Rapid Determination of Trace and Ultra Trace Level Elements in Diverse Silicate Rocks in Pressed Powder Pellet Targets by LA‐ICP‐MS using a Matrix‐Independent Protocol     

Pulok K. Mukherjee  Param P. Khanna  Naresh K. Saini 《Geostandards and Geoanalytical Research》2014,38(3):363-379

A simple, single sample preparation involving pressed rock powder pellets was utilised to determine the trace and ultra trace abundances of petrogenetically important elements including high field‐strength elements and REEs by laser ablation‐ICP‐MS. One of the elements predetermined by XRF spectrometry served as an internal standard. The influence of sample preparation parameters (grain size, pellet compactness and amount of binding media) on analytical performance was also investigated, including sample homogeneity issues at the laser sampling scale. Line scanning with a high repetition frequency (20 Hz) and large beam diameter (200 μm) ensured ablation from a larger sample surface area, eliminating issues related to sample heterogeneity. A median grain size of about 10 μm for silicate rock powders was found to be sufficiently representative at this scale of laser sampling. Granitic rocks or samples containing resistant minerals such as zircon needed extra grinding to achieve grain sizes down to < 5 μm for better precision for elements that are concentrated in these phases. Using ¹³⁷Ba as an internal standard, reasonable accuracies within 15–20% for most of the high mass trace elements were achieved; in the case of low mass elements, it may deviate up to 40%. Precision of measurements rarely exceeded 15% RSD.  相似文献   

Determination of U–Pb Ages for Young Zircons using Laser Ablation‐ICP‐Mass Spectrometry Coupled with an Ion Detection Attenuator Device     

Shuhei Sakata  Kentaro Hattori  Hideki Iwano  Takaomi D. Yokoyama  Tohru Danhara  Takafumi Hirata 《Geostandards and Geoanalytical Research》2014,38(4):409-420

We have developed new analytical procedures to measure precise and accurate ²³⁸U–²⁰⁶Pb and ²³⁵U–²⁰⁷Pb ages for young (~ 1 Ma) zircons using laser ablation‐ICP‐mass spectrometry. For young zircons, both careful correction for the background counts and analysis of very small Pb/U ratios (i.e., ²⁰⁶Pb/²³⁸U < 0.00016 and ²⁰⁷Pb/²³⁵U < 0.0001 for 1 Ma zircons) are highly desired. For the correction of the background, the contribution of the background signal intensities for the analytes, especially for the residual signal intensities for ²⁰⁶Pb and ²⁰⁷Pb, was defined through laser ablation of synthesised zircons (ablation blank) containing negligible Pb. The measured signal intensities for ²⁰²Hg, ²⁰⁶Pb and ²⁰⁷Pb signals obtained by the ablation blank were slightly higher than those obtained by data acquisition without laser ablation (gas blank). For the wider dynamic range measurements on Pb/U ratios, an attenuator device for the ion detection system was employed to extend the capability to monitor high‐intensity signals (i.e., > 3 Mcps). Through the attenuator device, the ion currents were reduced to 1/450 of the signal intensity without the attenuator. Because the switching time for the attenuator was shorter than 1 ms, signal intensities for only specific isotopes could be reduced. With attenuation of the ²³⁸U signal, counting statistics on ²⁰⁶Pb and ²⁰⁷Pb isotopes could be improved and counting loss on the ²³⁸U signal could be minimised. To demonstrate the reliability of this new analytical technique, ²³⁸U–²⁰⁶Pb and ²³⁵U–²⁰⁷Pb ages for three young zircon samples (collected from Osaka Group Pink Volcanic Ash, Kirigamine and Bishop Tuff) were measured. The data presented here demonstrate clearly that the present technique could become a major analytical tool for in situ U–Pb age determination of young zircons (~ 1 Ma).  相似文献   

Towards a Method for Quantitative LA‐ICP‐MS Imaging of Multi‐Phase Assemblages: Mineral Identification and Analysis Correction Procedures     

Bence Paul  Jon D. Woodhead  Chad Paton  Janet M. Hergt  John Hellstrom  C. Ashley Norris 《Geostandards and Geoanalytical Research》2014,38(3):253-263

Here, we present an approach to laser ablation ICP‐MS mapping of multi‐phase assemblages that permits the use of different internal standard elements, concentration values and reference materials for each mineral. In this way, we obtain not only broad pictures of elemental distributions within samples but can also extract high accuracy concentration data for any user‐selected region. This is accomplished by assigning regions of an image to corresponding mineral phases on a pixel‐by‐pixel basis. In this way, accurate trace element concentrations can be determined for each mineral phase, despite potential variations in their ablation characteristics. We present an example where elemental maps are constructed from ablation of a gabbroic sample that includes the phases apatite, amphibole and plagioclase. This work represents an important first step towards development of a method to produce highly accurate LA‐ICP‐MS elemental maps of multi‐phase samples.  相似文献   

