Reply to comments on ‘The investigations on K and L X-ray fluorescence parameters of gold compounds'

We reply to comments raised in Kumar and Puri (2011). The comments claim that our results may ;be considered inconsequential because of the detector efficiency at Ge K-edge energy and the procedure of the photo-peak area evolution. However, to obtain detector efficiency in different energies, the variation of the factor I₀Gε as a function of the energy was drawn and the error arising from the detector efficiency added to our results. Moreover, the peak fitting procedure was made by the software program and the values of the reduced χ² and coefficient of determination show that the fits are quite adequate. Therefore, our results may be considered consequential.     

Calculation of vacancy transfer probabilities from K to L shell using the X-ray fluorescence parameters

The probabilities for vacancy transfer from the K to the L shell (η_KL), have been calculated for eleven high atomic number elements using the measured K and L shells X-ray production cross-sections. The targets were excited by 123.6 keV photon from a ⁵⁷Co annular radioactive source. K and L X-rays emitted by samples were counted with a Si(Li) detector. The measured values of η_KL were compared with the theoretical values and our early papers.     

Chemical effect on L X-ray fluorescence cross-sections of Hg,Pb and Bi compounds

Chemical effect on the photon induced L X-ray fluorescence cross-sections (σ_Lα, σ_Lβ and σ_Lγ) for Hg, Pb and Bi compounds were investigated. The samples were excited by gamma rays with energy 59.5 keV from ²⁴¹Am radioisotope source. L X-rays emitted by samples were counted by a Si(Li) detector with resolution 160 eV at 5.9 keV. We observed chemical effect on the photon induced L X-ray fluorescence cross-sections (σ_Lα, σ_Lβ and σ_Lγ) for Hg, Pb and Bi compounds. Our values were compared with calculated theoretical values.     

Determination of gold by X-ray fluorescence methods

X-ray fluorescence methods for the determination of gold in silver beads and in hydrochloric acid solutions are described. These techniques may be applied to silver containing 0.2-5 % of gold and to solutions containing 0.004-0.1% of gold. Platinum, palladium, rhodium and indium do not interfere.     

X-ray fluorescence analysis of medieval gold coins and jewellery

A quantitative evaluation method was elaborated to determine the gold, silver and copper concentration of high gold content objects in a non-destructive way. The spectrum evaluation method rules out the effect of the differences in size, shape and surface. A long measuring time allows qualitative analysis of the trace elements: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Cd, In and Zn. Using this method, about 200 golden coins and jewellery from the 10th-15th century Hungary and Byzantium were analyzed. Some of the results are presented here.     

Structural properties of oligonucleotide monolayers on gold surfaces probed by fluorescence investigations

We present optical investigations on the conformation of oligonucleotide layers on Au surfaces. Our studies concentrate on the effect of varying surface coverage densities on the structural properties of layers of 12- and 24mer single-stranded DNA, tethered to the Au surface at one end while being labeled with a fluorescent marker at the opposing end. The distance-dependent energy transfer from the marker dye to the metal surface, which causes quenching of the observed fluorescence, is used to provide information on the orientation of the DNA strands relative to the surface. Variations in the oligonucleotide coverage density, as determined from electrochemical quantification, over 2 orders of magnitude are achieved by employing different preparation conditions. The observed enhancement in fluorescence intensity with increasing DNA coverage can be related to a model involving mutual steric interactions of oligonucleotides on the surface, as well as fluorescence quenching theory. Finally, the applicability of the presented concepts for investigations of heterogeneous monolayers is demonstrated by means of studying the coadsorption of mercaptohexanol onto DNA-modified Au surfaces.     

An X-ray fluorescence method for gold determination in ore samples

A new method for gold determination in ore is presented. By the method called PREFIX (preconcentration and X-ray fluorescence), it is possible to detect trace concentrations of gold down to the level of 0.2 g/g, without any device.     

Determination of mercury by total-reflection X-ray fluorescence using amalgamation with gold

Analysis by total-reflection X-ray fluorescence (TXRF) is unsuitable for determining mercury concentrations because the usual sample preparation produces evaporation and loss of this element as a consequence of its high vapour pressure and low boiling point.A method that has been developed to achieve this determination involves forming an amalgam while a thin layer of silver (obtained by sputtering or evaporation) is in contact with an ionic solution of Hg; subsequently, a traditional TXRF analysis is performed. This was the first method reported in the literature to apply the TXRF technique for reliably determining mercury concentrations with high sensitivity.This work shows how a similar procedure may be employed to measure mercury concentrations. This second method involves forming an amalgam of gold using microlitre quantities of the solution to be analysed. As gold is a highly malleable material, it allows the production of very thin films, the weight of which is a few orders of magnitude higher than the mass of mercury present in the amalgam. The determination is performed in the usual way using the TXRF technique. The sensitivity of this method (≈ 5 ppm) is inferior to that of the former method, and data processing is quite difficult because the peaks for mercury and gold overlap, but the experiment is simple to execute and improved sensitivity is expected to be attained by forming the amalgam with larger volumes of sample and with a more responsive data processing scheme.     

