微束X射线荧光和X射线吸收近边结构谱分析云南某铅锌矿区苔藓中铅的分布和形态

苔藓对重金属胁迫具有良好耐受性和一定的积累能力.本研究采集并测定了铅锌矿区苔藓和苔下土壤中重金属元素含量,利用微束X射线荧光光谱(Micro-X-ray fluorescence spectrometry, micro-XRF)测定了苔藓中重金属元素的分布,采用X射线吸收近边结构(X-ray absorption near edge structure, XANES)分析了苔藓中Pb的元素形态.研究表明,矿区苔藓具有较强的Pb、Zn、Cd、As积累能力,Pb和Zn最高含量可达1.06和1.23 mg/g, Cd和As最高含量可达30.5和13.2 μg/g.苔藓地上部(尤其是新生组织)是苔藓吸收并积累重金属的主要部位;矿区采集的小灰藓和匍枝青藓中部分金属元素分布规律不同,反应了不同苔藓种属对金属元素的吸收、积累和耐受机制的差异.XANES结果显示,Pb在小灰藓中主要以Pb3(PO4)2形态存在(约78%),表明生成Pb3(PO4)2沉淀可能是苔藓对Pb的耐受机制之一.     

原位微区同步辐射X射线荧光和近边吸收谱研究铅耐受细菌吸附-转化铅机理

为了从微观水平研究细菌生物吸附及转化铅机理,利用原位微区同步辐射X射线荧光(μ-SRXRF)及X射线吸收近边结构谱( XANES)研究云南兰坪铅锌矿区农田土壤样品中筛选的铅耐受性细菌吸附铅的分布特征及铅形态转化规律。土壤中具有铅耐受性的菌株主要为Arthrobacter sp.属(节杆菌属),采用μ-SRXRF对其吸附铅的含量进行快速简单直接分析,部分细菌吸附铅的含量高达5925μg/g,富集系数达14.8。XANES结果表明,细菌吸附 Pb 后存在形态为 PbS、(C17 H35 COO)2Pb 和 Pb5(PO4)3Cl 分别占58.0％,22.2％和19.8％,与培养基本身以有机态为主的Pb形态有明显差异,表明培养基中铅被细菌吸附后有向硫化物转化的趋势,这为研究重金属生物有效性的影响因素提供了实验参考。     

同步辐射X射线微探针研究石榴石中元素分布

北京正负电子对撞机(BEPC)提供同步辐射(SR)白光做激发源,束斑尺寸50μm×50μm,计数时间20s,位移200μm/步,扫描测量石榴石中元素(Fe,Mn,Ca)分布.得到清晰的元素分布图。     

X射线荧光光谱法测定农田底泥中8种元素

建立X射线荧光光谱法测定农田底泥样品中砷、铬、铜、锰、镍、铅、锌、铁8种元素含量的分析方法.以塑料环粉末压片法制样,选用50种土壤、水系沉积物标准物质拟合校准曲线,探讨各元素的测定条件.当待测样品与建立校准曲线的标准样品粒径均小于75μm时,能够有效减少矿物效应和粒度效应的影响,从而提高检测准确度;各元素在各自的含量范...     

能量色散X射线荧光光谱法测定中草药中的Cd元素

利用能量散射X射线荧光光谱（ED-XRF）法快速测定中草药中的Cd元素.方法对中草药进行简单预处理（粉碎）,使用X射线荧光光谱法建立中草药中Cd元素含量与相对强度的校正工作曲线,分析中草药样品中的Cd元素.Cd元素的检出限为0.083 mg/kg,定量限为0.207 mg/kg,定量限低于国家控制标准0.3 mg/kg.测量定量限以上的中草药样品时,其准确性与化学分析结果相当,重复性和稳定性等结果完全满足GB/T 4889-2008数据的统计处理标准.方法预处理时间不超过5 min,完成一个样品的检测时间不超过15 min,可应用于中草药生产企业中的重金属监控.     

X射线荧光光谱法测定除尘灰中砷、铅含量

以熔融制样法,采用X射线荧光光谱对除尘灰中的有害元素：砷、铅含量进行了测定。对样品的烧失温度进行了讨论,发现在950℃灼烧温度下灼烧2h时除碳完全。砷和铅的相对标准偏差为0.15 %和0.20 %。测试结果与化学分析法、原子吸收光谱法等相吻合。该方法制作工艺简单,分析速度快,样品可长期保存,还能满足其他元素的日常分析。     

