Combined Separation of Cu,Fe and Zn from Rock Matrices and Improved Analytical Protocols for Stable Isotope Determination   总被引：3，自引：0，他引：3       下载免费PDF全文

Paolo A. Sossi  Galen P. Halverson  Oliver Nebel  Stephen M. Eggins 《Geostandards and Geoanalytical Research》2015,39(2):129-149

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.  相似文献   

IsoSpike: Improved Double‐Spike Inversion Software          下载免费PDF全文

John B. Creech  Bence Paul 《Geostandards and Geoanalytical Research》2015,39(1):7-15

The double‐spike approach for correction of instrumental mass bias in mass spectrometry data is well established. However, there is very little consistency within the scientific community in terms of double‐spike data reduction. Double‐spike solutions require computer calculation, using either geometric or algebraic approaches, and are often performed using spreadsheet calculations that vary from group to group and between isotope systems. Here, we present IsoSpike, a generalised computer procedure for the processing of double‐spike mass spectrometry data, built as an add‐on for the Iolite data‐reduction package ( www.iolite.org.au ). Use of this software permits visualisation of mass spectrometry data in a time window, and rigorous treatment and screening of data. Additionally, IsoSpike uses an integration‐by‐integration approach where the double‐spike calculations are performed on every integration within an analysis, providing straightforward quantification of uncertainties on double‐spike‐corrected isotope ratios. The advantages of this approach over traditional methods are discussed here. Platinum stable isotope data are presented as an example data set, although the procedure is applicable to any double‐spike system. IsoSpike is freely available from www.isospike.org .  相似文献   

A Rapid Method for Determining Boron Concentration (ID‐ICP‐MS) and δ11B (MC‐ICP‐MS) in Vegetation Samples after Microwave Digestion and Cation Exchange Chemical Purification          下载免费PDF全文

Philippe Roux  Damien Lemarchand  Harold J. Hughes  Marie‐Pierre Turpault 《Geostandards and Geoanalytical Research》2015,39(4):453-466

We present in this article a rapid method for B extraction, purification and accurate B concentration and δ¹¹B measurements by ID‐ICP‐MS and MC‐ICP‐MS, respectively, in different vegetation samples (bark, wood and tree leaves). We developed a rapid three‐step procedure including (1) microwave digestion, (2) cation exchange chromatography and (3) microsublimation. The entire procedure can be performed in a single working day and has shown to allow full B recovery yield and a measurement repeatability as low as 0.36‰ (± 2s) for isotope ratios. Uncertainties mostly originate from the cation exchange step but are independent of the nature of the vegetation sample. For δ¹¹B determination by MC‐ICP‐MS, the effect of chemical impurities in the loading sample solution has shown to be critical if the dissolved load exceeds 5 μg g^?1 of total salts or 25 μg g^?1 of DOC. Our results also demonstrate that the acid concentration in the sample loading solution can also induce critical isotopic bias by MC‐ICP‐MS if chemistry of the rinsing‐, bracketing calibrator‐ and sample solutions is not thoroughly adjusted. We applied this method to provide a series of δ¹¹B values of vegetal reference materials (NIST SRM 1570a = 25.74 ± 0.21‰; NIST 1547 = 40.12 ± 0.21‰; B2273 = 4.56 ± 0.15‰; BCR 060 = ?8.72 ± 0.16‰; NCS DC73349 = 16.43 ± 0.12‰).  相似文献   

Improved Inter‐calibration of Faraday Cup and Ion Counting for In Situ Pb Isotope Measurements Using LA‐MC‐ICP‐MS: Application to the Study of the Origin of the Fangshan Pluton,North China          下载免费PDF全文

Wen Zhang  Zhaochu Hu  Lu Yang  Yongsheng Liu  Keqing Zong  Haijin Xu  Haihong Chen  Shan Gao  Lei Xu 《Geostandards and Geoanalytical Research》2015,39(4):467-487

