Improving signal-to-noise ratio for the forensic analysis of glass using micro X-ray fluorescence spectrometry

Micro X-ray fluorescence spectrometry (μXRF) is a standard technique used for the elemental analysis of glass fragments in forensic casework. The glass specimens encountered in casework are usually small (<1 mm), thin fragments that are partially transparent to the exciting X-ray beam. In addition to providing fluorescence from the small glass fragments, the primary beam X-rays can scatter within the chamber and provide noise in the measurements. To reduce scatter from the sample stage, the fragments are typically mounted on a thin plastic film and raised on an XRF sample cup (≤3 cm in height). However, at these heights, there may still be significant scatter from the sample stage, which adversely affects the signal-to-noise ratio (SNR) and the limit of detection (LOD). A plastic mount was designed and 3D-printed in-house to allow fragments to be raised as high as possible from the sample stage, thereby minimizing stage scatter. Most elements detected in glass showed an improvement in the SNR when using the 3D-printed mount for analyses. The greatest improvement (>30%) was observed for lower atomic number elements (Na and Mg) and higher atomic number elements (Sr and Zr). Another simple method to improve SNR is the use of primary beam filters; when using primary beam filters during analyses, elements with characteristic lines in the high-energy range (Rb, Sr, and Zr) showed the greatest improvement (>70%) in SNR. The impact of both strategies for the improvement of SNR is presented here.     

Use of highly energetic (116 keV) synchrotron radiation for X-ray fluorescence analysis of trace rare-earth and heavy elements

This study has revealed the advantages of the use of 116 keV X-rays as an excitation source of X-ray fluorescence (XRF) analyses. This technique is suitable for nondestructive multielemental analyses of heavy elements such as rare-earth elements. The lowest MDL value evaluated for the bulk analysis of a JG-1 standard reference sample (granite rock) was 0.1 ppm for W for a 500 s measurement. The spectrum of standard glass samples of SRM612 demonstrated clearly resolved K-line peaks of more than 30 elements, including all the existing rare-earth elements, at 50 ppm levels. The calibration curve for the determination of a rare-earth element shows a linear relation between the XRF intensity and concentrations from 10 to 0.03 ng. This powerful technique should be useful for nondestructive analyses of rare-earth and heavy elements in geological, geochemical and archaeological samples as well as industrial materials.     

The effects of absorption edge structure of atoms in x‐ray fluorescence analysis

The effects of the absorption edge structure in x‐ray fluorescence (XRF) manifest themselves as a very strong attenuation of the analytical line radiation when it is in the x‐ray absorption near edge structure (XANES) range. In this paper, this effect is exemplified by an ultra‐strong Ba‐caused attenuation of the Ce Lβ₁ line. This case was experimentally studied. Comparison of measured and calculated relative intensities has shown that the actual mass attenuation coefficient of the Ce Lβ₁ line in Ba is 1.6 times greater than known values. This is due to that the Ce Lβ₁ line is within the initial range of L3 Ba absorption edge, i. e. the XANES range. Such an effect of the absorption edge structure of atoms must be considered using the fundamental parameters method in quantitative XRF analysis. This paper also presents some other possible cases of this effect. Copyright © 2009 John Wiley & Sons, Ltd.     

Improvements of the low‐energy performance of a micro‐focus x‐ray source for XRF analysis with the SEM

X‐ray Fluorescence (XRF) with a scanning electron microscope (SEM) is a valuable completion of the analytical capabilities of SEMs. Small and compact micro‐focus x‐ray sources are mounted to the microscope chamber, and the x‐ray spectra are monitored with conventional EDS systems. Up to now the x‐ray tubes used for the micro‐focus x‐ray sources are equipped with beryllium windows about 100 µm thick. The poly‐capillary x‐ray lenses have their transmission maximum at photon energies around 10 keV. It drops down in both low‐ and high‐energy ranges. Hence, L‐radiation from an Mo or Rh target will be strongly attenuated, and the excitation of fluorescence in the soft x‐ray range becomes very ineffective. A new micro‐focus x‐ray source was developed. It is characterised by a lower self‐absorption in the tube target, thin beryllium windows and an x‐ray optics having a large distance between its foci and the maximum of transmission at about 5 keV. Thus K line fluorescence of light elements becomes effectively excited by the L‐radiation from Mo or Rh tube targets. The detection limit for sodium oxide in glass was found to be below 1 mass%. Copyright © 2009 John Wiley & Sons, Ltd.     

