过渡族金属元素同位素分析方法及其地质应用

由于同位素分析方法的改进和多接收电感耦合等离子体质谱仪 (MC ICP MS)的应用 ,近年来过渡族金属元素 (Cu ,Zn和Fe)同位素地球化学有了长足进步 ,成为国际地学领域的一个前沿研究方向。Cu同位素在自然界中的变化最大 ,δ65Cu值为 - 3.70‰～ +2 .0 5‰ ;Zn和Fe同位素变化比Cu同位素变化小 ,δ66Zn值为 - 0 .6 4‰～ +1.16‰ ,而δ56Fe值为 - 1.6 2‰～ +0 .91‰。自然界中各种无机过程 (从高温到低温 )和生物有机过程均能使Cu ,Zn和Fe同位素发生分馏。Cu、Zn和Fe在自然界中广泛分布于各类矿物、岩石、流体和生物体中 ,并广泛参与成岩成矿作用、热液活动和生命活动过程。因此 ,这些过渡族金属元素同位素已在陨石和宇宙化学、矿床学 ,海洋学和生物学等领域的研究中取得了显著成效 ,并将成为地球科学中具有巨大应用前景的一种新的地球化学手段。     

湖北古城锰矿Fe同位素特征及其地质意义

本文报导了湖北古城锰矿含锰层位中黄铁矿Fe同位素的研究结果,并利用黄铁矿Fe同位素对黄铁矿成因和大塘坡早期阶段沉积环境的氧化还原状态进行了制约。黄铁矿δ56Fe值变化范围为-0.13‰~+0.54‰,平均值为+0.22‰,显示相对于当时海水（0~-0.5‰）明显富集Fe的重同位素。本文认为黄铁矿的Fe来自海水中Fe2+部分氧化形成的Fe3+,这些Fe3+在成岩过程中被全部还原,与细菌硫酸盐还原作用形成的H2S结合最终以黄铁矿形式保存在沉积物中。大塘坡式锰矿含锰层位中黄铁矿Fe同位素特征表明,古城冰期（Sturtian冰期）结束之后,大塘坡早期阶段海洋深部已经开始氧化,但是并没有完全被氧化。     

玄武岩标准样品铁铜锌同位素组成

报道了三种玄武岩标准样品(BCR-2、BIR-1a和GBW 07105)的铁铜锌同位素数据。实验使用HNO3-HF混合酸消解玄武岩标准样品;AGMP-1阴离子交换树脂分离提纯样品中的铜铁锌,利用多接收等离子体质谱仪(MC-ICPMS)测定铁铜锌同位素比值,分析过程中使用样品-标准-样品交叉法校正仪器的质量分馏。实验得到BCR-2、BIR-1a和GBW 07105标准样品的高精度铁铜锌同位素组成(95%置信水平的不确定度)分别为:δ56FeBCR-2-IRMM014=0.070‰±0.018‰(2SD),δ65 CuBCR-2-SRM976=0.16‰±0.04‰(2SD),δ66 ZnBCR-2-IRMM3702=-0.072‰±0.020‰(2SD);δ56 FeBIR-1a-IRMM014=0.044‰±0.026‰(2SD),δ65CuBIR-1a-SRM976=0.027‰±0.019‰(2SD),δ66 ZnBIR-1a-IRMM3702=0.085‰±0.032‰(2SD);δ56FeGBW 07105-IRMM014=0.126‰±0.039‰(2SD),δ65 CuGBW 07105-SRM976=0.12‰±0.01‰(2SD),δ66ZnGBW 07105-IRMM3702=0.22‰±0.03‰(2SD)。这些数据在误差(不确定度)范围内与国际上已发表的数据是一致的。三个玄武岩标准样品的铁铜锌同位素组成数据的发表为铁铜锌同位素研究提供了统一的标准,使地质样品的铁铜锌同位素数据的质量监控成为可能。     

