岩石中Pb同位素的多接收等离子质谱测定——数据、分析和处理流程以及注意事项

作者在昆士兰大学利用多接收等离子质谱仪MicromassIsoprobe测定了7种USGS岩石参考标准AGV-1、AGV-2、BHVO-1、BHVO-2、BCR-2、BIR-1/1和W-2的Pb同位素组成,同时测定了标准物质NBS981的Pb同位素组成。采用~(203)Tl-~(205)Tl同位素作为内部标准进行同位素分馏校正。所获得达到NBS981和USGS岩石标准AGV-1、BHVO-1的同位素比值的精度可与热电离质谱双稀释剂法或三稀释剂法数据相媲美,甚至具有更高精度。而BHVO-2、AGV-2和BCR-2     

分步淋洗方法研究碧溪岭榴辉岩Pb同位素组成及其演化

根据大量年代学、地球化学和岩石学等方面的研究,前人对碧溪岭榴辉岩的形成及变质历史有了较明确的认识,但这些研究对超高压变质前后过程中元素和同位素的变化涉及较少。通过分步淋洗方法对碧溪岭榴辉岩中石榴石的Pb同位素研究发现,不同淋洗步骤的Pb同位素组成明显不同,但对不同的石榴石样品以及同一样品用不同的淋洗流程,得到的淋洗规律以及Pb同位素组成变化范围基本一致。不同淋洗步骤的Pb同位素组成构成等时线,给出表面年龄为30亿年左右,与前人报道的碧溪岭地区榴辉岩原岩形成及超高压变质的年龄数据有明显差异。结合前人研究可以判断,这些年龄不具有明确的地质意义,属于假等时线。但分步淋洗结果能反映碧溪岭榴辉岩中Pb同位素的来源可能由地幔组分和上地壳组分混合而成,地幔组分的Pb反映了碧溪岭榴辉岩的原岩是地幔成因的,上地壳组分的Pb表明在榴辉岩快速折返过程中,受到具有上地壳Pb同位素组成的含水流体交代     

热电离质谱计测定国家标准火成岩粉末Sr-Nd-Pb同位素组成

文章以美国地质调查局制备的标准岩石粉末（BCR-2玄武岩、BHVO-2玄武岩、AGV-2安山岩）作为参考物质，运用同位素稀释法和热电离质谱计同位素比值测量方法，分析中国三种火成岩标准粉末（GSR-1花岗岩、GSR-2安山岩、GSR-3玄武岩）Sr-Nd-Pb同位素组成，观察其同位素组成及均一性特征。分析结果表明：这三种火成岩岩石标准粉末都具有均一的Sr和Nd同位素组成；相比GSR-1花岗岩，GSR-2安山岩和GSR-3玄武岩的Pb同位素组成相对均一。GSR-1花岗岩的Pb同位素组成有较大的变化范围，不均一性特征可能受高U和高Th矿物的放射性成因Pb同位素组成叠加影响。根据测量结果，作者认为三种国家火成岩标准粉末适合作为Sr和Nd同位素组成分析的参考物质，GSR-2安山岩和GSR-3玄武岩也是理想的Pb同位素组成分析的参考物质。     

长春市城市土壤铅同位素组成特征及其来源解析

为查明长春市土壤铅的污染来源,采集了长春市表层(0～20 cm)土壤及城市环境污染端元(燃煤尘、汽车尾气尘,建筑尘)样品,采用X荧光光谱法(XRF)测定土壤Pb含量,用质谱仪测定各样品的铅同位素组成.分析结果表明,长春市表层土壤Pb平均质量分数44.72×10-6,是长春市土壤背景值(19.06×10-6)的2.35倍,已受到一定程度铅污染;长春市土壤铅同位素208Pb/207Pb和206Pb/207Pb比值变化较大,分别为2.249～2.473和1.158～1.213;各污染端元物质铅同位素组成差异较大,能很好区别各端元物质.运用铅同位素示踪技术追踪土壤铅的污染来源结果表明,长春市中心城区土壤铅污染主要来源于以热电二厂为代表的工业燃煤排放和历史汽车尾气残留,而与当前汽车尾气排放关系不大;建筑尘也一定程度上对城市土壤产生了影响.     

