Trace element study of human bone by X-ray emission analysis using an external proton beam

A simple proton beam (PIXE) arrangement developed for a low energy accelerator was used for the determination of absolute concentrations of nine trace elements in human bone samples. The 2.4 MeV proton beam was externalized through a thin (2 μm) aluminiummylar foil. Using an air cooling system, the foil withstood a high current (0.5–1 μA) for a long time. The samples were cooled to prevent damage and volatilization of elements. The induced X-rays were detected with a Si(Li) detector and the external beam was monitored with a second detector, measuring K X-rays induced in atmospheric argon. The mean (SD) trace element levels (ppm) measured in dense bone by comparison with hydroxyapatite/standard mixtures were: Cr<2.0, Mn<2.3, Fe 7.58 (1.55), Ni<2.4, Cu 3.58 (2.16), Zn 144 (27), Pb 12.2 (2.5), Br 12.4 (5.5) and Sr 47.7 (14.3). The detection limits for these elements achieved in this work were about 1 ppm when rather short measuring times (∼10 min) were used. The coefficient of variation of a single measurement, e.g. for Zn, was 3–4%. Because of the slow turnover of dense bone, such measurements provide a means of monitoring long term trace element exposure.     

Trace element analysis of placentas of alcoholics and controls with external beam PIXE

External beam PIXE analysis with a protonbeam of 2.4 MeV was used to study trace element concentrations in human placentas. The aim was to check the suitability of PIXE analysis regarding soft tissue samples. Sample preparation was kept as simple as possible to avoid contamination or losses due to volatilization. The element of interest /Fe, Cu, Zn, Se, Br, Rb, and Sr/ were easily detected. A comparison was made with placental samples of alcoholics and abstinent controls to determine whether trace element concentrations in the placenta play a role in the pathogenesis of fetal alcohol syndrome.     

Trace element analysis of waters by X-ray emission spectroscopy

X-ray emission spectroscopy is a rapid, simple and accurate method for multielement trace analysis of water. This is accomplished by trace elements precipitation with a nonspecific chelating agent APDC (ammonium-1-pyrollidine dithiocarbamate) and filtration through a Millipore filter. In that way the uniform targets suitable for X-ray analysis were made and elements in concentrations as low as few ppb could be determined. APDC chelation over broad pH ranges for different elements in seawater is discussed. The best pH range for simultaneous determination of these elements is found. Results of analysis of seawater samples taken near the island Krk in the Adriatic sea are presented.     

Trace elements in human fingernails: Measurement by proton-induced X-ray emission

The method of proton particle-induced X-ray emission (proton PIXE) has been employed to study the trace element composition of human fingernails. The samples were colleted from 51 subjects randomly selected from a working community of about 500 adults and they were analyzed by the thick-target external beam technique of the PIXE method. The samples were exposed to the proton beam as 1-mm thick pellets and irradiated with 2 MeV protons having 20 nA beam intensity. For 40 C irradiations, the concentration of fourteen elements, K, Ca, Ti, Mn, Fe, Ni, Cu, Zn, As, Se, Br, Rb, Sr and Pb, were measured by comparison with a calibration obtained from the NBS orchard leaf standard (SRM 1571). Some anomalous cases have been revealed from this study and they are attributed to environmental factors. The frequency distributions of the elements are presented and the results compared with available data.This research received financial support from the International Atomic Energy Agency, Vienna, under the research contract RC/2536/RBl.     

Trace element analysis by particle and photon-induced X-ray emission spectroscopy

The analytical use of particle- and photon-induced X-ray emission spectroscopy has become an important tool in trace element analysis, especially when only small amounts of sample material are available. The physical basis, experimental procedure and typical examples are reviewed.     

Trace element analysis of motor oil by CPAA method on external proton beam

Normal motor-oil was investigated by CPAA method using 12 and 18 MeV proton beams, which were extracted to the air. The samples were taken from the oil carter of a motor after different running times. The change of the amount of certain trace elements was detected with increasing time of use. By using this method the friction wear of the engine material can also be measured.     

Analytical use of proton-induced X-ray emission

Proton-induced X-ray emission, PIXE, is capable of simultaneous quantitative determination of 10–15 elements. An introduction to the physical properties of the method is given and detection limits are shown for a routine analysis of a thin aerosol sample. Examples of applications to both thick and thin samples are presented. Human tooth dentine is analysed for lead, with simple sample preparation, indicating lead values of a few ppm for Swedish children. Quantitative analyses of several other elements are obtained simultaneously. Cascade impactors are used for sampling aerosols in work environment during welding operations giving information of size distribution and concentrations of the elements present. The aerosol is dominated by particle sizes between 0.5 and 2 μm as measured by the impactor, but the size distributions are different for different elements and welding techniques and depend on the distance from the welding source. The relative abundance of the elements found in the aerosol indicates the presence of fractionation mechanisms.     

