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1.
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.  相似文献   

2.
J.L. Paquette  M. Tiepolo   《Chemical Geology》2007,240(3-4):222-237
Monazite [(LREE)PO4], a common accessory mineral in magmatic and metamorphic rocks, is complementary to zircon in U–Th–Pb geochronology. Because the mineral can record successive growth phases it is useful for unravelling complex geological histories. A high spatial resolution is required to identify contrasted age domains that may occur at the crystal-scale. Bulk mineral techniques such as ID-TIMS, applied to single monazite grains recording multiple overgrowths or isotope resetting can result in partly scattered discordant analytical points that produce inaccurate intercept ages. Laser ablation (LA)-ICPMS has been demonstrated to be a useful technique for U–Th–Pb dating of zircons, and this study tests its analytical capabilities for dating monazite. A sector field high resolution ICPMS coupled with a 193 nm ArF excimer laser ablation microprobe is capable of achieving a high spatial resolution and producing stable and reliable isotope measurements.

The U–Th–Pb systematic was applied to monazite grains from several samples: a lower Palaeozoic lens from high-grade terrains in Southern Madagascar, Neogene hydrothermal crystals from the Western Alps, a Palaeoproterozoic very high temperature granulite from central Madagascar and a Variscan leucogranite from Spain, directly on a polished thin section. The major aim was to compare and/or reproduce TIMS and EMP ages of monazite from a variety of settings and ages. The three independent 206Pb/238U, 207Pb/235U and 208Pb/232Th ratios and ages were calculated. Isotope fractionation effects (mass bias, laser induced fractionation) were corrected using a chemically homogeneous and U–Pb concordant monazite as external standard.

This study demonstrates that excimer laser ablation (ELA)-ICPMS allows U–Th–Pb dating of monazite with a high level of repeatability, accuracy and precision as well as rapidity of analysis. A spatial resolution almost comparable to that of EMP in terms of crater width (5 μm) produced precise 208Pb/232Th, 206Pb/238U and 207Pb/235U ratios for dating Palaeozoic to Precambrian monazites. The advantages of (ELA)-ICPMS isotope dating are precision, accuracy and the ability to detect discordance. In the case of late Miocene hydrothermal monazites from the Alps, a larger spot size of 25 μm diameter is required, and precise and accurate ages were obtained only for 208Pb/232Th systematics. Results from the Variscan granite show that in situ U–Th–Pb dating of monazites with (ELA)-ICPMS is possible using a 5 μm spot directly on thin sections, so that age data can be placed in a textural context.  相似文献   


3.
《Chemical Geology》2002,182(2-4):605-618
New developments in U–Pb dating of zircons by laser ablation (LA) ICPMS are described and, for the first time, a direct comparison of detrital zircons dated by LA ICPMS and SIMS methods is presented. True real-time mass bias correction is made by aspirating a Tl/U tracer at the same time as laser ablation. The method is similar to that described in Horn et al. (2000), except that enriched 233U rather than 235U is used in the tracer solution. Correction for laser-induced Pb/U elemental fractionation is based on a mathematical treatment of time-resolved data that is independent of laser ablation characteristics and does not require external standardisation. Internal corrections for mass bias and elemental fractionation eliminate the effects of variable sample matrix on isotopic ratios and improve the accuracy of U–Pb dating by laser ablation ICPMS. With the proper error propagation, the precision of U–Pb age determinations is only slightly worse than SIMS-based ion probe dating. However, LA ICPMS is capable of much more rapid analysis of the large number of zircons required for sediment provenance studies. There is excellent agreement between concordant laser ablation ICPMS and SIMS analyses of detrital zircons extracted from lower Silurian metasandstone from the Ulven Group (Skarfjell Formation) in the west Norwegian Caledonian nappes. Both LA ICPMS and SIMS U–Pb zircon ages indicate that sedimentary detritus of the Ulven Group was supplied from a terrain containing zircons of Archean, Proterozoic and early Ordovician age.  相似文献   

