Analytical possibilities of different X-ray fluorescence systems for determination of trace elements in aqueous samples pre-concentrated with carbon nanotubes

This study was aimed to achieve improved instrumental sensitivity and detection limits for multielement determination of V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Se, Pb and Cd in liquid samples by using different X-ray fluorescence (XRF) configurations (a benchtop energy-dispersive X-ray fluorescence spectrometer, a benchtop polarised energy-dispersive X-ray fluorescence spectrometer and a wavelength-dispersive X-ray fluorescence spectrometer).The preconcentration of metals from liquid solutions consisted on a solid-phase extraction using carbon nanotubes (CNTs) as solid sorbents. After the extraction step, the aqueous sample was filtered and CNTs with the absorbed elements were collected onto a filter paper which was directly analyzed by XRF.The calculated detection limits in all cases were in the low ng mL^− 1 range. Nevertheless, results obtained indicate the benefits, in terms of sensitivity, of using polarized X-ray sources using different secondary targets in comparison to conventional XRF systems, above all if Cd determination is required.The developed methodologies, using the aforementioned equipments, have been applied for multielement determination in water samples from an industrial area of Poland.     

Wavelength dispersive X-ray fluorescence imaging using a high-sensitivity imaging sensor

A new wavelength-dispersive X-ray fluorescence (WD-XRF) imaging spectrometer equipped with a high-sensitivity imaging sensor was developed in our laboratory. In this instrument, a straight polycapillary optic was applied instead of a Soller slit as well as a 2D imaging X-ray detector instead of X-ray counters, which are used in conventional WD-XRF spectrometers. Therefore, images of elemental distribution were available after a short exposure time. Ni Kα images and Cu Kα images were clearly obtained at corresponding diffraction angles for a short exposure time of 10 s. By optimizing the spectrometer, the time required for imaging is reduced, leading to XRF image movies. It is difficult to distinguish two peaks (Ti Kα (4.508 keV) and Ba Lα (4.465 keV)) due to the poor energy resolution of EDXRS. However, Ti and Ba images could be successfully observed by the WD-XRF imaging spectrometer. The energy resolution of the developed spectrometer was 25 eV at the Ti Kα peak.     

Determination of rare earth impurities in cerium dioxide and oxalate by X-ray fluorescence technique

A method for the determination of lathanum, praseodymium, neodymium and samarium oxides in cerium dioxide has been developed. The sample in the oxalate form is mixed with the binding material (boric acid) in the ratio 1∶1 pressed to form a double layer pellet over a boric acid backing pellet and irradiated by X-rays from a tungsten tube. The secondary X-rays are dispersed with a LiF (200) crystal in a Philips PW 1220 semiautomatic X-ray fluorescence spectrometer. The intensity of fluorescent X-rays is measured by a flow proportional counter. The minimum determination limit is 0.01% for lanthanum and samarium oxides and 0.02% for praseodymium and neodymium oxides. The precision at each concentration of the standards and theoretical minimum determination limit for each element have been calculated.     

Determination of calcium in uranium by X-ray fluorescence

Summary An X-ray fluorescence method for the analysis of calcium in uranium in the range of 20 to 500 ppm is described. U₃O₈ samples are mixed with boric acid binder and double-layer pellets are prepared. The pellets are analysed using Philips PW 1220 semi-automatic X-ray spectrometer. Calculated lower limits of detection are better than 5 ppm for calcium in uranium.

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Bestimmung von Calcium in Uran durch Röntgenfluorescenz

Zusammenfassung Ein Verfahren für den Bereich von 20–500 ppm wird beschrieben. Die U₃O₈-Proben werden mit BorsÄure als Bindemittel vermischt zu Doppelschicht-Tabletten gepre\t, die mit Hilfe eines halbautomatischen Philips PW 1220 Röntgenspektrometers analysiert werden. Die untere Nachweisgrenze liegt bei 5 ppm Ca.

