Contribution to the radionuclide X-ray fluorescence analysis of human blood and plasma

A photon-induced X-ray fluorescence method, which allows the simultaneous determination of iron, copper, zinc, bromine and rubidium in human blood and blood plasma samples is described. The method is reliable and has a good sensitivity for a wide range of elements.     

Error of sample preparation in pressing emitters for X-ray fluorescence analysis

When determining element concentrations in geological samples by X-ray fluorescence spectrometry using emitters obtained by pressing tablets from powder samples, we revealed the effect of a significant difference in line intensities of characteristic long-wavelength emission (ΔI _i) from opposite sides of the emitter. The effects of compacting pressure, mass of emitter, and its surface area on ΔI _i were investigated. It was shown that the account of this effect can reduce the error of sample preparation in using compacting pressures lower than 20 t.     

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 in vitro multielement X-ray fluorescence analysis of human soft tissues

Determination of Mn, Fe, Ni, Cu, Zn and Pb in human soft tissues by radionuclide X-ray fluorescence analysis /using²³⁸Pu and¹⁰⁹Cd sources/ is described.     

Application of radionuclide sources for excitation in energy-dispersive X-ray fluorescence analysis

Summary X-ray fluorescence (XRF) analysis is in broad application in many fields of science where elemental determinations are necessary. Solid and liquid samples are analyzed by this method. Solids are introduced in thin or thick samples as melted glass, pellets, powders or as original specimen. The excitation of X-ray spectra can be performed by specific and polychromic radiation of X-ray tubes, by protons, deuterons, -particles, heavy ions and synchrotron radiation from accelerators and by -particles, X- and -rays and by bremsstrahlung generated by ^–-particles from radionuclide sources. The radionuclides are devided into groups with respect to their decay mode and the energy of the emitted radiation. The broad application of radionuclides in XRF excitation is shown in examples as semi-quantitative analysis of glasses, as quantitative analysis of coarse ceramics and as quantitative determination of heavy elements (mainly actinides) in solutions. The advantages and disadvantages of radionuclide excitation in XRF analysis are discussed.

---

Anwendung von Radionuklidquellen zur Anregung in der Energie-dispersiven Röntgenfluorescenz-Analyse

Zusammenfassung Die Röntgenfluorescenzanalyse (RFA) ist auf all denen Gebieten der Wissenschaften verbreitet, in denen die Bestimmung der Elemente notwendig ist. Mit Hilfe dieser Methode können feste und flüssige Proben analysiert werden. Dünne oder dicke, feste Proben werden als geschmolzene Gläser, Tabletten, Pulver oder in Originalform eingesetzt. Die Anregung der Röntgenspektren erfolgt durch die spezifische und kontinuierliche Strahlung von Röntgenröhren, durch Protonen, Deuteronen, -Teilchen, schwere Ionen und Synchrotronstrahlung aus Beschleunigern und durch -Teilchen, Röntgen- und -Strahlung sowie durch von ^–-Teilchen erzeugte Bremsstrahlung von Radionuklidquellen. Die Radionuklide werden auf Grund ihrer Zerfallsart und auf Grund der Energie der emittierten Strahlung geordnet. Die breite Anwendung von Radionukliden für die Anregung bei der RFA wird an Hand von Beispielen wie der semiquantitativen Analyse von Gläsern, der quantitativen Analyse grober Keramik und der quantitativen Bestimmung schwerer Elemente (hauptsächlich der Aktinide) in Lösungen gezeigt. Die Vor- und Nachteile der RFA mit Radionuklidanregung werden diskutiert.

---

---

Dedicated to Prof. Dr. K. H. Lieser on the occasion of his 65th birthday

---

The author wishes to thank the Director of the Institute of Nuclear Chemistry at the Technische Hochschule Darmstadt, Prof. Dr. K. H. Lieser, for having the possibility to work in the field described in this paper.     

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.     

Determination of Fe and Zn in healing plants by radionuclide X-ray fluorescence analysis

Radionuclide X-ray fluorescence method was used for the determination of Fe and Zn in healing plants (Sage, Peppermint, Stinging, Common Agrimony, Milfoil, Ribwort, Tansy, White Dead-Nettle).²³⁸Pu exciting source and Si/Li semiconductor detector were used for the determination.     

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.

---

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.

     

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.

---

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.     

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.     

Determination of Fe and Zn in agricultural plants with special cultivation by radionuclide X-ray fluorescence analysis

Fe and Zn were determined in various parts of maize (Zea mays) in dependence on quantity of organic substrate EKOFERT as organic fertilizer in soil, using radionuclide X-ray fluorescence analysis. The increase of quantity of organic substrate EKOFERT in soil causes a decrease of heavy metal concentrations in certain parts of the plant.     

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。     

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。     

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.     

Determination of selected elements by radionuclide X-ray fluorescence analysis after the separation on different kinds of sorption materials

This paper aimed to the evaluation of different kinds of sorbent material preparation and to the evaluation of their characteristics at different pH conditions by X-ray fluorescence analysis. This method is suitable for identification and determination of elements in samples of different character, state and origin because it is a polycomponent, non-destructive, fast and simple analytical method. Moreover, it allows time-advantageous and reliable measurements. This paper studies problems concerning the determination of some selected elements (Mn, Fe, Ni, Cu, Zn, Pb) in pharmaceutical samples of sodium chloride in the solid state as well as in its solution by sorption on chelating extraction membrane 3M Empore™ and on the strongly acidic ion-exchanger Dowex 50Wx8. Conditions for the most effective sorption of determined elements are also interpreted.     

X-ray fluorescence spectrometry applied to the analysis of environmental samples

X-ray fluorescence spectrometry is an expanding technique in the field of environmental analysis for both air and water pollution studies. Its capabilities now include the determination of gaseous contaminants in air in addition to the established area of elemental analysis, covering airborn particulates and soluble trace elements in water.