A laser ablation multi‐collector inductively coupled plasma‐mass spectrometry (LA‐MC‐ICP‐MS) method was developed to obtain precise and accurate Pb isotopic ratio measurements in low‐Pb materials (< 10 μg g^?1) using a combination of Faraday cups and ion counters (FC–IC). The low abundance ²⁰⁴Pb (~ 1.4%) was collected using an IC. A NBS 981 standard solution was used to cross‐calculate the FC–IC gain and to investigate the signal response characteristics of the IC. A significant, continuous and linear decrease in the FC–IC gain was observed within 1 hr, but this drift could be corrected using the calibrator‐sample‐calibrator bracketing method. In addition, a non‐linear response of the IC used in this study was observed and corrected by a non‐linear correction algorithm, which was established by measuring a series of gravimetrically prepared NBS 981 standard solutions (NIST SRM 981). Compared with the conventional arrangement, the use of the newly designed X skimmer cone and Jet sample cone improved the signal intensities from Pb isotopes by a factor of 1.9. Compared with only Faraday cups, using a combination FC–IC array was found to enhance the measurement repeatability (RSD) of ^20xPb/²⁰⁴Pb by approximately one order of magnitude when the ²⁰⁴Pb intensity was < 8 mV. Eight natural glasses and the NIST SRM 612 reference material glass (as a calibration material) were measured to evaluate the new protocol for Pb isotope determination. The analytical results were in agreement with the reference values within 2s measurement uncertainties. For MPI‐DING ATHO‐G (5.67 μg g^?1 total Pb), KL2‐G (2.07 μg g^?1 total Pb) and ML3B‐G (1.38 μg g^?1 total Pb), the typical accuracies of ^20xPb/²⁰⁴Pb were 0.09% of preferred values with precisions of < 0.33% (2RSD). The Pb isotope ratios in feldspars from granodiorite and within mafic microgranular enclaves (MMEs) from the Fangshan pluton, North China, were measured using the present method. The Pb isotopic compositions of feldspars from the whole host granodiorite show that that are radiogenic in the margin zone and gradually become less radiogenic. For the MMEs, the Pb isotopic compositions of feldspars are highly variable and overlap with those of the whole host granodiorite. For single‐grain feldspar, the strong rim‐core‐rim variations of the Pb isotopic compositions and trace elements are interpreted to have been generated via magma mixing. These results suggest that the Fangshan pluton underwent magma mixing of mantle‐derived mafic magmas with felsic magmas, and the proportion of the mafic magma influx decreased over time.  相似文献   

Bias in the Determination of Zr,Y and Rare Earth Element Concentrations in Selected Silicate Rocks by ICP‐MS when Using Some Routine Acid Dissolution Procedures: Evidence from the GeoPT Proficiency Testing Programme          下载免费PDF全文

Philip J. Potts  Peter C. Webb  Michael Thompson 《Geostandards and Geoanalytical Research》2015,39(3):315-327

The analytical results for the modified river sediment, SdAR‐1 circulated in Round 31 of the GeoPT proficiency testing programme, revealed unexpected discrepancies for Zr, Y and most higher atomic number rare earth elements, in determinations made by ICP‐MS using acid attack digestion methods. This investigation compares these ICP‐MS results with those obtained for SdAR‐1 by three other methods: (a) ICP‐MS using fusion/sintering for sample digestion, (b) XRF analysis and (c) INAA. The distribution of results for the elements Rb, Sr, Ce, Y, Yb and Zr is examined and compared with those of the test material for Round 25 of GeoPT, Paraná basalt, HTB‐1. A substantial proportion (though not all) of Y, Yb and Zr determinations in SdAR‐1 by ICP‐MS/acid attack was variably low (sometimes very low) compared with other methods. A detailed evaluation of the procedures used to determine these results indicated that successful determinations by ICP‐MS/acid attack could be made if digestions were made at 180 °C for 48 hr using at least 2 ml HF per 100 mg of sample. We suggest that the more benign conditions (used by many laboratories) resulted in incomplete digestion of resistant minerals, such as zircon.  相似文献   

