Electro-deposition as a sample preparation technique for total-reflection X-ray fluorescence analysis

A one-step sample preparation by electro-deposition for total-reflection X-ray fluorescence (TXRF) analysis has been developed using a common three-electrode arrangement with a rotating disc as the working electrode. Several elements such as Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Cd, Pb, As and U have been determined simultaneously in saline matrix. A special electrode tip has been constructed as a holder for the TXRF sample carrier, which consists of polished glassy carbon. The influence of parameters such as time, pH value, and trace element concentration on the deposition yield has been examined for 14 elements. From repeatability studies, the uncertainty in deposition yields at the 95% confidence level has been found to be less than 20% for most of these elements. Typical detection limits range from 5 to 20 ng/l under the experimental conditions applied here. By an appropriate choice of the reference element and by calculation of yield factors, reliable quantification can be achieved directly by internal standardization. First results obtained for the standard reference material CRM 505 are presented.     

X-ray fluorescence spectrometry analysis for minerals with agaron gel for sample preparation

A mineral sample preparation with agaron gel used in X-ray fluorescence analysis was developed. Mineral samples were decomposed with aqua-regia. The sample solution mixed with agaron gel was heated to boiling and then it would become quasi-solid gel under normal temperature. The elements dispersed in gel medium could be detected by X-ray fluorescence spectrometry. The method has both advantages of the solution preparation method and the solid preparation method. In addition, this method was adapted in detecting high content ores due to its' avoiding the risk of using platinum crucibles. The method has been applied to the determination of lead, zinc and iron in zinc and lead concentrates successfully.     

Contribution to the sample preparation in the radionuclide X-ray fluorescence analysis of hair

Methods of sample treatment in XRF analysis of hair are studied in view of the effect on analytical results. A new method is proposed based on the incomplete ashing of hair followed by pellet preparation. Its suitability is estimated on the XRF analysis of real hair samples collected from 4 healthy adults.     

Automated sample preparation for X-ray fluorescence, plasma emission and atomic absorption spectrometry

Summary There exists an important disparity between the high throughput of modern spectrometers for the analysis of mineral products and the weak means for the isoformation of samples. To fill this gap the French Iron and Steel Research Institute (IRSID), with the financial help of the European Community for Steel and Coal, has developed several instruments able to rapidly prepare samples for X-ray fluorescence, plasma emission and atomic absorption spectrometries. These three devices are able to prepare beads, solutions or both. Using high frequency heating, effective mixing during the fusion-dissolution process as well as a judicious choise of a number of parameters. The samples obtained are of such a quality that the preparation and measurement reproducibilities are often very similar.

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Automatische Probenvorbereitung für die Röntgenfluorescenz-, Plasmaemissions- und Atomabsorptions-SpektrometrieProbenvorbereitung mittels PERL'X-2, PLASMASOL und SOL'X

Zusammenfassung Es besteht eine große Ungleichheit zwischen dem hohen Probendurchsatz der modernen Spektrometer zur Analyse anorganischer Produkte und den unzureichenden Mitteln der Probenaufbereitung. Aus diesem Grund hat das französische Forschungsinstitut für Eisenhüttenwesen (IRSID) mit der finanziellen Hilfe der Europäischen Gemeinschaft für Kohle und Stahl einige Geräte entwickelt, die es erlauben, schnell Proben für die Röntgenfluorescenz, die mit Plasma angeregte optische Emission und die Atomabsorption aufzubereiten. Diese drei Geräte können Perlen, Lösungen, oder beide zugleich herstellen. Dank einer Hochfrequenzheizung, einer guten Durchmischung während der Aufschmelzung-Verdünnung und gezielt gewählter Parameter sind die erhaltenen Proben von einer solchen Qualität, daß die Reproduzierbarkeit von Aufbereitung und Messung in vielen Fällen nahezu gleich ist.

