200~400目) 1 0.5mol/L盐酸 碳酸盐岩 0.82 / 0.12~0.2 Jamieson-Hanes等[28] 2012 AG1-X8 1 2mol/L硝酸 地下水 / / / Kitchen等[29] 2012 AG1-X8
AG1-X82 稀盐酸
稀盐酸溶液 / / < 8 Bonnand等[12] 2013 AG1-X8 (200~400目)
AG50W-X8 (200~400目)2 7mol/L盐酸
0.5mol/L盐酸海水 / 第一步>95 ≈0.5 Farkas等[20] 2013 AG1-X8 (100~200目) 1 6mol/L盐酸 硅酸盐 122900 90~95 15~20 Schiller等[30] 2014 AG1-X4 (200~400目)
AG50W-X8 (200~400目)
TODGA
TODGA
AG1-X4 (200~400目)5 6mol/L盐酸
0.5mol/L硝酸
6mol/L盐酸
14mol/L硝酸
8mol/L盐酸
6mol/L盐酸纯橄榄岩 1.55 / 几个ng Rodler等[31] 2015 AG1-X8
AG1-X82 0.5mol/L盐酸
0.5mol/L盐酸溶液 7.64 >70 4.07±0.63 Wang等[32] 2015 AG1-X8
AG1-X82 2mol/L硝酸+
0.6%过氧化氢碳酸盐岩 4 / < 0.1 注：表中的“/”表示文献中未明确说明。 3.1 阴离子树脂纯化方法
阴离子树脂法较早在美国伊利诺伊大学香槟分校地质系Johnson教授的研究组内开始使用。该纯化方法中使用的阴离子树脂一般是100~200目和200~400目的AG1-X8树脂。使用该树脂分离铬的基本原理是中性条件下可以较强地与Cr(Ⅵ)阴离子团结合，然后利用还原剂在树脂中将Cr(Ⅵ)还原为Cr(Ⅲ)后全部淋洗出。所以，应用该流程的前提是样品中的铬需要完全转化为Cr(Ⅵ)。要实现样品中Cr(Ⅵ)形态的统一，往往需要使用如过硫酸钾(氨)、高锰酸钾或氨水与双氧水混合的强氧化剂等；而还原剂一般使用亚硫酸(H2SO3)或稀硝酸与双氧水的混合液等。Ellis等[1](2002)使用氨水与双氧水的混合液先将样品中与50Cr-54Cr双稀释剂混合的铬完全转化为Cr(Ⅵ)后上柱，使用2mol/L、0.1mol/L盐酸淋洗基质元素，然后用0.1mol/L亚硫酸作为还原剂，在柱中将Cr(Ⅵ)还原为Cr(Ⅲ)直接流出，而氧化形成的SO42-吸附在树脂上。这种流程省去了Cr(Ⅲ)的洗脱过程，缩短了流程时间。不过对于高Fe、Ti的自然样品，收集的Cr(Ⅲ)淋滤液需要在后续步骤中同样使用AG1-X8树脂，用6mol/L盐酸除Fe、0.5mol/L氢氟酸除Ti等步骤。Kitchen等[29]在研究Cr(Ⅵ)还原过程中铬同位素的分馏系数时，使用了与Ellis同样的方法，也得到了较好的实验结果。Schoenberg等[23]对Ball等[18]以及Ellis等[1]的阴离子树脂纯化流程进行了完善，具体流程与上述步骤基本一致，差别在于使用了1mL 0.2mol/L过硫酸铵作为氧化剂，在140℃电热板上加热至少2h后将Cr(Ⅲ)完全氧化为Cr(Ⅵ)，再通过AGl-X8树脂，依次用20mL 0.2mol/L盐酸、16mL超纯水淋洗，使Cr(Ⅵ)与V、Ti和Fe等离子分离。然后，使用9mL 2mol/L硝酸-0.5%过氧化氢的混合酸液作为还原剂，将吸附在树脂上的Cr(Ⅵ)还原为Cr(Ⅲ)后直接淋洗出。这种纯化流程中铬的回收率往往因样品属性和铬含量而变化，且后续步骤中依然需要除去Fe、Ti等干扰元素，回收率一般≥60%。此流程的缺点在于使用过硫酸氨或高锰酸钾氧化Cr(Ⅲ)至Cr(Ⅵ)的过程中，通常会形成Fe、Mn氧化物的沉淀。这些沉淀会吸附极微量的Cr(Ⅵ)而导致铬的回收率降低，且氧化剂的引入也会提高铬的流程空白。因此，在使用该流程纯化铬时，本课题组建议选用铬空白较低的超纯过硫酸钾或过硫酸铵试剂。
3.2 阳离子树脂纯化方法
阳离子树脂法中，一般多使用100~200目和200~400目的AG50W-X8阳离子树脂，较少使用AG50W-X12树脂。使用该树脂分离铬的基本原理是稀酸介质中该树脂能够较强地与Cr3+和CrCl2+结合，而与CrCl2+阳离子结合较弱。因此，如果样品溶液中出现不同铬的离子形态，用酸淋洗时其淋出的位置会不同。这样，铬阳离子形态的统一便成为该纯化流程的关键因素。Trinquier等[22]和Davies[33]分离纯化铬时，采用了两步阳离子交换法。首先在氨水和双氧水的混合液中将铬全部氧化成Cr(Ⅵ)，使样品通过AG50W-X8(200~400目)阳离子树脂，Fe、Ti和Mg等基体中的阳离子被吸附在树脂中，而Cr(Ⅵ)流出，收集流出液并蒸干后用2mL 0.15mol/L硝酸完全溶解，同时稀硝酸也会把Cr(Ⅵ)还原为Cr(Ⅲ)。溶液再次通过AG50W-X8(200~400目)阳离子树脂，用0.5mol/L氢氟酸和1mol/L盐酸淋洗残余的基质元素，再用2mol/L盐酸洗脱铬。该流程对较高铬含量样品的总回收率均超过80%。
对于陨石样品，Qin等[25]对上述阳离子交换法进行了修正。在样品完全消解之后，使样品中铬以Cr3+的形态存在。用8mL 2mol/L硝酸溶解样品，通过AG50-X8阳离子树脂，并用35mL 2mol/L硝酸洗脱基质元素，再用10mL 4mol/L硝酸将铬从阳离子树脂中洗脱并收集。收集液蒸干后使用6mol/L盐酸溶解残余物，利用AG1-X8(100~200目)阴离子树脂进行铁、铬分离。Bonnand等[27]对铬含量较低的碳酸盐样品进行分离纯化时，提出了单柱阳离子交换法，但该柱并不同于常用的10mL标准Bio-Rad聚丙烯柱，而是内径为6.4mm的美国Savillex公司生产的PFA柱(柱长20cm)，使用了2.9mL的AG50-X8树脂，并用0.5mol/L盐酸代替1mol/L盐酸来洗脱铬。近年，Larsen等[9]详细阐述了Cr3+阳离子及CrCl2+和CrCl2+络合阴离子在单柱阳离子交换树脂中的铬同位素分馏幅度，强调了铬形态统一的重要性，并藉此利用内径3.2mm、柱长为12cm的单柱开发出阳离子树脂纯化流程。该流程的优点是高铬样品的回收率均在95%以上，但缺点在于使用的浓盐酸要在140~150℃下密闭保持18h以使铬的形态达到统一。不过，需要强调说明的是，该流程对高铬和含基质元素较低的碳酸盐岩较为有效，并不适合用于低铬高铁、钒、钛基质元素的样品，特别是部分可能以阳离子形式存在的钒随铬会一起淋洗出来，除钒的效果并不理想。因此，阳离子交换法多针对高含量铬和成分比较单一如碳酸盐岩之类的样品。
