A comparison of the performance of a fundamental parameter method for analysis of total reflection X-ray fluorescence spectra and determination of trace elements,versus an empirical quantification procedure

The performance has been compared of two different quantification methods — namely, the commonly used empirical quantification procedure and a fundamental parameter approach — for determination of the mass fractions of elements in particulate-like sample residues on a quartz reflector measured in the total reflection geometry. In the empirical quantification procedure, the spectrometer system needs to be calibrated with the use of samples containing known concentrations of the elements. On the basis of intensities of the X-ray peaks and the known concentration or mass fraction of an internal standard element, by using relative sensitivities of the spectrometer system the concentrations or mass fractions of the elements are calculated. The fundamental parameter approach does not require any calibration of the spectrometer system to be carried out. However, in order to account for an unknown mass per unit area of a sample and sample nonuniformity, an internal standard element is added. The concentrations/mass fractions of the elements to be determined are calculated during fitting a modelled X-ray spectrum to the measured one. The two quantification methods were applied to determine the mass fractions of elements in the cross-sections of a peat core, biological standard reference materials and to determine the concentrations of elements in samples prepared from an aqueous multi-element standard solution.     

Analysis of rare-earth elements in soil sample by using laser-ablation ion trap mass spectrometry

Laser-ablation ion trap mass spectrometry (LA-ITMS) is applied for the analysis of rare-earth elements in soil samples. The target elements studied in this work were ytterbium (Yb) and samarium (Sm). The isotopic compositions of these elements were analyzed for standard samples with chip shape, the western phosphate rock sample (NIST SRM-694), and soil samples collected near our laboratory. For metal samples of Sm and Yb, isotopes of these elements as well as oxide forms were clearly identified. For the case of soil samples only a tentative assignment on the mass peaks were performed due to the complicated mass spectra that originated from the oxide forms of various rare-earth elements.     

Spatially resolved ultra-trace analysis of elements combining resonance ionization with a MALDI-TOF spectrometer

A combined setup for spatially resolved mass analysis of trace amounts of elements and macromolecules is presented. Using a MALDI-TOF mass spectrometer, a laser spectroscopic setup for resonant ionization of neutral atoms has been implemented. This allows for an efficient and selective detection of trace elements by means of resonance ionization mass spectrometry (RIMS). The instrumental scheme is described, and methodological developments are presented. In a first application pure, laser desorption/ionization with TOF-MS was used to measure mass distributions of cosmic nanodiamonds. For further applications regarding the spatially resolved ultra-trace analysis of elements in solid samples, an implanted target was used to characterize both laser desorption/ionization and laser desorption/resonance ionization for the detection of trace elements within. A perspective of the setup is given and future investigations are outlined.     

Analysis of radioactive metals by spark source mass spectrometry

A spark source mass spectrograph with photographic plate recording has been adapted for the analysis of plutonium and americium metals. Over seventy elements can be determined simultaneously in these metals. A comparison has been made between results obtained by mass spectrography and by conventional methods for impurity elements. The operations involved in handling radioactive materials in the mass spectrograph are also discussed.     

Determination of trace elements and correction of mass spectral interferences in superalloy analyzed by glow discharge mass spectrometry

Mass spectral interference was investigated systematically during the determination of trace elements in superalloy by glow discharge mass spectrometry (GD-MS); moreover the main mass spectral interference and interference level of isotopes were provided in detail. According to the mass spectral interference of elements, different methods were selected for interference correction. The effects of mass spectral interference were removed efficiently by using correction methods such as selecting isotopes without interference, matching sample matrices and deducing interference with multivariable linear regression. The determination results of three superalloy samples show that trace elements such as B, Mg, Ga, As, Ag, In, Sn, Sb, Te, Tl, Pb and Bi were determined successfully after interference correction.     

Trace analysis of glasses by magnetically enhanced rf GDMS

A radiofrequency (rf) glow discharge ion source coupled to a commercial double-focusing mass spectrometer was used for the direct trace element analysis of glass samples. By utilizing an additional ring-shaped magnet located behind the flat sample in an rf glow discharge ion source compared with a configuration without a magnet, the sputtering and ionization efficiency of glass samples was enhanced and the detection power for trace elements was improved. The detection limits for elements determined by rf glow discharge mass spectrometry at low mass resolution (m/Δm = 300) are 10–100 ng/g. Possible interferences of atomic ions of analyte and molecular ions which limited the determination of some elements (e.g. Ti, Mn, Fe, Ni, Co, Cu, Zn) could be resolved at the mass resolution of m/Δm = 3000. The detection limits for these elements were found to be about 100 ng/g. Relative sensitivity factors (RSFs) for all elements of interest with respect to Sr (internal standard element) were determined in the range of 0.2–3.     

