Trace element load in cancer and normal lung tissue

Samples of malignant and benign human lung tissues were analysed by two complementary methods, i.e., particle induced X-ray emission (PIXE) and total reflection X-ray fluorescence (TRXRF). The concentration of trace elements of P, S, K, Ca, Ti, Cr, Mn, Fe, Cu, Zn, Se, Sr, Hg and Pb was determined in squamous cancer of lung tissue from 65 people and in the benign lung tumour tissue from 5 people. Several elements shows enhancement in cancerous lung tissue of women in comparison to men, i.e., titanium show maximum enhancement by 48% followed by Cr (20%) and Mn (36%). At the same time trace element concentration of Sr and Pb are declaimed by 30% and 20% in women population. Physical basis of used analytical methods, experimental set-up and the procedure of sample preparation are described.     

MULTIELEMENT ANALYSIS IN GINSENG AND ITS SOIL

The multielement analysis and investigation on ginseng and soil samples have been conducted by X-ray fluorescence (XRF) with a nation approved standard matter for the quality control in measurements. The absorptivity of trace elements are different for various parts of ginseng. Concentrated elements and their degrees of concentration are also different. Ca and Sr are concentrated in the main root and their degrees of concentrations increased with growing ages. The absorptivities of element are higher in rhizome and fibrous root than in main root. In addition, the dried weight of ginseng's root increases exponentially with growing ages.     

生物样品的同步辐射定量分析

叙述了用同步辐射微探针对生物薄样中向量元素进行定量分析的方法，利用自制的微束标樯测定每个测量点的向量元素面密度并同时根据其在１７－２０ｋｅＶ能区中的Ｃｏｍｐｔｏｎ散射强度确定该测量点的样品质量厚度，成功地实现了元素浓度测量。     

能量色散X射线分析中对中厚靶的吸收校正

本文讨论了在能量色散X射线荧光分析中影响准确定量的厚靶基体吸收效应,着重研究了中厚靶的吸收校正方法。以头发样品为例,分别介绍了采用辐射体测得吸收校正系数和化学加入法测得经校正后的相对灵敏度等方法,建立了正确分析中厚靶样品的定量方法和计算程序。比较各种修正方法之间的一致性好于5％。     

Calculation of depth-dependent elemental concentration with X-ray fluorescence using a layered calibration method

Depth-dependent elemental concentration can be assessed using either multiple-angle or confocal X-ray fluorescence (XRF) measurements. This work presents a different approach based on a layered calibration method. The depth-dependent elemental concentration was modeled as multiple layers of uniform elemental concentrations. The unknown elemental concentration in each layer can be calculated using a single-angle XRF measurement, layered calibration data, and a priori knowledge of the concentration behavior as a function of depth. The method was verified using a commercial portable X-ray spectrometer and four-layer stacks of polyester resin discs doped with various concentrations of arsenic. This approach is particularly suitable for quantitative in vivo measurements of arsenic and selenium concentrations in the human skin since minimal ionizing radiation exposure constrains the number of XRF measurements.     

Accelerator-based trace element analysis of foods and agriculture products

An accelerator-based analytical method for measuring trace elements in foods and agricultural products was developed, optimized, validated and compared using reference standards. The method’s initial phase is a new, rapid and effective digestion process of a small mass analyte in an aqueous media containing H₂O₂. Digestion is initiated by radicals formed in water with pulsed UV (PUV) induced (laser) photolysis, which rapidly react with organic matter. After digestion, trace metals are pre-concentrated as carbamates and deposited as thin targets onto Teflon filters. Conventional particle induced X-ray emission (PIXE) or X-ray fluorescence (XRF) methods are then used to analyze elements in the sample. When foods and other agricultural commodities (i.e., soils, feeds) are analyzed, the combined method named pulsed UV (PUV)/PIXE results in enhanced detection of trace elements such as Fe, Co, Ni, Cu, Zn and Pb at ∼1 mg/kg (1 ppm) levels, without lengthy, acid-based digestions. It provides improvements in digestion kinetics and processing time enhancing analytical sensitivity and element recovery. Precision and recovery yields were confirmed with food reference standards. The analysis of edible foods from contaminated agricultural areas is also reported.     

