镝原子量测量-热电离质谱法的应用

用已知化学纯度的 16 2 Dy、16 4Dy两种浓缩同位素通过化学计量 ,配制人工合成校准样品 ,测量质谱计系统误差校正系数 K,校正用该仪器测量的来自地球不同地域矿物和试剂样品镝 ( Dy)元素天然同位素丰度比 ,求出自然界 Dy同位素丰度的真值。用该真值和它的核素质量 ,计算 Dy原子量 1 62 .4 995 ( 1 7)。上述测量经 IUPAC国际原子量委员会 ( UPAC-CAWIA)评审确认推荐报告中提供的测量值为 Dy原子量新的国际标准值 ,测量方法评为最佳测量     

锗原子量的新测定(英文)

用两种高富集锗同位素配制的标准混合溶液系列 ,以标定一台 MAT-2 62热电离质谱仪 ,求得 4个同位素丰度比的校准因数 ,从而测得 5种天然锗样品的 4个同位素丰度比的真值。由此计算天然锗 5种同位素的丰度值如下 :2 0 .37± 0 .0 5　　原子 %70 Ge2 7.38± 0 .0 4　　原子 %72 Ge7.76± 0 .0 5　　原子 %73 Ge36.66± 0 .0 5　　原子 %74 Ge7.83± 0 .0 5　　原子 %76Ge再各乘以已知的原子质量 ,得出锗原子量的新值为 :Ar( Ge) =72 .639± 0 .0 0 4这些精确数值的置信度为 95%。优于文献上所有已知的相应值。     

质谱学报第13卷总目录(1992年)

文肠 同位素质谱用热表面电离质谱法测量高电离电位元素锑同位素丰度同位素稀释质谱法测定反应堆辐照元件样品中”Sm和’sosm含量Lead IsotoPe Analysis by Mass SPee-trometry and Its Applieation in Ar-ehaeometry避开衫干扰的钱同位素质谱分析石油稳定同位素地球化学新进展IDMS分析中化学处理特点及空白消除方法同位素稀释质谱(I DMS)文献介绍(1989ee1991)1.同位素稀释质谱(IDMS)文献介绍(1989~1991)1. 无机质谱离子注入样品的二次离子质谱(S IMS)定量分析粉末样品中某些杂质元素的同位素稀释二次离子质谱定量分析方法的研究…     

锑,铕,铈,铒同位素丰度和原子量测量

用已知化学纯度的两种浓缩同位素通过化学计量,配制人工合成样品,用来测量质谱计系统误差校正系数,校正用该仪器测量的来自地球不同地域矿样和试剂样品中锑（Ｓｂ）、铕（Ｅｕ）、铈（Ｃｅ）、铒（Ｅｒ）四种元素天然同位素丰度比,求出这些元素同位素丰度的真值。用该真值和已知的上述四元素核素质量,计算得原子量分别为１２１．７５９７（７）Ｓｂ、１５１．９６４４（９）Ｅｕ、１４０．１１５７（８）Ｃｅ、１６７．２５９１（９）Ｅｒ     

校准质谱法测定铕原子量

使用有确定化学纯度的高纯同位素~(151)Eu_2O_3和~(153)Eu_2O_3以配制标准溶液,并由此配制6种混合溶液,用来测定一台固体源热电离质谱计的质量岐视效应,从而校准天然铕的同位素丰度比。引用确知的有关核素质量,计算得出铕原子量为151.964±0.003,与国际现行值很好地符合。     

Neptune多接收器等离子体质谱精确测定锶同位素组成

报道了近两年来在Neptune多接收器等离子体质谱(MC-ICP-MS)上对NIST SRM987的测试结果。针对实际地质样品,Neptune MC-ICP-MS和热电离质谱(TIMS)进行了平行测定。Neptune MC-ICP-MS可以精确测定锶同位素组成,与传统的TIMS相比,MC-ICP-MS可以获得与TIMS相媲美的数据精度,而且分析时间短,效率高。对于等离子体载气———氩气中少量氪的干扰,可以直接扣除;对于样品中少量铷(Rb/Sr<0.01)的干扰,同样可以直接扣除,从而获得准确的锶同位素组成。     