基本参数法在能量色散X射线荧光分析金属样品中的应用

在X射线荧光分析中,基本参数法是校正元素间吸收增强效应的数学方法之一。我们使用带有不锈钢窗的~(241)Am59.6keVγ射线作为激发源,用Si(Li)半导体探测器和多道脉冲幅度分析器作为实验手段。采用无标样法,即绝对测量法,因而具有更大的广泛性和实用性。实验中,我们除了考虑元素间的二次、三次荧光吸收增强作用外,对样品中元素     

进口氧化皮化学特性及X射线荧光光谱分析

采用玻璃片法熔融进口氧化皮样品,并应用X射线荧光光谱法测定其中全铁和硅、铝、磷、钙、镁、钛、砷、铅等15种杂质元素的含量.根据氧化皮成分含量范围,利用多个铁矿石标准样品、部分标准样品添加基准物质Fe2O3配制系列校准物质,建立工作曲线.结果表明,该方法能准确、快速地对氧化皮进行分析,测量值与经典方法或标准值比较没有显著性差异.     

微纳米VO2膜层高温相变原位X射线衍射测试方法研究

通过设计、自制加热样品台结合商业X射线衍射仪的小角掠入射衍射模式,开发了微纳米膜层的原位高温相变测试方法,解决了样品表面微纳米膜层材料（厚度 < 10 μm）的高温相变难以原位测量的问题.研究了样品台与膜层表面的温度分布特征,验证了自制加热样品台的控温效果,原位测试了不同温度下二氧化钒（VO₂）膜层的X射线衍射图谱,揭示了VO₂膜层的高温相变行为.     

活性炭表面基团的定性和定量分析

利用过硫酸铵对石油焦基活性炭进行了氧化处理, 并使用元素分析、 傅里叶变换红外光谱(FTIR)、 带质谱检测的程序升温脱附(TPD-MS)、 X射线光电子能谱(XPS)和X射线吸收近边结构(XANES)等方法对样品进行了分析和表征, 并对不同表征方法所得结果进行了对比分析. 结果表明, 元素分析所得结果与TPD-MS分析结果较吻合, XPS和XANES分析所得含氧量结果偏小.     

Localization and chemical forms of cadmium in plant samples by combining analytical electron microscopy and X-ray spectromicroscopy

Cadmium (Cd) is a metal of high toxicity for plants. Resolving its distribution and speciation in plants is essential for understanding the mechanisms involved in Cd tolerance, trafficking and accumulation. The model plant Arabidopsis thaliana was exposed to cadmium under controlled conditions. Elemental distributions in the roots and in the leaves were determined using scanning electron microscopy coupled with energy dispersive X-ray microanalysis (SEM-EDX), and synchrotron-based micro X-ray fluorescence (μ-XRF), which offers a better sensitivity. The chemical form(s) of cadmium was investigated using Cd L_III-edge (3538 eV) micro X-ray absorption near edge structure (μ-XANES) spectroscopy. Plant μ-XANES spectra were fitted by linear combination of Cd reference spectra. Biological sample preparation and conditioning is a critical point because of possible artifacts. In this work we compared freeze-dried samples analyzed at ambient temperature and frozen hydrated samples analyzed at −170 °C. Our results suggest that in the roots Cd is localized in vascular bundles, and coordinated to S ligands. In the leaves, trichomes (epidermal hairs) represent the main compartment of Cd accumulation. In these specialized cells, μ-XANES results show that the majority of Cd is bound to O/N ligands likely provided by the cell wall, and a minor fraction could be bound to S-containing ligands. No significant difference in Cd speciation was observed between freeze-dried and frozen hydrated samples. This work illustrates the interest and the sensitivity of Cd L_III-edge XANES spectroscopy, which is applied here for the first time to plant samples. Combining μ-XRF and Cd L_III-edge μ-XANES spectroscopy offers promising tools to study Cd storage and trafficking mechanisms in plants and other biological samples.     

基于SRXRF和XANES研究Pb对玉米种子萌芽的影响及其分布和形态特征

以受不同浓度Pb胁迫下的玉米种子萌芽试验为基础,结合SRXRF研究Pb对玉米种子萌芽的影响和Pb在玉米种子的微区分布特征,利用X射线吸收近边结构技术(XANES)对萌芽玉米种子不同部位中Pb的化学形态进行分析,藉以了解种子对Pb的吸收和转化规律。结果表明,玉米种子的发芽率、根芽伸长量随培养溶液中Pb(NO3)2浓度增加而降低。种子发芽率、平均芽长、平均根长与暴露Pb浓度间的方差分析P-value分别为2.0×10!3,1.4×10!4和2.39×10!8,均小于0.01,为极显著差异,说明Pb胁迫对种子萌芽和根芽生长造成了极显著影响,且对根长抑制作用更大。SRXRF分析结果表明,种皮和胚结构是玉米种子富集Pb的主要部位,Pb富集在胚结构中将抑制种子萌芽。各种子样品的Pb-LⅢ(13035 eV)边XANES谱图相同,为同一种Pb形态,拟合结果显示其含74.3%的氯化磷酸铅和24.2%硬脂酸铅,说明Pb主要以氯化磷酸铅的形式沉积于玉米体内,并有少部分以与羧基结合的有机铅形式存在。     