4.
A new method has been developed for the simultaneous determination of Pb abundance and Pb isotopic composition with high precision and accuracy for small test portion masses by thermal ionisation mass spectrometry. In this method, a 205pb-204pb double spike is added to samples prior to the chemical separation of Pb, and the isotopic composition of the spike-sample mixture is determined rigorously by the double spike technique using a 207Pb-204Pb spike. The isotopic composition and concentration of Pb in the sample are then obtained by utilising the principle of isotope dilution. Using this technique, replicate determinations of Pb from NIST SRM 981 and GSJ JP-1 (peridotite; 0.07 μg g−1 Pb) were performed. The measured concentration and isotopic data were identical, within uncertainty, to published data or to data that were determined independently in this study. The application of this method to U-Pb dating and the determination of the "initial" Pb isotopic composition was also tested. Lead isotopic compositions and the concentrations of Pb, Th and U were determined for a single batch of samples, through the addition of 205pb-204pb, 230Th and 235U spikes to samples prior to chemical separation. Also in these experiments, we confirmed that this routine gives accurate data for Pb, Th and U concentrations and Pb isotopic compositions.  相似文献   

5.
The accuracy of 231Pa-235U measurements can be readily assessed using a secular equilibrium reference material (RM), but a secular equilibrium RM is also required to calibrate the 233Pa spike used in 231Pa determinations. The only silicate RM commonly accepted to be in secular equilibrium is Table Mountain Latite (TML) and so an additional reference is required. Our measurements on the widely available USGS BCR-2 (Basalt Columbia River) rock powder yielded (231Pa/235U) = 0.997 ± 0.013 2s (n = 10), indicating its value as a secondary reference to test the fidelity of U-Pa determinations. Such a reference material additionally provides a useful check on data reduction, which our literature survey highlights can lead to discrepancies of up to 53% between reported (231Pa/235U) activity ratios and corresponding U and Pa concentration data.  相似文献   

6.
Data are reported for rare earth elements (REE) in three geological glass reference materials (BIR-1G, BHVO-2G and BCR-2G) using a UV (266 nm) laser ablation ICP-MS system and the classical (HF-HClO4) acid decomposition method, followed by conventional nebulisation ICP-MS. External calibration of laser ablation analyses was performed using NIST SRM reference materials with internal standardisation using 29Si and 44Ca. Replicate analyses of reference basaltic glasses yielded an analytical precision of 1-5% (RSD) for all the elements by solution ICP-MS and 1-8% (RSD) by laser ablation ICP-MS. The relative differences between the REE concentrations measured by solution and laser ablation ICP-MS compared with the reference values were generally less than 11 % for most elements. The largest deviations occurred for La determined by solution ICP-MS in BIR-1G. The results of both solution and laser ablation ICP-MS agreed well, generally better than 7%, with the exception of La, Pr and Sm in BIR-1G. The measured REE laser ablation data for BIR-1G, BHVO-2G and BCR-2G agreed with the previously published data on these basaltic reference glasses, within a range of 0-10% for most elements. No significant influences were observed for the predicted spectral interferences on some REE isotopes in the analysis of basaltic glasses.  相似文献   

7.
A direct method for the determination of lead isotopic ratios by laser ablation-inductively coupled plasma-quadrupole mass spectrometry (LA-ICP-QMS) is presented. Samples of lake sediments were ground and pressed as pellets before being analysed. Mass bias was corrected by analysing an external calibration sample manufactured with pure silica doped with NIST SRM 981 solution. The efficiency of the mass bias correction was checked by comparing the ICP-MS data with lead isotopic ratios determined by thermal ionisation mass spectrometry (TIMS). The average long term reproducibilities were 0.40%, 0.40%, 0.20% and 0.30% (RSD) respectively for the 206Pb/204Pb, 207Pb/204Pb, 206Pb/207Pb and 208Pb/206Pb ratios. The method was applied to the study of lake sediment samples, in order to determine the amount and origin of historical contamination by lead.  相似文献   

8.
Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) is a microanalytical tool especially suitable for providing fast and precise U-Pb geochronological results on zircon grains. A new 193 nm excimer laser adapted to a micromachining workstation, equipped with a newly designed two-volume ablation cell and coupled with a quadrupole ICP-MS, is presented here. The system was tuned routinely to achieve sensitivities in the range of 3000 cps/μg g−1 for 238U (< 2% RSD), with a 34 μm spot size, at 5 Hz and ∼ 8 J cm−2, while ablating the NIST SRM 612 glass reference material. The system was capable of providing fast (< 1.5 minutes each analysis) and precise (generally < 1.5% 1s errors) 206Pb/238U zircon ages. The ages of widely used reference material zircons (Plesovice, 337 Ma; Temora, 416 Ma; R33, 418 Ma; Sri Lanka, 564 Ma; 91500, 1065 Ma) could be precisely matched, with an accuracy on isotopic ratios that ranged from ∼ 2 to ∼ 6%, depending on the homogeneity of the natural reference materials.  相似文献   

