Chemical shift and intensity ratio values of dyspersium, holmium and erbium L X-ray emission lines

A systematic study of L X-ray spectrum has been made on the elements Dy, Ho and Er in the pure form elements and compounds to look into the influence of chemical effect. The vacancies were created by 59.54 keV γ-rays from an ²⁴¹Am radioactive source. The L X-ray emission spectra of heavy elements taken with the currently available Si(Li) detectors show four or five distinct peaks. Corrections for sample absorption and spectrometer efficiency were applied to the measured relative intensities. The results show agreement with the theoretical predictions of Scofield (Scofield, 1974a).     

Submicron hard X-ray fluorescence imaging of synthetic elements

Synchrotron-based X-ray fluorescence microscopy (XFM) using hard X-rays focused into sub-micron spots is a powerful technique for elemental quantification and mapping, as well as microspectroscopic measurements such as μ-XANES (X-ray absorption near edge structure). We have used XFM to image and simultaneously quantify the transuranic element plutonium at the L₃ or L₂-edge as well as Th and lighter biologically essential elements in individual rat pheochromocytoma (PC12) cells after exposure to the long-lived plutonium isotope ²⁴²Pu. Elemental maps demonstrate that plutonium localizes principally in the cytoplasm of the cells and avoids the cell nucleus, which is marked by the highest concentrations of phosphorus and zinc, under the conditions of our experiments. The minimum detection limit under typical acquisition conditions with an incident X-ray energy of 18 keV for an average 202 μm² cell is 1.4 fg Pu or 2.9 × 10⁻²⁰ moles Pu μm⁻², which is similar to the detection limit of K-edge XFM of transition metals at 10 keV. Copper electron microscopy grids were used to avoid interference from gold X-ray emissions, but traces of strontium present in naturally occurring calcium can still interfere with plutonium detection using its L_α X-ray emission.     

Determination of uranium in human urine by total reflection X-ray fluorescence

Uranium has been classified as a toxic chemical. It affects the kidneys, with nephritis being the primarily chemically-induced effect in animals and humans. Intermediate-term studies on animals indicate that increased uranium doses are positively correlated with various biochemical effects and histopathological changes. Since the kidneys efficiently excrete in urine the major portion of solubilized uranium circulating in blood, an increased urinary uranium excretion can provide a sensitive quantitative measure of exposure, especially in the case of acute exposure. In the present work a method was developed for the quantitative determination of uranium in human urine. It combines the chemical treatment of urine, which results in a significant pre-concentration of uranium, with its subsequent detection by means of total reflection X-ray fluorescence (TXRF). The method has been proven to be relatively fast, offering detection limits that allow for monitoring uranium intake above normal levels.     

Kb/Ka X-ray intensity ratios in calcium and potassium compounds

Summary Kb/Ka X-ray intensity ratios of some K and Ca compounds were studied. The samples were excited with 59.5 keV g-rays emitted from 75 mCi ²⁴¹Am radioisotope source and characteristic K X-ray from the samples were counted by means of an Si(Li) detector which has a resolution 155 eV at 5.9 keV. We found that Kb/Ka X-ray intensity ratios are changed by chemical effect for different K and Ca compounds. The experimental values were compared with the calculated theoretical values for elemental K and Ca.     

Chemical-effect variation of Kβ/Kα X-ray intensity ratios in 3d elements

Chemical effects on Kβ/Kα X-ray intensity ratios for some Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn compounds are studied experimentally. The X-ray spectra were measured by using a Si (Li) solid state detector with high resolution. The vacancies were produced by heavily filtered ²⁴¹Am gamma rays. It is found that the Kβ/Kα X-ray intensity ratios measured with compounds deviated up to 43% from the corresponding values of the pure elements. The values for pure elements are compared with the other experimental and with theoretical values.     

Influence of chemical effect on the K-shell X-ray production cross-sections and radiative Auger ratios of Zn complexes

In this study, _σK_α${\sigma }_{{\text{K}}_{\mathrm{\alpha }}}$, _σK_β${\sigma }_{{\text{K}}_{\mathrm{\beta }}}$ production cross-sections, KLM/K_α and KMM/K_β radiative Auger intensity ratios of Zn in different complexes were measured. The samples were excited by 59.5 keV γ-rays from a ²⁴¹Am annular radioactive source. K X-rays emitted by samples were counted by an Ultra-LEGe detector with a resolution of 150 eV at 5.9 keV. The charge transfer effects on central Zn atom was investigated by using the behaviors of different ligands in these complexes.     