喀斯特高原湖泊生物地球化学过程中的锌同位素特征

采用多接收电感耦合等离子体质谱仪(MC-ICP-MS)对喀斯特高原湖泊红枫湖、阿哈湖水体及其主要支流水体悬浮物和一些生物样品中的锌同位素进行了测定,测试精度小于0.11‰(2SD).结果显示,红枫湖水体与其主要支流水体悬浮物中的δ66Zn变化范围分别为-0.29‰～0.26‰和-0.04‰～0.48‰,阿哈湖水体与其主要支流水体悬浮物中的δ66Zn变化范围分别为-0.18‰～0.27‰和-0.179‰～0.46‰,均表现出支流中的锌同位素组成较重的特点.两湖生物样品中的δ66Zn变化范围较大,为-0.35‰～0.57‰,说明湖泊生态系统中各端员的锌同位素组成存在一定差异.根据同位素组成分析,湖泊主要入湖河流及所携带的陆源物质是阿哈湖泊水体中锌的主要来源,锌同位素是一种较好的物源示踪工具.红枫湖夏季δ66zn与Chla(叶绿素)呈显著的正相关(R=0.97),主要是藻类对锌的有机吸附和吸收过程导致锌同位素组成发生变化.此外,湖泊水体悬浮物中的锌同位素组成均在夏季较轻,表明大气的干湿沉降可能是一个较负的锌同位素源.水体悬浮物中的δ66Zn变化范围小于生物样品中的δ66Zn变化范围,说明由于生物作用过程导致的锌同位素分馏大于非生物过程.     

白云鄂博地区相关地质单元的铁同位素特征及其对白云鄂博矿床成因的制约

白云鄂博Fe-REE-Nb矿床是世界著名的巨型多金属矿床,它的成因一直是个激烈争论的问题,观点主要集中在沉积成因和岩浆成因上,而铁的物质来源问题是争论的焦点之一。近年来Fe同位素的快速发展为解决白云鄂博铁矿的成因提供了新思路。对白云鄂博地区发育的白云鄂博群尖山组铁质板岩、宽沟北沉积型铁矿、腮林忽洞微晶丘、灰绿岩墙这些相关地质单元的Fe同位素组成特征进行了研究,为白云鄂博矿床成因研究提供了最直接的参考。结果表明,尖山组铁质板岩的δ56Fe值为-0.49‰～0.48‰,平均值为-0.03‰±0.84‰,2SD,n=5;宽沟北沉积型铁矿的δ56Fe值为-0.68‰～0.23‰,平均值为-0.10‰±0.78‰,2SD,n=5;腮林忽洞微晶丘δ56Fe值为-0.64‰～0.12‰,平均值为-0.28‰±0.57‰,2SD,n=6;辉绿岩的Fe同位素组成δ56Fe值集中在0.11‰～0.16‰。腮林忽洞微晶丘总体上比白云鄂博赋矿白云岩富集Fe的轻同位素,Fe同位素组成变化也相对更大,表明两者可能有不同的成因。白云鄂博地区尖山组铁质板岩、宽沟北沉积型铁矿与世界其他地区含铁沉积建造的Fe同位素组成类似,其共同特征是,Fe同位素变化较大,总体上δ56Fe大于0‰。这一特征与白云鄂博铁矿的Fe同位素组成差别较大。白云鄂博矿床的δ56Fe集中在0‰附近,与白云鄂博地区灰绿岩、世界不同地区火成岩和岩浆型铁矿的Fe同位素组成特征一致。表明白云鄂博铁矿可能不是沉积成因的,更有可能与岩浆作用有关。     