Thermal,X-ray. And neutron-activation investigations of compounds of niobium and tantalum

The thermography of the sodium and potassium salts of metaniobate and metatantalate as well as the dichelate of niobium with n-propyl-3,4,5-trihydroxybenzoate (PTB) is investigated in atmospheres of air, nitrogen, and carbon dioxide; and their thermal decomposition products are identified. The niobyl dichelate (dichelate(1)) is isolated and its structure has been shown to be K[NbO(C₆H₂(OH)(O₂)-(COO)C₃H₇)₂]2(PTB)·3H₂O.     

The measurement of Pu and U in reprocessing plant solutions by tube excited K X-ray fluorescence

The feasibility of measuring plutonium and uranium concentrations in reprocessing plant solutions by tube-excited energy dispersive XRF spectrometry is described. By using the K-series lines, materials compatible with a reprocessing plant can be used for construction of the sample cell. Calibration data for Pu and U solutions in the range 1–10 g/l are given. Measurements are presented which demonstrate that fission product activity at the 100 μCi/ml level and passive radiation from Pu isotopes and their daughters present only a minor interference to the analyte signal.     

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.     

Chemical state analysis of fluorine in various compounds using X-ray fluorescence spectra

F Kα X-ray fluorescence (XRF) spectra of various fluorides were measured and to investigate the chemical state of fluorine in xHoF₃-20BaF₂-10AlF₃-(70 − x)GeO₂ (mol%, x = 10-50) glass. The main peak (Kα_1,2) position and the relative intensity of the satellite peak attributable to Kα_3,4 were discussed relating to the M-F bond covalency. Results showed that the fluorine in xHoF₃-20BaF₂-10AlF₃-(70 − x)GeO₂ (mol%, x = 10-50) glass had a completely different chemical state from that of starting materials. Quantitative analyses of the glasses were also undertaken using XRF measurements for each component. These results suggest that 30% fluorine in the 50HoF₃-20BaF₂-10AlF₃-20GeO₂ system is substituted by oxygen through pyrohydrolysis of the fluorides.     

Chemical effects on L shell fluorescence yields of Ba, La and Ce compounds

Chemical effects on the average L shell fluorescence yields (v_L) for Ba, La and Ce compounds were investigated. Samples were excited by gamma-rays with 59.5 keV energy photons from a ²⁴¹Am radioisotope source. L X-rays emitted by samples were counted by a Si(Li) detector with a resolution 155 eV at 5.9 keV. Chemical effects on the average L shell fluorescence yield (v _L) for Ba, La and Ce compounds were observed. The values are compared with theoretical and experimental ones for the pure elements.     

Influence of chemical effect on the Kβ/Kα X-ray intensity ratios for calcium and potassium compounds

K_β/K_α X-ray intensity ratios of some K and Ca compounds were studied. The samples were excited by 5.96 keV γ-rays emitted from (50 mCi ⁵⁵Fe filtered annular) radioisotope source and characteristic K X-ray from the samples were measured by a Si(Li) detector, with a resolution of 0.16 keV at 5.9 keV. The experimental values were compared with the calculated theoretical values for K and Ca.     

X-ray investigations on a homologous series of mesogenic azo compounds complexed with palladium (II)

The X-ray diffraction experimental data concerning a homologous series of p-alkyl-p'-alkoxy-azobenzene cyclopalladated chloro-bridged dimers, both as powder and monodomain samples, are reported. These results, compared with those obtained for the parent non-metallated materials, suggest a model for the molecular arrangement wherein the alkoxy and alkyl chains are roughly coplanar with the palladium-containing rigid core and, depending on the chain length, bent towards each other.     

On the use of L X-ray fluorescence for bone lead evaluation

The use of L X-ray fluorescence for the determination of the concentration of Pb in human bone has been reported in the literature. A critique of the utility of the method and the shortcomings as an analytical approach in the evaluation of human exposure to Pb are addressed.