Reinforcing Isotope and Atomic-Weight Concepts in General Chemistry Using Internet-Based Mass-Spectral Data

This paper describes how isotope and atomic-weight concepts are enhanced for students using mass-spectral data from interactive Internet sites. The class considers mass spectra for compounds containing only monoisotopic elements and later for polyisotopic elements. Students calculate molecular weights based on data they acquire from mass spectra on the Internet.     

广州市夏、冬季室内外PM2.5中元素组分的特征与来源

通过采集广州市9个居民住宅室内、外的PM2.5样品,测定分析PM2.5中18个元素组分的质量浓度,分析讨论其污染、分布特征并解析其污染来源。经过比较得知,广州市PM2.5中元素污染较严重;不同类型住宅PM2.5中元素浓度存在空间分布特征;大部分元素浓度具有夏季比冬季低的变化特征;室内与室外元素浓度比值介于0.4974～2.0497之间;元素浓度的室内、室外相关拟合结果说明冬季室内空气受室外空气影响比夏季时情况更明显;基于富集因子分析,Se、As、S、Pb、Br、Zn和Cl元素高度富集;Ni、V、Cu元素中等富集,主要来自人为源,而Cr、Sr、K、Mn、Ca和Ti元素不富集,主要来自自然源。     

Inorganic trace analysis by mass spectrometry

Mass spectrometric methods for the trace analysis of inorganic materials with their ability to provide a very sensitive multielemental analysis have been established for the determination of trace and ultratrace elements in high-purity materials (metals, semiconductors and insulators), in different technical samples (e.g. alloys, pure chemicals, ceramics, thin films, ion-implanted semiconductors), in environmental samples (waters, soils, biological and medical materials) and geological samples. Whereas such techniques as spark source mass spectrometry (SSMS), laser ionization mass spectrometry (LIMS), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), glow discharge mass spectrometry (GDMS), secondary ion mass spectrometry (SIMS) and inductively coupled plasma mass spectrometry (ICP-MS) have multielemental capability, other methods such as thermal ionization mass spectrometry (TIMS), accelerator mass spectrometry (AMS) and resonance ionization mass spectrometry (RIMS) have been used for sensitive mono- or oligoelemental ultratrace analysis (and precise determination of isotopic ratios) in solid samples. The limits of detection for chemical elements using these mass spectrometric techniques are in the low ng g⁻¹ concentration range. The quantification of the analytical results of mass spectrometric methods is sometimes difficult due to a lack of matrix-fitted multielement standard reference materials (SRMs) for many solid samples. Therefore, owing to the simple quantification procedure of the aqueous solution, inductively coupled plasma mass spectrometry (ICP-MS) is being increasingly used for the characterization of solid samples after sample dissolution. ICP-MS is often combined with special sample introduction equipment (e.g. flow injection, hydride generation, high performance liquid chromatography (HPLC) or electrothermal vaporization) or an off-line matrix separation and enrichment of trace impurities (especially for characterization of high-purity materials and environmental samples) is used in order to improve the detection limits of trace elements. Furthermore, the determination of chemical elements in the trace and ultratrace concentration range is often difficult and can be disturbed through mass interferences of analyte ions by molecular ions at the same nominal mass. By applying double-focusing sector field mass spectrometry at the required mass resolution—by the mass spectrometric separation of molecular ions from the analyte ions—it is often possible to overcome these interference problems. Commercial instrumental equipment, the capability (detection limits, accuracy, precision) and the analytical application fields of mass spectrometric methods for the determination of trace and ultratrace elements and for surface analysis are discussed.     