同位素稀释质谱法测定聚丙烯塑料中Hg的含量

采用同位素稀释电感耦合等离子体质谱法（ID-ICP-MS）测定了聚丙烯塑料中Hg元素的含量。样品处理采用高压密封焖罐酸溶样技术,将样品与²⁰²Hg稀释剂混合,通过所加稀释剂的量和测量混合样品中²⁰⁰Hg/²⁰²Hg的丰度比,准确计算出样品中Hg元素的含量,同时对测量结果的不确定度进行分析和评定。该方法与传统方法相比具有准确度高、不确定度小、受外界污染及样品损失影响小等优点,适用于国家计量单位对标准物质进行定值。     

涂样量对纳克级硼同位素测定的影响

在石墨存在下 ,用正热电离质谱法 ,使用Cs2 BO2+离子测定了含 1 0 0、50、2 0ng和 1 0ngB的NISTSRM 951硼酸标样中的硼同位素的组成。结果表明 ,随着涂样量的减少 ,硼同位素丰度测定比值 ( 1 1 B/1 0 B)和测定精度有所下降。本文也给出了VG -3 54正热电离质谱测定纳克级硼同位素组成的最佳条件。结果表明 ,当涂样量大于 1 0 0ngB时 ,硼同位素丰度比的测量精度最佳 ,1 0ngB是正热电离质谱法使用法拉第杯检测硼同位素组成的最低限量。本研究为开展低硼含量的海洋微体古生物 ,古土壤 ,河水等地质样品中的硼同位素组成质谱测定提供了依据。     

应用ICP-MS测定国际比对果汁样品中铅、镉和锡的含量

建立了微波消解、电感耦合等离子体质谱法（ICP-MS）同时测定国际比对果汁样品中铅、镉和锡的方法。应用微波消解进行样品前处理,采用在线内标校正基体干扰,采用干扰方程抑制质谱干扰,使用工作曲线计算出样品中铅、镉和锡元素的含量。测定结果表明,铅、镉和锡元素的检出限分别为0.021、0.016和0.052μg/L,相对标准偏差（RSD〈5%）,加标回收率介于90%～105%,用该方法测定FAPAS国际比对果汁样品,反馈的统计结果显示铅、镉和锡元素的Z值分别为-0.4、0.1和-0.2,结果均为满意。该方法快速、简单、精确,适于果汁中铅、镉和锡的测定。     

大米粉比对考核样品中镉含量定值研究

大米是我国居民的传统主食之一,其安全与否关乎民生。针对一些地区存在大米镉污染的现象,本工作制备了4种大米的系列比对考核样品,并测定了其中的镉含量。制备过程采用气流粉碎、混匀技术;定值则采用同位素稀释质谱法,定值结果与标准加入法相核验,获得了量值分别为（149.5 ±3.8）、（181.8 ± 5.1）、（387.4± 9.3）、（436.8 ±13.6）μg/g的4种比对考核样品;其不确定度评定考虑了定值过程、样品的不均匀性及不稳定性等各因素。定值过程中,着重研究了Sn核素及Zr、Mo等氧化物对Cd测量的干扰。研究发现：¹¹²Sn对¹¹²Cd、¹¹⁴Sn对¹¹⁴Cd的质谱干扰、Zr的氧化物对¹¹²Cd产生质谱干扰均可忽略不计;4个样品中Mo含量较高且浓度不同,同时样品中¹¹²Cd/¹¹¹Cd、¹¹⁴Cd/¹¹¹Cd接近天然镉的同位素比值。说明无论是¹¹²Sn、⁹⁶Zr¹⁶O、⁹⁶Mo¹⁶O、⁹⁵Mo¹⁶O对¹¹²Cd、¹¹¹Cd的影响均不大,但其引入的不确定度应予考虑。     