3.3 阴阳离子树脂联用纯化方法
阴阳离子树脂联用交换法，是指阴离子和阳离子型树脂的交替使用，也是当前使用较多的一种纯化方法。阴离子树脂一般使用100~200目或200~400目的AG1-X8树脂，阳离子树脂一般使用100~200目或200~400目的AG50W-X8树脂。Ball等[18]使用阴阳离子交换法，率先对水体中Cr(Ⅵ)和Cr(Ⅲ)的同位素进行了分析。首先在近中性条件下将水样通过AG1-X8阴离子交换树脂，Cr(Ⅵ)被吸附在树脂上，而Cr(Ⅲ)随基体元素流出并收集；再用5mL 2mol/L硝酸将Cr(Ⅵ)还原为Cr(Ⅲ)时淋洗出并收集。随基体元素流出的Cr(Ⅲ)收集液用超纯水稀释至150~175mL，再通过AG50W-X8阳离子交换树脂，用5mL 5mol/L硝酸洗脱，收集液蒸干溶解后待测试。Bonnand等[12]在分析海水的铬同位素组成时也采用了类似的方法，首先用6mL 7mol/L盐酸溶解样品，将Cr(Ⅵ)还原为Cr(Ⅲ)，通过AG1-X8(200~400目)阴离子交换树脂后Fe吸附在树脂上，Cr(Ⅲ)直接流出并收集；然后将铬溶液蒸干后溶于6mL 0.5mol/L盐酸，再通过AG50W-X8(200~400目)阳离子交换树脂，之后用4 mL 0.5mol/L盐酸洗脱铬，将收集到的铬溶液蒸干后溶于0.6mol/L硝酸待上机测试，该流程报道的第一阶段铬回收率到达了95%。Yamakawa等[24]提出了三阶段阴-阳-阳离子交换法。首先将样品通过AG1-X8阴离子交换柱，用4mL 6mol/L盐酸洗脱并收集，该步除Fe之后使用AG50W-X8阳离子交换柱，将第一步的洗脱液通过树脂，利用1mol/L盐酸使Cr与Ni分离，最后将上一步的收集液通过AG50W-X8阳离子交换柱，分别使用1mL 0.5mol/L硝酸、3mL 0.5mol/L氢氟酸和10mL 1mol/L盐酸淋洗，除去Na、Ti和V等离子，再用5mL 1.8mol/L盐酸洗脱铬。此方法铬的回收率达到86%~90%。Frei等[19]在示踪星球撞击的研究中，采用了多阶段阴阳离子交换法。先使样品通过AG1-X8阴离子交换柱，用6mol/L盐酸除Fe并洗脱铬。之后使用过硫酸铵将Cr(Ⅲ)氧化为Cr(Ⅵ)通过AG1-X8阴离子交换柱，使Cr(Ⅵ)与Ti、V和碱金属离子分离，加入2mol/L硝酸将Cr(Ⅵ)还原为Cr(Ⅲ)后通过AG50W-X8阳离子交换树柱，用5mol/L硝酸洗脱铬后再用AG1-X8阴离子交换树脂做进一步的纯化，除去SO42-等阴离子团，该流程报道的铬回收率可达95%~99%。
然而，上述流程对于低铬含量高基质的样品而言，利用盐酸除Fe的第一步就往往会出现过载现象。在本课题组纯化BCR-2标样中的铬时，该步骤明显存在铬的丢失。近期，Schiller等[30]参考了Frei等[19]的方法，实施了五步分离纯化，使用树脂的顺序为：AG1-X8树脂、AG50W-X8树脂，两次TODGA树脂和AG1-X8树脂，但遗憾的是文中并没有报道铬的回收率。Li等[34]提出使用Ln特效树脂与AG1-X8阴离子树脂结合的两柱步骤纯化铬，使用高锰酸钾作为氧化剂。该流程中第一道Ln树脂能够有效去除约99.8%的Fe和Ti、约20%的V。铬的整体回收率可以达到95%以上，且空白降低到0.2ng以下。不过该流程中使用了高锰酸钾，在氧化Cr(Ⅲ)时也同时氧化了低价Fe、Mn等元素，容易形成铁锰氧化物的沉淀，导致沉淀对Cr(Ⅵ)的微量吸附而使收集液中的铬回收不全。因此，采用高锰酸钾作为氧化剂并不适用于铁锰结核或BIF铁矿石等样品。最近，Zhu等[35]在综合对比分析前期铬同位素分馏纯化流程的基础上，提出了三步四柱的纯化方案。首先是使用阳离子(AG50W-X8)和阴离子(AG1-X8)树脂组合的两个连续柱，分别在10.5mol/L和6mol/L的盐酸介质中有效去除>99%的Ca和Fe以及大部分Ni、Cu、Zn等基质元素，然后利用AG1-X8树脂在4mol/L氢氟酸介质中除去>99%的Ti和>90%的V。最后利用过硫酸氨(钾)氧化Cr(Ⅲ)为Cr(Ⅵ), 再次利用AG1-X8树脂除去残余的微量基质元素以获得高纯的铬溶液。该流程对于约3mg/kg的花岗岩样品，铬的回收率仍然可以达到80%以上；对植物样品，铬的回收率则可以达到95%以上。该纯化方案的特点是简单、灵活易调整，且过柱时间短，几乎适用于各类地质与环境样品，是一种具有广谱性的分离纯化流程。
4. 铬同位素的质谱测定
目前，铬同位素组成的高精度测定主要使用两种类型的仪器，一种是多接收器热电离质谱仪(MC-TIMS)；另一种是多接收器电感耦合等离子体质谱仪(MC-ICP-MS)。下面就这两种仪器的使用分别进行叙述。
4.1 多接收器热电离质谱法
早期研究中，铬同位素组成的测定几乎都在TIMS上完成，包括陨石中放射性成因的53Cr和过量54Cr的研究[4, 35-38]，以及地下水中与铬同位素质量分馏相关的研究等[1, 18]。
Shields等[36]于1966年首次使用热电离质谱法进行了铬同位素组成的测定。样品用1%的硝酸储存，采用单带铂灯丝，测定铬同位素时电流信号在37~60min内比较稳定。在此基础上，后续研究者使用硅胶-硼酸激发剂代替硅胶-磷酸激发剂，发现硅胶-硼酸激发剂条件下的电流信号比硅胶-磷酸激发剂更稳定。在采用钨灯丝后，取得了更好的测试效果[4-5, 37]。Ball等[18]沿用了这种技术，为利用MAT261测定水中的铬同位素组成，使用钽灯丝代替钨灯丝，测试过程中硅胶和硼酸用量分别为20μg和0.25μmol/L，铬用量为700ng。随后，Ellis等[1, 38]在Ball等的基础上，将双稀释剂法应用到TIMS测定铬同位素组成中，同样采用硅胶-硼酸作为激发剂，使用铼带灯丝。这些结果表明，TIMS测试过程中铬的电离度和信号稳定性与灯丝材料并无直接关系，且硅胶-硼酸作为激发剂可以获得更好的重现性，但其分析精度≥0.2‰(δ53/52Cr)仍然制约着高精度铬同位素的分析。
