Combined Sr isotope and trace element analysis of melt inclusions at sub-ng levels using micro-milling, TIMS and ICPMS   总被引：1，自引：0，他引：1  

R. Harlou  D.G. Pearson  G.M. Nowell  C.J. Ottley  J.P. Davidson 《Chemical Geology》2009,260(3-4):254-268

This paper describes a technique, which allows precise and accurate Sr isotope measurement combined with trace element analysis of individual melt inclusions, of sample sizes  1 ng of Sr. The technique involves sampling by micro-milling, chemical dissolution, micro Sr column chemistry, TIMS, and ICPMS analyses. A 10% aliquot of each sample solution is used for trace element analysis by double focusing magnetic sector field ICPMS, while Sr is chemically separated from the remaining 90% and used for ⁸⁷Sr/⁸⁶Sr determinations by TIMS.During the development of the technique outlined above, we documented in detail the potential sources of blank contributions and their magnitude. The average size and Sr isotope composition of our laboratory total procedural blank during this study was 5.4 pg ± 0.3 pg Sr (n = 21) with an ⁸⁷Sr/⁸⁶Sr of 0.7111 ± 0.0002 (2SE, n = 3). The total procedural Rb blank was 1.9 ± 0.7 pg (n = 21). The total procedural blank was found to have minimal effect (< 150 ppm shift) on the ⁸⁷Sr/⁸⁶Sr of sample material containing down to  250 pg Sr. Applying a blank correction allows ‘in house’ standards of this size to be corrected back to within 175 ppm of their accepted values. By applying blank corrections we can confidently measure the Sr isotope composition on sample sizes down to  25 pg Sr to an accuracy better than 400 ppm.The utility of the technique is illustrated by application to a suite of melt inclusions from NW Iceland and their host olivines. It is shown that the effect of a small amount of entrainment of the host olivine during sampling of 50 μm melt inclusions has a negligible effect on the measured Sr isotope and trace element composition. Furthermore, where melt inclusions are < 50 μm it is possible to obtain Sr isotope and trace element data on multiple melt inclusions hosted in a single olivine. This provides similar information to that of the single melt inclusions.  相似文献   

High‐Precision Measurement of 187Os/188Os Isotope Ratios of Nanogram to Picogram Amounts of Os in Geological Samples by N‐TIMS using Faraday Cups Equipped with 1013 Ω Amplifiers     

Guiqin Wang  Hauke Vollstaedt  Jifeng Xu  Wengui Liu 《Geostandards and Geoanalytical Research》2019,43(3):419-433

N(¹⁸⁷Os)/N(¹⁸⁸Os) ratios of six geological reference materials were measured using static Faraday cups (FCs) with 10¹³ Ω amplifiers by N‐TIMS. Our results show that the repeatability precision was 2–3‰ (2 RSD, n = 3), when taking ~ 1 g of BHVO‐2 with 76 pg g^?1 of Os mass fraction and ~ 2 g of BCR‐2 with 21 pg g^?1 of Os mass fraction for each sample, whether measured by FCs or by secondary electron multiplier. The repeatability precision measured by FCs was 1–0.2‰ (2 RSD, n = 3) when taking ~ 1 g of BIR‐2 with 350 pg g^?1 of Os mass fraction, ~ 1 g of WGB‐1 with 493 pg g^?1 of Os mass fraction or ~ 0.5 g of WPR‐1 with 13.3 ng g^?1 of Os mass fraction for each sample, which is much better than those measured by secondary electron multiplier. Instead, when taking ~ 2 g of AGV‐2 with 4 pg g^?1 Os mass fraction, the repeatability precision measured by secondary electron multiplier is 3–4‰ (RSD, n = 3), which is better than those measured by FCs. Of the six reference materials analysed, WPR‐1 and BIR‐1a are the most homogeneous with regard to Os isotopic composition (2 RSD of 0.08% and 0.23%, respectively) when test portion masses are 0.5–1 g.  相似文献   

Determination of Radiogenic 87Sr/86Sr and Stable δ88/86SrSRM987 Isotope Values of Thirteen Mineral,Vegetal and Animal Reference Materials by DS‐TIMS     

Jean‐Michel Brazier  Anne‐Dsire Schmitt  Eric Pelt  Damien Lemarchand  Sophie Gangloff  Tho Tacail  Vincent Balter 《Geostandards and Geoanalytical Research》2020,44(2):331-348