阿尔泰东南缘泥盆纪花岗质岩石的锆石U-Pb年龄、成因演化及构造意义：钙碱性-高钾钙碱性-碱性岩浆演化新证据   总被引：3，自引：0，他引：3  

宋鹏  童英  王涛  秦切  张建军  宁东旭 《地质学报》2017,91(1):55-79

中国阿尔泰广泛发育的花岗质岩石已获得大量研究,但是其东南缘研究薄弱,制约了对整个阿尔泰造山带构造岩浆演化的认识。本文新获得阿尔泰东南缘四个花岗质岩体(昆格依特、库吉尔特、布铁乌及卡拉特玉别)锆石U-Pb年龄,分别为382±4Ma、381±4Ma、385±5Ma和363±6Ma。岩石学、地球化学特征等显示这些花岗质岩石具有高钾钙碱性、准铝质—弱过铝质的I型特点,全岩εNd(t)值为-2.42~-0.53,Nd模式年龄tDM为1.6~1.3Ga;锆石εHf(t)值为-3.44~+13.26,绝大多数为正值,锆石Hf二阶段模式年龄tDM-2为2.5~0.6Ga,表明源区物质组成复杂,有较多的新生幔源物质参与花岗质岩石的形成,并含有古老地壳成分。综合已有年龄分析显示,中国阿尔泰花岗质岩石的形成时代可分为480~440Ma(峰期460Ma)、420~390Ma(峰期400Ma)、390~370Ma(峰期380Ma)、370~360Ma(峰期365Ma)、360~350Ma。处于岩浆发育峰期的早泥盆世(420~390Ma)多为准铝-过铝质的钙碱性系列;中晚泥盆世(390~360Ma)多为准铝—弱过铝质的高钾钙碱性系列;370~360Ma为高钾钙碱性系列。该地区363Ma的高钾钙碱性花岗质岩石的确定,为进一步厘定整个阿尔泰泥盆纪花岗质岩浆由钙碱性(480~390Ma),到高钾钙碱性(390~360Ma),再到354Ma的布尔根碱性花岗岩的演变特点提供了新的证据,进一步揭示阿尔泰造山带该时期由俯冲增生演变到碰撞及后碰撞的演化过程。  相似文献   

诸广山南部高坪地区细粒花岗岩LA-ICP-MS锆石U-Pb年龄及其地质意义   总被引：1，自引：0，他引：1  

虞航  蔡煜琦  李伟林  黄国龙  庞雅庆  江卫兵  张闯 《地质论评》2017,63(3):781-792

诸广山南部高坪地区钻探工程揭露到较多细粒花岗岩岩脉,部分岩脉与矿体空间关系密切。本文利用LA-ICP-MS锆石U-Pb定年法测得区内两组细粒花岗岩年龄分别为252.9±1.9 Ma(MSWD=1.8)和244±2 Ma(MSWD=1.4)。结合细粒花岗岩中晶质铀矿U-Pb定年结果,证实其形成于印支期。本文结合粤北地区铀成矿规律及区域铀成矿特征,对高坪地区铀成矿潜力及找矿方向进行初步探讨,认为:(1)印支期,诸广山南部先后广泛侵入粗粒斑状黑云母花岗岩与细粒花岗岩,其中细粒花岗岩多沿断裂发育;(2)至燕山晚期,沿断裂侵入基性脉岩;(3)高坪地区细粒花岗岩与基性脉岩叠合部位为铀成矿的有利空间。  相似文献   

A Practical Approach for Collecting Large‐n Detrital Zircon U‐Pb Data sets by Quadrupole LA‐ICP‐MS          下载免费PDF全文

William A. Matthews  Bernard Guest 《Geostandards and Geoanalytical Research》2017,41(2):161-180

A measurement procedure for the rapid acquisition of U‐Pb dates for detrital zircons by quadrupole LA‐ICP‐MS was developed. The procedure achieves a threefold increase in measurement efficiency compared with the most commonly used methods. Utilising reduced background counting times and a shortened ablation period, a throughput of ~ 130 measurements/h can be achieved. The measurement procedure was characterised and validated using data from thirty‐nine sessions acquired over a twelve‐month period. Systematic measurement error in ²⁰⁶Pb/²³⁸U dates for reference materials used for quality control with ages between 28.2 and 2672 Ma was < 1.5%. Average measurement uncertainty, including both random and systematic components, was 1–4% (2s). Interrogation of time‐resolved calculated dates and signal intensities for each measurement allows for the detection and elimination of portions of measurements exhibiting age heterogeneities, zoning, lead loss and contamination by common lead. The measurement procedure diminishes the need to acquire cathodoluminescence imagery for routine detrital zircon applications further increasing throughput and reducing cost. The utility of the measurement procedure is demonstrated by the measurement of samples previously characterised by LA‐MC‐ICP‐MS.  相似文献   

Investigating the Influence of Non‐Spectral Matrix Effects in the Determination of Twenty‐Two Trace Elements in Rock Samples by ICP‐QMS          下载免费PDF全文

Tetsuya Yokoyama  Yuichiro Nagai  Yu Hinohara  Tomohiko Mori 《Geostandards and Geoanalytical Research》2017,41(2):221-242