9.
This paper reports an investigation into the suitability of the neutron-activation method, by use of the reaction 238 U(n,γ) 239 U with detection of the gamma-rays from the daughter 239 Np, for the determination of uranium in 10 proposed reference materials. 182 Ta was used to monitor the neutron flux. The precision of measurement varied from 0.92 to 2.7 per cent. Results compare favourably with those obtained by other analytical procedures, and show that this established method can be used to yield useful and independent results in the preparation of uranium reference materials.  相似文献   

10.
小秦岭地区是我国最重要的金矿产区之一, 目前对该区金矿床成矿作用存在两种不同的观点, 即与秦岭造山带造山作用有关的早中生代成矿和与中国东部构造体制大转折有关的晚中生代成矿.在矿床地质研究的基础上, 利用激光剥蚀ICP-MS方法对小秦岭矿集区北矿带秦南金矿床的热液独居石进行了U-Th-Pb定年, 获得了高精度的年龄数据, 为北矿带金矿床成矿时代和成矿构造背景提供了新的制约.岩相学研究表明, 所研究的独居石具有完好的晶形, 与载金矿物黄铁矿和石英的结构关系表明它们近于同时形成.13个独居石颗粒的U-Th-Pb同位素组成在206Pb/238U-207Pb/235U和206Pb/238U-208Pb/232Th图解上均位于谐和线上或其附近, 其206Pb/238U和208Pb/233Th加权平均年龄分别为120.9±0.9 Ma(MSWD=1.0)和122.6±1.9 Ma(MSWD=2.6), 在误差范围内完全一致.本次定年结果与小秦岭南矿带众多典型金矿床的Re-Os年龄和40Ar/39Ar年龄一致, 表明独居石的U-Th-Pb同位素体系自矿物形成后一直处于封闭体系, 其U-Pb和U-Th-Pb年龄可以解释为秦南金矿床的成矿时代, 从而表明秦南金矿床形成于燕山期.对已有可靠年龄数据的统计分析表明, 小秦岭地区绝大多数金矿床形成于早白垩世, 证明该区金成矿作用集中发生于晚中生代, 可能与华北克拉通岩石圈减薄作用有关.   相似文献   

11.
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。  相似文献   

12.
We found that the suppression of signals for 88Sr, 140Ce and 238U in rock solution caused by rock matrix in ICP-MS (matrix effects) was reduced at high power operation (1.7 kW) of the ICP. To make the signal suppression by the matrix negligible, minimum dilution factors (DF) of the rock solution for Sr, Ce and U were 600, 400 and 113 at 1.1, 1.4 and 1.7 kW, respectively. Based on these findings, a rapid and precise determination method for Rb, Sr, Y, Cs, Ba, REE, Pb, Th and U using FI (flow injection)-ICP-MS was developed. The amount of the sample solution required for FI-ICP-MS was 0.2 ml, so that 1.8 mg sample was sufficient for analysis with a detection limit of several ng g-1. Using this method, we determined the trace element concentrations in the USGS rock reference materials, DTS-1, PCC-1, BCR-1 and AGV-1, and the GSJ rock reference materials, JP-1, JB-1, -2, -3, JA-1, -2 and -3. The reproducibilities (RSD %) in replicate analyses (n=5) of BCR-1, AGV-1, JB-1, -2, -3, JA-1, -2, and -3 were < 6 %, and typically 2.5%. The difference between the average concentrations of this study for BCR-1 and those of the reference values were < 2%. Therefore, it was concluded that the method can give reliable data for trace elements in silicate rocks.  相似文献   

13.
The geochemistry of Re-Os and the recent use of Re as a non-traditional stable isotope both need accurate and precise quantification of 187Re/185Re ratios. This paper reports rhenium isotopic data obtained from the analysis of a standard solution and geological samples by MC-ICP-MS. We show that measured isotopic ratios are modified by matrix effects that cannot be accounted for by the standard solution bracketing technique. The bias resulting from measurements on a spiked (185Re-enriched) sample is shown to alter the apparent Re concentration by several percent. When spiking samples and calibrators with tungsten, simultaneous measurement of tungsten and rhenium isotopes compensates for the matrix-induced modification of mass bias. Rhenium and tungsten are shown to have different fractionation factors. This may be due to the fact that the two elements fractionate in a different but systematic way, or that the reference isotopic ratios used for elemental Re and W are incoherent with one another. The consistency of fractionation through time can be used to obtain an empirical relationship between W and Re measured ratios from a standard solution to obtain a sample's fractionation-corrected 187Re/185Re spiked ratio on samples containing pg g−1 levels of Re, even if some matrix capable of affecting mass bias remains in the final solution.  相似文献   