The role of mass spectrometry in atomic weight determinations

The 1914 Nobel Prize for Chemistry was awarded to Theodore Richards, whose work provided an insight into the history of the birth and evolution of matter as embedded in the atomic weights. However, the secret to unlocking the hieroglyphics contained in the atomic weights is revealed by a study of the relative abundances of the isotopes. A consistent set of internationally accepted atomic weights has been a goal of the scientific community for over a century. Atomic weights were originally determined by chemical stoichiometry--the so-called "Harvard Method," but this methodology has now been superseded by the "physical method," in which the isotopic composition and atomic masses of the isotopes comprising an element are used to calculate the atomic weight with far greater accuracy than before. The role of mass spectrometry in atomic weight determinations was initiated by the discovery of isotopes by Thomson, and established by the pioneering work of Aston, Dempster, and Nier using sophisticated mass spectrographs. The advent of the sector field mass spectrometer in 1947, revolutionized the application of mass spectrometry for both solids and gases to other fields of science including atomic weights. Subsequently, technological advances in mass spectrometry have enabled atomic masses to be determined with an accuracy better than one part in 10(7), whilst the absolute isotopic composition of many elements has been determined to produce accurate values of their atomic weights. Conversely, those same technological developments have revealed significant variations in the isotope abundances of many elements caused by a variety of physiochemical mechanisms in natural materials. Although these variations were initially seen as an impediment to the accuracy with which atomic weights could be determined, it was quickly realized that nature had provided a new tool to investigate physiochemical and biogeochemical mechanisms in nature, which could be exploited by precise and accurate isotopic measurements. Atomic weights can no longer be regarded as constants of nature, except for the monoisotopic elements whose atomic weights are determined solely by the relative atomic mass of that nuclide. Stable isotope geochemists developed mass spectrometric protocols by the adoption of internationally accepted reference materials for the light elements, to which measurements from various laboratories could be compared. Subsequently, a number of heavy elements such as iron, molybdenum and cadmium have been shown to exhibit isotope fractionation. The magnitude of such isotope fractionation in nature is less than for the light elements, but technological developments, such as multiple collector-inductively coupled plasma-mass spectrometry, have enabled such fractionation effects to be determined. Measurements of the atomic weights of certain elements affect the determination of important fundamental constants such as the Avogadro Constant, the Faraday Constant and the Universal Gas Constant. Heroic efforts have been made to refine the accuracy of the atomic weight of silicon, with the objective of replacing the SI standard of mass--the kilogram--with the Avogadro Constant. Improvements in these fundamental constants in turn affect the set of self-consistent values of other basic constants through a least-squares adjustment methodology. Absolute isotope abundances also enable the Solar System abundances of the s-, r-, and p-process of nucleosynthesis to be accurately determined, thus placing constraints on theories of heavy element nucleosynthesis. Future developments in the science of atomic weight determinations are also examined.     

同位素稀释质谱法对深海沉积物中镉的定值研究

文章介绍了用同位素稀释质谱法（IDMS）对深海沉积物中畅的定值方法,通过一系列的工作测定了国家深海沉积物标准物质GSMS－2中的镉含量,获得满意的结果。     

ID-TIMS 准确测定国际关键比对大米粉中痕量镉

The method of isotope dilution thermal ionization mass spectrometry able to trace to SI was developed to accurately measure trace amount of cadmium in the rice powder sample from CCQM-K24 international key comparison organized by CCQM(Comité Consultatif pour la Quantité de Matière, Paris). By comparison with our previous work, there was much improvement in aspects of digestion of the rice powder sample, separation of cadmium from the sample and dry-mass correction. As a result, the blank of this procedure was reduced and the measurement precisions of isotopic ratios of cadmium were increased. In addition, the uncertainty evaluation of the entire process of measurement was profoundly studied. The analytical result of this work (14.53±0.15) nmol/g was in agreement with the certified value.     