Synchrotron-induced X-ray fluorescence from rat bone and lumber vertebra of different age groups

The fluorescence spectra from rat bones of different age groups (8, 56 and 78 weeks) and lumber vertebra were measured with 8, 10 and 12 keV synchrotron X-rays. We have utilized the new hard X-ray micro-spectroscopy beamline facility, X27A, available at NSLS with a primary beam spot size of the order of ∼10 μm. With this spatial resolution and high flux throughput, X-ray fluorescent intensities for Ca and other trace elements were measured using a liquid-nitrogen-cooled 13-element energy-dispersive high-purity germanium detector. Regarding the lumber vertebra, we acquired the fluorescence spectra from the left, right and middle portions and calcium accumulation was evaluated and compared with the other samples. We have identified the major trace elements of Ca, Ni, Fe and Zn and minor trace elements of Ti, Cr and Mn in the sample. The percentage of scattered radiation and trace element contributions from these samples were highlighted at different energies.     

Elemental depth profiles in marine sediments of Singapore coastal waters

Thirty-eight core sediment samples were recently collected from different locations of the Singapore coastal region. The aim of the project was to trace the history of marine pollution in various coastal regions and to determine the impact of industrial activities. Two nuclear analytical techniques were employed in this study: particle induced X-ray emission (PIXE), Rutherford backscattering (RBS) as well as X-ray fluorescence (XRF). Combined together these techniques provide an excellent tool to determine elemental concentrations of more than 30 elements with detection limits as low as few ppm. Our results show that elemental concentrations in most of the regions do not show a significant variation with depth. However, in regions where industrial and shipping activities are high, for example the Port of Singapore area and the northern part of Johore Straits, the concentrations of metals like Cr, Ni, Cu, Zn, Sn and Pb were found to have an obvious decreasing trend with the depth. In these cores, concentrations in the top 10–15 cm were sometimes ten times higher than the corresponding base line concentrations. Elemental depth profiles of Ni, Cu, Zn, As, Sn and Pb and their mean concentrations in various regions are reported and discussed.     

PIXE and XRF analysis of particulate matter samples: an inter-laboratory comparison

PIXE and XRF are very effective techniques in atmospheric aerosol investigation, therefore they are extensively used by the authors. In this work an inter-laboratory comparison of the results obtained analysing several samples (collected on different substrata) with both techniques is presented: the samples were analysed by PIXE (in Florence, at the 3 MV Tandetron accelerator of LABEC laboratory) and by XRF (in Genoa and Milan, where two Oxford XRF instruments are operational). The results of the three sets of measurements are in good agreement for all the analysed samples.The aim of this work was also to compare PIXE and XRF performance in atmospheric aerosol analysis with the routine set-up currently in use at the three laboratories, to determine the best technique to be applied depending on the substratum used for aerosol sampling and the main elements of interest for each specific research project. Results of the comparison between the minimum detection limits of both techniques will be shown for all the measured elements, for different substrata (Teflon, polycarbonate and cellulose mixed esters).     

XRF法分析人发微量元素精度的改善

本文介绍在用国产Si(Li)谱仪、微机多道和放射源做的X荧光分析仪上提高灵敏度、降低探测限、改善分析精度的一些方法,并给出合肥地区人发微量元素含量的平均值。     

源激发X射线荧光测定头发中Ca、Fe、Cu、Zn、Pb的方法优化

同位素源激发X射线荧光（XRF）已广泛应用于头发中的微量元素测定。中国原子能科学研究院曾经建立了源激发X射线荧光分析技术分析头发样品,Pb的检测限（LLD）约10μg/g。本工作在原来工作的基础上优化仪器参数,降低背景信号强度,提高了灵敏度,尤其是对Pb的灵敏度,使Ca、Fe、Cu、Zn、Pb的检测限分别达到19、1.2、1.1、0.62、1.1μg。首次采用V做内标元素,取样量为0.5g,仪器的短期稳定性相对标准偏差（RSD）为0.38%,长期稳定性相对标准偏差为0.98%。     

X-ray scattering in X-ray fluorescence spectra with X-ray tube excitation - Modelling, experiment, and Monte-Carlo simulation

X-ray scattering may contribute significantly to the spectral background of X-ray fluorescence (XRF) spectra. Based on metrological measurements carried out with a scanning electron microscope (SEM) having attached a well characterised X-ray source (polychromatic X-ray tube) and a calibrated energy dispersive X-ray spectrometer (EDS) the accuracy of a physical model for X-ray scattering is systematically evaluated for representative samples. The knowledge of the X-ray spectrometer efficiency, but also of the spectrometer response functions makes it possible to define a physical spectral background of XRF spectra. Background subtraction relying on purely mathematical procedures is state-of-the-art. The results produced by the analytical model are at least as reliable as those obtained by Monte-Carlo simulations, even without considering the very challenging contribution of multiple scattering. Special attention has been paid to Compton broadening. Relevant applications of the implementation of the analytical model presented in this paper are the prediction of the limits of detection for particular cases or the determination of the transmission of X-ray polycapillary lenses.     