14.
A simple sample treatment method for the accurate and precise determination of iodine in soil, sediment and biological samples by inductively coupled plasma-mass spectrometry (ICP-MS) is described. Iodine in samples was extracted in screw top PTFE-lined stainless steel bombs using a 10% v/v ammonia solution at 185 C for 18 hours (overnight), after which the extract was introduced into the ICP-MS for direct measurement. 126Te was employed as the internal standard to compensate for matrix effects and instrument drift. The limit of detection (LOD, three times the standard deviation of the procedural blank solution, expressed as the concentration in the sample solution) was 0.003 ng ml--1. The limit of quantitation (LOQ, ten times the standard deviation of the procedural blank solution, expressed as the concentration in the solid samples, dilution factor DF = 100) was 0.01 μg g--1 (dry mass). The accuracy and precision of the method were demonstrated by analysing different Chinese geological certified reference materials (soils, stream sediments and a hair sample). The measured concentrations were in a good agreement with the certified values indicating that bias in the method was not significant. The precision (n = 10) for different concentrations ranged from 1.82% to 4.32% RSD. Comparison of the ammonia extraction procedure with a "sintering" method indicated that there was no significant difference in results obtained with the two methods for geological soil and stream sediment samples. However, for biological samples, such as hair, kelp, tea etc., the results obtained by the sintering method were far below those of the ammonia extraction method. The ammonia extraction has advantages, as it is simpler than the "sintering" method, and has a lower procedural blank, better detection limits and reproducibility. Due to the simplicity of the method, a high rate of sample throughput is possible.  相似文献   

15.
当前分析化学技术正向着痕量微区方向发展。这使得我们能够用更小更少的样品直接得到更多的地球化学信息。在诸多微区测试技术中,激光剥蚀等离子质谱（LA-ICPMS）技术发展最快。其地质应用较广,激光探针等离子体质谱能够进行固体样品的微区微量元素和同位素的分析,具有灵敏度高、简便、快速的特点,同样具有在同位素定年上的潜力。近年来又研制出激光剥蚀多道接收等离子质谱（LA-MC-ICPMS）仪,使得微区同位素分析开始了新的革命。而多种微区技术综合应用为近几年分析地球化学新的趋势。  相似文献   

16.
The 5-km deep Chinese Continental Scientific Drilling Main Hole penetrated a sequence of ultrahigh pressure (UHP)-metamorphic rocks consisting mainly of eclogite, gneiss and garnet-peridotite with minor schist and quartzite. Zircon separates taken from thin layers of schist and gneiss within eclogite were investigated. Cathodoluminescence images of zircon grains show that they have oscillatory zoned magmatic cores and unzoned to patchy zoned metamorphic rims. Zircon rims contain rare coesite and calcite inclusions whereas cores contain inclusions of both low- P minerals (e.g. feldspar, biotite and quartz) and coesite and other eclogite-facies minerals such as phengite and jadeite. The zircon cores give highly variable 206Pb/238U ages ranging from 760 to 431 Ma for schist and from 698 to 285 Ma for gneiss, and relatively high but variable Th/U ratios (0.16–1.91). We suggest that the coesite and other eclogite facies mineral inclusions in zircon cores were not magmatic but formed through metasomatic processes caused by fluids during UHP metamorphism, and that the fluids contain components of SiO2, Al2O3, K2O, FeO, MgO, Na2O and H2O. Metasomatism of the Sulu UHP rocks during continental subduction to mantle depths has partly altered magmatic zircon cores and reset isotopic systems. This study provides key evidence that mineral inclusions within magmatic zircon domains are not unequivocal indicators of the formation conditions of the respective domain. This finding leads us to conclude that the routine procedure for dating of metamorphic events solely based on the occurrence of mineral inclusions in zoned zircon could be misleading and the data should be treated with caution.  相似文献   

17.
A comparison between HBr-HCl and HBr-HNO3 based anion chemistry is presented to test the efficiency of Pb purification in the preparation of samples for isotope ratio measurement by ICP-MS. It was found that the small advantages in yield and blank offered by the HNO3-based method were more than compensated by the more effective matrix removal of the HCl-based method. Apart from very zinc rich matrices (e.g., sphalerite), a careful single pass purification using HBr and HCl removed more than 99.9% of the matrix. In preparation for the isotope ratio analysis, a small (2–5% m/v) liquid sample aliquot was analysed to determine U, Th and Pb concentrations by solution quadrupole ICP-MS. This allowed accurate prediction of the expected ion signal and permitted optimal spiking with Tl, if desired, for mass bias correction. Long-term results for international rock reference materials showed reproducibilities of better than 1% (Th/U) and 1.5% (U/Pb). For most geological applications, such analyses obviate the need for isotope dilution concentration measurements.  相似文献   