Human hair analysis by PIXE: Pattern recognition of trace element composition

The feasibility is explored of classifying human hair specimens according to their trace metal composition as determined by PIXE. Protons of 3.5 MeV were used to analyse 150 samples by energy-dispersive spectrometry using a Si(Li) detector. The methods of the Minimal Spanning Tree and Non-Linear Mapping were used to establish correlation among the specimens. As a result of distinct groupings obtained by these methods it was inferred that these techniques could usefully be applied to environmental pollution studies.     

Trace analysis of lithium metal by PIXE

A rapid method is described for simultaneous trace determination of metallic impurities in lithium metal by Particle Induced X-ray Emission (PIXE) technique. The impurities were preconcentrated by ion-exchange separation using a weak cation exchanger, Bio Rex-70 and analyzed by 2.34 MeV protons. The reliability of the method was tested by analyzing synthetic samples having several metallic impurities at 1–5 ppm range.     

Proton induced X-ray emission (PIXE) analysis on thick samples exemplified on the rare earth elements

Summary Proton Induced X-ray Emission (PIXE) analysis calibration curves (i.e. intensity of analytical signal as a function of concentration c _i ) are determined on thick solid samples with rare earth element concentrations c _i 0.3g/g. The calibration curves are linear at low concentrations c _i 0.3 weight% at proton energies 1.7E _PO 2.5MeV. The precision of the quantitative analysis amounts to ±4 %. The shape of the curves at higher concentrations may be understood by simple qualitative considerations.Distortions by interelement-effects caused by additional other rare earth elements j in concentrations c _j 2 weight% are not detectable. The agreement between the experimental and the calculated intensities for different matrices is very good at low concentrations c _i 1 weight% of analyte.

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Protoneninduzierte Röntgenspektralanalyse (PIXE) dicker Proben am Beispiel der Seltenen ErdelementeI. Experimentelle Bestimmung von Eichkurven, Genauigkeit und Matrixeffekten

Zusammenfassung Es werden Eichkurven (d. h. Intensität des Analysensignals in Abhängigkeit von der Analytkonzentration c _i ) für die protoneninduzierte Röntgenspektralanalyse (PIXE) dicker Festkörperproben mit Seltenen Erdelementen im Konzentrationsbereich c _i 0,3g/g aufgenommen. Diese Eichkurven verlaufen bei niedrigen Konzentrationen c _i 0,3 Gewichts-% und Protonenenergien 1,7E_PO2,5MeV linear. Die Genauigkeit der quantitativen Analyse beträgt ±4 %. Der Verlauf der Eichkurven bei höheren Konzentrationen kann durch einfache qualitative Überlegungen verstanden werden.Es werden keine Störungen durch Interelementeffekte beobachtet, die durch zusätzliche andere Seltene Erdelemente j in Konzentrationen c _j 2 Gewichts-% hervorgerufen werden. Die Übereinstimmung der experimentellen und berechneten Intensitäten für verschiedene Matrices ist bei niedrigen Analytkonzentrationen c _i 1 Gewichts-% sehr gut.

Dedicated to Karl Gleu at the occasion of his 80th birthday     

Proton induced X-ray emission (PIXE) analysis on thick samples exemplified on the rare earth elements

Summary A semiempirical procedure is developed for the calculation of the signal intensity for thick sample PIXE experiments. The calculated X-ray intensity emerged out of a thick sample is factorized into the overall produced intensity within a thick sample and an effective transmission factor for the X-ray self-absorption.The accuracy of this procedure is limited by the reliability of the experimental input parameters to about ±25%.We find as an important result of this study: The signal intensity is calculated as a function of the various experimental parameters, i.e. proton energy and sample composition including interelement- and matrix effects. This function is presented as a closed equation, which can be applied very easily, i.e. without large scale computers, to calculate the sample elemental concentration. The mass absorption coefficient of the sample most strongly influences the effective transmission term.Enhancement corrections are calculated for additional interfering rare earth elements j. No significant interelement-effects appear at concentrations c _j 2 weight%, where analysis by PIXE may be interesting. The calculated results agree well with experimental data for the rare earth elements in different matrices.Dedicated to Karl Gleu on the occasion of his 80th birthday     

Trace element analysis of hair of mentally retarded children

Unlike previously reported Zn and Se levels were found to be the same in the hair of mentally retarded children and controls. Non-essential toxic Ag concentration was low whereas that of Hg, Au and Sc rather high in mentally retarded children.     

Trace element exposure in man by instrumental neutron activation analysis of hair

A nondestructive instrumental neutron activation technique was used to analyze human hair samples collected from people living in metropolitan and rural areas in Korea. Samples were also collected from factory workers and cancer patients. Hair from metropolitan area residents contain higher concentrations of Ca, Mg, Zn, Cu, Na, Br, Mn, I and S than rural area residents. Concentrations of I and S from cancer patients, Mg, Zn, Al, Na, Mn and As from glassware workers were relatively higher. The results show that the trace element concentrations of the hair are possibly related to the trace element concentrations in the body.     