Determination of uranium content in Th, U mixed oxides using EDXRF

An energy dispersive X-ray fluorescence (EDXRF) technique has been developed for the determination of U content in the range 2-80% in mixed oxides of thorium and uranium. The experimental parameters for XRF measurements were optimized using 1 cm diameter pellets made from 1:1 mixture of thorium-uranium mixed oxide standards and cellulose. Calibration plots were established using both L_α as well as L_β peaks of uranium. The reproducibility of the determination was evaluated to be better than 3% for L_α peak, while for L_β peak, it was better than 4%. The measured values of the uranium concentration in the synthetic samples were found to be in good agreement with the added values. Simultaneously Th was also determined using its L_α peak. The present method will be useful for fast routine measurements of mixed oxide samples of Th and U, without the need for dissolution.     

Absolute mass thickness determination of thin samples by X-ray fluorescence analysis

An absolute method for mass thickness determination of thin samples by X-ray fluorescence analysis has been developed. The method is based on the experimental determination of the fluorescence intensities of the sample's constituent elements in reflection and transmission geometries. The samples studied were elemental and compound foils. A set of numerical calculations, Monte Carlo simulations and experimental measurements with thin samples including super-conductor monocrystals were performed with very good results. The range of thicknesses which can be determined by the proposed technique depends on the sample's composition, the excitation energy and the geometrical arrangement.     

Biomedical research at LIPSION - Present state and future developments

Since its commissioning in 1998 the high energy ion nanoprobe LIPSION has been developed into a versatile tool for a variety of applications in biomedical research. It includes quantitative trace element analysis with sub-micron spatial resolution and 3D-element imaging, as well as 2D- and 3D-microscopy of density distributions. The analytical methods base on particle induced X-ray emission spectrometry (PIXE) and PIXE-tomography, Rutherford backscattering spectrometry (RBS), as well as scanning transmission ion microscopy (STIM) and STIM-tomography.The continuous developments led to improved capabilities for trace element analysis. For sub-micron analysis the spatial resolution could be improved to 0.3 μm for high resolution work and to 0.5 μm for routine analysis. On the other hand, LIPSION was optimized for high sample throughput in quantitative element imaging maintaining a lateral resolution of 1-2 μm. Recently the methods of PIXE- and STIM-tomography of biological specimens have been extended to limited angle tomography to avoid the complicated preparation of free-standing samples.Besides its analytical applications, the nanoprobe is also used for targeted irradiation of living cells with counted single ions for radiobiological research. It is capable of irradiating up to 20,000 cells per hour. Furthermore, we have developed a technique to achieve confined cell growth based on the proton beam writing technique (PBW) and agar. The paper presents an overview of the current biomedical research fields at LIPSION and gives an outlook on prospective developments.     

Evidence for lead diagenesis in ancient bones of the Southern Andes

Skeletal samples from pre-Colonial Peru and Bolivia, dating from AD 300 to 1450, were sampled and analyzed for lead content using a non-destructive X-ray fluorescence (XRF) technique. A total of 99 lead measurements were made on bones recovered from three regions of the Southern Andes. Predominantly trabecular bones demonstrated clearly higher lead concentrations than predominantly cortical bones. The magnitudes of lead concentrations and the differences between bony areas that are predominantly cortical and those that are trabecular, indicate diagenesis as the major contributor to observed lead levels. Diagenetic contributions of lead are less substantial in cortical bone. Soil sample analyses confirmed significant quantities of lead in the sediments. Repeated measurements of a tibia and femur from a single individual suggest that the cortical shafts of these bones have similar susceptibilities to lead diagenesis. This is significant for designing alternative sampling strategies in areas where preservation is poor and a specific bone may not be present in all individuals. The XRF system used in this study demonstrates an improved precision of measurement compared with previously reported applications.     

用同步辐射X荧光分析血浆蛋白质的微量元素

用同步辐射X荧光(SRXRF)分析技术与凝胶色谱生化分离相结合，分析了用抗肿瘤药物顺铂处理过的和未处理过的小鼠血浆的大分子蛋白质。对以轻元素为基体的小量样品，用X荧光谱中的康普顿散射强度作为质量的因子，获得了在大于22ku分子量的蛋白质中Pt、S、Ca、Fe、Ni、Cu、Zn、Se、Br和Sr等元素含量在不同样品问的相对变化。由此推测，经顺铂处理后，Pt元素可与血浆中的大分子蛋白结合，含CM和S的大分子蛋白含量明显升高，而含Zn的减少。