Uncertainty of Quantitative X-ray Fluorescence Micro-Analysis of Metallic Artifacts Caused by Their Curved Shapes.

This paper summarizes the effects of irregular shape on the results of a quantitative X-ray fluorescence (XRF) micro-analysis. These effects become relevant when an XRF analysis is performed directly on an investigated material. A typical example is XRF analyses of valuable and historical objects whose measurements should be performed non-destructively and non-invasively, without taking samples. Several measurements and computer simulations were performed for selected metallic materials and shapes to evaluate the accuracy and precision of XRF. The described experiments and the corresponding Monte Carlo simulations were related to the XRF device designed and utilized at the Czech Technical University. It was found that the relative uncertainty was typically about 5-10% or even higher in quantitative analyses of minor elements due to irregular shapes of surfaces. This must be considered in cases of the interpretation of XRF results, especially in the cultural heritage sciences. The conclusions also contain several recommendations on how to measure objects under hard-to-define geometric conditions with respect to reduction in the surface effect in quantitative or semi-quantitative XRF analyses.

DETERMINATION OF URANIUM AND THORIUM SURFACE DISTRIBUTION IN GEOLOGICAL SAMPLES: COMPARISON OF TABLETOP MACRO AND MICRO-XRF SCANNING.

This paper describes the identification and quantification of uranium, thorium and other chemical elements in a low-grade uranium ore, using macro and micro-X-ray fluorescence scanning. The result of such scanning is their surface distribution determined in flat samples. The basic parameters of both setups are described. The investigation was focused mainly on the improvement of the lateral resolution in the laboratory tabletop macro-XRF and its comparison with micro-XRF scanning. A standard reference material NIST 610 was used as a homogeneous reference silicate material of a known composition. The measurements have demonstrated how the macro-XRF with a quite wide X-ray beam can be competitive with the micro-XRF scanning. The capabilities of both devices were established, utilizing measurements of selected uranium-bearing sediments samples, from the Brevniste deposit in the Czech Republic.

CONFOCAL X-RAY FLUORESCENCE ANALYSIS OF SAMPLES FORMED FROM HOMOGENEOUS LAYERS: COMPARISON OF SIMULATIONS WITH EXPERIMENTAL MEASUREMENTS.

Confocal X-ray fluorescence analysis is a non-destructive method that enables the determination of the elements depth distribution in the examined sample. Accurate determination of the elements depth distributions in various samples from measured depth profiles is very demanding, and generally, a valid procedure has not been developed as yet. The main aim of this work was to design and test a universal simplified calculation procedure, which would allow the calculation of the approximate shape of the depth profiles for a sample formed from layers of a given thickness and composition. To confirm the proposed calculation method, the standard reference material NIST 1412 was used, which is formed by a homogeneous multicomponent glass containing oxides of several measurable elements. This research compares the results of the measured and calculated depth profiles in the glass reference material, where the resulting depth curves correspond almost perfectly.

X-ray Fluorescence Analysis of Pigments in Gothic Frescoes, Coats of Arms, and Polychromy on Sculptures on the Triforium in St. Vitus Cathedral on the Territory of the Czech Kingdom in the 14th Century.

Pigments in the paints used for the coats of arms, polychromy on sculptures, and pigments in frescoes characterize not only the epoch but also individual creators or groups of artists involved in their creation. X-ray fluorescence analysis is a non-destructive method suitable for determining the chemical composition of these artifacts. This article covers the results of measurements of selected objects, and compares them with similar objects from the territory of the Czech Kingdom in the 14th century.

CALIBRATION OF A TABLETOP CONFOCAL MICROBEAM X-RAY FLUORESCENCE SPECTROMETER FOR A QUANTITATIVE DEPTH PROFILES EVALUATION.

Confocal micro-beam X-ray fluorescence analysis (confocal micro-XRF) is a non-destructive analytical tool for investigation of sample composition that enables acquiring three-dimensionally resolved information. This work describes a calibration procedure of a laboratory confocal micro-XRF setup, which leads to determination of its characteristic parameters. The calibration is performed using a tabletop confocal micro-XRF spectrometer designed recently at the Czech Technical University in Prague. The calibration procedure performed within this work comprises the essential steps of the setup characterization: excitation spectrum calculation, experimental determination of energy-dependent confocal volume size and integral sensitivity and calculation of the spectrometer sensitivity function. The results of the setup calibration will be used for development of a procedure enabling quantitative evaluation of the measured depth profiles.

