同位素稀释-火花源质谱法分析人参样品中微量元素

本文采用同位素稀释-火花源质谱法定量分析了吉林野山参,园参及高丽参中30多种微量元素的含量。测定下限2μg/g,相对标准偏差在5～28％以内。     

Accuracy and long-term reproducibility of lead isotopic measurements by multiple-collector inductively coupled plasma mass spectrometry using an external method for correction of mass discrimination

The precision of isotopic measurements of Pb by thermal ionization mass spectrometry (TIMS) is limited by the fact that this element does not possess an invariant isotope ratio that can be used for the correction of mass fractionation by internal normalization. Multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS) can overcome this limitation, because with plasma ionization, elements with overlapping mass ranges are thought to display identical mass discrimination. With respect to Pb, this can be exploited by the addition of Tl to the sample solutions; the mass discrimination factor obtained for Tl can then be used for the correction of the measured Pb isotope ratios. In this article we present the results of a detailed study that investigates the accuracy and precision of such an external correction technique for mass discrimination based upon the results of multiple analyses of a mixed standard solution of NIST SRM-981 Pb and SRM-997 Tl. Our data indicate that normalization of the Pb isotope ratios to the certified isotopic composition of SRM-997 Tl produces Pb isotopic results that are significantly lower than recently published reference values by TIMS. This systematic offset can be eliminated by renormalization of the Pb data to a different Tl isotopic composition to obtain an empirically determined mass discrimination factor for Pb that generates accurate results. It is furthermore shown that a linear law is least suited for the correction of mass discrimination, whereas a power or exponential law function provide significantly more accurate and precise results. In detail, it appears that a power law may provide the most appropriate correction procedure, because the corrected Pb isotope ratios display less residual correlations with mass discrimination compared to the exponentially corrected data. Using an exponential or power law correction our results, obtained over a period of over seven months, display a precision (2σ) of better than 60 parts per million (ppm) for ²⁰⁸Pb/²⁰⁶Pb and ²⁰⁷Pb/²⁰⁶Pb and of better than 350 ppm for ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb. This represents a significant improvement compared to conventional TIMS techniques and demonstrates the potential of MC-ICPMS for routine, high-precision measurements of Pb isotopic compositions.     

甲烷部分氧化制合成气 Ⅰ．甲烷在过渡金属上的活化

文中用同位素交换（Ｄ_２─ＣＨ_４）反应来测量四种过渡金属负载型催化剂对甲烷的活化能力，并与Ｓｖｅｎｓｓｏｎ等从头算的计算结果作了比较，表明最有效活化甲烷分子的Ｃ─Ｈ键的金属是铑（Ｒｈ）．文中还测定了在甲烷部分氧化制合成气反应中，四个不同催化剂的催化活性与选择性，并与它们对甲烷的活化能力进行对比，可以看出甲烷部分氧化反应中，反应活性高的催化剂有效地活化甲烷，断裂Ｃ─Ｈ键，而且氘代甲烷产物分布以形成ＣＤ_４产物为主要成份．     

The optimal amount of isotopic spike solution for ultratrace analysis by isotope dilution mass spectrometry

 Inductively coupled plasma mass spectrometry (ICP-MS) and high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) are powerful methods of determining metallic impurities in the low- and sub-ppt level in process media such as ultra-pure water used in semiconductor and wafer manufacturing. By using mass spectrometers for analysis, an isotope dilution analysis (IDMS) is possible. The reproducibility of an IDMS is unmatched. For concentration levels near the instrument detection limit a novel method is reported to find the optimal amount of isotopic spike solution. This optimal value can be derived by the law of propagation of uncertainty combined with the Poisson statistics of the measured number of counts. Generally, an excess of isotopic spike solution should be used to provide results of lowest possible uncertainty. The results are presented in a diagram for easy practical use. Received: 14 October 1997 · Accepted: 13 February 1998     

Hydrogen substitution effect on the solubility of perhalogenated compounds in ionic liquid [bmim][PF6]

Solubility behaviors of binary mixtures of CFCl₃ (R-11), CFCl₂-CF₂Cl (R-113), CHCl₃ (R-20), CDCl₃ (R-20-d), CHCl₂–CF₃ (R-123) with room-temperature ionic liquid [bmim][PF₆] (1-butyl-3-methylimidazolium hexafluorophosphate) have been investigated using the volumetric and cloud-point methods, since all the systems show liquid–liquid equilibria (LLE). Large immiscibility (LLE) gaps of the perhalogenated compounds (R-11 and R-113) in the ionic liquid have been drastically reduced by the addition of only one hydrogen (or deuterium) in these compounds. The R-123 + [bmim][PF₆] binary system belongs to the Type-V fluid behavior. Noticeably large negative values (−2 to −8 cm³ mol⁻¹) of the excess molar volume in the ionic liquid-rich side solution have been observed for all the present systems. Experimental LLE data have been well correlated by the use of the NRTL (non-random two liquid) activity coefficient model.     