Development of a high‐resolution confocal micro‐XRF instrument equipped with a vacuum chamber

A confocal micro‐X‐ray fluorescence (micro‐XRF) instrument equipped with a vacuum chamber was newly developed. The instrument is operated under a vacuum condition to reduce the absorption of XRF in the atmosphere. Thin metal layers were developed to evaluate the confocal volume, corresponding to depth resolution. A set of thin metal layers (Al, Ti, Cr, Fe, Ni, Cu, Zr, Mo, and Au) was prepared by a magnetron sputtering technique. The depth resolutions of the new instrument were varied from 56.0 to 10.9 µm for an energy range from 1.4 to 17.4 keV, respectively. The lower limit of detection (LLD) was estimated by comparison with a glass standard reference material NIST SRM 621). The LLDs obtained by a conventional micro‐XRF were compared with the LLDs obtained by a confocal micro‐XRF instrument. The LLDs were improved in the measurement under confocal configuration because of the reduction of background intensity. Finally, layered materials related to forensic investigation were measured. The confocal micro‐XRF instrument was able to nondestructively obtain the distribution of light elements that cannot be detected by measurement in air. Copyright © 2013 John Wiley & Sons, Ltd.     

Distribution of Pb and Zn in slices of human bone by synchrotron µ‐XRF

Synchrotron radiation‐induced micro x‐ray fluorescence analysis (µ‐XRF) at HASYLAB beamline L was used to determine the distribution of Pb and other trace elements in slices of human bone. Using a focused synchrotron x‐ray beam of about 15 µm in diameter it was found that Pb was mostly located at the outer border of the cortical bone in various samples. Ratios of Pb intensities of cortical and trabecular bone varied from 0.027 for hip head to 0.408 for proximal tibia. Additionally Ca, Zn and Sr distributions were simultaneously recorded. A remarkable association between Pb and Zn content could be observed. Copyright © 2004 John Wiley & Sons, Ltd.     

Design and performance evaluation of SDD based X-ray spectrometer for future planetary exploration

Silicon Drift Detector (SDD) based X-ray spectrometer has been developed for obtaining the elemental composition of unknown samples by detecting fluorescent X-rays in the energy region 1–25 keV by a non-destructive process. The use of new technology X-ray detector provides good energy resolution for detecting the elements separated with ～150 eV apart. Here we present the design of a complete X-ray spectrometer intended for use in the future space-born experiment. The low energy threshold of <1 keV and the energy resolution of ～150 eV at 5.9 keV, as measured from the system is comparable to the standard spectrometers available off-the-shelf. We evaluated the system performance for different signal peaking time, as well as for different input count rates and show that the performance remains stable for incident count rate up to 20,000 counts per second. We have also carried out a ‘proof of concept’ experiment of measuring fluorescent X-ray spectrum from various standard XRF samples from the USGS catalog irradiated by the laboratory X-ray source ²⁴¹Am with 1 mCi activity. It is shown that intensities of various characteristic X-ray lines are well correlated with the respective elemental concentrations. A specific effort has been made while designing the developed X-ray spectrometer to use electronic components which are available in space grade so that the same electronic design can be used in the upcoming planetary missions with appropriate mechanical packaging.     

Experimental evaluation of X‐ray optics applied for microanalysis

The performance of x‐ray capillary lenses has been evaluated. The tests were carried out using an x‐ray tube set‐up. A single glass capillary with tapered inner channel, a monolithic glass polycapillary, and an in‐house manufactured single metallic capillary with parabolic inner channel were characterized in terms of gain, spatial resolution, and element detection limits. The spatial resolution of a confocal set‐up utilizing a monolithic glass polycapillary and a polycapillary conical collimator has also been measured. The highest gain of about 2500 was observed for the glass polycapillary. The maximum gain achieved with the single glass capillary was equal to about 25, and the gain of the metallic capillary was only slightly greater than 1. For the glass capillary and polycapillary lenses, significant filtering of the higher‐energy photons (energy > 8 keV) was observed. The lowest relative detection limits were obtained with an ordinary cylindrical collimator and the polycapillary lens. Similar absolute detection limits were achieved with the use of the polycapillary and single capillary lenses. A relation between the ratios of the detection limits of elements achieved with different x‐ray lenses and the lens parameters (spatial resolution and gain) has been proposed and was verified experimentally. The monolithic polycapillary lens was found to be an optimum focusing device for an x‐ray tube‐based scanning spectrometer. This type of x‐ray lens can be coupled with a polycapillary conical collimator or a polycapillary half‐lens to make a confocal x‐ray microscope capable of depth profiling with a spatial resolution equal to about 30 micrometers. Copyright © 2008 John Wiley & Sons, Ltd.     