ISOTOPIC TRACING OF POLLUTANT LEAD SOURCES IN SUBURB SOIL OF JINGZHOU CITY,CHINA

对荆州市郊的农田区、交通区和工业区土壤、汽车尾气、染料和煤等样品进行了铅含量和铅同位素组成研究.铅含量分析结果表明,工业区和交通区土壤均已受到一定的铅污染,其Pb含量平均值(32.80 μg/g和26.28 μg/g)均高于中国土壤平均值,但工业区受到的铅污染更严重.农田区土壤的Pb含量平均值(24.84μg/g)虽稍低,但也指示该区部分土壤已开始受到铅污染.土壤酸溶相Pb含量与全土Pb含量成显著正相关,指示土壤中的Pb主要分布在酸溶相中.铅同位素组成分析结果表明,工业区、交通区和农田区土壤以及土壤不同相(全土、土壤酸溶相和残渣相)具有不同的Pb同位素组成,且土壤的206Pb/204Pb和208Pb/204Pb比值大致具有如下规律:土壤残渣相＞全土＞士壤酸溶相.但是,全土的两组Pb同位素比值平均值更接近于酸溶相的.煤、汽车尾气和染料等环境样品具有比土壤变化范围更大的Pb同位素组成.208Pb/204Pb与206Pb/204Pb相关关系图显示,土壤酸溶相大致位于残渣相、汽车尾气和染料与煤组成的三角形内,表明土壤同时受到了汽车尾气、染料和煤的影响.综合对比分析所有样品的Pb含量和Pb同位素组成,结果表明自无Pb汽油的使用,交通区的Pb污染已大大降低,但工业区受到的Pb污染在加重.为防止土壤铅污染的进一步加重,今后需重点防范工业Pb的排放与污染.     

高温熔融研制钾长石玻璃标准物质初探

激光剥蚀多接收等离子体质谱(LA-MC-ICPMS)是进行原位微区分析微量元素和同位素的重要技术之一,标准样品与样品之间的基体匹配是解决影响该技术准确分析的基体效应和分馏效应的首选方案。长石(特别是长石微区)的Pb同位素组成是示踪岩石形成和演化历史的重要途径,而LA-MC-ICPMS技术则是进行长石Pb同位素原位微区分析的关键技术,然而目前国内外尚没有合适的长石Pb同位素分析标准。文章研究探讨了利用高温炉进行原位微区分析钾长石中Pb同位素组成所用外部标准物质合成条件,结果表明,常规的74μm(200目)碎样无法得到均一的钾长石玻璃,需要将初始钾长石粉末研磨至1300目以下;高温炉合成温度为1680℃;熔融时间为2 h;采用液氮方式淬火。制成的钾长石玻璃除表面具有轻微的不均一性外,内部的Pb同位素比值为1.90779±0.00009(208Pb/206Pb,2s),0.75899±0.00004(207Pb/206Pb,2s),20.909±0.002(206Pb/204Pb,2s),15.871±0.002(207 Pb/204 Pb,2s)和39.888±0.005(208 Pb/204 Pb,2s),相应的相对标准偏差(RSD)分别为0.007%、0.008%、0.016%、0.016%和0.021%。表明利用本研究方法合成的钾长石玻璃可作为潜在的钾长石中Pb同位素组成原位微区分析外部校准物质。     

钙同位素化学分离方法研究

报道了在本实验室建立的地质样品钙同位素化学分离方法。通过对比不同离子交换柱类型、树脂体积、淋洗酸浓度及类型、上样量及样品岩性等影响化学分离效果的因素,确定了采用AG MP-50(100-200目)树脂及HCl淋洗的化学分离流程。该流程在确保高回收率的条件下实现了Ca与K、Sr等干扰元素的有效分离和质谱测量过程中基体效应的有效控制,经这套化学分离方法提纯的NIST SRM 915a、IAPSO大西洋标准海水及一些USGS标样的测试结果与文献值在误差范围内一致,表明本文建立的化学分离流程可满足热电离质谱(TIMS)高精度测定地质样品钙同位素的要求。     