在最近十年的研究中，随着MC-TIMS的开发成功和广泛应用，铬同位素已能够在静态模式下测试[39]，不用跳杯即可进行所有铬同位素及其可能干扰元素的监控。新一代TIMS的高压系统比早期仪器更加稳定，磁场和电子透镜系统的性能也得到很大改善，这些改进的新型TIMS在铬同位素测试精度上比上代仪器测定的精度提高了一个数量级。秦礼萍[40]采用MC-TIMS进行了铬同位素组成的分析，将硅胶和饱和硼酸加入点样中，提高了铬离子化的温度，避免了低温下有机物的干扰。对1μg量的铬同位素分析表明，δ53/52Cr的分析精度可提高到0.05‰，而ε53Cr的精度达到了0.05‰，ε54Cr的精度为0.1‰。不过，对200ng量的铬稳定同位素进行分析时，其精度＜0.1‰(δ53/52Cr)。近期，Li等[34]开发了以溶于0.4mol/L磷酸中的Nb2O5作为激发剂，使用该激发剂测量灵敏度提高了近10倍。利用100ng量的铬标准溶液测定其同位素时，δ53/52Cr的精度可提高至0.02‰(2SD)，但在其报道实际自然样品的δ53/52Cr值时，多次测量样品的长期外精度依然是0.05‰(2SD)左右。因此，在目前使用TIMS测试铬同位素时，尝试使用Li等[34]开发的激发剂有可能是比较好的一种选择。
4.2 多接收器电感耦合等离子体质谱法
多接收器电感耦合等离子体质谱是20世纪90年代中后期研发的一种质谱仪。其显著特点是具有双聚焦、中高分辨功能和配置有多个法拉第接收器(Faraday cup)和离子计数器。MC-ICP-MS与TIMS相比，样品以溶液方式进样，分析速度快于后者，分析效率远高于TIMS，且分析精度基本与TIMS相当，已日渐成为高精度铬同位素分析的首选仪器。
目前，进行铬同位素高精度分析的MC-ICP-MS仪器类型主要有Nu PlasmaⅠ型、Ⅱ型和Ⅲ型高分辨(HR)MC-ICP-MS，以及美国ThermoFisher公司的Neptune、Neptune Plus型MC-ICP-MS。在前者的仪器类型中，由于Nu PlasmaⅠ型仪器只配置了12个固定位置的法拉第杯，进入法拉第杯的离子束是通过电子光学系统调谐的，静态分析模式下不能进行56Fe的监控，需要动态模式跳杯测量。同时，为了提高信号的灵敏度，且能够消除40Ar12C+、40Ar16O+、40Ar14N+等多原子离子和50Ti-50V与54Fe对50Cr和54Cr的同质异位素干扰，通常采用膜去溶干法进样和采样锥与高灵敏度截取锥的组合模式，在中高分辨模式下进行铬同位素分析。因此，使用Nu PlasmaⅠ型(HR)MC-ICP-MS测量自然样品的δ53/52Cr值，报道的长期外精度通常在0.08‰左右。对于Nu PlasmaⅡ和Ⅲ型(HR)MC-ICP-MS，由于该仪器配置了16个法拉第杯，故在静态模式下即可进行49Ti、51V、50Cr、51Cr、52Cr、53Cr、54Cr和56Fe等同位素的同时监控和测量，借助膜去溶干法进样和增强型高灵敏度锥，样品量为100ng时测试的铬同位素长期外精度明显优于0.08‰。Neptune与Neptune Plus型MC-ICP-MS具有良好的稳定性和高灵敏度，一般配置有9~10个法拉第杯，相较于Nu Plasma型MC-ICP-MS具有较高的40Ar16O+、40Ar14N+等干扰信号。因此，使用湿法进样和采用普通H型采样锥与X型高灵敏度锥的组合，在200 ng/mL或更高铬浓度的情况下，利用中高分辨和静态模式进行铬同位素分析，不仅可以有效地消除40Ar16O+、40Ar14N+等干扰信号和通过监控49Ti、51V、56Fe扣除50Ti、50V和 54Fe等同质异位素对50Cr和54Cr的干扰，而且也可以得到较高精度的δ53/52Cr数据。Schoenberg等[23]利用Neptune Plus型MC-ICP-MS进行了地幔包体、超基性岩等固体样中铬同位素组成的测定，使用50Cr-54Cr作为双稀释剂，测试精度达到了±0.08‰。Bonnand等[12]在分析海水和海洋碳酸盐的铬同位素组成时，也使用了50Cr-54Cr双稀释剂校正样品处理过程中的同位素分馏及仪器的质量歧视效应，海水样品的分析精度达到了0.05‰，碳酸盐样品的分析精度为0.06‰。Schiller等[30]对硅酸盐物质中铬同位素组成进行分析时，测试中总样品消耗量为30~60μg，分析精度也在0.05‰。此外，在空白降至0.2ng或更低的情况下，使用Neptune Plus型MC-ICP-MS和配置膜去溶干法进样系统，20ng/mL的铬浓度足够可以进行高精度的铬同位素测试。也就是说，实际进行化学纯化的样品中只要有200ng量的铬，便可以保证铬同位素的高精度、准确分析。
表 2中总结了近年来文献中有关TIMS和MC-ICP-MS测试铬同位素的精度对比。可以看出MC-ICP-MS测试铬同位素的精度与TIMS相当，并且MC-ICP-MS还具有TIMS无可比拟的优势：①操作更加简单，经过分离纯化的样品只需蒸干后用稀硝酸溶解即可用于质谱测量；②样品用量相对较少，当前使用TIMS测定铬同位素组成时，需要铬样品量一般为600~700ng以上，而MC-ICP-MS最低可至100ng以下，最低可到10ng左右[12, 44]；③分析效率高，即使采用标准-样品交叉法(SSB)且单个样品测试次数为3次，其分析效率也至少高于TIMS四倍，而使用双稀释剂则可以高于十倍以上。基于以上原因，如今越来越多的研究者都采用MC-ICP-MS进行铬同位素组成的测定。
表 2 TIMS和MC-ICP-MS测定铬同位素组成精度对比Table 2. Comparison of the precition of TIMS and MC-ICP-MS instrument仪器名称 仪器型号 作者 研究日期 样品类型 精度(‰) 校正方法 VG336 Ball等[18] 2000 地下水 ±0.13 双稀释剂法 VG354 Ellis等[38] 2004 溶液 ±0.2 双稀释剂法 TIMS Finnigan MAT 261 Sikora等[41] 2008 溶液 ±0.2 双稀释剂法 IsotopX/GV IsoProbe T Frei等[2] 2009 BIF ±0.08 双稀释剂法 Triton TIMS Qin等[25] 2010 陨石 ±0.1 双稀释剂法 IsotopX/GV IsoProbe T Rodler等[31] 2015 溶液 ±0.08 双稀释剂法 ThermoFinnigan SIS Schoenberg等[23] 2008 硅酸盐 ±0.1 双稀释剂法 Thermo Scientific Neptune Jamieson-Hanes等[28] 2012 地下水 ±0.1 双稀释剂法 GV IsoProbe-P Farkas等[20] 2013 硅酸盐 ±0.066 双稀释剂法 ThermoFisher Scientific Neptune Bonnand等[12] 2013 海水 ±0.047 双稀释剂法 MC-ICP-MS ThermoFisher Neptune Plus Schiller等[30] 2014 硅酸盐 ±0.05 双稀释剂法 Nu Plasma Wang等[32] 2015 溶液 ±0.08 双稀释剂法 ThermoFisher Scientific NeptunePlus Schoenberg等[42] 2016 陨石 ±0.044 双稀释剂法 ThermoFisher Neptune Bonnand等[43] 2016 月球玄武岩 ±0.025 双稀释剂法 4.3 铬同位素测量时的质量歧视校正