This work presents new ⁸⁷Sr/⁸⁶Sr and δ^88/86Sr_SRM987 isotopic values of thirteen mineral, vegetal and animal reference materials. Except for UB‐N, all our results are consistent with previously published data. Our results highlight intermediate precisions among the best presently published and a non‐significant systematic shift with the calculated δ^88/86Sr_SRM987 mean values for the three most analysed reference materials in the literature (i.e., IAPSO, BCR‐2 and JCp‐1). By comparison with the literature and between two distinct digestions, a significant bias of δ^88/86Sr_SRM987 values was highlighted for two reference materials (UB‐N and GS‐N). It has also been shown that digestion protocols (nitric and multi‐acid) have a moderate impact on the δ^88/86Sr_SRM987 isotopic values for the Jls‐1 reference materials suggesting that a nitric acid digestion of carbonate can be used without significant bias from partial digestion of non‐carbonate impurities. Different δ^88/86Sr_SRM987 values were measured after two independent Sr/matrix separations, according to the same protocol, for a fat‐rich organic reference material (BCR‐380R) and have been related to a potential post‐digestion heterogeneity. Finally, the δ^88/86Sr_SRM987 value differences measured between animal‐vegetal and between coral‐seawater reference materials agree with the previously published results, highlighting an Sr isotopic fractionation along the trophic chain and during carbonate precipitation.  相似文献   

Chemical Procedures for Rhenium Extraction from Geological Samples: Optimising the Anion Resin Bead Clean‐up Step     

Gang Yang  Aaron Zimmerman  Nicole C. Hurtig  Svetoslav V. Georgiev  Vineet Goswami  Judith L. Hannah  Holly J. Stein 《Geostandards and Geoanalytical Research》2020,44(2):231-242

Rhenium–osmium geochronometry for samples with low Re and complex matrices requires improved Re extraction methods. Here, we investigate plausible controls on efficiency and efficacy of Re extraction during our anion resin bead purification. Four different protocols are compared, each isolating a single variable to test. Rhenium concentrations for solutions at each step of each protocol document differences in chemical recovery/yield. The negative‐thermal ionisation mass spectrometry (N‐TIMS) signal intensity serves as a proxy for Re yield and purity. These data document correlations between the N‐TIMS signal intensity and (a) the duration of anion resin bead conditioning prior to loading with Re‐bearing solution, and (b) both duration and strength of nitric acid used during rinsing of the Re‐loaded anion resin bead. The optimal protocol improved Re signal intensity around fourteen times compared with our current Re extraction protocol, an aggregate of 2.4 times improvement in chemical recovery (yield) and 5.8 times improvement in emission efficiency (purity). Repeated N‐TIMS isotopic measurements on our in‐house Re standard solution (1407) verify that our optimal protocol‐3 does not fractionate Re isotopes. The improved anion resin bead method considerably lowers the Re detection limit and allows Re‐Os isotopic analysis of picogram‐level Re hosted in geological samples with complex matrices.  相似文献   

新疆别也萨麻斯矿区钽锰矿的矿物学特征及其TIMS U-Pb定年     

何晗晗  艾尔肯&#;吐尔孙  王登红  王瑞江  陈振宇 《岩矿测试》2020,39(4):609-619

钽矿是我国的紧缺资源,近年来对别也萨麻斯地区钽矿取得了找矿新进展,包括新矿点的发现以及花岗伟晶岩型稀有金属资源的找矿突破。区内伟晶岩脉广泛发育,为探究含矿脉体的成矿时代、查明区内典型铌钽矿物的矿物学特征,本文以L18号伟晶岩脉中的钽锰矿为研究对象,对其物理性质、化学成分、地质年代等进行了分析。应用电子探针测试钽锰矿的化学组成,热电离质谱法(TIMS)测定其U-Pb年龄,确定含矿脉体的形成年代。结果表明,研究区钽锰矿中Ta_2O_5含量为51.58%～74.80%,均值68.49%,Nb_2O_5含量为6.15%～27.63%;部分主量元素分布不均,未表现出规律的分带性,但矿物颗粒中心部位的CaO含量较边部低,横剖面上SiO_2含量相对稳定,TiO_2与WO_3显示不规律波动。这种特征表明钽锰矿并非单纯由结晶分异作用形成,而是可能受到了后期交代作用的影响。钽锰矿的U-Pb年龄为160Ma,说明钽锰矿化发生于晚侏罗世早期,与围岩海西期二云母花岗岩相差甚远,后者并非L18号脉体的成矿母岩。  相似文献   