多接收器等离子体质谱法Zn同位素比值的高精度测定

详细报道了Zn同位素比值的多接收器等离子体质谱(MC-ICP-MS)高精度测定方法,包括:MC-ICP-MS Zn同位素测量过程中的质量歧视校正、同质异位素干扰评估、基质效应调查和同位素测量的长期重现性检验.研究表明,在测定条件下,运用标样一样品交叉法能有效地进行仪器质量歧视校正.同质异位素干扰的评估通过3种方式进行,即:在高分辨状态下同质异位数干扰信号的直接测定,低分辨状态下Zn同位素原始数据间相关关系的检验和低分辨下浓度梯度效应研究.结果表明,在低分辨模式下,尽管66Zn、67Zn、68Zn的同质异位素干扰信号很小,但的确存在,要获得准确同位素比值,必须使标样和样品的浓度在合适的范围内匹配.在基质效应方面,主要考察Fe对Zn同位素比值测定的影响.结果表明,当溶液中Fe/Zn(质量比)不大于0.2时,Fe对Zn同位素比值测定无影响.重复性测定中,δ66ZnGSB-Romil=6.96‰±0.11‰(2sd),δ67ZnGSB-Romil=10.4‰±0.20‰(2sd),δ68ZnGSB-Romil=13.8‰±0.22‰(2sd),达到国际同类实验室先进水准.运用所建立的方法,对地质岩石成分分析国家标准物质GBW 07270(闪锌矿)进行了Zn同位素平均成分测定为:δ66Zn=6.71‰±0.03‰(20),δ67Zn=10.08‰±0.05‰(20),δ68Zn=13.37‰±0.07‰(2σ).     

女山单斜辉石巨晶锂同位素组成的离子探针分析

应用离子探针技术测定了一组女山单斜辉石巨晶的锂同位素组成。结果表明,无论是不同样品之间还是同一样品内部,锂同位素组成都是均一的,δ7Li=(+8.0±2.7)‰,明显高于MORB值(+1.5‰～+5.1‰)。巨晶的锂同位素组成直接继承自地幔源区,高δ7Li的特征暗示源区受到过俯冲海洋板块析出流体的交代作用。结合Sr Nd同位素的资料来看,交代流体可能来自于蚀变洋壳而不是海洋沉积物。     

MC-ICP-MS高精度Cu、Zn同位素测试技术

过渡族元素同位素是国际上同位素地球化学研究的热点。测试技术的限制是制约过渡元素同位素研究发展的关键。笔者利用Neptune型多接收等离子质谱(MC-ICP-MS),采用Cu、Zn互为内标的方法对仪器的质量歧视进行了校正,对基质效应和测试方法的重现性进行了检验,建立了高精度的Cu、Zn同位素测试技术。在5个月内对实验室标准IMRCu和IMRZn进行了测量,结果分别为δ65CuNIST976=(0.34±0.08)‰(2SD,n=32),δ66ZnJMCZn=(-9.64±0.05)‰(2SD,n=26),δ67ZnJMCZn=(-14.37±0.16)‰(2SD,n=26),δ68ZnJMCZn=(-19.01±0.08)‰(2SD,n=26),分析精度达到国际同类实验室先进水平。对Cu、Zn同位素参考物质进行了对比测量,分析结果与报道值在误差范围内完全一致。     

洋壳蚀变过程中Cu和Zn同位素分馏:对海洋Cu和Zn循环的制约

<正>铜(Cu)和锌(Zn)属于第一过渡族金属元素,分别有2种(63Cu、65Cu)和5种(64Zn、66Zn、67Zn、68Zn、70Zn)稳定同位素。Cu-Zn都属于生命元素,它们在海洋中的地球化学循环对海洋生产率发挥着重要作用。现有研究表明,海水的δ65Cu和δ66Zn分别为ca.0.9‰和ca.0.5‰,显著重于河水的Cu-Zn同位素组成(δ65Cu=ca.0.6‰和δ66Zn=ca.0.3‰);说明海洋中至少存在一个具有轻Cu-Zn同位素组成的储库。海底Fe-Mn结壳和碳酸盐岩石海洋Cu-Zn输出的重要渠道。已有研究表明,三大洋中的Fe-Mn结壳的δ65Cu和δ66Zn分别为0.44±0.23‰和1.04     