相较于TIMS的微小质量歧视效应(Mass Bias)，MC-ICP-MS的质量歧视效应远大于TIMS。较大的质量歧视效应必然影响着测试结果的准确度和精密度[45-48]。因此，与Fe、Cu、Zn等非传统稳定同位素类似，在进行高精度铬同位素分析时，也要进行质量歧视效应的校正。非传统稳定同位素的质量歧视校正方法主要有标准-样品交叉法(Standard-Sample Bracketing，SSB)[49-55]、元素外标法(Element Doping，ED)[56]和双稀释剂法(Double Spike，DS)[16, 57-59]。标准-样品交叉法是同位素标准与样品的交替轮流测试，其基本原理是假定仪器足够稳定且在标准与样品的交替轮流测试过程中质量歧视效应相同，这样，将样品测试值与前后两个标样测试值的均值相比，就可以抵消仪器对样品的质量歧视[49-50]。因此，计算样品的比值时，即可以利用标样获得的仪器分馏系数(β)均值进行计算；也可以依据前后两个标样实测比值的均值进行计算。然而，该方法应用的前提条件是纯化样品的铬回收率要达到100%，或者在未达到100%回收但大于95%的前提下，需要定量评估回收率对δ53/52Cr比值漂移的影响程度，以此确定铬的最低上样量。在实践中，铬的回收率往往很难高于95%，SSB法在铬同位素的测定中较少使用。元素外标法是利用外标元素B的同位素与待测元素A同位素的质量数相近，且尽量选择彼此不存在同质异位素干扰的同位素和假定A与B表现出一致的质量歧视效应(其实测比值取对数后存在线性关系)，再根据两者间的线性关系获得仪器的分馏系数从而求得待测元素的同位素比值。亦或使用元素外标法与标准-样品交叉法的联合，数据处理时使用标准-样品交叉法进行校正。此方法在铬同位素测定中很少使用，但理论上使用56Fe、57Fe或54Fe即可对53Cr、52Cr进行校正。当前铬分析技术研究中还未有文献报道该类方法，原因是元素外标法与标准-样品交叉法类似，都要保证样品纯化过程中铬回收率尽量接近100%。
由于受到样品纯化过程中铬回收率的制约，高精度铬同位素分析时常用的质量歧视校正方法是双稀释剂法(DS)。同位素双稀释剂法的数学原理在许多文献中已有详细论述[35]，其核心思想是利用已知比值的双稀释剂来校正样品纯化和仪器测试过程中的分馏。与86Sr/88Sr=0.1194、146Nd/144Nd=0.7219等内标校正方法类似，双稀释剂法也属于内标校正，用已知比值的同位素双稀释剂求得分馏系数，再返回应用于其他同位素对的比值求解。该过程与Sr、Nd等内标校正的差别在于，需要数学上的迭代计算剔除双稀释剂成分的影响后提取δ53/52Cr值。同位素双稀释剂法保留了内标校正方法的特点，不必刻意去追求较高的回收率。但需要注意的是，双稀释剂的选择有一定的经验法则，且双稀释剂间以及稀释剂与样品之间都应该注意最佳的混合比，以保证同位素测试时的高精度和准确度。对铬同位素而言，50Cr-54Cr常被用作双稀释剂，在单稀释剂50Cr与54Cr比值在1.0~1.5之间混合时，54Cr稀释剂/52Cr样品的最优比在0.35左右，但在0.2~2.0的混合范围均有效，其分析精度理论上不存在显著性差异[27, 35, 60-61]。作者所在实验室采用双稀释剂法进行了铬同位素的高精度分析，主要原因有以下几方面：①可用于多种类型样品的分析，如大气颗粒物、水、矿石、纯金属等，通过双稀释剂方法可较好地控制数据质量和进行国际同行的比对；②可用于低浓度样品的铬同位素分析，并且测试时所需样品量少，如对于含量低于2μg/g以下的铬样品，依据流程空白，选择~300ng量的铬进行纯化即可，同时也可获得待测元素更为准确的浓度；③双稀释剂技术可同时校正纯化分离与样品测试过程中的分馏，避免了因回收率等问题引起的漂移，具有较高的准确度。近年来，在采用双稀释剂法测试铬同位素的研究中，Schoenberg等[23]、Zink等[16]和Pérez-Fodich等[62]在不同的质谱仪上测量的δ53/52CrSRM979同位素值外部重现性可以达到0.035‰(2SD)。作者所在实验室对铬同位素标准溶液的长期测试结果为δ53/52CrSRM979＝0.01‰±0.04‰(2SD)，δ53/52CrSRM3112a＝-0.07‰±0.04‰(2SD)，与国际水平一致。
4.4 铬同位素测量时的干扰评估
与TIMS仪器干扰少的优势相比较，MC-ICP-MS进行铬同位素测定时，明显存在多原子离子和同质异位素的干扰。如表 3所示，由于MC-ICP-MS使用氩气作为载气，离子化过程中氩气可与酸介质中的H、N、O和基质中的离子结合，产生多原子离子，如40Ar14N+和40Ar16O+等会对54Cr、54Fe和56Fe等产生干扰。因此，针对多原子离子的干扰，通常使用中分辨(≥5000)或高分辨(≥8500)模式就可以很好地将它们分开。50Ti、50V和54Fe分别对50Cr和54Cr产生同质异位素的干扰，这些干扰可通过监控49Ti、51V和56Fe的信号加以扣除。但在其扣除过程中，如果存在过高的Ti/Cr、V/Cr和Fe/Cr比值，往往会导致错误的结果。因此，一方面在样品化学纯化过程中尽量消除Ti、V和Fe；另一方面也要对Ti/Cr、V/Cr和Fe/Cr浓度比值的有效范围进行评估。Bonnand等[43]报道了铬同位素比值对Fe、Ti和V三种干扰元素的敏感程度，其顺序为Ti>Fe>V。Zhu等[35]报道了Neptune Plus型MC-ICP-MS湿法测试铬同位素时样品溶液中允许的Ti/Cr和Fe/Cr临界值。如图 2所示，当Ti/Cr和Fe/Cr比值均小于0.05时，待测液的Ti和Fe不会对铬同位素组成造成明显的影响。