     

Sapphire sample carriers for silicon determination by total-reflection X-ray fluorescence analysis

Sapphire is presented as a new sample carrier material for total-reflection X-ray fluorescence spectrometry (TXRF). A comparison with conventional sample carrier materials such as quartz glass, Perspex®, glassy carbon and boron nitride demonstrates that sapphire has all the physical and chemical properties required for TXRF micro and trace analysis. Moreover, sapphire sample carriers allow the determination of silicon in many matrices in a comparatively simple way. Especially for airborne particulate matter, acid digestion can be avoided by cool-plasma ashing of suitable filter materials directly on the sample carrier. This technique has been successfully applied to environmental samples.     

Remarks on the sample preparation of oxidic materials for X-ray analysis

Summary The universal method which is established in practice and has the best reproducibility is indicated in a critical comparison of different techniques for producing melting fusion tablets for the X-ray analysis. By studying fusion tablets with methods of local analysis, users of the tablet technique shall be made critical. The different objectives of analytical problems with the analysis of oxides are discussed.

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Bemerkungen zur Probenvorbereitung oxidischer Materialien für die Röntgenfluorescenzanalyse

Zusammenfassung Ausgehend von einem kritischen Vergleich verschiedener Techniken zur Herstellung von Schmelzaufschluß-Tabletten für die RFA wird auf die in der Praxis bewährte Universalmethode mit der besten Reproduzierbarkeit hingewiesen. Durch die Untersuchung von Schmelztabletten mit Hilfe lokalanalytischer Methoden sollen Anwender der Tablettentechnik zur Kritik angeregt werden. Die unterschiedlichen Zielsetzungen analytischer Aufgaben bei der Untersuchung von Oxiden werden diskutiert.

     

An ion exchanger-epoxy resin pelletization method for sample preparation in X-ray fluorescence analysis. Microanalysis of metal ions in industrial waste water

Flame atomic emission and atomic absorption detection limits are compared on an absolute basis for the easily determined element, copper. Remarkably similar detection limits are obtained with a variety of atomization and sample introduction system combinations. Heated graphite atomizers offer significantly lower minimum detectable quantities.     

Effect of the sample matrix on measurement uncertainty in X-ray fluorescence analysis

The estimation of measurement uncertainty, with reference to univariate calibration functions, is discussed in detail in the Eurachem Guide “Quantifying Uncertainty in Analytical Measurement”. The adoption of these recommendations to quantitative X-ray fluorescence analysis (XRF) involves basic problems which are above all due to the strong influence of the sample matrix on the analytical response. In XRF-analysis, the proposed recommendations are consequently applicable only to the matrix corrected response. The application is also restricted with regard to both the matrices and analyte concentrations.In this context the present studies are aimed at the problems to predict measurement uncertainty also with reference to more variable sample compositions. The corresponding investigations are focused on the use of the intensity of the Compton scattered tube line as an internal standard to assess the effect of the individual sample matrix on the analytical response relatively to a reference matrix. Based on this concept the estimation of the measurement uncertainty of an analyte presented in an unknown specimen can be predicted in consideration of the data obtained under defined matrix conditions.     

Choice of optimum conditions of emitter preparation for X-ray fluorescence analysis of aerosols

The nonuniformity of aerosol distribution over filter surface was studied. It was found that the distribution depends on the properties of the studied object and on the sampler type: particle concentration is often higher in the center of the filter, but in some cases, they shift to the edges; the uniform distribution of particles is observed rarely. It was shown that, if the emitter in X-ray fluorescence analysis (XRF) is a disk 3 cm in diameter cut from the center of a filter 5 cm in diameter, the systematic error of the results of analysis may be higher than 0.30. Recommendations on the choice of the conditions of sampling aerosols and emitter preparation are formulated. If these conditions are met, the results of XRF analysis of nonuniform filters are characterized by s_r = 0.05, which satisfies the admissible error.     