Energy‐dispersive XRF spectrometer for Ti determination (TITAN)

An energy‐dispersive XRF analyser was designed and constructed for determining Ti in plant and peat materials at low (ppm) concentrations. The XRF analyzer for Ti analysis (TITAN) uses monochromatic excitation obtained from a crystal diffraction monochromator and Co target x‐ray diffraction tube. In addition to precise and sensitive analyses of Ti, other minor elements (Ca, K, Cl, S, P, Ba) in powdered plant and peat samples can be measured with only a minimum of sample preparation (drying, milling). The limits of detection obtained are K 2.5, Ca 1.5, Ti 0.9, Cr 0.7 and Mn 0.5 ppm using a 600 s acquisition time. The instrument was used to determine Ti concentrations in pre‐anthropogenic peat samples up to 9000 years old. Copyright © 2004 John Wiley & Sons, Ltd.     

Nondestructive elemental depth profiling of Japanese lacquerware ‘Tamamushi‐nuri’ by confocal 3D‐XRF analysis in comparison with micro GE‐XRF

We have applied recently two XRF (micro x‐ray fluorescence) methods [micro‐Grazing Exit XRF (GE‐XRF) and confocal 3D‐XRF] to Japanese lacquerware ‘Tamamushi‐nuri.’ A laboratory grazing‐exit XRF (GE‐XRF) instrument was developed in combination with a micro‐XRF setup. A micro x‐ray beam was produced by a single capillary and a pinhole aperture. Elemental x‐ray images (2D images) obtained at different analyzing depths by micro GE‐XRF have been reported. However, it was difficult to directly obtain depth‐selective x‐ray spectra and 2D images. A 3D XRF instrument using two independent polycapillary x‐ray lenses and two x‐ray sources (Cr and Mo targets) was also applied to the same sample. 2D XRF images of a Japanese lacquerware showed specific distributions of elements at the different depths, indicating that ‘Tamamushi‐nuri’ lacquerware has a layered structure. The merits and disadvantages of both the micro GE‐XRF and confocal micro XRF methods are discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

Analysis of Limoges painted enamels from the 16th to 19th centuries by using a portable micro x‐ray fluorescence spectrometer

Material analysis of Limoges painted enamels was undertaken by using an x‐ray fluorescence spectrometer equipped with a low‐power x‐ray tube, polycapillary x‐ray optics and a silicon drift chamber detector. The spectrometer, which includes helium purging for detecting elements down to sodium, can easily be assembled and dismantled within 1 h. A quantification method for enamel and glass objects was developed and verified using standard materials. The layer arrangement and possible influence on the XRF measurements were especially considered in theoretical calculations. Over 160 painted enamels from the late Renaissance and Revival periods in the 19th century in various collections were investigated. Comparison of the quantitative results from objects which are securely dated and attributed by art historians allowed a more reliable attribution of pieces with doubted authenticity. Copyright © 2004 John Wiley & Sons, Ltd.     

样品厚度对薄膜法X射线荧光光谱测量的影响研究

分别以富集有Cr,Pb和Cd三种元素的尼龙薄膜样品及玻璃纤维滤膜为研究对象,采用滤膜叠加的方式,通过XRF光谱仪测量不同样品厚度下薄膜样品的XRF光谱,根据测得的尼龙薄膜样品中Cr,Pb,Cd元素及玻璃纤维滤膜中Ca,As和Sr元素特征XRF性质的变化,研究样品厚度对薄膜法XRF光谱测量的影响。结果表明：薄膜样品厚度对不同能量区间上元素特征谱线荧光性质的影响并不相同。元素特征谱线能量越大,元素特征X射线荧光穿透滤膜到达探测器的过程中损失越少;但由薄膜样品厚度增加引起的基体效应却越强,相应特征谱线位置处的背景荧光强度就越大,因此样品厚度增加所引起的基体效应对薄膜法XRF光谱测量的灵敏度影响就越大。对于特征谱线能量较低(能量小于7 keV)的元素,以增加薄膜样品厚度的方式来增加待测组分的质量厚度浓度,并不能有效地提高薄膜法XRF光谱测量的灵敏度;对于特征谱线能量较高的元素(能量＞7 keV),可以通过适当增加样品厚度以增加被测组分的质量厚度浓度的方式来提高XRF光谱测量的灵敏度,薄膜样品厚度在0.96～2.24 mm内,更有利于XRF光谱的测量与分析。该研究为大气及水体重金属薄膜法XRF光谱分析中薄样制备及富集技术提供了重要的理论依据。     