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图 2 加入了不同的量Fe、Ti的NIST 979溶液的分析结果方块表示加入不同量Ti的分析结果，圆圈表示加入不同量Fe的分析结果(Zhu et al., 2018[35])。Figure 2. Analytical results of NIST 979 solution that different quantities of added Fe and Ti. The squares represent the analytical results of adding different quantities of Ti, and the circles represent the analytical results of adding different quantities of Fe (Zhu et al., 2018[35])表 3 铬同位素的同质异位素及多原子离子干扰Table 3. Isobaric and polyatomic interference for Cr isotope同位素 49Ti 50Cr 51V 52Cr 53Cr 54Cr 56Fe 同质异位素 - 50Ti+, 50V+ - - - 54Fe+ - 双电荷离子 98Mo++
98Ru++100Mo++
100Ru++102Pd++
102Ru++104Pd++
104Ru++106Pd++
106Cd++108Pd++
108Cd++112Sn++
112Cd++多原子团离子 36Ar13C+
14N35Cl+
15N34S+
16O33S+
17O32S+
12C37Cl+
13C36S+36Ar14N+
38Ar12C+
14N36S+
15N35Cl+
16O34S+
17O33S+
18O32S+
13C37Cl+36Ar15N+
38Ar13C+
14N37Cl+
15N36S+
16O35Cl+
17O34S+
18O33S+
38Ar13C +36Ar16O+
38Ar14N+
40Ar12C+
15N37Cl+
16O36S+
17O35Cl+
18O34S+36Ar17O+
38Ar15N+
40Ar13C+
16O37Cl+
17O36S+
18O35Cl+36Ar18O+
38Ar16O+
40Ar14N+
17O37Cl+
18O36S+36Ar20Ne+
38Ar18O+
40Ar16O+5. 存在问题与展望
由于铬在自然界的存在形式及其地球化学行为对环境的氧化还原条件非常敏感，铬同位素被广泛用于示踪古海洋与古大气的氧化还原状态与演化，以及深部核幔、岩浆分异等过程。要获取高精度的铬同位素组成，其重要前提是样品中铬的良好化学分离纯化，而铬的分离纯化是利用铬形态或其存在形式的差异，通过离子交换树脂来实现。铬在水体和固体样品消解液中的形态变化决定了样品分离纯化的方法有所差异。水体中铬可依据其价态的差别，利用阴和阳离子交换树脂实现Cr(Ⅲ)和Cr(Ⅵ)的分离，藉此可实现不同价态铬的同位素测试。地质或环境样品中的铬，在消解样品过程中统一铬的价态后，也可根据相应的纯化流程进行提纯。
近年来铬的分离纯化及仪器测定方面都取得了显著进展，低含量样品铬的回收率已达到80%以上；MC-ICP-MS作为高精度测试铬同位素的首选仪器，其分析精度也已达到0.04‰(2SD)。然而，一些困扰的问题依然存在。首先是铬的分离纯化方面，流程空白依然是需要关注的重点问题。为了降低流程空白，一些高纯试剂被使用，但进口试剂的昂贵和使用的有效期，制约了某些良好纯化流程的推广使用；其次是低铬高基质样品中铬回收率的问题，特别是高Mn含量样品，如何避免使用氧化剂和进一步消除Mn的纯化流程仍需要进一步完善；最后是膜去溶进样系统的使用，该进样系统与高灵敏度Neptune Plus或Nu plasma Ⅲ型MC-ICP-MS联接，可对10~20 ng/L进样的铬浓度样品进行同位素测试，但适宜的校正和干扰扣除技术还有待进一步验证。由于受到分离纯化方法的制约，双稀释剂法仍是目前铬同位素测试中首选的方法。因此，开发一个高回收、普适性强、效率高的分离纯化方法是亟待解决的问题，而如何降低流程空白、除去干扰元素和彻底分离不同形态的铬是未来进行超低含量铬及其形态同位素高精度测试的一个可能发展趋势。
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表 1 不同文献报道的自然界Yb-Lu同位素组成
Table 1 Natural Yb and Lu isotopic compositions reported in different references
测量方式 172Yb/171Yb 173Yb/171Yb 174Yb/171Yb 176Yb/171Yb 176Yb/172Yb 176Yb/173Yb 173Yb/172Yb 174Yb/172Yb 176Lu/175Lu 文献来源 TIMS 1.526374 1.124778 2.216312 0.885860 0.580369 0.787586 0.736896 1.452011 - [67] TIMS+MC-ICPMS 1.526400 1.124800 2.216300 0.885900 0.580385 0.787607 0.736897 1.451979 0.02656 [6] TIMS 1.532075 1.132685 2.242466 0.901821 0.588627 0.796180 0.739314 1.463679 0.02655 [61] MC-ICPMS 1.532227 1.132685 2.242716 0.901864 0.588597 0.796218 0.739241 1.463697 - [61] MC-ICPMS 1.530570 1.130172 2.235486 0.897145 0.586151 0.793813 0.738400 1.460558 - [66] TIMS - - - - - 0.795200 - - 0.02656 [68] TIMS 1.525914 1.123456 2.215594 0.884110 0.579397 0.786956 0.736251 1.451979 0.02645 [63] MC-ICPMS 1.526049 1.123575 2.215790 0.884081 0.579327 0.786847 0.736264 1.451979 0.02645 [63] TIMS 1.529607 1.129197 2.232678 0.895504 0.585447 0.793045 0.738227 1.459642 0.02655 [65] TIMS 1.531736 1.132338 2.241970 0.901691 0.588673 0.796310 0.739251 1.463679 0.02655 [65] TIMS 1.532105 1.132554 2.242509 0.901976 0.588717 0.796409 0.739215 1.463679 - [69] MC-ICPMS 1.530245 1.131999 2.238963 0.900121 0.588220 0.795161 0.739750 1.463140 - [70] MC-ICPMS - - - - 0.587150 - - 1.461820 - [62] MC-ICPMS - 1.132685 - - - 0.796390 - - - [71] 注：“-”代表无数据。 
下载: 导出CSV
表 2 主要富铪矿物标样的REE-Hf同位素组成特征
Table 2 REE-Hf isotopic compositions of Hf-rich mineral standards
标准溶液 年龄(Ma) 年龄类型 160Gd/177Hf 161Dy/177Hf 176Yb/177Hf 176Lu/177Hf 176Hf/177Hf Hf (μg/g) σ 参考文献 JMC475 - - - - - - 0.282160 - - [4, 83-84] 锆石 年龄(Ma) 年龄类型 160Gd/177Hf 161Dy/177Hf 176Yb/177Hf 176Lu/177Hf 176Hf/177Hf Hf (μg/g) σ 参考文献 Zr 2-1 0 - 0.000001 0.000005 0.000002 0.000000 0.282209±9 6105 330 [85] Zr 3-1 0 - 0.000001 0.000006 0.001997 0.000504 0.282213±8 6819 382 [85] Zr 3-2 0 - 0.000001 0.000005 0.002283 0.000568 0.282210±10 7598 304 [85] Zr 4-1 0 - 0.000012 0.000003 0.001426 0.000356 0.282230±7 10011 300 [85] Zr 4-2 0 - 0.000010 0.000004 0.002033 0.000524 0.282234±8 8648 796 [85] MUNZirc 0 0 - - - 0.000130±65 0.000007±4 0.282135±7 - - [58] MUNZirc 1 0 - 0.000534 0.004097 0.029±13 0.00147±67 0.282135±7 8933 - [58] MUNZirc 2 0 - 0.000282 0.002999 0.078±37 0.0029±12 0.282135±7 10415 - [58] MUNZirc 3 0 - 0.001090 0.010273 0.109±29 0.0044±15 0.282135±7 9232 751 [58] MUNZirc 4 0 - 0.005968 0.037853 0.321±64 0.0127±24 0.282135±7 11790 601 [58] FM0411 1.2±0.1L 206Pb/238U 0.0006 0.0027 0.0058±13 0.00017±2 0.282983±4 9323 422 [20, 86-87] 61.308A 2.488±0.004 206Pb/238U - - 0.030697 0.00186 0.282977±14 5780 - [88] 61.308B 2.508±0.002 206Pb/238U - - 0.030772 0.00228 0.282977±6 5537 - [88] Penglai 4.4±0.1 206Pb/238U 0.0019 0.0059 0.0140±80 0.00038±20 0.282906±10 5152 355 [86, 89-90] FCT 28.402±0.023 206Pb/238U 0.0036 0.0109 0.055±11 0.00210±43 0.282538±16 10773 1055 [91-92] SK10-2 32.10±0.49L 206Pb/238U - - - - 0.282752±53 - - [44, 93-94] GHR1 48.106±0.023 206Pb/238U - - 0.048±30 0.0019±12 0.283050±17 - - [95] Monastery 90.1±0.5 206Pb/238U - - 0.00061±16 0.000009 0.282738±8 - - [45, 96-99] KIM-5 90±3S 206Pb/238U 0.0001 0.0004 0.000430 0.000015±4 0.282660±24 9114 192 [100-102] Jilin 117.63±0.04 206Pb/238U 0.0054 0.0140 0.0310±14 0.00082±35 0.282926±14 9135 510 [103] Qinghu 159.38±0.12 206Pb/238U 0.0019 0.0063 0.026±13 0.00068±21 0.283002±4 11750 802 [104-105] LV-11 ~290 206Pb/238U - - 0.166±11 0.0026±2 0.282837±28 - - [106] Plesovice 337.13±0.37 206Pb/238U 0.0018 0.0061 0.005107 0.000125 0.282482±12 11167 - [98-99, 107] TEMORA-1 416.75±0.24 206Pb/238U 0.0039 0.0173 0.032±15 0.00110±30 0.282685±11 7801 - [20, 38, 51, 108-110] TEMORA-2 418.37±0.14