少量AG1-X4阴离子交换树脂分离地质标样中的铁及铁同位素测定

报道了利用少量AG1-X4阴离子交换树脂分离地质样品中Fe及测定Fe同位素的方法。对少量AG1-X4和AG MP-1树脂的分离效果进行了比较,测定了经过AG1-X4分离后的地质标样BCR-2、BHVO-2、BIR-1a、AGV-2、W-2、GSP-2、COQ-1、DTS-2b、JB-2、Jsd-1、GBW07105和GBW07267的Fe同位素组成,其结果与文献参考值在误差范围内一致。这些数据的发表对于地质样品Fe的化学分离和同位素测定提供了参考依据。此方法可以大大减少化学试剂用量,是一种快速有效分离铁的方法。     

AG-MP-1M阴离子交换树脂分离-表面热电质谱法测定沉积物中的铅同位素组成

利用新型阴离子交换树脂分离沉积物中的重金属Pb,采用表面热电离质谱法(TIMS)测定了沉积物样品中的Pb同位素组成。新型树脂为大孔径阴离子树脂AG-MP-1M,淋洗液采用低浓度的盐酸,避免了使用难以纯化的氢溴酸,可有效地降低试剂空白。通过对铅同位素标准物质NIST NBS-981的重复测试,方法的精密度(<0.5%,2s)和准确度均达到了应用研究的要求。对5个实际沉积物样品中的铅同位素组成进行测定,获得了理想的分析效果。     

大型高分辨率多接收等离子体质谱准确测定地质标样的铁同位素组成

使用AGMP-1M阴离子交换树脂提纯样品中的Fe同位素,利用Nu1700大型多接收等离子体质谱在高分辨率模式下测定铁同位素比值,采用标样-样品交叉法校正仪器的质量歧视效应,对回收率、化学流程本底、酸度效应、浓度效应进行了检验,建立了可靠的高精度铁同位素分析技术。本文测定了常用地质标准样品(BCR-2,BHVO-2,AGV-2,GSR-2,GSR-3)的Fe同位素组成,测定结果与文献报道值在误差范围内一致,其测试精度优于(BCR-2,BHVO-2,AGV-2,GSR-3)0.03‰(2SD)。GSR-2可能受Fe含量较低(TFe_2O_3=4.95%)和均一性的影响,获得的δ~(56)Fe和δ~(57)Fe的测试精度分别为0.05‰和0.07‰(2SD)。     

一次溶样分离地质样品中Pb-Sr-Nd方法的可行性研究

现有的地质样品中Pb、Sr、Nd分离分析方法是对Pb和Sr - Nd分别采用两份样品进行分离,多消耗一份样品量,因而制约了样品量少的研究.本文提出了基于HNO3 - HF - HClO4混合酸熔融样品,采用AG1 - X8、AG50W - X8和HDEHP组合离子交换柱,对同一份地质样品一次溶样,连续分离Pb、Sr、Nd.用该方法对国际标准样品AGV -2、BHVO-2中的Pb、Sr、Nd进行分离,回收率均优于95％,全流程空白分别为Pb＜ 0.2 ng,Sr＜1.5 ng,Nd＜1.1 ng.用多接收器-电感耦合等离子体质谱(MC -ICP - MS)进行同位素比值测定,结果表明本研究提出的一份样品连续分离后的同位素测定结果与传统方法利用两份样品分别进行分离的结果在误差范围内完全一致.本文的研究可实现微量岩石样品的Pb、Sr、Nd同位素准确分析,对于珍贵样品的同位素组成研究具有重要意义.     