微波消解-高分辨电感耦合等离子体质谱 (HR-ICP-MS)法测定煤炭中35种痕量金属元素

高分辨电感耦合等离子体质谱可以区分干扰元素和目标元素微弱的质量数差别,能解决大多数多原子、氧化物干扰问题,在煤炭痕量元素分析领域受到关注,但煤炭样品中痕量金属元素尤其是稀土元素受到的质谱干扰挑战未被系统地报道.采用HNO3-HF混酸微波消解煤炭样品,优化了消解时间、赶酸、复溶等前处理条件,研究了煤炭中V、Cr、Mn、C...     

草药中 11种元素的聚焦微波辅助萃取-等离子体质谱法测定

利用ICP－MS对青钱柳叶、龙胆草以及秦皮中的11种金属元素进行测定。应用CEM Star-Ⅱ聚焦微波萃取系统,采用正交设计实验研究了温度、时间、料液质量体积比对浸取效率的影响。结果表明,温度是影响提取效率的主要因素,提取时间对某些元素影响也比较明显,但料液比对几乎所有元素的影响都很小。钒元素在微波萃取条件下溶出率很低。     

Monte Carlo Simulation of Degradation of Porous Poly(lactide) Scaffolds, 1

Summary: Monte Carlo method was used to simulate the degradation of porous PLA scaffolds. The simulated volume was assumed to be divided homogeneously between the pore and solid PLA with the ratio equal to the bulk porosity of the scaffold. The volume was divided into surface and bulk elements where the surface elements were in direct contact with the aqueous degradation medium, while the bulk elements were surrounded by the pore and solid PLA. The effect of degradation time on PLA ester groups and carboxylic acid end‐groups for surface and bulk elements, pH, PLA degradation rate and mass loss, and PLA molecular weight distribution was simulated. For surface elements, pH remained constant at 7.4 over the entire time of degradation, while for bulk elements its value decreased significantly to as low as 5.8. The highest drop in pH within the scaffold was observed for the highest porosity of 90%. There was a lag time of at least 7 weeks in the mass loss for surface as well as bulk elements for porosities ranging from 70 to 90%. The mass loss for bulk elements was considerably faster than the surface elements. This difference in the rate of mass loss between the surface and bulk elements could affect the 3D morphology and dimensional stability of the scaffold in vivo as degradation proceeds. The simulation predicts that, due to differences in the rate of bulk and surface degradation, hollow structures could form inside the scaffold after 19, 17, and 15 weeks for initial porosities of 70, 80, and 90%, respectively.

A schematic diagram illustrating the degradation of an element on the outer surface of the scaffold (surface element) versus an element within the volume of the scaffold (bulk element).     

微量进样/ICP-MS体系中的基体效应研究

考察了自行组装的高效微量进样系统在22μL/min低提升量下电感耦合等离子体质谱的基体效应.质量数和电离电位不同的基体元素质量浓度为2g/L时,低质量数分析元素受到一定的干扰,而对于高质量数分析元素,其信号几乎不受基体元素干扰,归一化信号值接近1.对于体积分数为5%的有机基体样品溶液,此微量高效雾化系统测得的归一化信号值多接近0.5.实际样品中常见的基体元素K,Na,Ca和Mg质量浓度低于500mg/L,以及乙醇和乙酸体积分数小于1%时,微量进样系统均不产生显著干扰.     

Nuclear systematics

Summary The abundance pattern of s-process nuclides confirms severe mass separation in the Sun and in the parent star that gave birth to the Solar System. The most abundant elements in the interior of the Sun are Fe, Ni, O, Si and S. These five, even-Z elements with high nuclear stability comprize the bulk material of ordinary meteorites and rocky planets close to the Sun. The Sun and other stars operate as giant, magnetic mass-separators that selectively move lightweight elements, and the lighter mass isotopes of each element, to the surface.     

A miniature mass analyser for in-situ elemental analysis of planetary material-performance studies

The performance of a laser ablation mass analyser designed for in-situ exploration of the chemical composition of planetary surfaces has been investigated. The instrument measures the elemental and isotopic composition of raw solid materials with high spatial resolution. The initial studies were performed on NIST standard materials using IR laser irradiance (< 1 GW cm⁻²) at which a high temporal stability of ion formation and sufficiently low sample consumption was achieved. Measurements of highly averaged spectra could be performed with typical mass resolution of m/Δm ≈ 600 in an effective dynamic range spanning seven decades. Sensitive detection of several trace elements can be achieved at the ~ ppm level and lower. The isotopic composition is usually reproduced with 1% accuracy, implying good performance of the instrument for quantitative analysis of the isotopic fractionation effects caused by natural processes. Using the IR laser, significant elemental fractionation effects were observed for light elements and elements with a high ionization potential. Several diatomic clusters of major and minor elements could also be measured, and sometimes these interfere with the detection of trace elements at the same nominal mass. The potential of the mass analyser for application to sensitive detection of elements and their isotopes in realistic samples is exemplified by measurements of minerals. The high resolution and large dynamic range of the spectra makes detection limits of ~100 ppb possible.     