416.78±0.33206Pb/238U 0.0020 0.0078 0.035±14 0.00109 0.282686±8 9362 239 [97-98, 109, 111-112] R33 419.26±0.39
420.53±0.16206Pb/238U 0.0047 0.0184 0.070±29 0.001990±87 0.282764±14 9764 1373 [50-51, 98, 109, 111] M127 524.36±0.16 206Pb/238U 0.0017 0.0060 0.0177±14 0.000654±64 0.282396±4 12400 500 [113] GZ7 530.26±0.05 206Pb/238U 0.0020 0.0059 0.012528 0.00049 0.281666±4 10060 290 [114] SA01 535.08±0.32 206Pb/238U 0.0031 0.0055 0.0127±87 0.00045±28 0.282293±7 9797 563 [115] SA02 535.10±0.24 206Pb/238U 0.0148 0.0205 0.0203±62 0.00064±17 0.282287±16 8976 507 [116] GZ8 543.92±0.06 206Pb/238U 0.0010 0.0036 0.006325 0.00024 0.281662±5 11600 240 [114] BB12 557.4±6.8 206Pb/238U 0.0005 0.0011 0.007068 0.000062 0.281677±11 6177 - [117] BR266
Z6266559.0±0.2
559.27±0.11206Pb/238U 0.0007 0.0025 0.004910 0.000217 0.281630±10 8778 258 [97, 118-121] BB17 559.2±6.0 206Pb/238U 0.0013 0.0032 0.010624 0.000141 0.281677±6 8085.5 - [117] BB9 560.2±4.7 206Pb/238U 0.0005 0.0011 0.006797 0.000052 0.281675±14 6008 - [117] M257 561.3±0.3 206Pb/238U 0.0005 0.0013 0.002986 0.000096 0.281518±11
0.281544±1810610 - [35, 49, 110, 122] BB16 562±3L 206Pb/238U 0.0002 0.0006 0.00134±47 0.000050±17 0.281669±12 8807 - [123-124] CZ3 563.9±1.3 206Pb/238U 0.0001 0.0004 0.00098±1 0.000034±1 0.281732±7 12980 250 [20, 34, 121, 125-126] Peixe 564±4 206Pb/238U 0.0016 0.0069 0.022229 0.000835 0.281944±29 4958 201 [50, 127-128] Tanz 566.16±0.78 206Pb/238U - - - - 0.281820±7 - - [129] SL7 569±3S 206Pb/238U - - - - 0.281620±30 - - [13] LKZ-1 570.0±2.5 206Pb/238U 0.0003 0.0011 0.00358±35 0.000104±1 0.281794±16 7740 310 [130] GJ-1 601.86±0.37 206Pb/238U 0.0013 0.0033 0.00590±42 0.000238±5 0.282000±5 6681 57 [51, 131-134] Mud tank 731.65±0.49 206Pb/238U 0.0011 0.0034 0.003204 0.000093 0.282507±6 11800 - [97-98, 100, 132, 135] WJS810 816.88±0.49 206Pb/238U - - 0.017655 0.000779 0.282534±6 9671 - [136] 91500 1065.4±0.3
1066.4±0.3
1066.01±0.61207Pb/206Pb 0.0005 0.0023 0.00739±45 0.00031±14 0.282308±6 5900 300 [20, 38, 51, 88, 119, 132, 137-138] FC-1
AS3
AS571099±0.6
1099.1±0.5
1098.6±0.3
1098.47±0.16
1098.70±0.16
1099.96±0.58207Pb/206Pb 0.0054 0.0201 0.0450±19 0.001262 0.282184±16 11031 1222 [97-99, 111, 119, 139-144] CN92-1UQ-Z1 1142.8±0.8 207Pb/206Pb - - 0.020±10 0.00080±12 0.282172±16 - - [20, 145] LH94-15 1830.3±1.9 207Pb/206Pb - - - - 0.281730±6 - - [146-147] QGNG 1851.6±0.6
1851.5±0.3207Pb/206Pb - - 0.0181±48 0.000731 0.281612±4 - - [51, 97-99, 119, 148] Phalaborwa 2052.2±0.8 207Pb/206Pb - - 0.014±11 0.0004±3 0.281234±11 - - [20, 149] KV01 EKC02-51 3227.2±0.2 207Pb/206Pb 0.0019 0.0066 0.0149±42 0.00068±17 0.280810±13 10410 675 [119, 150] OG1 3465.4±0.6