A Common Reference Material for Cadmium Isotope Studies – NIST SRM 3108     

Wafa Abouchami  Stephen J. G. Galer  Tristan J. Horner  Mark Rehkämper  Frank Wombacher  Zichen Xue  Myriam Lambelet  Melanie Gault‐Ringold  Claudine H. Stirling  Maria Schönbächler  Alyssa E. Shiel  Dominique Weis  Philip F. Holdship 《Geostandards and Geoanalytical Research》2013,37(1):5-17

Research into natural mass‐dependent stable isotope fractionation of cadmium has rapidly expanded in the past few years. Methodologies are diverse with MC‐ICP‐MS favoured by all but one laboratory, which uses thermal ionisation mass spectrometry (TIMS). To quantify the isotope fractionation and correct for instrumental mass bias, double‐spike techniques, sample‐calibrator bracketing or element doping has been used. However, easy comparison between data sets has been hampered by the multitude of in‐house Cd solutions used as zero‐delta reference in different laboratories. The lack of a suitable isotopic reference material for Cd is detrimental for progress in the long term. We have conducted a comprehensive round‐robin assay of NIST SRM 3108 and the Cd isotope offsets to commonly used in‐house reference materials. Here, we advocate NIST SRM 3108 both as an isotope standard and the isotopic reference point for Cd and encourage its use as ‘zero‐delta’ in future studies. The purity of NIST SRM 3108 was evaluated regarding isobaric and polyatomic molecular interferences, and the levels of Zn, Pd and Sn found were not significant. The isotope ratio ¹¹⁴Cd/¹¹⁰Cd for NIST SRM 3108 lies within ～ 10 ppm Da^?1 of best estimates for the Bulk Silicate Earth and is validated for all measurement technologies currently in use.  相似文献   

岩石样品中低含量铂族元素和锇同位素比值的高精度测量方法   总被引：9，自引：1，他引：9  

杨竞红  GerharBRUGMANN 《岩石学报》2001,17(2):325-331

铂族元素（Os,Ir,Pt,Ru,Rh,Pd)具有强亲铁性和强亲铜性，为一组地球化学性质相近的相容元素，铂族元素包含两个同位素衰变体系（^190Pt-^186Os和^187Re-^187Os)。近年来，铂族元素和Re-Os同位素在研究各类不同地持作用过程中，尤其是在地幔岩石的研究中，作用独特，效果显著。由于地幔岩石的铂族元素含量较低，因此高精度，高灵敏度的分析测试方法的研究就显得十分重要。以往的分析方法（如常规的ICP－MS和中子活化分析方法），对含10^-9-10^012级低含量铂族元素的产品分析精度一般较差（＞15％－100％）。所采用的分析流程通常也无法同时获得样品的铂族元素含量和Os同位素比值。本文采用新的熔样方法（HAP－S高温高压釜酸溶法），新的化学流程（溶剂萃取和阴离子交换树脂柱）和新的分析仪器（多接收等离子体质谱MC－ICPMS和负离子热电离质谱N－TIMS）。用同位素稀释法对低含量地幔橄榄岩样品同时测定的铂族元素含量和Os同位素比值，获得了高精度的分析结果。对所分析的地橄榄样品中的铂族元素分配曲线和Os同位素组成的地质意义进行了初步探讨。  相似文献   

Calcium Isotopic Fractionation during Ion‐Exchange Column Chemistry and Thermal Ionisation Mass Spectrometry (TIMS) Determination          下载免费PDF全文

Hong L. Zhu  Zhao F. Zhang  Gui Q. Wang  Yu F. Liu  Fang Liu  Xin Li  Wei D. Sun 《Geostandards and Geoanalytical Research》2016,40(2):185-194

Significant isotopic fractionation can occur during column chemistry and determination by mass spectrometry. Improper correction may produce uncertainties in the isotopic composition of geological samples. We investigated calcium isotopic fractionation during these two processes and set up a model to check data quality. The δ^44/40Ca_915a value of IAPSO seawater in different Ca cuts (e.g., 0–20, 20–40, 40–60, 60–80 and 80–100%) on column chemistry ranged from ~ 4‰ to 0‰. The more Ca was eluted, the lower the δ^44/40Ca_915a value of the elution was found. The isotopic fractionation of calcium on the column appeared to follow the exponential law. However, TIMS instrumental fractionation during Ca runs did not always follow the exponential law due to mixing effects from sample reservoirs on the filament. Our results show that errors could be caused if the instrumental fractionation deviates from the exponential law, especially when the fractionation degree is large. To improve the measurement uncertainty, a model is proposed to check the behaviour and degree of instrumental fractionation, which will provide a quick and reasonable verdict on the data quality of TIMS runs.  相似文献   

