基于PCA-BP神经网络的EDXRF分析测定地质样品中铁、钛元素含量的应用研究

为实现地质样品中元素含量的准确预测,提出了基于主成分分析(PCA)的改进型BP神经网络模型。采用X荧光光谱法,对新疆西天山地质样品中Fe,Ti,V,Pb和Zn等元素进行测量,将得到的X荧光计数作为输入变量,应用该模型对未知地质样品中Fe和Ti元素进行定量预测。结果表明：主成分分析与改进型BP神经网络模型取得了较好的预测效果,预测结果与化学分析值的相对误差小于3%,为地质样品元素含量预测提供了一种新型有效的方法。     

An EDXRF method for determination of uranium and thorium in AHWR fuel after dissolution

A fast energy dispersive x‐ray fluorescence (EDXRF) method requiring only microgram amounts of analytes, i.e. uranium (U) and thorium (Th), in their mixtures in solution form is described. Calibration solutions and samples covering the fuel composition range (0–5% of U in U + Th) of advanced heavy water reactor (AHWR) were prepared by mixing uranium and thorium solutions. A known fixed amount of internal standard yttrium (Y) was added to these solutions. EDXRF spectra of calibration solutions and samples were measured by taking 20 µl aliquots on 30 mm diameter filter papers, after drying, using a Rh target tube operated at 40 kV and 500 µA. Calibration plots were made by plotting U/Y, U/Th and Th/Y amount ratios against the respective intensity ratios of Th Lα, U Lα and Y Kα. In the first set, U was determined using Y as an internal standard, and for Th determination, U, thus determined, was used as an internal standard since the amounts of Th and Y were kept constant in the calibration solutions and samples. In the second set, both U and Th were varied and determined using Y as internal standard. The results of U and Th determinations showed a precision of about 3% (1s) and the results deviated from the expected values by <3% in most of the cases. This approach has an advantage that it requires only microgram amounts of sample, thus mitigating radiation hazards associated with radioactive samples as well as the amount of radioactive analytical waste generated is quite less. Copyright © 2009 John Wiley & Sons, Ltd.     

白云鄂博矿中铈铁钙EDXRF分析的基体效应研究

由于用Energy-Dispersive X-Ray Fluorescence(EDXRF)测量白云鄂博矿中铈元素含量的基体效应主要来自铁和钙,而这两个元素含量的变化非常大,使得通常用的标样方法不适用。以白云鄂博矿元素平均含量为基础制备一组测试样品,采用最小二乘法线性多元拟合来确定铁、钙对铈含量和X射线荧光光谱信号之间的线性关系系数的影响。这样确定的系数反映了铈在测量时发出的荧光强度被铁增强和被钙吸收的基体效应,且适用于大幅度变化的场合。当系数被用来通过EDXRF测量白云鄂博矿中铈的含量时相对误差小于10％。     

绿松石成分的EDXRF方法研究

利用激光剥蚀电感耦合等离子体质谱仪(LA-ICP-MS)测试方法对来自湖北的26块表面相对干净、颜色均匀的绿松石样品进行定值,每个样品表面按照“田字格”的方式逐一测试9个点,用于评价绿松石成分的均匀性。数据结果显示,绿松石样品中Al,P,K,Cu,Fe,V,Cr和Zn的平均变异系数在5.4%以下,而CaO和SiO₂的平均变异系数分别为34.8%和16.2%,说明绿松石中Si和Ca元素存在明显的不均匀性。选取其中的21个样品作为参考标准样品,5个作为未知样品,采用能量色散型X射线荧光光谱仪(EDXRF)建立绿松石的工作曲线,用于测定绿松石的成分。研究结果显示主量元素Al,P和Cu工作曲线的相关系数在92.3%~94.3%之间,平均相对误差在4.6%~9.7%;微量元素Fe,Cr和Zn的相关系数达到0.990以上,K和V元素工作曲线的相关系数分别为0.939和0.972,这五种元素平均相对误差范围在7.2%~13.9%;而Si和Ca元素工作曲线的相关系数分别为0.958和0.866,且在5个未知样品中,Si和Ca元素的平均相对误差分别为348%和27.8%,这与绿松石中Si和Ca元素的含量低和不均匀性,以及仪器方法的检出限等影响因素有关。重复性实验显示Al,P,Cu,Fe和Zn元素的相对标准偏差(RSD)均在1%以内,精密度较高;V,Cr,K,Ca和Si元素的RSD在1.34%~10.17%之间。该研究为快速、准确、无损地定量测定绿松石中Al,P,Cu,Fe,Cr,Zn,V和K等元素的含量提供了一种新思路和新方法,可运用于实验室的绿松石检测鉴定。     