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     

A re-assessment of nickel-doping method in iron isotope analysis on rock samples using multi-collector inductively coupled plasma mass spectrometry

Element doping has been proved to be a useful method to correct for the mass bias fractionation when analyzing iron isotope compositions. We present a systematic re-assessment on how the doped nickel may affect the iron isotope analysis in this study by carrying out several experiments. We find three important factors that can affect the analytical results, including the Ni:Fe ratio in the analyte solutions, the match of the Ni:Fe ratio between the unknown sample and standard solutions, and the match of the Fe concentration between the sample and standard solutions. Thus, caution is required when adding Ni to the analyte Fe solutions before analysis. Using our method, the δ⁵⁶Fe and δ⁵⁷Fe values of the USGS standards W-2a, BHVO-2, BCR-2, AGV-2 and GSP-2 are consistent with the recommended literature values, and the long-term (one year) external reproducibility is better than 0.03 and 0.05‰ (2SD) for δ⁵⁶Fe and δ⁵⁷Fe, respectively. Therefore, the analytical method established in our laboratory is a method of choice for high quantity Fe isotope data in geological materials.

     

Determination of Zirconium, Niobium, Hafnium and Tantalum at ng g-1 Levels in Geological Materials by Direct Nebulisation of Sample HF Solution into FI-ICP-MS

We have developed a rapid and accurate method to determine Zr, Nb, Hf and Ta (denoted as HFSE) in geological samples by inductively coupled plasma-mass spectrometry fitted with a flow injection system (FI-ICP-MS). The method involves sample decomposition by HF followed by HF dissolution of HFSE coprecipitated with insoluble M and Ca fluoride residues formed during the initial HF attack. This HF solution was directly nebulized into an ICP mass spectrometer. An external calibration curve method and an isotope dilution method (ID) were applied for the determination of Nb and Ta, and of Zr and Hf, respectively. Recovery yields of HFSE were > 96% for peridotite, basalt and andesite compositions, apart from Zr and Hf for peridotite (> 85%). No matrix effects for either signal intensities of HFSE or isotope ratios of Zr and Hf were observed in basalt, andesite and peridotite solutions down to a dilution factor of 100. Detection limits in silicate rocks were 40, 2, 1 and 0.1 ng g-1 for Zr, Nb, Hf and Ta, respectively. This technique required only 0.1 ml of sample solution, and thus is suitable for analysing small and/or precious samples such as meteorites, mantle peridotites and their mineral separates. We also present newly determined data for the Zr, Nb, Hf and Ta concentrations in USGS silicate reference materials DTS-1, PCC-1, BCR-1, BHVO-1 and AGV-1, GSJ reference materials JB-1, -2, -3, JA-1, -2 and -3, and the Smithsonian reference Allende powder.     

Neodymium and Strontium Isotope Data for USGS Reference Materials BCR-1, BCR-2, BHVO-1, BHVO-2, AGV-1, AGV-2, GSP-1, GSP-2 and Eight MPI-DING Reference Glasses

We have measured ⁸⁷Sr/⁸⁶Sr and ¹⁴³ Nd/¹⁴⁴ Nd isotope ratios in different batches and aliquots of the new US Geological Survey (USGS) reference materials (RMs) BCR-2, BHVO-2, AGV-2 and GSP-2 and the original USGS RMs BCR-1, BHVO-1, AGV-1 and GSP-1 by thermal ionisation mass spectrometry. In addition, we also analysed the eight Max-Planck-Institut-Dingwell (MPI-DING) reference glasses. Nearly all isotope ratios obtained in the different aliquots and batches agree within uncertainty limits indicating excellent homogeneity of the USGS powders and the MPI-DING glasses. With the exception of GSP-2, the new USGS RMs are also indistinguishable from the ratios found in the original USGS RMs (⁸⁷Sr/⁸⁶Sr: 0.704960, 0.704958 (BCR-1, -2), 0.703436, 0.703435 (BHVO-1, -2), 0.703931, 0.703931 (AGV-1, -2); ¹⁴³ Nd/¹⁴⁴ Nd: 0.512629, 0.512633 (BCR-1, -2), 0.512957, 0.512957 (BHVO-1, -2); 0.512758, 0.512755 (AGV-1, -2)). This means that for normalisation purposes in Sr and Nd isotope geochemistry BCR-2, BHVO-2 and AGV-2 can well replace BCR-1, BHVO-1 and AGV-1 respectively.     