Time‐resolved x‐ray fluorescence for monitoring the intake of mineral nutrients in living plants

We have applied a time‐resolved means of measurement for studying living plants. The intake of mineral nutrients in a living plant such as stevia has been observed by this measuring instrument. A solution containing K, Ca, Mn, Fe, Cu, and Zn compounds was used as the mineral nutrient solution. The concentrations of the standard solutions were specifically chosen to obtain optimal intensities of the x‐ray peaks. The time dependence of the x‐ray fluorescence (XRF) intensity showed specific intake processes depending on the type of element. In addition, the experimental results suggest differences in the translocation of each element in the stevia stem. We conclude that time‐resolved XRF is a powerful technique for studying living plants. Copyright © 2007 John Wiley & Sons, Ltd.     

Development of a compact XRF probe using a ring‐type secondary target

Recently, on‐site analysis is being performed in many fields, and the use of compact instruments is required. In this article, we developed a compact x‐ray fluorescence (XRF) probe using a ring‐type secondary target. Employing the ring‐type target, coaxial optical geometry (irradiation and detection) could be achieved. We applied this probe to standard steel materials and standard solutions. In addition, a solid sample in solution was directly measured. As an application of the XRF probe, the monitoring of a chemical reaction was demonstrated that enabled observation of an increase in metallic ions. Copyright © 2008 John Wiley & Sons, Ltd.     

X‐ray fluorescence spectrometry in Dar es Salaam

Energy‐dispersive x‐ray fluorescence (EDXRF) analysis has been established at the University of Dar es Salaam, Faculty of Science, Department of Physics. Calibration was conducted using thin films from Micromatter (USA) for secondary target XRF. We report on the performance of the spectrometer including the detection limits attained, which range from 0.01 to 10 ng cm^?2 using collimators of 6 and 8 mm diameter under excitation conditions of 50 kV, 35 mA. The accuracy of the measurements was checked using IAEA SOIL‐7 and NIST 3087a Certified Reference Materials. The experimental values differed by <5% from the certified values. The total reflection x‐ray fluorescence (TXRF) facility added as a module to the existing XRF system provides detection limits between 0.1 and 100 pg for most of the elements measured. Copyright © 2005 John Wiley & Sons, Ltd.     

A risk assessment study of heavy metals in ambient air by WD‐XRF spectrometry using aerosol‐generated filter standards

A risk assessment study of the air quality in the surrounding of roads covered with slags coming from the non‐ferrous metal industry was performed. A monitoring campaign was carried out at three locations in Flanders by collecting the PM10 fraction and the total suspended particulates (TSP) of the airborne dust particles, entrapping heavy metals, on membrane filters. The heavy metal concentration on the dust filters was determined by wavelength‐dispersive x‐ray fluorescence (WD‐XRF) spectrometry. The XRF calibration curves were set up with filter standards prepared in the laboratory using an aerosol‐generated loading system. The acquired WD‐XRF results were confirmed by inductively coupled plasma atomic emission spectrometric (ICP‐AES) measurements after acid digestion on a selected number of filters. Electron probe microanalysis (EPMA) confirmed that aerosol‐loaded filter standards and dust filters with a concentration level of the analyzed element below 3300 ng cm^?2 were homogeneously distributed. Dust filters with higher concentrations, and especially filters loaded with the TSP fraction, reflected an inhomogeneous distribution of the analyzed element on the filter. The WD‐XRF analytical results acquired in the monitoring campaign revealed that the concentration of Pb on the dust filters never exceeded the immission standard (yearly average) of 2000 ng m^?3. It can be stated that the impact on human health is limited and can still be reduced by covering the polluted roads with a layer of asphalt. Further evaluation of soil and water samples from the nearby surroundings reveals that the heavy metal content in the slags makes an important contribution to environmental pollution, especially the contamination of groundwater. Copyright © 2003 John Wiley & Sons, Ltd.     