Multispectroscopic Characterization of Oil on Copper Painting

A small plate of oil on copper painting from the Italian Renaissance period was characterized by means of noninvasive spectroscopic methods. The study was conducted by the use of energy-dispersive X-ray fluorescence, X-ray diffraction, and Raman and diffuse reflectance infrared Fourier transform spectroscopies to determine the technology production process in such kinds of artworks. Results allowed us to characterize the copper alloy of the support media; the preparation layer, which is composed by white lead; and the pictorial layer of variable composition (green copper sulphate compounds, red lead, carbon black, brown earth pigments, gold, vermilion, and white lead). The complementarity of the techniques used in this study has proven to be highly effective.     

Detection limits of high temperature superconducting materials on various substrates by energy dispersive X-ray fluorescence and proton induced X-ray emission methods

Application of energy dispersive X-ray fluorescence (EDXRF) and proton induced X-ray emission (PIXE) methods has been demonstrated for determining the elemental composition of thin film superconducting materials. The results of analysis carried out by EDXRF method have been compared with those obtained by PIXE method. Thin films of YBa₂Cu₃O₇ superconducting material were deposited on various substrates such as thin mylar sheet and thick substrates of SrTiO₃, MgO and Al₂O₃. In thin backing the minimum detection limits obtained for Cu, Y, Ba by the PIXE method are 20 ng, 70 ng and 800 ng respectively and the corresponding values by the EDXRF method are 3000 ng, 600 ng and 1000 ng. Detection limits for samples on thick backings deteriorated to a large extent by both methods.     

钙、铁、硅(碱度)X荧光分析仪在攀钢炼铁厂的应用

采用钙、铁、硅（碱度）X荧光分析仪进行烧结球团中Si、Ca、Fa元素（碱度）含量的测定，结果表明，该仪器满足烧结球团中元素（碱度）快速、准确分析的要求。     

Determination of Cr(III) and Cr(VI) in industrial and environmental liquid samples by EDXRF method

A rapid, sensitive and selective procedure for determination of Cr(III) and Cr(VI) in environmental and industrial liquid samples via preconcentration with ammonium pyrrolidine dithiocarbamate (APDC) and determination by means of the EDXRF was described. The effect of pH in the range of 3-11 on the recovery of Cr(III) and Cr(VI) has been investigated separately and in combination of these two species. The influence of organic matter, carbonate species and elements V, Mn and Fe on the recovery of each chromium specie (separately/in combination) over whole pH range was also tested in order to simulate condition occurring in natural waters that usually contain certain amount of dissolved organic matter and carbonate ions. Cr(VI) and Cr(III) have shown different behaviors in reaction with APDC at different pH ranges and therefore it is possible to separate those two species. It was found that Cr(VI) creates complex with APDC only in the pH range from 3 to 5 with quantitative recovery (app. 98%) at pH 3, but there was no recovery of Cr(III) at that pH. On the contrary, in pH range from 6 to 11, reaction with Cr(III) and APDC reviled that the only reaction product is Cr(OH)₃ instead of the expected Cr(III)-APDC complex. All reaction products were characterized by IR spectroscopy.     

X-Ray Fluorescence Analysis of Iron in Ore Dressing Processes

The investigation of iron using off - line energy dispersive X-ray fluorescence, in iron ore dressing process, is presented. Techniques have been developed to determine the quality control of grinding, homogenization, separation, classification processes and residue material in dry basis of iron deposit. The laboratory trials on a wide variety of iron ores indicated that the range of ore grades is from 28–40 % Fe and maximum value is to be found 70 % Fe for processed ore. The results obtained increased the knowledge and performance of the dressing process which is of basic importance for its improvement and future automation.     

Sediments of Galician Continental Shelf: elemental composition and accumulation rates

A geochemical study was carried out in sediment cores along the Galician Continental Shelf and at the mouth of the Vigo and Pontevedra Rias. Multielemental analysis was performed by Instrumental Neutron Activation Analysis and Energy Dispersive X-ray Fluorescence Spectrometry. Sedimentological and geochemical characterisation (lithogenic, biogenic and anthropogenic elements) indicates different supplies for the fine-grained, deposited sediments. No significant heavy metal enrichment could be detected in coastal sediments despite the current sediment contamination in adjacent Rias. Variations in the accumulation rates suggest different factors controlling the sedimentation processes including sediment sources and geomorphology.