Implications of Pb isotope signatures of rocks and iron oxide Cu-Au ores in the Candelaria-Punta del Cobre district,Chile

Lead isotope ratios of ores of the Candelaria-Punta del Cobre iron oxide Cu-Au deposits and associated Early Cretaceous volcanic and batholithic rocks have been determined. For the igneous rocks, a whole-rock acid attack technique based on the separate analyses of a leachate and the residual fraction of a sample was used. The lead isotope systematics of leachate–residue pairs are significantly different for unaltered and altered igneous rocks of the Candelaria-Punta del Cobre district. Residues of unaltered igneous rocks likely represent the common lead. In contrast, residues of all the altered igneous rocks except two samples have higher Pb isotope ratios than those of unaltered magmatic rocks and cannot represent common lead. We suggest that this is a result of the hydrothermal alteration suffered by these rocks and that the common lead composition of the altered igneous (volcanic and plutonic) rocks must have been similar to that of the unaltered batholith rocks. The conclusion that the altered volcanic rocks originally had a similar common lead isotope composition as the batholith is consistent with geological and geochemical arguments (e.g., setting, regional geologic evolution, ages and relative distribution of volcanic and intrusive rocks, magmatic affinities), which indicate that these rocks were derived from similar Early Cretaceous parent magmas. The modification of the leachate–residue pair lead isotope systematics of most altered igneous rocks is consistent with a selective removal of lead and uranium from these rocks by an oxidized hydrothermal fluid. The result of the hydrothermal leaching has been to alter magmatic rocks in a way that (1) their leachable fraction is presently a mix of common lead similar to that of the ore event and of radiogenic lead evolved from a source with a consistently high Th/U, and that (2) their residual fraction has less common lead than unaltered rocks. The outcrop area with altered volcanic rocks displaying anomalously high lead isotope ratios extends over 25 km along the eastern margin of the batholith. Since lead of the ores in the Candelaria-Punta del Cobre district has the same isotopic composition as the common lead of unaltered magmatic rocks of the area, the lead isotope data are consistent with a derivation of the ore lead (and by inference of other metals like Cu) both directly from a magmatic fluid exsolved during crystallization of the batholith and/or from hydrothermal leaching of the volcanic rocks originally having similar isotopic compositions as the batholith.Editorial handling: B. Lehmann     

High-Precision Trace Element Data for the USGS Reference Materials BCR-1, BCR-2, BHVO-1, BHVO-2, AGV-1, AGV-2, DTS-1, DTS-2, GSP-1 and GSP-2 by ID-TIMS and MIC-SSMS

Different batches of the new US Geological Survey (USGS) reference materials (RMs) BCR-2, BHVO-2, AGV-2, DTS-2 and GSP-2 and the original USGS RMs BCR-1, BHVO-1, AGV-1, DTS-1 and GSP-1 have been analysed by isotope dilution using thermal ionisation mass spectrometry (ID-TIMS) and by multi-ion counting spark source mass spectrometry (MIC-SSMS). The concentrations of K, Rb, Sr, Ba and the rare earth elements were determined with overall analytical uncertainties of better than 1% (ID-TIMS) and 3% (MIC-SSMS). The analyses of different aliquots and batches of BCR-2, BHVO-2, AGV-2 and GSP-2, respectively, agree within 1%, i.e. approximately the analytical uncertainties of the data. This indicates an homogeneous distribution of the trace elements in these RMs. Differences in element concentrations of up to 17% in different aliquots of the depleted RM DTS-2 are outside the analytical uncertainty of our data. They may be attributed to a slightly heterogeneous distribution of trace elements in this dunite sample. Our trace element data for BCR-2, BHVO-2, AGV-2 and GSP-2 agree within about 3% with preliminary reference values published by the USGS. They also agree within 1-6% with those of the original RMs BCR-1, BHVO-1, AGV-1 and GSP-1. Large compositional differences are found between DTS-2 and DTS-1, where the concentrations of K, Rb, Sr and the light REE differ by factors of 2 to 24.     