天山中西段古生代花岗岩TIMS法锆石U-Pb同位素定年及岩石地球化学特征研究   总被引：23，自引：0，他引：23  

徐学义  马中平  夏祖春  夏林圻  李向民  王立社 《西北地质》2006,39(1):50-75

通过对天山中西段古生代花岗岩的锆石TIMS法U-Pb同位素定年,表明中天山托克逊南—库米什北侵入于奥陶纪可可乃克群中的碱长花岗岩形成时代为395.1±0.9Ma,花岗闪长岩体形成于393.5±2.7Ma,石英闪长岩体形成于327.3±0.9Ma,斜长花岗岩体形成时代为424.1±1.1Ma,并揭示出中天山中段库米什地区的3期构造岩浆事件,分别相当于早志留世、中泥盆世和早石炭世。中天山哈希勒根大坂黑云母花岗岩形成于286.8±0.8Ma。对伊犁石炭—二叠纪裂谷带中花岗侵入岩类的锆石TIMS法U-Pb同位素定年,表明霍城果子沟角闪花岗岩形成于351.9±1.6Ma,昭苏煤矿花岗闪长岩体形成时代为348.4±0.8Ma,新源则克台角闪辉长岩体形成于308.2±1.2Ma。南天山巴音布鲁克地区侵入于巴音布鲁克群中的石英闪长岩体形成时代为446.8±1.2Ma,独—库公路南段库尔干道班14.6km和15.2km处的角闪斜长花岗岩体与黑云母花岗岩体分别形成于426.3±1.9Ma和425.1±1.8Ma。对花岗岩的岩石地球化学研究表明,中天山托克逊南—库米什北志留纪—早泥盆世花岗岩为钙碱系列,轻稀土富集,微量元素洋脊花岗岩标准化具有Rb、Th、Ba富集,Ta、Nb亏损的分配型式,形成于火山弧环境;石炭—二叠纪花岗岩为钙碱系列,准铝—过铝质花岗岩,轻稀土富集程度较前者低,微量元素洋脊花岗岩标准化具有Rb、Th富集,Ba略亏损和高场强元素亏损的特点,形成于后碰撞(post-collision)构造环境。伊犁石炭—二叠纪裂谷带中石炭—二叠纪花岗岩为过铝质花岗岩,轻稀土富集,微量元素洋脊花岗岩标准化分配型式同样具有Rb、Th富集,Ba明显亏损和高场强元素亏损的特点,亦形成于后碰撞(post-collision)构造环境。南天山库尔干花岗岩为Al2O3含量高的钙碱性系列、过铝质花岗岩,稀土元素含量中等(157.89×10-6~81.81×10-6),轻稀土富集,Eu负异常明显,微量元素洋脊花岗岩标准化呈现出K、Rb、Th、Ba富集和Nb、Ta、Zr、Hf高场强元素亏损的特点,其形成时代与天山古生代洋盆俯冲时限相当,为岛弧构造环境。依据Sr-Nd-Pb同位素回时计算结果,本次研究所取的花岗岩初始锶同位素比值高,介于0.70435~0.70982,εNd(t)值多小于零或为很低的正值,T2DM或TDM均远大于岩体形成年龄,δ18O‰多大于10,个别为6.7,显示出古老壳源物质在花岗岩浆的形成过程中起了重要作用。同时,鉴于花岗岩的εNd(t)均在0左右变动,同样说明,新生地壳在花岗岩浆的形成过程中同样起着重要作用。花岗岩的εNd(t)值与前寒武纪岩石的εNd(t)对比研究表明,中天山库米什北志留纪斜长花岗岩体可能是中新元古界斜长角闪岩部分熔融的产物,而石炭—二叠纪花岗岩既有中新元古界片麻岩或片岩部分熔融生成,亦有新生地壳部分熔融受到古老地壳混染后岩浆结晶产物。伊犁石炭—二叠纪花岗岩和南天山库尔干志留纪花岗岩均显示出新生地壳部分熔融,并受古老地壳混染的Nd同位素信息。  相似文献   

热电离质谱铀系法测定碳酸盐标样   总被引：5，自引：0，他引：5  

王兆荣  彭子成 《岩矿测试》1998,17(4):268-270

用高精度热电离质谱（ＴＩＭＳ）铀系法测定碳酸盐标样的年龄,测定结果与α谱仪铀系法进行比较,铀含量和年龄值均吻合。方法对Ｕ的回收率可达９５％,Ｔｈ为９２％。ＴＩＭＳ铀系法具有样品用量少、测试时间短、精度高的优点。  相似文献