Determination of trace elements in Syrian medicinal plants and their infusions by energy dispersive X-ray fluorescence and total reflection X-ray fluorescence spectrometry

X-ray fluorescence (XRF) and total-reflection X-ray fluorescence (TXRF) techniques suited well for a multi-element determination of K, Ca, Mn, Fe, Cu, Zn, Rb, and Sr in some Syrian medicinal plant species. The accuracy and the precision of both techniques were verified by analyzing the Standard Reference Materials (SRM) peach-1547 and apple leaves-1515. A good agreement between the measured concentrations of the previously mentioned elements and the certified values were obtained with errors less than 10.7% for TXRF and 15.8% for XRF. The determination of Br was acceptable only by XRF with an error less than 24%. Furthermore, the XRF method showed a very good applicability for the determination of K, Ca, Mn, Fe, Cu, Zn, Rb, Sr, and Br in infusions of different Syrian medicinal plant species, namely anise (Anisum vulgare), licorice root (Glycyrrhiza glabra), and white wormwood (Artemisia herba-alba).     

Influence of X-ray tube spectral distribution on uncertainty of calculated fluorescent radiation intensity

The relative radiation intensity (R_i) defined as fluorescent radiation intensity of analyte in specimen to fluorescent radiation intensity of pure element or compound, e.g., oxide is used in calculation in both fundamental parameter methods and in theoretical influence coefficient algorithms. Accuracy of calculated R_i is determined by uncertainties of atomic parameters, spectrometer geometry and also by X-ray tube spectral distribution. This paper presents the differences between R_i calculated using experimental and theoretical X-ray tube spectra evaluated by three different algorithms proposed by Pella et al., Ebel, and Finkelshtein–Pavlova. The calculations are performed for the most common targets, i.e., Cr, Mo, Rh and W. In this study, R_i is calculated for V, Cr, Mn, Fe, Co, Ni, Cu and Mo in steels as an example. The differences between R_i calculated using different X-ray tube spectrum algorithms are presented when pure element standard, multielement standard similar to the analyzed material and one pure element standard for all analytes is used in X-ray fluorescence analysis. The differences between R_i for intermediate-thickness samples (and also for thin films) and for X-ray tube, which ran for many hours, are also evaluated.     

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.     

x-射线荧光光谱法测定重整催化剂中铂、铕、铈

使用X 射线荧光光谱仪 ,采用人工合成标样 ,粉末直接压片和经验系数校正基体效应的方法 ,建立了重整催化剂中铂、铕、铈含量的测定方法。测定铂、铕、铈的相对标准偏差依次为 :0 .5 9%、0 .72 %、0 .75 %。     

X射线荧光光谱理论强度计算中激发因子的选择

激发因子是X射线荧光强度理论计算中的重要参数。对目前常用的四种激发因子算法进行了较为详细的比较,并设计了一种评价激发因子算法的实验方法,即用人工合成试样测定了八对能量接近的X射线特征谱线的强度比,然后根据不同的激发因子算法用理论方法计算出这些谱线对的强度比值,以两者的接近程度来判断这四种激发因子算法的适用性。结果表明,使用NRLXRF程序修改版中的激发因子算法计算出来的理论强度比与实测值之间的相对偏差最小。     

X射线荧光光谱法测定含铁原料中钾、钠、锌含量

由于钠、钾为轻元素,极易受其它元素干扰,因此在生产中普遍采用电感耦合等离子体原子发射光谱(ICP-AES)法测定,但较长的分析周期不能满足高效的生产节奏。采用熔融制样,建立X射线荧光光谱法测定含铁原料中的钾、钠、锌的含量。通过实验确定了熔解铁矿石的稀释比为1∶8,在1 150℃熔融12min,K、Na、Zn的测定范围在0.01%~0.5%。用来测定含铁原料中的有害元素,结果与ICPAES法测定结果一致,满足生产检验周期和准确度的要求。     

Application of total-reflection X-ray fluorescence spectrometry in material analysis

X-ray fluorescence spectrometry with total reflection conditions is applied in the qualitative and quantitative determination of impurities in thin layers of Ti, TiO₂, and HfO₂ prepared by evaporation and of SiO₂, TiO₂, and Ta₂O₅ prepared by ion beam sputtering. The same method is used to examine stainless steel discs, which have to be used as reference materials,Dedicated to Professor Günther Tölg on the occasion of his 60th birthday     

Synthesis, crystal structure and optical investigation of the new phosphates: Na7Mg13Ln(PO4)12 (Ln=La, Eu)

Two new isostructural rare earth phosphates Na₇Mg₁₃Ln(PO₄)₁₂ (Ln=La, Eu) have been synthesized and investigated by X-ray diffraction and optical measurements. They crystallize in the orthorhombic system with the Cmc2₁ space group (Z=4). The crystal structure exhibits a new type of framework built up from LnO₈ (Ln=La, Eu), MO₆ (M=0.5Mg+0.5Na) and MgO_x (x=5, 6) polyhedra and PO₄ tetrahedra linked by common corner, edge or face. It can be described in terms of [Mg₄MP₄O₂₂]_∞ layers stacked along the a direction. These layers are interconnected by [Mg₄LnP₄O₃₆]_∞ undulating chains spreading along the b direction. This framework delimits 6 distinct cavities occupied by Na⁺ cations. The results of the optical study of Na₇Mg₁₃La_1−xEu_x(PO₄)₁₂ (x=0, 0.02, 0.1, 1) reveal the presence of two different Eu³⁺ ion environments whereas the X-ray study predicts the existence of only one Eu site. This difference can be explained by the possible presence of the europium element in the sodium sites with small occupancies which cannot be detected by the X-ray structural determination.     