     

X-ray fluorescence analysis of terbium oxide and oxalate for rare earth impurities

Summary A method for the determination of samarium, europium, gadolinium, dysprosium, holmium and yttrium oxides in terbium oxide is described. The sample is converted to terbium oxalate, mixed with boric acid binder in the ratio 21, pelleted at a pressure of 20 tons over a boric acid backing pellet and irradiated with X-rays from a tungsten tube operated by Philips PW 1140 generator. The secondary X-rays thus generated are analysed by a LiF(200) crystal in Philips PW 1220 X-ray fluorescence spectrometer. The minimum determination limit is 0.01% for all rare earth oxides determined except for yttrium oxide for which it is 0.005%.

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Zusammenfassung Eine Methode zur Bestimmung der Oxide von Samarium, Europium, Gadolinium, Dysprosium, Holmium und Yttrium in Terbiumoxid wurde beschrieben. Die Probe wird zu Terbiumoxalat umgesetzt, mit Borsäure im Verhältnis 2 1 gemischt, mit 20 Tonnen Druck auf eine Borsäuretablette aufgepreßt und mit Röntgenstrahlen aus einer Wolframröhre bestrahlt, die mit einem Philips-Generator PW 1140 gespeist wurde. Die dabei entstehenden Sekundärstrahlen wurden mit Hilfe eines LiF-Kristalls (200) in einem Philips PW 1220 Röntgenfluoreszenz-Spektrometer analysiert. Die untere Grenze der Bestimmbarkeit liegt bei 0,01% für alle bestimmten Seltenerden-Oxide mit Ausnahme von Yttriumoxid mit 0,005%.

     

X-Ray fluorescence analysis of thulium oxide for rare earth impurities

A wavelength dispersive X-ray fluorescence spectrometric method has been developed for the analysis of thulium oxide to determine the neighbouring rare earth impurities. The sample is taken in oxalate form and the analysis is done on a Philips PW 1220 spectrometer with a LiF (200) crystal. The detection limit for holmium, lutetium and yttrium is 0.002%, for dysprosium and erbium 0.005% and for, ytterbium it is 0.01%. The precision at each concentration of the standards and the theoretical detection limits have been calculated. Intensity correction factors for the line overlaps have been determined.     

Determination of zirconium and hafnium in solution by X-ray fluorescence spectrometry

The samples were introduced into the XRF spectrometer in ordinary flat bottom polyethylene bottles for the estimation of Zr or Hf in presence of one another in solution. By using high voltage (50 kV) and high current (50 mA) least limits of detection obtained were an order of magnitude better than other conventional analytical techniques. Relations of intensity to concentration in various concentration ranges have been determined and the results are compared with those of other analytical techniques.     

高压覆膜制样X射线荧光光谱法测定多金属矿中的多种元素

采用新的制样技术——高压(1800 kN)覆膜(3.6μm Polyester Film)制样,波长色散X射线荧光光谱测定多金属矿中19种组分。该制样技术对高硅锌矿石GBW07237(SiO282.95%),不加黏结剂,也能制出理想的样片。测定结果显示1800 kN制备样品多数组分的灵敏度、精密度和检出限较400 kN制备的样品有所改善。15个多金属矿标准物质建立校准曲线,使用Rh Kα的瑞利散射线作内标测定Cu、Pb、Zn、As和Rh Kα的康普顿散射线作内标测定Sb、Ag、Sn、Bi、Mo及经验系数法校正基体效应。Cu、Pb、Zn、Mn、As、Sb、Ag、Sn、Bi、Mo的测定结果与化学法相符,可同时分析其中的Cd、S、Fe、SiO2、Al2O3、MgO、CaO、Na2O、K2O等成分。实现了固体直接进样测定多金属矿中的多种元素。高压覆膜制样技术是制样技术的突破,国内外尚未见报道。     

Röntgenspektroskopische Bestimmung von Atomladungen in Schwefelverbindungen

X-Ray Spectroscopical Determinations of Atomic Charges in Sulphur Compounds Using an X-ray vacuum spectrometer the chemical shifts of the S Kα. lines of different compounds were measured with high accuracy. The informations on the charge distributions obtained by the S Kα shifts, are comparable with those got from photoelectron spectroscopic investigations. The sulphur charges determined X-ray spectroscopically are in a good agreement with the values from MO calculations.