俯冲进变质过程中铁同位素分馏行为——以大别—苏鲁造山带为例

<正>大量研究表明,上地幔铁同位素组成是不均一的,上地幔平均值为δ56Fe=0.025±0.025‰[1]。玄武岩具有比上地幔整体偏重的铁同位素组成,因产出构造环境不同其δ56Fe略有不同:洋中脊玄武岩(MORB)δ56Fe=0.105±0.039‰(2SD,n=46);洋岛玄武岩(OIB)δ56Fe=0.121±0.075‰(2SD,n=61);岛弧玄武岩(IAB)δ56Fe=0.060±0.089‰(2SD,n=25)。地幔部分熔融过程中,铁同位素存在显著分馏,显著不同于其他类     

Two pulses of mineralization and genesis of the Zhaxikang Sb–Pb–Zn–Ag deposit in southern Tibet: Constraints from Fe–Zn isotopes

Zhaxikang is one large Sb–Pb–Zn–Ag deposit located in the North Himalaya of southern Tibet. To date, the genesis of this deposit still remains controversial. Here, we present new pyrite Fe and sphalerite Zn isotopic data for the first three stages of mineralization, Fe–Zn isotopic data for Mn–Fe carbonate that formed during the first two stages of mineralization, and Zn isotopic data for the slate wall rocks of the Jurassic Ridang Formation to discuss the genesis of the Zhaxikang deposit. The overall δ⁵⁶Fe and δ⁶⁶Zn values range from −0.80‰ to 0.43‰ and from −0.03‰ to 0.38‰, respectively. The δ⁵⁶Fe values of Mn–Fe carbonates are lighter than those of associated pyrite in six mineral pairs, indicating that the iron carbonates are preferentially enriched in light Fe isotopes relative to pyrite. The sphalerite has lighter δ⁶⁶Zn values than associated Mn–Fe carbonates in three mineral pairs.The δ⁵⁶Fe values of pyrite that formed during the first three stages of mineralization gradually increase from stage 1 (−0.33‰ to −0.09‰) through stage 2 (−0.30‰ to 0.19‰) to stage 3 (0.16‰–0.43‰). In comparison, the sphalerite that formed during these stages has δ⁶⁶Zn values that gradually decrease from stage 1 (0.16‰–0.35‰) through stage 2 (0.09‰–0.23‰) to stage 3 (−0.03‰ to 0.22‰). These data, in conjunction with the observations of hand specimens and thin sections, suggest that the deposit was overprinted by a second pulse of mineralization. This overprint would account for these Fe–Zn isotopic variations as well as the kinetic Rayleigh fractionation that occurred during mineralization. The temporally increasing δ⁵⁶Fe and decreasing δ⁶⁶Zn values recorded in the deposit are also coincident with an increase in alteration, again supporting the existence of two pulses of mineralization. The δ⁵⁶Fe values of the first pulse of ore-forming fluid were calculated using theoretical equations, yielding values of −0.54‰ to −0.34‰ that overlap with those of submarine hydrothermal solutions (−1‰ to 0‰). However, the δ⁵⁶Fe values of the stage 3 pyrite are heavier than those of typical submarine hydrothermal solutions, which suggests that the second pulse of mineralization was probably derived from a magmatic hydrothermal fluid. In addition, the second pulse of ore-forming fluid has brought some Fe and taken away parts of Zn, which results the lighter δ⁶⁶Zn values of sphalerite and heavier δ⁵⁶Fe values of pyrite from the second pulse of mineralization. Overall, the Zhaxikang deposit records two pulses of mineralization, and the overprint by the second pulse of mineralization causes the lighter δ⁶⁶Zn values and heavier δ⁵⁶Fe values of modified samples.     

Development of Cu and Zn Isotope MC-ICP-MS Measurements: Application to Suspended Particulate Matter and Sediments from the Scheldt Estuary