18.
We report new data on the trace element concentrations of Mg, Cr, Mn, Co, Ni, Cu, Zn, Sr, Cd, Ba, La, Ce, Nd, Pb and U in USGS carbonate reference materials (MACS-1 and MACS-2) and compare solution ICP-MS and LA-ICP-MS trace element determinations on landfill calcites using calibration to different reference materials (MACS-1 and MACS-2 carbonate and NIST SRM 612 glass). Very good agreement (differences below 10% relative) was found between laser ablation and solution ICP-MS data for MACS-1 with higher concentrations of trace elements (values between 100 and 150 μg g−1), with the exception of Cu and Zn. Similarly good agreement was found for MACS-2 with lower trace element concentrations (units to tens of μg g−1), with the exception of Cr, Co and Zn. The MACS-1 reference material for calibration of LA-ICP-MS was found to be extremely useful for in situ determination of trace elements in real-world carbonate samples (landfill calcites), especially those present in calcite in higher concentrations (Mn, Sr, Ba; < 5% RSD). Less accurate determinations were generally obtained for trace elements present at low concentrations (∼ units of μg g−1). In addition, good agreement was observed between the instrument calibration to MACS and NIST SRM 612 glass for in situ measurements of trace elements in landfill calcites K-2, K-3 and K-4 (differences below 15% relative for most elements). Thus, the application of MACS carbonate reference materials is promising and points to the need for the development of new carbonate reference materials for laser ablation ICP-MS.  相似文献   

19.
An igneous zircon reference material (OG1) was characterised for U-Pb isotopes by ID-TIMS, and utilised to evaluate SIMS (SHRIMP) instrumental mass fractionation (IMF) of radiogenic Pb isotopes (207Pb*/206Pb*). The TIMS 207Pb*/206Pb* reference value for OG1 was 0.29907 ± 0.00011 (95% confidence limit), 3465.4 ± 0.6 Ma. The high 207Pb* (∼ 30 μg g−1), negligible common Pb, and isotopic homogeneity permitted precise (± 1–2‰) 207Pb*/206Pb* measurements within the analytical sessions. External reproducibility of mean 207Pb*/206Pb* ratios between sessions was demonstrated for one instrument, yielding a mean IMF of +0.87 ± 0.49‰. The mean 207Pb*/206Pb* ratios between instruments were dispersed beyond uncertainties, with session IMF values from +3.6 ± 1.7‰ to −2.4 ± 1.3‰, and a grand mean IMF value (twenty-six sessions) of +0.70 ± 0.52‰, indicating a tendency towards elevated 207Pb*/206Pb*. The specific causes of variability in IMF are unclear, but generally reflect subtle differences in analytical conditions. The common practice in SIMS of assuming that IMF for Pb+ is insignificant could result in systematic age biases and underestimated uncertainties, of critical importance for precise correlation of Precambrian events. Nevertheless, a zircon RM such as OG1 can be readily incorporated into routine dating to improve 207Pb*/206Pb* accuracy and external reproducibility.  相似文献   

20.
The high sensitivity, minimal oxide formation and single internal standard capability of high resolution inductively coupled plasma-mass spectrometry (HR-ICP-MS) is demonstrated in the direct determination of Sc, Y and REE in the international reference materials: basalts (BCR-1, BHVO-1, BIR-1, DNC-1), andesite (AGV-1) andultramafics (UB-N, PCC-1 and DTS-1). Time consuming ion exchange separation or preconcentration were found to be unnecessary. Smooth chondrite normalized plots of the REE in PCC-1 and DTS-1 were obtained in the range 0.8-50 ng g-1 (0.01-0.1x chondrite). Method precision was found to be digestion dependent with an average external repeatability of 2-4% for the basalts, AGV-1 and UB-N, and 10% for PCC-1 and DTS-1. The mass peak due to 45Sc was completely resolved from 29Si16O and 28Si16O1H spectral interferences using medium resolution, which casts doubt on the accuracy of Sc determinations using quadrupole ICP-MS. Literature values for Y in rock reference materials were found to be approximately 9% high after HR-ICP-MS and XRF analysis.  相似文献   

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