X-ray fluorescence determination of bromine in halogenated organic compounds using quasisolid emitters

A series of quasi-solid emitters is proposed for the X-ray fluorescence determination of bromine in different bromine-containing compounds. It is shown that sucrose-based glasses are the best emitters for analyzing alkali solutions of halogenated organic compounds, saccharose-based glasses and polymer films are best for analyzing powder samples, and organic gels offer most promise for analyzing liquid (at normal conditions) samples. It is noted that the proposed method can expand the possibilities of commercially produced element analyzers, which are currently intended for determining only C, H, O, N, and S in organic compounds and cannot be used for determining halogens.     

X-ray Peltier cooled detectors for X-ray fluorescence analysis

The recent results on development of X-ray Si(Li), Si-planar and CdTe p-i-n detectors cooled by Peltier coolers for fabrication of laboratory and portable XRF analysers for different applications are discussed.

Low detection limits of XRF analysers are provided by increasing of detectors sensitive surface; improvement of their spectrometrical characteristics; decreasing of front-end-electronics noise level; Peltier coolers and vacuum chambers cooling modes optimization.

Solution of all mentioned tasks allowed to develop Peltier cooled detectors with the following performances:

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Advantages and disadvantages of all types of detectors for X-ray fluorescence analysis are compared. Spectra are presented. Application of different XRF analysers based on developed detectors in medicine, environmental science, industry, cryminalistics and history of art are demonstrated.     

熔融制样-X射线荧光光谱法测定锆钛矿中主次成分

为准确测定锆、钛及其共伴生有用有害杂质元素含量,采用稀释比1∶20的四硼酸锂-偏硼酸锂混合熔剂,先将样品700℃预氧化7 min,再1 050℃熔融19 min制样,建立了熔融制样-X射线荧光光谱法测定锆钛矿中SiO₂、Al₂O₃、Fe₂O₃、CaO、MgO、MnO、TiO₂、K₂O、Na₂O、P₂O₅、ZrO₂等11种主次成分的分析方法。采用标准样品加入光谱纯的方式配制锆钛矿的标准系列样品解决锆钛矿石标准样品不足的问题。结果表明,各组分的检出限在0.004%～0.13%,各组分测定结果的相对标准偏差(RSD,n=12)在0.060%～2.6%。对实际样品进行测定,测定值与传统方法测定值一致,并具有操作简便,分析周期短的优点,解决了锆钛矿石前处理过程中锆钛易水解,分析周期长的问题,对综合评价锆钛矿资源具有重要意义。     

X射线荧光光谱法测定除尘灰中砷、铅含量

以熔融制样法,采用X射线荧光光谱对除尘灰中的有害元素：砷、铅含量进行了测定。对样品的烧失温度进行了讨论,发现在950℃灼烧温度下灼烧2h时除碳完全。砷和铅的相对标准偏差为0.15 %和0.20 %。测试结果与化学分析法、原子吸收光谱法等相吻合。该方法制作工艺简单,分析速度快,样品可长期保存,还能满足其他元素的日常分析。     

Urine sample preparation for proteomic analysis

Sample preparation for both environmental and more importantly biological matrices is a bottleneck of all kinds of analytical processes. In the case of proteomic analysis this element is even more important due to the amount of cross‐reactions that should be taken into consideration. The incorporation of new post‐translational modifications, protein hydrolysis, or even its degradation is possible as side effects of proteins sample processing. If protocols are evaluated appropriately, then identification of such proteins does not bring difficulties. However, if structural changes are provided without sufficient attention then protein sequence coverage will be reduced or even identification of such proteins could be impossible. This review summarizes obstacles and achievements in protein sample preparation of urine for proteome analysis using different tools for mass spectrometry analysis. The main aim is to present comprehensively the idea of urine application as a valuable matrix. This article is dedicated to sample preparation and application of urine mainly in novel cancer biomarkers discovery.     