Simultaneous speciation of mercury and butyltin compounds in natural waters and snow by propylation and species-specific isotope dilution mass spectrometry analysis

A robust method has been developed for simultaneous determination of mercury and butyltin compounds in aqueous samples. This method is capable of providing accurate results for analyte concentrations in the picogram per liter to nanogram per liter range. The simultaneous determination of the mercury and tin compounds is achieved by species-specific isotope dilution, derivatization, and gas chromatography–inductively coupled plasma mass spectrometer (GC–ICP–MS). In derivatization by ethylation and propylation, reaction conditions such as pH and the effect of chloride were carefully studied. Ethylation was found to be more sensitive to matrix effects, especially for mercury compounds. Propylation was thus the preferred derivatization method for simultaneous determination of organomercury and organotin compounds in environmental samples. The analytical method is highly accurate and precise, with RSD values of 1 and 3% for analyte concentrations in the picogram per liter to nanogram per liter range. By use of cleaning procedures and SIDMS blank measurements, detection limits in the range 10–60 pg L^–1 were achieved; these are suitable for determination of background levels of these contaminants in environmental samples. This was demonstrated by using the method for analysis of real snow and seawater samples. This work illustrates the great advantage of species-specific isotope dilution for the validation of an analytical speciation method—the possibility of overcoming species transformations and non-quantitative recovery. Analysis time is saved by use of the simultaneous method, because of the use of a single sample-preparation procedure and one analysis.     

Determination of chloride ion in aqueous samples by isotope-dilution Fourier-transform flame infrared emission (ID-FIRE) spectrometry

An isotope dilution method for the determination of chloride ion in aqueous samples is described. The method makes use of the isotopic shift in the rotational lines of the 1–0 band of HCl emitted in the near infrared region of the spectrum by vibrationally excited HCl molecules present in a hydrogen/entrained air flame. Chloride ion in the sample is converted to chlorine gas by electrolysis and swept into a hydrogen/entrained air flame where it is converted into HCl. Because isotope dilution is an absolute method of analysis, matrix effects are minimized, and the chlorine generation step need not be quantitative. With the system described in this paper, samples must contain at least 9 mg of chloride ion per ml, and a 2-ml sample is required. Over the range from 10 to 30 mg Cl⁻ ml⁻¹, the average error was −0.96%, and the average relative standard deviation was 3.3% for seven samples using seven of the more intense lines in the P branch. Compared with standard silver nitrate titrations, the isotope dilution procedure was not affected by such common interferences as bromide ion and iodide ion. The technique was applied to several seawater samples from different regions.     

Measurement of labile Cu in soil using stable isotope dilution and isotope ratio analysis by ICP-MS

Isotope dilution is a useful technique to measure the labile metal pool, which is the amount of metal in soil in rapid equilibrium (<7 days) with the soil solution. This is normally performed by equilibrating soil with a metal isotope, and sampling the labile metal pool by using an extraction (E value), or by growing plants (L value). For Cu, this procedure is problematic for E values, and impossible for L values, due to the short half-life of the ⁶⁴Cu radioisotope (12.4 h), which makes access and handling very difficult. We therefore developed a technique using enriched ⁶⁵Cu stable isotope and measurement of ⁶³Cu/⁶⁵Cu ratios by quadrupole inductively coupled plasma mass spectrometry (ICP-MS) to measure labile pools of Cu in soils using E value techniques. Mass spectral interferences in detection of ⁶³Cu/⁶⁵Cu ratios in soil extracts were found to be minimal. Isotope ratios determined by quadrupole ICP-MS compared well to those determined by high-resolution (magnetic sector) ICP-MS. E values determined using the stable isotope technique compared well to those determined using the radioisotope for both uncontaminated and Cu-contaminated soils.     

稀土离子在多孔阳离子交换剂内的扩散动力学

研究了稀土离子在Amberlyst15、D001、XN1010多孔树脂内的自扩散。结果表明,扩散过程遵循二级分散扩散机制。用粒内扩散方程求算了有效粒内扩散系数e,将e分解为树脂孔道扩散系数p及树脂固相扩散系数s,p与该离子在外部溶液中的自扩散系数相近,而s接近于与实验用的多孔树脂交联度相同的凝胶树脂内的自扩散系数值。     

A generalized equation describing isotope exchange kinetics at solid-liquid interface

A generalization of the kinetic equation for the isotope exchange at solid—liquid interface is presented. The generalized equation may be used to describe kinetics of the isotope exchange process limited by surface reactions and diffusion without assumption of spherical symmetry of solid particles.

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Eine generalisierte Gleichung für die Kinetik des Isotopenaustausches an Fest-Flüssig-Phasengrenzen

Zusammenfassung Es wird eine generalisierte kinetische Gleichung angegeben, die die Kinetik des Isotopenaustausches an Fest-Flüssig-Phasengrenzen beschreibt, wobei der Austauschprozeß durch Oberflächenreaktionen und Diffusion ohne der Annahme sphärischer Symmetrie für die festen Partikel begrenzt ist.