The present study evaluates several critical issues related to precision and accuracy of Cu and Zn isotopic measurements with application to estuarine particulate materials. Calibration of reference materials (such as the IRMM 3702 Zn) against the JMC Zn and NIST Cu reference materials were performed in wet and/or dry plasma modes (Aridus I and DSN‐100) on a Nu Plasma MC‐ICP‐MS. Different mass bias correction methods were compared. More than 100 analyses of certified reference materials suggested that the sample‐calibrator bracketing correction and the empirical external normalisation methods provide the most reliable corrections, with long term external precisions of 0.06 and 0.07‰ (2SD), respectively. Investigation of the effect of variable analyte to spike concentration ratios on Zn and Cu isotopic determinations indicated that the accuracy of Cu measurements in dry plasma is very sensitive to the relative Cu and Zn concentrations, with deviations of δ⁶⁵Cu from ?0.4‰ (Cu/Zn = 4) to +0.4‰ (Cu/Zn = 0.2). A quantitative assessment (with instrumental mass bias corrections) of spectral and non‐spectral interferences (Ti, Cr, Co, Fe, Ca, Mg, Na) was performed. Titanium and Cr were the most severe interfering constituents, contributing to inaccuracies of ?5.1‰ and +0.60‰ on δ^68/64Zn, respectively (for 500 μg l^?1 Cu and Zn standard solutions spiked with 1000 μg l^?1 of Ti or Cr). Preliminary isotopic results were obtained on contrasting sediment matrices from the Scheldt estuary. Significant isotopic fractionation of zinc (from 0.21‰ to 1.13‰ for δ⁶⁶Zn) and copper (from ?0.38‰ to 0.23‰ for δ⁶⁵Cu), suggest a control by physical mixing of continental and marine water masses, characterized by distinct Cu and Zn isotopic signatures. These results provide a stepping‐stone to further evaluate the use of Cu and Zn isotopes as biogeochemical tracers in estuarine environments.     

Combined Separation of Cu,Fe and Zn from Rock Matrices and Improved Analytical Protocols for Stable Isotope Determination

Isotope ratios of heavy elements vary on the 1/10000 level in high temperature materials, providing a fingerprint of the processes behind their origin. Ensuring that the measured isotope ratio is precise and accurate depends on employing an efficient chemical purification technique and optimised analytical protocols. Exploiting the disparate speciation of Cu, Fe and Zn in HCl and HNO₃, an anion exchange chromatography procedure using AG1‐×8 (200–400 mesh) and 0.4 × 7 cm Teflon columns was developed to separate them from each other and matrix elements in felsic rocks, basalts, peridotites and meteorites. It required only one pass through the resin to produce a quantitative and pure isolate, minimising preparation time, reagent consumption and total analytical blanks. A ThermoFinnigan Neptune Plus MC‐ICP‐MS with calibrator‐sample bracketing and an external element spike was used to correct for mass bias. Nickel was the external element in Cu and Fe measurements, while Cu corrected Zn isotopes. These corrections were made assuming that the mass bias for the spike and analyte element was identical, and it is shown that this did not introduce any artificial bias. Measurement reproducibilities were ± 0.03‰, ± 0.04‰ and ± 0.06‰ (2s) for δ⁵⁷Fe, δ⁶⁵Cu and δ⁶⁶Zn, respectively.     

硫酸盐的氧同位素测量方法

硫酸盐不仅是常见矿物,还是自然界少数几个具有氧同位素非质量分馏效应的矿物之一。硫酸盐矿物的氧同位素组成,特别是硫酸盐的氧同位素非质量分馏效应,可以为研究其形成过程和条件提供大碹有用信息,揭示一些元素浓度甚至单个同位素比值测量无法获得的特殊作用过程。但由于硫酸盐的氧同位素分析技术难度大,这一方法在国内尚未建立起来。论文介绍了BrF5法测量硫酸盐氧同位素组成的实验装置、分析流程和测量结果。该方法是目前唯一可以同时测量硫酸盐^17O／^16O和^18O／^16O比值的方法。对BaSO4国际氧同位素标准样品NBS-127和一种BaSO4化学试剂进行了多次重复测量。测量的NBS-127国际标样的δ^18Ov-SMOW=（9．20±0．11）‰,与标准值完全一致;BaSO4化学试剂的δ^18Ov-SMOW=（14．64±0．13）‰。分析精度（标准偏差）达到0．13％。（1σ）,优于国外（0．15～0．29）‰（1σ）的水平     