甲胎蛋白纯品的同位素稀释质谱法测定

建立了基于特征肽段的甲胎蛋白的液相色谱-同位素稀释串联质谱检测方法。选取3条同位素标记的甲胎蛋白特征肽段作为内标,准确称其质量后与酶切后的甲胎蛋白样品定量混合,采取Phenomenex Kinetex 2.6 μm C18色谱柱分离,电喷雾三重四极杆串联质谱多反应监测模式（MRM）测定,并对最优酶切条件、酶切效率以及定值结果的不确定度进行了考察和评定,得到的甲胎蛋白标准物质的最终测量结果为（0.329±0.016）mg/g。     

表面热电离同位素稀释质谱法的计算及质量分馏效应校正

表面热电离同位素稀释质谱法(ID-TIMS)是国际公认的基准方法之一。本文以稀释分析锶同位素为例,详细介绍了其计算和推导过程,提出基于指数近似模式的稀释分析同位素分馏校正的方法。该方法适用于校正含有两对参考比值的元素静态多接收稀释分析同位素比值的质量分馏,与指数校正方法和对数校正方法相比,计算过程更简单。还讨论了稀释剂同位素比值准确度对稀释分析同位素比值的影响及其质量分馏的校正方法,通过数学迭代计算质量分馏系数,得到稀释剂测量的质量分馏系数和准确的同位素比值。采用建立的质量分馏校正方法稀释分析NBS987,结果表明,在误差范围内与其参考值（⁸⁷Sr/⁸⁶Sr=0.710237±8（1σ））一致。     

电感耦合等离子体质谱法(ICP-MS)测定运动员食品中铅、砷、镉、铜

Inductively coupled plasma mass spectrometry (ICP-MS) was applied to determine copper, arsenic, cadmium, lead in athletic food using Sc, Ge, In, Bi as an internal standard. The linear correlation factor for four elements are higher than 0.999. Recoveries of spiked samples are in the range of 85.5%-115.5% and precision was fine, RSD is lower than 5.0%. And these are close agreement with the reference values in three standard reference materials of GBW08503, NBS1568, GBW08571. It indicates that the method is simple, rapid, sensitive and accurate, which can meet the demand for copper, arsenic, cadmium, lead analysis in athletic food.     

铕浓缩同位素全蒸发-1012Ω高阻信号放大器的热电离质谱分析方法

浓缩同位素是校正质谱法、同位素稀释质谱法和双稀释剂法等同位素质谱分析技术的基础,其化学纯度及丰度量值的准确性直接影响着分析结果的准确性。但由于浓缩同位素中低丰度同位素的离子信号较难准确测量,且缺乏合适的标准物质校正,给高精准的同位素丰度分析带来挑战。本文建立了适用于微量铕浓缩同位素样品纯化的锌还原-萃取色层法,纯化后的151 Eu和153 Eu两种浓缩同位素纯度优于99.99%,有效消除了其他稀土元素杂质的干扰。通过采用1012Ω信号放大器的法拉第杯接收样品中的低丰度同位素离子信号,建立了铕浓缩同位素的全蒸发-热电离分析方法。两种浓缩同位素样品的主丰度测量结果分别为151 Eu 0.9683676(11)和153 Eu 0.9876851(21),测量重复性比1011Ω信号放大器的法拉第杯以及文献中校正质谱法的测量结果提高了3倍。     

超声提取-ICP-MS法测定土壤中有效态铅和镉

本实验以DTPA为提取剂,建立了超声提取-电感耦合等离子体质谱（ICP-MS）测定土壤中有效态铅和镉的方法。实验考察了超声提取时间、溶液稀释倍数、测定条件等因素,并对基体干扰的消除进行了对比研究。在优化的ICP-MS 条件下,有效态铅和镉在1~200 μg/L浓度范围内线性关系良好,方法检出限分别为0.019 mg/kg、0.001 4 mg/kg,相对标准偏差小于6%（n=6）。用国家土壤标准物质进行方法精密度和准确度验证,相对误差小于5%（n=6）,该测定结果与国家标准方法（GB/T 23739-2009）一致,经t检验表明两者无显著性差异。该方法简便快捷、检出限低,具有良好的准确度和精密度,可满足大批量农业土壤污染调查样品中有效态铅和镉的分析要求。     

石墨炉原子吸收光谱高精度、高灵敏度地测定蜂蜜中的铅和镉

介绍了一种用于改进处理和优化测定的方法,该方法能精准地用石墨炉原子吸收光谱法测定蜂蜜中的铅和镉。在优化条件下,铅和镉测定的相对标准偏差分别为4.45%和7.49%,回收率分别约达93%～106%和95%～108%。