3466.09±0.33207Pb/206Pb 0.0037 0.0096 0.033±13 0.00119±26 0.280633±34 9346 641 [99, 151-153] 斜锆石 年龄(Ma) 年龄类型 160Gd/177Hf 161Dy/177Hf 176Yb/177Hf 176Lu/177Hf 176Hf/177Hf Hf (μg/g) σ 参考文献 SK10-2 32.9±0.5S 206Pb/238U - - 0.0063±13
0.0206±950.00023±4 0.282739±13 - - [20, 64, 154] Kovdor 378.54±0.23
378.5±1.4206Pb/238U 0.0003 0.0005 0.000772 0.000025 0.282767±5 7806 319 [64, 155-157] OG-1 411.91±0.25 206Pb/238U - - 0.0036±13 0.000067±11 0.282694±7 - - [64] Karlshamn 954.2±1.1 207Pb/206Pb - - - 0.000113 0.282228±5 - - [1] FC-1
FC-4b1101.41±0.50
1099.6±1.5207Pb/206Pb - - 0.0073±23 0.000109±28 0.282167±5 - - [64, 144, 156] SA003 1256.2±1.4 207Pb/206Pb - - 0.049±17 0.00067±14 0.282167±5 - - [64] Sorkka 1256.2±1.4 207Pb/206Pb - - 0.056±36 0.00066 0.282149±10 - - [1, 64] Phalaborwa 2059.60±0.35 207Pb/206Pb 0.0002 0.0002 0.000078±33
0.000102±120.0000027±8
0.00000467±1
0.0000033±60.281229±11
0.281206±19
0.281187±1413224 450 [2, 20, 158] 钛锆钍矿 年龄(Ma) 年龄类型 160Gd/177Hf 161Dy/177Hf 176Yb/177Hf 176Lu/177Hf 176Hf/177Hf Hf (μg/g) σ 参考文献 Phala-ZrkA 1937±32S 207Pb/206Pb 0.5824 0.3145 0.024362 0.000424±9 0.281296±5 4364 - [159] 异性石 年龄(Ma) 年龄类型 160Gd/177Hf 161Dy/177Hf 176Yb/177Hf 176Lu/177Hf 176Hf/177Hf Hf (μg/g) σ 参考文献 LV01 376±6L 206Pb/238U - - 0.092430 0.00277 0.282761±18 2986 - [160] 金红石 年龄(Ma) 年龄类型 160Gd/177Hf 161Dy/177Hf 176Yb/177Hf 176Lu/177Hf 176Hf/177Hf Hf (μg/g) σ 参考文献 SR-1 0 - - - - - 0.281879±8 42500 710 [161] SR-2 0 - - - - - 0.281888±7 3990 280 [161] SR-2B 0 - - - - - 0.281874±9 2790 81 [161] SR-3 0 - - - - - 0.281877±23 388 45 [161] SR-3A 0 - - - - - 0.281882±26 416 45 [161] R19 489.4±3.3 206Pb/238U - - - 0.002089 0.282163±17 8.645 - [162-163] JDX 509±8S 206Pb/238U - - 0.00020±15 0.000018±4 0.281795±15 50.1 0.7 [164-165] R10/R10b 1090±5
1089.23±0.96207Pb/206Pb - - 0.00038±48 0.000026±81 0.282178±12 38.8 1.5 [162, 165-166] Sugluk-4 1720.8±4.7 207Pb/206Pb - - 0.00008±39 0.000003±16 0.281172±107 51.3 9.3 [165-166] RMJG 1751.5±4.3 207Pb/206Pb - - 0.000017 0.000001 0.281652±6 103 17 [167] PCA-S207 1865.0±7.5 207Pb/206Pb - - 0.0006±17 0.000019±49 0.281246±146 37 13 [165-166] Diss - - - - - - 0.283258±17 5.081 0.049 [162] R1 - - - - - 0.000013 0.283097±8 49 9 [161] 铌铁矿族矿物 年龄(Ma) 年龄类型 160Gd/177Hf 161Dy/177Hf 176Yb/177Hf 176Lu/177Hf 176Hf/177Hf Hf (μg/g) σ 参考文献 713-79 218±2L 206Pb/238U - - 0.000017 0.000001 0.282749±28 712 - [74, 168] NP-2 380.3±2.4 206Pb/238U - - 0.005372 0.000239 0.282169±32 211 - [74, 169] Coltan139 505.4±1.0 206Pb/238U - - 0.147949 0.003503 0.281991±3 454 - [74, 170] U-3 966±12L 206Pb/238U - - 0.000040 0.000002 0.281703±26 1430 - [74] U-1 971±12L 206Pb/238U - - 0.000725 0.000021 0.281845±38 469 - [74] 注：上标L代表LA-ICPMS，上标S代表SIMS，“-”代表暂无数据。
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