Monte Carlo simulation of X-ray fluorescence spectra: Part 4. Photon scattering at high X-ray energies

The photon scattering model of a Monte Carlo simulation code for synchrotron radiation X-ray fluorescence (SRXRF) spectrometers is evaluated at high X-ray energies (60–100 keV) by means of a series of validation experiments performed at Beamline BW5 of HASYLAB. Using monochromatic X-rays, Compton/Rayleigh multiple scattering experiments were performed on polypropylene, Al and Cu samples. Especially in the case of the first two matrices multiple Compton scattering occurs with high probability. This work demonstrates that the simulation model provides a reliable estimate of the spectral distribution of the multiply scattered linearly polarized photon beam as observed by an HPGe detector. Next to variations in sample composition and thickness, the ability of the code to simulate various detection geometries has also been verified. As an application of the code, the achievable detection limits of SRXRF for rare earth elements as obtained with white beam and monochromatic (80 keV) excitation are compared.     

Micro-X-ray absorption near edge structure spectroscopy investigations of baroque tin-amalgam mirrors at BESSY using a capillary focusing system

An elliptically shaped glass monocapillary with a spatial resolution of 5 μm has been used for the fine focusing of the pre-focused X-ray beam produced by the graded-crystal monochromator beamline, KMC-2. The flux density gain of 50 was experimentally measured. The microprobe has been used in the energy range of 3.5–15 keV. Micro-X-ray fluorescence analysis (μXFA) and micro-X-ray absorption near edge structure spectroscopy (μXANES) measurements on test samples and investigations of baroque tin-amalgam mirrors were done.     

Depth profile and microscopic structure of gold-implanted aluminum using X-ray spectroscopies

Ion-implanted gold in polycrystalline aluminum was studied with energies ranging from 100 keV to 500 keV and a dose density of 1 × 10¹⁶ ions/cm². The centroid depths of the implantation profiles were determined by Angle-Resolved Self-Ratio X-ray Fluorescence Spectrometry using synchrotron radiation of the electron storage ring ELSA at the University of Bonn. A linear correlation between the implantation energy and the centroid depth of the profile was found. Comparing these results to TRIM calculations a range enhancement of the experimental data up to 10% is observed. X-ray Absorption Near Edge Structure (XANES) spectroscopy was used at the Au-L_III edge to investigate surface modification due to the implantation process on a microscopic scale. For all energies the implantation leads to nanocrystalline precipitates of the intermetallic compound AuAl₂.     

Characterization of small particles by micro X-ray fluorescence

Micro X-ray fluorescence was used to study both homogeneous and heterogeneous particle systems. Specifically, homogeneous glass microspheres and heterogeneous soil particle samples were prepared by both bulk and single particle sample preparation methods for evaluation by micro X-ray fluorescence. Single particle sample preparation methods allow for single particles from a collected sample to be isolated and individually presented to the micro X-ray fluorescence instrument for analysis. Various particle dispersion methods, including immobilization onto Tacky Dot™ slides, mounting onto double-sided sticky tape affixed to polypropylene film, or attachment to polypropylene film using 3M Artist's Adhesive, were used to separate the sample particles for single particle analysis. These methods were then compared and evaluated for their ability to disperse the particles into an array of single separated particles for optimal micro X-ray fluorescence characterization with minimal background contribution from the particle mounting surface. Bulk methods of particle sample preparation, which included pellet preparation and aerosol impaction, used a large quantity of collected single particles to make a single homogeneous specimen for presentation to the instrument for analysis. It was found that single particle elemental analysis by micro X-ray fluorescence can be performed if the particles are well separated (minimum separation distance = excitation source beam diameter) down to a particle mass of ∼ 0.04 ng and a mean particle diameter of ∼ 0.06 μm. Homogeneous particulates can be adequately characterized by micro X-ray fluorescence using either bulk or single particle analysis methods, with no loss of analytical information. Heterogeneous samples are much harder to characterize, and both single particle as well as bulk analyses must be performed on the sample to insure full elemental characterization by micro X-ray fluorescence.     