西昆仑慕士塔格-公格尔印支期侵入岩岩石与锆石地球化学特征及研究意义     

宋樾  王建  刘金霖  包真艳 《吉林大学学报(地球科学版)》2015,(5):1418-1435

西昆仑造山带南侧的麻扎-康西瓦缝合带,是古特提斯洋闭合的位置。慕士塔格-公格尔作为昆仑山的主峰,紧邻该缝合带的东北侧分布,主要岩性为花岗闪长岩和黑云母二长花岗岩。作者系统研究了两种岩性的地球化学及年代学特征,探讨了岩石成因,反演了古特提斯洋的构造演化历史。岩体岩浆锆石LA-ICP-MS U-Pb测年结果显示,花岗闪长岩和黑云母二长花岗岩的成岩年龄分别为(213.0±0.5)~(215.4±0.9)Ma和(220.6±0.5)~(222.1±0.4)Ma,是晚三叠世岩浆活动的产物。两种岩性均为高硅(w(SiO2)65%)、富碱(w(K2O+Na2O)6%)、钙碱性-高钾钙碱性、准铝质(A/CNK1),富集大离子亲石元素(LILE)和轻稀土元素(LREE),亏损高场强元素(HFSE)和重稀土(HREE)。微量元素组成特征、低锆石饱和温度及高分异指数显示慕士塔格-公格尔花岗岩体为高分异I型花岗岩。岩体锆石的εHf(t)值变化范围较小,为-4.46~-0.17,指示岩浆以壳源为主。综合研究表明,慕士塔格-公格尔花岗岩体可能是同碰撞造山环境下,老的下地壳受地幔热源影响部分熔融,形成的长英质壳源岩浆侵入地壳内部而冷却结晶形成。  相似文献   

土壤中痕量氨基甲酸酯和三唑类农药的样品提取方法研究     

张晶  饶竹  刘艳  李晓洁  黄毅 《岩矿测试》2015,34(6):692-697

本文对比研究了QuEChERS、加速溶剂萃取和超声提取三种方法,结合液相色谱-串联质谱法解决了土壤中18种极性强、热稳定性差的痕量氨基甲酸酯和三唑类农药提取难题。研究表明,Qu ECh ERS法的基体加标回收率为76.3%~121.0%(除涕灭威为27.5%外),超声提取法为71.0%~100.0%(除涕灭威为4.7%,涕灭威亚砜为137.8%外),加速溶剂萃取法大多低于70%(甲硫威、涕灭威、三唑醇几乎没有回收),可见QuEChERS法比另两种提取方法结果更优,最终确定为检测氨基甲酸酯类和三唑类农药的样品提取方法。涕灭威回收率偏低、涕灭威亚砜回收率偏高与提取方法的热效应有关;仲丁威、甲萘威等组分的回收状况与土壤类型相关。  相似文献   

震源参数因素对玉树地震库仑破裂应力图像及其与余震活动统计关系的影响   总被引：1，自引：0，他引：1       下载免费PDF全文

王莹  吴小平  赵韬 《地震学报》2011,33(5):595-604

2010年4月14日青海省玉树发生MS7.1强震, 根据国内外3个机构公布的5套玉树地震震源参数,计算了玉树地震产生的库仑破裂应力变化,研究了震源参数的差异对库仑破裂应力变化及其与余震活动关系的影响． 结果表明,由于不同来源震源参数存在差异,计算得到的库仑破裂应力变化图像也存在不同程度差异,从而影响库仑破裂应力变化与余震活动的关系．在震源断层参数中,断层滑动角和位错量的影响大于其它参数．此外还发现对余震统计时间的长短也会影响库仑破裂应力变化与余震活动关系的统计结果．   相似文献   

2010年4月14日玉树7.1级地震前异常特征及强震动力学关系探讨     

马玉虎  陈玉华 《中国地震》2011,27(2):136-146

系统地分析了2010年4月14日玉树7.1级地震的地震活动性异常、前兆异常以及震前动物反常行为.研究表明,玉树7.1级地震前异常并不丰富,但觉察到的异常突出.其中中长期异常有6级、5级和4级的平静区;前兆观测有玉树表层水温、德令哈表层水温和平安电磁波等显著异常;同时震前1周还存在数量较多的动物宏观异常现象;主震前130min发生了一次4.7级地震.结合1996年以来巴颜喀拉地块边界的强震震源机制解,探讨了玉树地震孕育的动力学过程.结果表明,1996年喀喇昆仑山口7.1级、1997年玛尼7.5级和2010年玉树7.1级地震是同一动力学过程下的强震事件,且中长期存在的不同震级档平静区演化可能与上述动力学过程有关.还对强震原地复发、前震识别和玉树地震中的前兆观测等科学问题进行了讨论.  相似文献   

两次乌恰Ms5.1地震前后南天山重力场动态变化特征     

朱治国  李杰  刘代芹 《内陆地震》2011,25(3):263-268

利用南天山流动重力网2009～2011年的测量资料,研究了乌恰两次Ms5.1地震前后重力场的时空动态演化特征.研究表明,在两次乌恰Ms5.1地震前后,重力场变化表现出“活跃—平静—活跃”特征,两次地震发生在重力场异常上升和下降变化过程中,且震中位置处于重力变化高梯度带且靠近“0”等值线附近.  相似文献