Lead post-mortem intake in human bones of ancient populations by (109)Cd-based X-ray fluorescence and EDXRF

In this work we measured the lead concentration in human bones of Middle Age by means of a portable X-ray fluorescence system based on ¹⁰⁹Cd radioactive source. The detection system consists on a Ge hyperpure detector. This system, conceived for in vivo Pb analysis in bone, is portable, non-destructive and is based on lead K lines detection.

The analysed bones are part of two collections of bones both from the end of Middle Age and submitted for some years to a lead polluted burial environment. The bones of one collection were buried initially on the soil in a convent, in Lisbon (Portugal) and further on, kept in a lead coffin for around 100 years. The second collection contains bones buried permanently on the soil around an old church on the south of Portugal. This place became a parking car for around 20 years.

In this work we studied the distribution of Pb in cortical bone, and trabecular regions from the outside surface to the inner part of the bone and the results are compared with the obtained ones by energy dispersive X-ray fluorescence (EDXRF).

The obtained values present a strong contamination of Pb in spongy bones kept in the lead coffin with concentrations ranging from 250 to 350 μg Pb/g bone mineral, and 4 to 7 μg Pb/g bone mineral for bones buried in the soil. Good agreement was observed between the results obtained by the two techniques.     

X射线荧光光谱仪快捷、准确测定水玻璃主次量元素

本方法介绍了采用X射线荧光光谱仪测定液体水玻璃中的Al2O3、CaO、MgO、Fe2O3、K2O、Na2O、SiO2的含量。研究了适合直接测定液态水玻璃的制样方式、仪器分析参数,建立了工作曲线并录入数据库中。将该方法对未知样品的测定结果与化学法、ICP-AES法对比分析,证实具有良好的准确度,精密度试验显示RSD在0.38%~14.26% 之间。结果显示本方法的准确度、精密度完全可以满足对水玻璃中上述元素的测定要求。     

X射线荧光光谱法快速测定费托蜡中铁

通过对费托蜡(合成蜡、渣蜡)创新制样与装样、测试条件优化,利用仪器自带的基本参数法无标样半定量分析软件,建立了X射线荧光光谱(XRF)测定费托蜡中Fe的方法。测定的相对标准偏差<1%、典型分析时间10 min/样,无需标样。与ICP-AES测定结果相比较,相对误差低于10%,同时降低了蜡样测试对仪器真空度或分光晶体产生的不良影响。     

X射线荧光光谱法测定地质样品中的硫和氟

采用粉末压片制样-X射线荧光光谱法研究地质样品中硫(S)和氟(F)元素的快速测定方法。通过分级过筛实验优化确定样品粒度,探讨样品粒度对测定结果的影响,并进行实际样品和标准物质验证。结果显示,样品粒度为85μm时,经实际样品和标准物质验证,测定结果与化学值和标准认定值相符,且相对标准偏差(RSD)均小于2%。方法具有准确度高、检出限好、测试范围宽、简便快速等优点,能确保样品分析结果的准确性,实现了地质样品中S和F的快速测定。     

A road map to assess critical materials content in boron industrial wastes using sustainable micro-X-ray fluorescence and total reflection X-ray fluorescence instrumentation

Turkey is the leading country in the world in terms of boron production and sale. Increasing boron production goes along with an increasing generation of boron wastes. The pollution of the soil and the air around the waste piles, as well as the occupation of several square kilometers of ground, are major environmental problems. It is, therefore, very important to make use of the wastes to both protect the environment and create revenue. This work presenteda road map for fast screening of boron waste for critical elements followed by determination of the elements using small footprint low power instrumentation. The sample preparation was kept to a minimum. A procedure that allowed an assessment of critical materials in industrial production waste with minimal consumption of hazardous acids, energy, and time was presented. The samples were first screened for valuable and hazardous elements by micro-X-ray fluorescence (XRF). Samples with considerable contents of Cs, Rb, and Aswere then prepared as slurries for the total reflection XRF (TXRF) measurement. To evaluate the TXRF procedure, a standard reference material was analyzed. As a result, Rb and Cs in concentrations up to 420 ± 70 and 1500 ± 200 mg/kg were detected in some of the waste forms. The time savings were in order of a factor of 3 when comparing the prescreening combined micro-XRF and TXRF approach to an all TXRFanalysis approach.