Changes in lysyl oxidase (LOX) distribution and its decreased activity in keratoconus corneas.

Inadequate cross-linking between collagen lamellae is a characteristic feature of keratoconus corneas. The formation of covalent bonds between collagen and elastin fibrils, which maintain the biomechanical properties of the cornea, is mediated by the cuproenzyme lysyl oxidase and four lysyl oxidase-like enzymes. The aim of this study was to determine the distribution of lysyl oxidase and the total lysyl oxidase activity (lysyl oxidase and the four lysyl oxidase-like enzymes) in control and keratoconic corneas. Seven control and eight keratoconic corneas were used for the imunohistochemical detection of lysyl oxidase in corneal cryosections using two different antibodies. The total lysyl oxidase activity in the culture medium of corneal fibroblasts from six explanted keratoconic and four control corneas was measured using a fluorometric assay in the presence and absence of the lysyl oxidase inhibitor beta-aminopropionitrile and determined as the production of H(2)O(2) in nM per µg of total protein. In the control tissue, the most intense signal for lysyl oxidase was present in the corneal epithelium, in which perinuclear dots brightly projecting from more or less homogenous cytoplasmic staining may represent the lysyl oxidase propeptide. Less intense staining was present in keratocytes, the extracellular matrix and in the corneal endothelium. The epithelium of the limbus and the perilimbal conjunctiva showed intense to very intense staining. The distribution of lysyl oxidase was clearly decreased in at least five of the eight keratoconic specimens. The most marked signal reduction was observed in the stromal matrix and in keratocytes. Moreover, the signal in pathological specimens revealed a more irregular pattern, including the presence of intra- and extracellular clumps in the epithelium. Interestingly, endothelial cells showed no or very weak staining in areas just beneath negative stromal tissue. The mean activity of total lysyl oxidase in the keratoconic samples (2.60 ± 2.23 nM H(2)O(2)/µg of total protein) was more than 2.5-fold lower than in control tissue (6.83 ± 2.53 nM H(2)O(2)/µg of total protein), and the decrease was statistically significant (p = 0.0178). The location of lysyl oxidase in the healthy cornea, limbus and perilimbal conjunctiva was described. We hypothesize that the restricted lysyl oxidase distribution in keratoconic corneas, and particularly the decrease of total lysyl oxidase activity in cultured keratoconic fibroblasts, is one potential reason for the inadequate collagen cross-linking that is a hallmark of this disease.

X-ray fluorescence analysis of archaeological finds and art objects: recognizing gold and gilding.

Many cultural heritage objects were gilded in the past, and nowadays they can be found in archeological excavations or in historical buildings dating back to the Middle Ages, or from the modern period. Old gilded artifacts have been studied using X-ray fluorescence analysis and 2D microanalysis. Several techniques that enable the user to distinguish gold and gilded objects are described and then applied to investigate artifacts. These techniques differ in instrumentation, data analysis and numbers of measurements. The application of Monte Carlo calculation to a quantitative analysis of gilded objects is also introduced.

X-ray fluorescence in investigations of cultural relics and archaeological finds.

Some characteristic features of X-ray fluorescence (XRF) analysis make it an ideal method for investigations of cultural relics and archaeological finds. It has therefore become a standard method used in archaeometry. Paintings, frescos, manuscripts, pottery, metalwork, glass, and many other objects are analysed with the aim of recognising their materials, production technologies and origin, and for identifying counterfeits. This paper reviews various techniques used in XRF analyses of works of art, summarises the advantages and limitations of the method, and presents some typical examples of its use. The general review is supplemented by some techniques used and some results achieved at CTU-FNSPE in Prague.

Testing Monte Carlo computer codes for simulations of electron transport in matter.

In this paper, three Monte Carlo codes were tested for electron transport in various materials. MCNPX (version 2.4.0), Penelope (version 2003) and EGSnrc codes were used for modeling simple problems. These problems were focused on bremsstrahlung, energy deposition in matter, electron ranges and production of secondary electrons by gamma radiation. The electrons were primary particles, except in the last exercise, where photons were used. Various materials, e.g., water, lead and tungsten were used. The energy of the primary particles was within the energy range from 20 to 450 keV. The simulation results were compared with each other.