In situ micro X-ray absorption near edge structure study of microbiologically reduced selenite (SeO32−)

The possibility exists that life originated from high-pressure, high-temperature environments fueled by the reduction of metal ions. These environments or their modern equivalent cannot be studied by standard microbiological techniques, but, metal reduction and oxidation kinetics may be accessible to X-ray analyses. We have evaluated the compatibility, the sensitivity and the efficiency of μX-ray absorption near edge structure (μXANES) and μX-ray fluorescence (μXRF) to study the kinetics of selenite reduction by prokaryotes under controlled pressure and temperature using a dedicated diamond anvil cell. These tests were performed in quartz capillaries, but the experimental set up was designed so as to accommodate the diamond anvil cell. Using μXRF coupled with μXANES, we show that we can detect and quantify Se species in solution from as low as 2 ppm. Lower quantification levels could be readily obtained by increasing counting time or incident flux and changing detectors. The chemical composition of mixtures of different selenium species has been directly determined by a combination of individual μXANES spectra made from standard solutions. The sensitivity of this method is sufficiently high to allow the study of the speciation of selenium in solution in situ and in vivo in the diamond anvil cell under controlled pressure and temperature.     

Iron (Fe) speciation in xylem sap by XANES at a high brilliant synchrotron X-ray source: opportunities and limitations

The development of highly brilliant synchrotron facilities all around the world is opening the way to new research in biological sciences including speciation studies of trace elements in plants. In this paper, for the first time, iron (Fe) speciation in xylem sap has been assessed by X-ray absorption near-edge structure (XANES) spectroscopy at the highly brilliant synchrotron PETRA III, beamline P06. Both standard organic Fe-complexes and xylem sap samples of Fe-deficient tomato plants were analyzed. The high photon flux provided by this X-ray synchrotron source allows on one side to obtain good XANES spectra in a reasonable amount of time (approx. 15 min for 200 eV scan) at low Fe concentrations (sub parts-per-million), while on the other hand may cause radiation damage to the sample, despite the sample being cooled by a stream of liquid nitrogen vapor. Standard Fe-complexes such as Fe(III)-succinate, Fe(III)-α-ketoglutarate, and Fe(III)-nicotianamine are somehow degraded when irradiated with synchrotron X-rays and Fe(III) can undergo photoreduction. Degradation of the organic molecules was assessed by HPLC-UV/Vis analyses on the same samples investigated by X-ray absorption spectroscopy (XAS). Fe speciation in xylem sap samples revealed Fe(III) to be complexed by citrate and acetate. Nevertheless, artifacts created by radiation damage cannot be excluded. The use of highly brilliant synchrotrons as X-ray sources for XAS analyses can dramatically increase the sensitivity of the technique for trace elements thus allowing their speciation in xylem sap. However, great attention must be paid to radiation damage, which can lead to biased results.

A new X-ray pinhole camera for energy dispersive X-ray fluorescence imaging with high-energy and high-spatial resolution

A new X-ray pinhole camera for the Energy Dispersive X-ray Fluorescence (ED-XRF) imaging of materials with high-energy and high-spatial resolution, was designed and developed. It consists of a back-illuminated and deep depleted CCD detector (composed of 1024 × 1024 pixels with a lateral size of 13 μm) coupled to a 70 μm laser-drilled pinhole-collimator, positioned between the sample under analysis and the CCD. The X-ray pinhole camera works in a coaxial geometry allowing a wide range of magnification values.The characteristic X-ray fluorescence is induced on the samples by irradiation with an external X-ray tube working at a maximum power of 100 W (50 kV and 2 mA operating conditions).The spectroscopic capabilities of the X-ray pinhole camera were accurately investigated. Energy response and energy calibration of the CCD detector were determined by irradiating pure target-materials emitting characteristic X-rays in the energy working-domain of the system (between 3 keV and 30 keV).Measurements were performed by using a multi-frame acquisition in single-photon counting. The characteristic X-ray spectra were obtained by an automated processing of the acquired images. The energy resolution measured at the Fe–Kα line is 157 eV.The use of the X-ray pinhole camera for the 2D resolved elemental analysis was investigated by using reference-patterns of different materials and geometries. The possibility of the elemental mapping of samples up to an area of 3 × 3 cm² was demonstrated.Finally, the spatial resolution of the pinhole camera was measured by analyzing the profile function of a sharp-edge. The spatial resolution determined at the magnification values of 3.2 × and 0.8 × (used as testing values) is about 90 μm and 190 μm respectively.     

超积累植物富集机制研究方法进展

按照重金属由土壤到根经茎,最后转移至叶细胞的运输流程,概述了超积累植物对重金属离子的富集机制,详细描述了各步骤中重金属离子含量和形态分析方法,重点分析了微质子激发X荧光、扩展X-射线吸收精细结构(extended X-ray absorption fine structure,EXAFS)、X-射线吸收近边缘结构等分析手段在植物不同部位重金属离子含量和形态分析中的应用。