废弃物燃烧产生的可吸入颗粒物中金属元素的排放特性研究

将纸屑、甘蔗渣、木粉、谷壳、垃圾衍生燃料（RDF）五种废弃物进行燃烧，采集其烟气中可吸入颗粒物（PM10）样品并分析，获得了颗粒物中金属元素的质量分数和排放特性，并与其相应的原料和灰烬中的金属元素质量分数比较。结果显示，废弃物燃烧的颗粒物中金属元素的种类与燃烧的物料有关；纸屑的颗粒物中金属元素的质量分数最低，RDF的最高，其余三种生物质废弃物的质量分数较相近；在五种样品中，一些重金属的质量分数很高，比土壤中的质量分数高出很多倍；金属元素在灰烬和颗粒物中的分布情况与金属元素的性质密切相关，且在可吸入颗粒物上有明显的富集。     

Characterization of high purity gallium

Multi-step wet analytical procedures were tested on gallium samples of different purity grades. Results obtained were compared with those of spark source mass spectrometry (SSMS) and glow discharge mass spectrometry (GDMS). It was found that multi-step procedures, as applied, with preconcentration factors of 200 are suitable to determine most of the detectable elements in high purity gallium in the ng/g-range. The results thus obtained agree well with those obtained by mass spectrometry. The sensitivity of the multi-step and mass spectrometry methods is not sufficient to detect traces of the investigated elements in super purity gallium, i.e. better than 6 N. These qualities can be differentiated, however, by single crystal resistivity measurement.     

Selektive chemische Trennverfahren für die Aktivierungsanalyse

Relative sensitivity factors (RSF) of 32 elements in the concentration range 1–10⁴ ppm (mass of element/ mass of electrode) have been determined for spark source mass spectrometric analysis. Graphite and silver powder was used as conductive material. The RSF of about two thirds of the elements under investigation were found to be dependent on their concentration in the electrodes. This is thought to be due to volatilization at high temperatures whereby the concentration of these elements at the electrode surfaces is diminished. In general RSF's at silver powder electrodes are higher and necessary sparking times are shorter than those at graphite electrodes. Therefore the use of silver powder for determinations of concentrations <10³ ppm is advantageous although experimental results show greater scatter due to inhomogeneity of the electrode.     

Development and certification of the new SRM 695 trace elements in multi-nutrient fertilizer

During the past seven years, several states within the US have enacted regulations that limit the amounts of selected non-nutritive elements in fertilizers. Internationally, several countries, including Japan, China, and Australia, and the European Union also limit the amount of selected elements in fertilizers. The elements of interest include As, Cd, Co, Cr, Cu, Hg, Mo, Ni, Pb, Se, and Zn. Fertilizer manufacturers and state regulatory authorities, faced with meeting and verifying these limits, need to develop analytical methods for determination of the elements of concern and to validate results obtained using these methods. Until now, there were no certified reference materials available with certified mass fraction values for all elements of interest in a blended, multi-nutrient fertilizer matrix. A new standard reference material (SRM) 695 trace elements in multi-nutrient fertilizer, has been developed to help meet these needs. SRM 695 has recently been issued with certified mass fraction values for seventeen elements, reference values for an additional five elements, and information values for two elements. The certificate of analysis includes an addendum listing percentage recovery for eight of these elements, determined using an acid-extraction inductively-coupled plasma optical-emission spectrometry (ICP–OES) method recently developed and tested by members of the Association of American Plant Food Control Officials.     

ICP－MS分析人血清中微量元素

用ＩＣＰ－ＭＳ分析人血清中２２种元素。为克服基体抑制效应。采用内标元素Ｓｃ和Ｉｎ分别校正质量数８０以下和８０以上元素的测定，获得满意的结果。通过对牛血清标准物质的测定，检验分析结果的准确性和方法的可靠性。