Immuno-based sample preparation for trace analysis

Immuno-based sample preparation techniques are based upon molecular recognition. Thanks to the high affinity and high selectivity of the antigen–antibody interaction, they have been shown to be a unique tool in the sampling area. Immuno-based sample preparation methods include the widely encountered immunoaffinity extraction sorbents, so-called immunosorbents, as well as membrane-based or ultrafiltration techniques. This review describes the new developments and applications that have occurred in recent years with emphasis on (i) the antigen–antibody interactions, (ii) and their importance for the properties and use of immunosorbents, (iii) multiresidue extractions, (iv) the on-line coupling to chromatographic or electrophoretic separations, and (v) the high potential for improving MS detection. The recent use of artificial antibodies for sample pretreatment, so-called molecularly imprinted polymers, is also described.     

X射线荧光光谱熔融法测定锶永磁铁氧体中各组分含量

本文使用自制标准样品,采用混合熔剂熔融样品,用X射线荧光光谱法(XRF)测定锶永磁铁氧体半成品中Fe,Sr,Si等元素的含量.熔融制样有效地消除了矿物效应,并降低了基体效应的影响.实验结果表明,本法准确度高,重现性好,平行测定11次相对标准偏差(RSD)可达到0.1%.该方法用于实际样品分析,其结果与传统化学分析方法结...     

Radioisotope sources for X-ray fluorescence analysis

Problems involved in developing radioisotope sources and the characteristics of potentially useful radioisotopes for X-ray fluorescence analysis are presented. Some of the isotopes, which are not in use but look very promising, are indicated.     

X射线荧光光谱分析

作为《分析试验室》定期评述“X射线荧光光谱分析”系列评论第八篇,本文收集国内学者在1998年7月至2000年6月期间公开发表在国内外期刊和国际会议文集上的129篇论文,并对此期间对我国X射线荧光光谱分析的概况、发展和国际上的地位进行了讲述,内容包括仪器及维修、基体校正、数据处理方法、谱分析方法的研究、标样及样品制备、全反射X射线荧光光谱、同步辐射光源X射线荧光光谱、粒子激发X射线发射、X射线荧光光谱分析方法研究及其应用。     

Photopolymerized microtips for sample preparation in proteomic analysis

We demonstrate a novel method for the fabrication of disposable plastic microtips, which we name "EasyTip", by a photopolymerization technique. C18 reversed-phase (C18) and ion metal affinity chromatography (IMAC) beads were immobilized on a plastic pipette tip, made of polypropylene materials, by photo-initiated polymerization. The fabricated EasyTips can be manipulated using commercial pipettes for wash/elution of minute amount of biological samples (< 10 microL) and can be applied for mass spectrometry (MS)-based proteomic analysis, in which the detection sensitivity depends critically on the optimal sample preparation. The recovery of a sample of 25 fmol of tryptic hemoglobin digest loaded in a C18 EasyTip was near 100% and we estimated the loading capacity to be around 0.4-2.0 microg of total proteins or peptides, which is well above a sufficient quantity for MS analysis. The effectiveness of the C18 EasyTips in enhancing the detection sensitivity of matrix-assisted laser desorption/ionization (MALDI)-MS signal, and thus providing a greater sequence coverage, was also demonstrated by the analysis of hemoglobin digest and the in-gel digested epidermal growth factor receptor (EGFR) protein from A431 cell lysate. We also demonstrated the usefulness of the immobilized IMAC EasyTips in extracting the signal of tryptic phosphopeptides of beta-casein (10 pmol) having one and four phosphorylation sites by using an IMAC EasyTip prior to off-line analysis by MS. The combination of IMAC EasyTips and MALDI-MS allowed the unambiguous identification of phosphopeptides based on the phosphatase assay as well as the post-source decay. Compared to other miniaturized devices, this fabrication method is simple, cheap, and requires less human intervention. Moreover, the method of manipulating the EasyTips is straightforward and can be automated readily by a robotic system for high-throughput analysis.