Precise lead isotope measurements by the double spike technique: A reconsideration

A reappraisal of the “Double Spike Method” for correction of the mass discrimination in lead isotope analysis is presented in view of the possible efficiency of this method, especially as related to the improved performance of the new multi-collector mass spectrometers.First, the effects of mass discrimination during lead isotope analysis, using the silica-gel phosphoric acid method, are discussed in order to verify the validity of the linear discrimination law. In this discussion, we give evidence of a slight bias of the isotopic composition of the SRM 981 NBS lead standard, commonly used for mass discrimination calibrations.A rigorous way to deal with the propagation of the within-run statistical errors on the precision of the double spike correction is then presented. This allows the optimization of the parameters of the method (spike isotopic composition and precision, spiking proportion) and the calculation of the respective error associated with each corrected isotopic ratio. The perturbation of the double spike correction due to analytical contamination, which has caused previous failure in the application of the method, is avoided by preparation of the mixture between the spike and the sample at the very end of the chemical separation procedure.Using a single collector mass spectrometer, examples of application on lead standards and on a set of samples suggest a possible improvement in the precision by a factor of 3 compared to the usual method of fractionation normalization and confirm the usefulness of the method with the new generation of mass spectrometers.     

Sr and Pb isotopic composition of five USGS glasses (BHVO-2G, BIR-1G, BCR-2G, TB-1G, NKT-1G)

Sr isotopic compositions and Rb / Sr ratios of three USGS glasses (BHVO-2G, BIR-1G, BCR-2G) are identical to those of the original USGS reference materials. NKT-1G and TB-1G give values of 0.70351 and 0.70558, respectively. Pb isotopic ratios were measured by the standard-sample bracketing technique on an MC-ICP-MS, which give results that are comparable in accuracy and reproducibility to double spike analyses. However, assessment of the reproducibility of the technique is hampered by inhomogeneous contamination of all USGS reference materials analysed. This contamination is likely to be the reason why the USGS glasses do not all have the same Pb isotopic composition as their unfused originals. Powdered glasses, distributed for characterisation of the glasses by bulk analytical techniques, do not all have the same Pb isotopic compositions as the solid glass material, and can therefore not be used for this purpose.     

LA-MC-ICPMS分析古老熔体包裹体Pb同位素组成中的误差评价

目前应用LA-MC-ICPMS分析熔体包裹体Pb同位素,由于没有同时测试U和Th的信号,导致熔体包裹体Pb同位素的研究仅局限于中生代以来的样品。本文应用LA-MC-ICPMS分析了玻璃样品以及存在显著U-Th衰变影响的古老熔体包裹体的Pb同位素组成,评价了U/Pb和Th/Pb分析误差对初始Pb同位素比值校正的影响。实验中以国际玻璃标样NKT-1G为外部标样,采用"标样-样品-标样法"进行仪器漂移和质量歧视校正,结果表明,国际玻璃标样BHVO-2G、TB-1G的208Pb/206Pb和207Pb/206Pb分析精度优于0.30%(2RSD),与推荐值的偏差小于0.30%,然而232Th/206Pb和238U/206Pb分析结果显示了较大分散性(外精度约5.0%)。根据误差传递计算,样品的年龄对初始铅的误差有很大影响。对于古生代以来的样品(年龄小于540 Ma),即使测试的232Th/206Pb和238U/206Pb与真值偏差达到10%,经过U-Th衰变校正后的Pb同位素比值与真值的偏差依然小于0.80%。因此本方法可以将熔体包裹体等地质样品的Pb同位素研究由新生代样品(年龄小于65 Ma)扩展到古生代样品。