Some applications of proton-induced X-ray emission spectrometry in the elemental analysis of metallurgical materials

Summary A proton-induced X-ray emission (PIXE) procedure for the determination of iron, chromium and tin in zircaloy, zirconium in pure hafnium, and yttrium in titanium alloy has been proposed. After suitable acid dissolution of the samples, aliquots were deposited onto membrane filters and irradiated by a 2.5-MeV proton beam from a cyclotron or a Van de Graaff accelerator. Calibration was achieved making use of the standard addition method. Preliminary separations are not required and the PIXE results have been well compared with those obtained by other accepted methods of analysis. Precision, accuracy and limits of detection for the elements of interest are discussed. The results demonstrate the feasibility of PIXE as an alternative analytical technique for metallurgical materials.

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Anwendung der protonen-induzierten Röntgenemissions-Spektrometrie (PIXE) zur Elementanalyse metallurgischer Materialien

Zusammenfassung Ein PIXE-Verfahren zur Bestimmung von Fe, Cr und Sn in Zircaloy, von Zr in reinem Hafnium und von Y in Titanlegierung wird beschrieben. Nach entsprechender Lösung der Probe in Säure wird ein aliquoter Teil auf einem Membranfilter niedergeschlagen und mit 2,5-MeV-Protonen bestrahlt (Cyclotron oder Van-de-Graaff-Beschleuniger). Eichung erfolgt mit Hilfe des Standardzugabe-Verfahrens. Vortrennungen sind nicht erforderlich. Die Ergebnisse lassen sich gut mit denen anderer Verfahren vergleichen. Präzision, Genauigkeit und Nachweisgrenzen werden diskutiert. Die Resultate bestätigen die Brauchbarkeit des PIXE-Verfahrens zur Analyse metallurgischer Materialien.

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Research Associate of the National Fund for Scientific Research (Belgium)     

Trace element profiles in the hair of Nasopharyngeal carcinoma (NPC) patients

The trace element profiles of the scalp hair of NPC patients, aged between 30 and 69, were measured using neutron activation analysis and compared with those of normal healthy people within the same age bracket. The washing method of using detergent and washing powder was found to be comparable to that of using ether. Difference in the mean concentration of each element in the two groups was tested by Student's t-test. A significantly lower value of strontium (Sr) and significantly higher values of arsenic (As), iron (Fe) and vanadium (V) were found in the hair of NPC patients. The relative values of As and Fe found were consistent with the results of other findings on NPC patients, using different measuring methods. The V content in the hair of NPC patients was three times that of healthy people.     

Trace element analysis via heavy ion induced X-ray fluorescence

Ohne ZusammenfassungWork supported by the National Science Foundation, Grant MPS 75-17746.     

Lead determinations in human bone by particle induced X-ray emission (PIXE) and graphite furnace atomic absorption spectrometry (GFAAS)

Chronic lead (Pb) intoxication has been linked to Alzheimer's disease (AD). Lead, like many heavy elements, tends to accumulate in bone. PIXE is a powerful analytical tool which permits the determination of Pb at the g/g level without requiring sample digestion. GFAAS is one of the most sensitive methods for the determination of Pb and is capable of determining ng/g levels in solution. For bone analyses by GFAAS, sample dissolution and a matrix modifier are required. Rib bone samples were analyzed for Pb by PIXE and GFAAS. IAEA Animal Bone (H-5) was used as a secondary standard for Pb with both methods to ensure accuracy. The range of Pb concentrations in human rib bone was 1.4–11.5 g/g for the trabecular surface by PIXE, 1.3–45 g/g for the cortical surface by PIXE, and 1.54–11.75 g/g for whole bone by GFAAS. No significant difference (p>0.05) was found for AD versus control for either surface or for whole bone.     

Trace element determination in tomato puree using particle induced X-ray emission and Rutherford backscattering

Particle induced X-ray emission (PIXE) and Rutherford backscattering spectrometry (RBS) were used to determine the concentrations of trace elements in samples of 12 tomato puree brands sold in the Mexican market. While RBS offered information about the main elements present in the matrix, PIXE gave results on trace elements. As a whole, data for 17 elements (C, N, O, Na, Mg, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, and Zn) were obtained. To evaluate the results, a comparison with brands from USA, Japan, Colombia, and Chile was carried out, using tomato purees produced following the domestic technology recipe. Additionally, the results were considered in the light of the Codex Alimentarius and the Mexican standard. It was found that all of the brands fall within the limits established by these standards, being of the same order of magnitude as the foreign brands. This revised version was published online in July 2006 with corrections to the Cover Date.