The influence of non‐spectral matrix effects on the determination of twenty‐two trace elements (Rb, Sr, Y, Cs, Ba, lanthanides, Pb, Th and U) in rock samples using ICP‐MS was investigated. Three types of multi‐element solutions were synthesised containing the twenty‐two trace elements, In, Tl and ten major rock‐forming elements with varying mass fractions mimicking the compositions of basalt, peridotite and dolomite. The synthetic solutions were conditioned to have dilution factors (DF) of 1000–10000. The extent of sensitivity suppression relative to the DF = 10000 solution became more significant for smaller DF solutions, which was not constant across different elements in a single solution but displayed general dependence on m/z. This indicates that at least two internal standards (e.g., In and Tl) are required for the correction of sensitivity variation. On the basis of the results, a new isotope dilution‐internal standardisation method for the determination of twenty‐two trace elements with ICP‐MS was developed, in which the sensitivity variation was corrected by monitoring two enriched isotopes, ¹¹³In and ²⁰³Tl. This method, coupled with the quantitative correction of interference from oxides and hydroxides, achieved precise determination of twenty‐two trace elements in some rock reference materials with reproducibilities of ±2% for basaltic to andesitic samples.  相似文献   

Method Development and Optimisation of Sodium Peroxide Sintering for Geological Samples          下载免费PDF全文

Syed Nadeem Hussain Bokhari  Thomas C. Meisel 《Geostandards and Geoanalytical Research》2017,41(2):181-195

This work provides a measurement procedure for the complete digestion of rock samples containing refractory minerals such as zircon and chromite. Their dissolution by wet acid digestion is often incomplete but, although providing complete digestions, alkali fusion techniques can result in solutions with a high blank and total dissolved solid content. It was established by the systematic study with reference material trachyandesite MTA‐1 that a 1:6 sample to sodium peroxide (Na₂O₂) ratio is conservative for the complete digestion and recovery of all the analytes especially those contained in zircon. The sample decomposition time was 120 min for the zircon‐bearing rhyolite reference material MRH‐1. Complete digestion of chromite was obtained in the harzburgite RM MUH‐1. The sample solutions were stable for at least 1 year. Accurate measurements of SiO₂, Al₂O₃, TiO₂, P₂O₅ and K₂O could be made with ICP‐MS by not discarding the supernatant of the sinter solution and by using geological reference materials for external calibration. HF digestions are slow, not universal, and may form new mineral/phases that are insoluble under high temperature conditions. The validated sample decomposition procedure combined with ICP‐MS presents an alternative to the use of HF in routine analysis of difficult to digest geological materials.  相似文献   

Application of Laser‐Induced Breakdown Spectroscopy and Hyperspectral Images for Direct Evaluation of Chemical Elemental Profiles of Coprolites          下载免费PDF全文

Marco Aurélio Sperança  Francisco Wendel Batista de Aquino  Marcelo Adorna Fernandes  Alejandro Lopez‐Castillo  Renato Lajarim Carneiro  Edenir Rodrigues Pereira‐Filho 《Geostandards and Geoanalytical Research》2017,41(2):273-282

This study demonstrates the application of laser‐induced breakdown spectroscopy (LIBS) and hyperspectral imaging to the investigation of coprolite and fossil samples. Solid samples from the Permian (seven coprolites and one fossil), Cretaceous (one coprolite) and Oligo‐Miocene (two coprolites) periods were directly analysed, and emission spectra from 186 to 1042 nm were obtained in several areas covering coprolite/fossil and rock material. Initial exploratory analyses were performed using principal component analysis with the data set normalised by the norm (Euclidean norm = 1). After identification and selection of emission lines of eleven elements (Al, Ca, Cr, Fe, K, Mg, Mn, Na, Ni, P and Si), the signals were normalised again by the relative intensity of the selected element. Phosphorus was identified mainly in the coprolites, while K and Na were primarily found in the rock material. In several cases, there was a positive correlation between Ca and P. A sample from the Oligo‐Miocene series was also analysed using inductively coupled plasma‐optical emission spectrometry (ICP‐OES) (rock and coprolites were analysed separately). Based on the quantitative results from ICP‐OES, it was confirmed that the tendency was the same as that observed with the results obtained from LIBS directly in the solid sample.  相似文献   

Determination of Platinum‐Group Elements and Gold in Ferromanganese Nodule Reference Samples          下载免费PDF全文

Evgeniya D. Berezhnaya  Alexander V. Dubinin 《Geostandards and Geoanalytical Research》2017,41(1):137-145

A measurement procedure for determining of Ru, Pd, Ir, Pt and Au mass fractions in ferromanganese deposits by inductively coupled plasma‐mass spectrometry after acid digestion and anion exchange preconcentration is presented. To eliminate incomplete recovery after sorption preconcentration of the platinum‐group elements (PGE) and Au, a standard addition method was used. Detection limits ranged from 0.02 ng (Pd, Ir) to 0.19 ng (Ru). The measurement results for ferromanganese nodule reference material NOD‐A‐1 and NOD‐P‐1 agree with earlier reported values. Intermediate precision of PGE concentration data for nodule reference materials in this work was 5–24% (1s) and could reflect sample heterogeneity.  相似文献