X-ray fluorescence analyzers for investigating postmediaeval pottery from Southern Moravia.

This paper deals with an investigation of ceramic archaeological finds with the use of in-situ X-ray fluorescence analysis. Firstly, three configurations of X-ray fluorescence analyzers constructed and used at the Czech Technical University in Prague are described and compared for use in a non-destructive survey of siliceous materials. Detection limits, depth of analysis, the relation of the analyzed area, the homogeneity of the samples, and variations in the element concentrations are discussed. Secondly, many shards of postmediaeval pottery from Southern Moravia are analyzed with X-ray fluorescence analysis and some of them also with electron microprobe analysis. Selected results are described.

Application of X-ray fluorescence in investigations of Bohemian historical manuscripts.

In this work we present the application of X-ray fluorescence analysis (XRFA) in an investigation of the Land Register and the Register of the Court of the Kingdom of Bohemia and the manuscript of the Homiliary of the Opatovice Monastery from the 12th century. Radionuclide sources emitting radiation at an appropriate energy level and an X-ray tube were used to excite the characteristic radiation. A spectrometric Si(Li) detector and a Si-PIN detector with Peltier cooling were used to detect the excited characteristic radiation. Several types of pigments were identified and compositions of inks used within almost 5 centuries in the offices at the Prague Castle were determined.

Recognition of pigment layers in illuminated manuscripts by means of Kalpha/Kbeta and Lalpha/Lbeta ratios of characteristic X-rays.

X-ray fluorescence analysis with an evaluation of the Kalpha/Kbeta or Lalpha/Lbeta count rate ratios enables a layered structure to be recognized, because the measured ratio of two lines of one element depends on the depth distribution of this element in the analyzed objects. Several specimens consisting of layers of various pigments were analyzed to demonstrate the possibilities of the proposed technique. Then the Lalpha/Lbeta technique was applied in an investigation of cinnabar distribution in mediaeval manuscripts.

Gamma spectrometric measurements of depth-related radionuclide distribution in walls.

The method for depth-related radionuclide distribution was evolved for approximate determination of the spatial lay-out of radionuclides in materials. The method is based on different attenuation coefficients for various energies of gamma radiation. For each material, the attenuation coefficient decreases with rising energy of radiation. It is therefore possible to assess the location of radionuclides in a material owing to attenuation on the track which a photon has to pass through the material. In this case, gamma lines with energies 609 and 1764 keV produced by nuclide (214)Bi were used for depth-related radionuclide distribution. This application should be suitable for locating radionuclides in the walls of buildings where high dose rates from gamma radiation occur. These doses are caused by natural radionuclides, mainly radium daughters. The presence of radionuclides in houses poses a high risk associated with inhalation of radon and its decay products. For suitable remediation, it is necessary to know the radionuclide depth distribution.

Data analysis from monitoring of radionuclides in the nuclear power plant Temelin ecosystem area.

Changes in the ecosystem occur naturally, however, can also be due to man's activity. The unique ecosystem monitoring based on studying contamination of the bioindicators by man-made radionuclides has been providing data from the area of nuclear power plant (NPP) Temelin (CR) using laboratory gamma spectrometry for past 8 years. The increase in radioactivity in the NPP ecosystem area resulting from its operation is evaluated through comparison with a zero level of (137)Cs mass activities and by obtained data trend analysis.

K(alpha)/K(beta) ratios of fluorescence X-rays as an information source on the depth distribution of iron in a low Z matrix.

This paper describes how the K(alpha)/K(beta) count rate ratio of the characteristic X-rays of a given element can be applied to determine the depth at which a layer or a grain of that element is located. The theoretical background and a basic description of the K(alpha)/K(beta) technique are given in the introduction. The experimental part of the paper deals with measurements of thick standard pure iron, intermediately thick iron foils, and layers prepared with a powder of Prussian blue. All these specimens were analyzed alone, and they were also analyzed overlaid with a low Z matrix. The light matrix consisted of sheets of paper of known thickness. Paper was chosen, because we take into account the subsequent application of this technique to surveys of historical monuments. The relation between the K(alpha) count rate, the K(alpha)/K(beta) count rate ratio, and the distribution of iron in the paper matrix are presented here.