Evaluation of effects of irregular shape on quantitative XRF analysis of metal objects

Quantitative XRF analysis of metal alloys can be obtained by using the general fundamental parameter method based on the comparison of x‐ray line fluorescence intensities with those obtained from reference standard pellets in identical experimental conditions. Corrections for auto absorption and secondary excitation effects are fundamental to obtaining quantitative results. When analyzing a real object with irregular, or at least nonpellet‐shaped, geometry and/or of incorrect positioning, an additional correction factor for x‐ray fluorescence line intensities must be entered. In this paper we review the problem of the contributions to the error specific to an irregular surface or incorrect positioning intrinsic to the fundamental parameter method, in the more enlarged context of considering a real experimental setup in which irradiation and detection angles are not exactly constant, as assumed in the fundamental parameter method. They are accounted for by the corrective irregular shape factors. In principle, these factors must be separately calculated for each value of excitation and characteristic x‐ray energies, and the relative precision in the quantitative determination of elemental concentrations with the fundamental parameter method can be estimated from the relative amplitude of the variation of shape factor values depending on the exciting energy spectrum. One obtains the result that the correction due to irregular shape or incorrect positioning of the object under examination tends to the limit 1, or, more generally, to a constant value independent of the excitation and emission x‐ray energies in the limiting case where the direction of the exciting radiation coincides with that of the detected fluorescence x‐rays. The results of calculations of the relative precision of XRF quantitative analysis are shown for gold‐based alloy objects in some specific cases of surface roughness and positioning of the object. Dispersion around the nominal values for the angles of incoming and outgoing x‐ray directions is assumed as determined by the geometric conditions in two selected instrumental setups. A nominal value of 45° was assumed for both the angles in the first case. In the second case, we considered an irradiation setup where the condition of coincidence for incoming and outgoing x‐ray directions is nearly achieved by employing an annular silicon drift detector (SDD) with a central hole, which allows the passage of the exciting x‐rays. An interesting result obtained in the latter case is that, looking only at the dependence on the irregular shape, an attainable precision on the order of <1‰ can be achieved. In view of the possible applications of quantitative XRF analysis to jewellery, employing SDD detectors capable of very high counting rates should allow a statistical error under the above‐mentioned limit in a reasonably short measuring time. However, concerning the error deriving from intrinsic x‐ray tube instability, an investigation aimed at achieving a stable enough system is still needed. Copyright © 2006 John Wiley & Sons, Ltd.     

Energy‐dispersive x‐ray fluorescence analysis of modern coloured glasses from Marinha Grande (Portugal)

The elemental composition (K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Ba, Nd and Pb) of modern coloured glasses was obtained by energy‐dispersive x‐ray fluorescence (EDXRF) spectrometry. This non‐destructive technique is frequently used in the analysis of historical glass objects. Two reference glasses were also measured to assess the overall accuracy of the EDXRF method. Reference and unknown glasses were analysed without any preparation. The coloured glass samples studied belong to the Glass Museum of Marinha Grande and were chosen from two distinct collections, which were characterized by the different concentrations of some elements (K, Ti, Cr, Mn, Fe, Ba and Pb). The determined major elements allowed the identification of two raw materials used in glass manufacture, sand and lime. Multivariate statistical analysis, namely principal component extraction, simplified the identification of some of the colouring chemical elements, associating them with the different colours of the glass objects. Copyright © 2003 John Wiley & Sons, Ltd.     

EPMA and µ‐SRXRF analysis and TEM‐based microstructure characterization of a set of Roman glass fragments

A set of Roman glass fragments, excavated at Bliesbruck–Reinheim (French–German border), were analysed by electron probe microanalysis (EPMA) and micro‐synchrotron radiation‐induced x‐ray fluorescence (µ‐SRXRF) in order to determine the major, minor and trace chemical composition. Based on this analysis, five classes of mono‐coloured glass could be discerned. However, one piece of this set was not mono‐coloured, but consisted of a mixture of brown and white opaque glass. This fragment was investigated using EPMA and transmission electron microscopy (TEM) in order to gain a better insight into its microstructure. Both colours proved to contain small crystalline inhomogeneities. Structural information reveals the form in which the detected elements are present and helps to explain the appearance (e.g. colour) of the material. Copyright © 2004 John Wiley & Sons, Ltd.     

土壤重金属铅元素的X射线荧光光谱测量分析

在实验室条件下,利用NITON XLt793型便携式X射线荧光光谱重金属分析仪测量并分析土壤中铅元素的X射线荧光光谱特性。分别以铅的L_α(10.55 keV)和L_β(12.61 keV)特征谱线作为分析线,分析了不同基体元素对分析线的影响;测定在不同铅浓度下的特征谱线强度变化。结果表明铅的质量分数在10×10-6～1 800×10-6范围内,元素的光谱强度与浓度之间呈现较好的线性关系;建立了铅元素的定标曲线,并计算得到铅的检出限为7.89×10-6。