Ba同位素分析方法综述

随着实验技术的进步以及多接收电感耦合等离子体质谱仪（MC-ICP-MS）和热电离质谱仪（TIMS）的发展,近年来Ba 同位素的分析方法取得了显著进展。分析精度（δ^138/134Ba,2SD）从之前的1 ‰ 提高到好于0.05 ‰。文章综述了近年来高精度Ba 同位素分析方法（溶液法）的发展历程,总结了国内外实验室关于不同类型样品的消解、Ba 元素化学纯化流程以及Ba 同位素质谱测定等方法,并对国内外多个实验室已发表的各类标准物质的Ba 同位素组成进行统计。研究结果可为Ba 同位素激光原位分析提供参考,为后续分馏机理解析和应用研究提供技术支撑。     

锂同位素及其地质应用研究进展

锂同位素示踪是近几年发展起来的一门新兴的稳定同位素地球化学方法,锂有两个稳定同位素：^6Li和^7Li。自在界锂同位素的组成变化很大,其δ^6Li值变化幅度超过60‰,现代大洋水的δ^6Li值为－31．0‰,洋中脊玄武岩（BORB）的δ^6Li值为－4．7‰--3.7‰,由于锂同位素存在大的分馏和不同地质体中在截然不同的δ^6Li值,因此锂同位素地质应用前景十分广泛。目前,锂同位素在研究星云形成过程和宇宙事件,洋壳蚀变和海底热液活动,壳－幔物质循环和板块俯冲作用过程,判断卤水起源和演化等方面的研究中成效显著。     

Resolving impact volatilization and condensation from target rock mixing and hydrothermal overprinting within the Chicxulub impact structure

This work presents isotopic data for the non-traditional isotope systems Fe, Cu, and Zn on a set of Chicxulub impactites and target lithologies with the aim of better documenting the dynamic processes taking place during hypervelocity impact events, as well as those affecting impact structures during the post-impact phase. The focus lies on material from the recent IODP-ICDP Expedition 364 Hole M0077A drill core obtained from the offshore Chicxulub peak ring. Two ejecta blanket samples from the UNAM 5 and 7 cores were used to compare the crater lithologies with those outside of the impact structure. The datasets of bulk Fe, Cu, and Zn isotope ratios are coupled with petrographic observations and bulk major and trace element compositions to disentangle equilibrium isotope fractionation effects from kinetic processes. The observed Fe and Cu isotopic signatures, with δ^56/54Fe ranging from ?0.95‰ to 0.58‰ and δ^65/63Cu from ?0.73‰ to 0.14‰, mostly reflect felsic, mafic, and carbonate target lithology mixing and secondary sulfide mineral formation, the latter associated to the extensive and long-lived (>10⁵ years) hydrothermal system within Chicxulub structure. On the other hand, the stable Zn isotope ratios provide evidence for volatility-governed isotopic fractionation. The heavier Zn isotopic compositions observed for the uppermost part of the impactite sequence and a metamorphic clast (δ^66/64Zn of up to 0.80‰ and 0.87‰, respectively) relative to most basement lithologies and impact melt rock units indicate partial vaporization of Zn, comparable to what has been observed for Cretaceous-Paleogene boundary layer sediments around the world, as well as for tektites from various strewn fields. In contrast to previous work, our data indicate that an isotopically light Zn reservoir (δ^66/64Zn down to ?0.49‰), of which the existence has previously been suggested based on mass balance considerations, may reside within the upper impact melt rock (UIM) unit. This observation is restricted to a few UIM samples only and cannot be extended to other target or impact melt rock units. Light isotopic signatures of moderately volatile elements in tektites and microtektites have previously been linked to (back-)condensation under distinct kinetic regimes. Although some of the signatures observed may have been partially overprinted during post-impact processes, our bulk data confirm impact volatilization and condensation of Zn, which may be even more pronounced at the microscale, with variable degrees of mixing between isotopically distinct reservoirs, not only at proximal to distal ejecta sites, but also within the lithologies associated with the Chicxulub impact crater.