External Micro-PIXE Measurements: Preliminary Results on Volcanic Rocks from Nyiragongo Volcano

The external microbeam facility at the 3 MV Tandetron accelerator of the LABEC Laboratory of INFN in Florence has been used to determine, by PIXE, major, minor and trace element abundances of minerals and groundmass in the lavas from the active Nyiragongo Volcano (Democratic Republic of Congo), which is well known for its lava lake intra-crateric activity [e.g. 1, 2]. During the last eruption of this volcano (January, 2002), two main flows entered the Goma town producing major devastation, forcing the rapid exodus of about 300,000 people and causing the death of 150 persons [3]. After this eruption, the interest of the scientific community on this volcanic area suddenly increased. In this respect, determination of major and trace element abundances in mineral phases and groundmass of lavas may allow to constrain the evolution of magma within the volcanic system from a quantitative view point, thus helping to better understand the way this volcano works. PIXE measurements have been performed in a two-detector setup that makes it possible to simultaneously detect and quantify all elements from Na to the heaviest ones; possible compositional zoning effects in the crystals can also be reliably measured thanks to the good space resolution of the microbeam facility (better than 10 μm) and to the possibility of performing one- and bi-dimensional scans over the areas of interest. Concentration maps of all elements can be obtained, both on-line and a posteriori: the data are collected with a list-mode acquisition system, which allows the distribution of any detected element to be reconstructed after completing the scan.     

Signal-to-background in EPMA: Measurement and Monte Carlo calculation

By the method of Monte Carlo calculation, the dependence of the signal-to-background ratio of detected X-rays on the energy of electrons as well as on the thickness of the sample was calculated. The range of energy was 40 ÷ 120 keV, the range of thickness was approximately 8 ÷ 80 g/cm² (40 ÷ 400 nm at density = 2 g/cm³). The results were compared with measurements in electron microscope on thin resin standard for biological microanalysis. The measured dependence of signal-to-background ratio on the energy of electrons has the maximum at 80 keV, the calculated one changes at increased thickness from a monotonic form to one with a maximum at a particular thickness. The absolute values (Hall correction procedure was used for measured values) differs mainly at the highest energy used (120 keV); the difference is probably caused by unproper correction of measured value of background at this energy. Simultaneously, the source distribution of emitted X-ray photons is calculated. Its knowledge gives the possibility to estimate simply the interaction volume diameter and, by this way, to determine the spatial resolution of electron probe X-ray microanalysis.     

Application of EPMA to the localization and speciation of mercury in contaminated parts of chemical plants

The positions of enrichment of mercury and its compounds in surface layers and within the micro structure of metallic materials originating from closed-down chemical plants were detected by electron probe microanalysis. Energy dispersive X-ray spectrometry is useful for the analysis of mercury. However, the energy resolution is not sufficient for detecting small amounts of sulphur and to measure quantitatively the chemical bonding state of mercury as sulphide or chloride. Therefore, it was also necessary to use a wavelength dispersive X-ray spectrometer. The results show that mercury is mainly present in surface layers, and only in small amounts directly at the surface of the bulk material. On the basis of the results obtained, a decontamination process for mercury contaminated parts can be developed which is necessary prior to waste deposition or recycling of those materials.Dedicated to Professor Dr. rer.nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

Identification by Electron Probe Microbeam Analysis of Submicron Borides in Joints of Nickel Base Superalloys

The phases formed at the interface between an intermetallic (NiAl) and a nickel base superalloy joined by combustion synthesis were investigated, particularly the eutectic phases. Owing to their small size, the characterisation of these phases using a Castaings electron microprobe encounters difficulties. The analysis volume size is generally too large to differentiate the phases from their surrounding matrix, even by using low accelerating voltage. Moreover, the eutectic phases contain boron, which is difficult to characterise by EPMA. Independently of the phases shape, the characterisation can be solved by viewing this complex system as a surrounding matrix and a multi layer system. The results of these simulations revealed the presence of two categories of borides: the eutectic boride MM₂B₂ (M=Mo and M=Co, Cr) and the solid solution boride [Cr_1–x (Mo, W)_x]B.     

Monte Carlo Simulation of Electron Transport and X-Ray Generation. II. Radiative Processes and Examples in Electron Probe Microanalysis

Theoretical models for Monte Carlo simulation of radiative processes, i.e. bremsstrahlung and characteristic x-ray emission, are presented. Possible strategies for simulating electron transport are briefly described. For mechanisms involving energy loss and angular deflections, difficulties for strict implementation of accurate numerical differential cross sections still remain due to the strong correlations between these variables. Practical solutions for the case of inelastic collisions and bremsstrahlung emission are described. Comparisons of simulation results with experimental data for several problems of interest in electron probe microanalysis are presented.     

Characterization of the Element Distribution Within TiN Coatings with SIMS

 The distribution of the relevant elements within TiN coatings, made with two different physical deposition methods as the conventional dc vacuum arc method and the filtered high current pulsed arc method (Φ-HCA) are characterized and finally compared. Despite the rougher surface of the dc-arc produced TiN layer, which is due to accumulated droplets, there is no evidence of different stoechiometric composition of Ti and N on the surface. The interface of the dc-arc produced TiN layer (600 nm) is 10 times wider than the one made with the new filtered high current pulsed arc method (60 nm). However the TiN layer made by Φ-HCA shows an inhomogeneous distribution of aluminum and chlorine in the vertical direction, whereas the dc-arc sample is homogeneous. Furthermore, the TiN layer made by Φ-HCA shows vertically an obvious local maximum of chlorine at a depth of about 130 nm. This vertical local maximum has an homogeneous distribution in horizontal direction, which means that a thin, chlorine enriched layer has been incorporated inside the TiN layer. Nevertheless, quantification by SIMS shows that aluminum as well as chlorine concentrations of both samples are too low to influence any TiN properties. Received January 3, 2000. Revision April 4, 2000.     

Detection Limits of Grazing-Exit EPMA for Particle Analysis

 In conventional electron probe microanalysis (EPMA), the electron-induced X-rays are measured at large take-off angles of about 45°. In the grazing exit EPMA (GE-EPMA) method, they are measured at small angles (< 1°). X-rays emitted from deep positions can not be detected at grazing exit angles due to refraction effects at sample-vacuum interface; therefore, it is possible to measure X-rays emitted only from near the surface with a low background. GE-EPMA is especially suitable for the analysis of particles deposited on a flat sample carrier. The detection limits of GE-EPMA were investigated for artificial particles (Al₂O₃, Fe₂O₃ and PbO₂ , particle sizes: 1 ∼ 18 μm) deposited on flat sample carriers of Au thin films–Si wafers. The detection limits improved with decreasing exit angle. The detection limits for characteristic X-rays at an exit angle of approximately 1.1° were 2–4 times lower than at 45°. A minimum detection limit of ca. 0.1% was obtained for Al in small particles.     

Electron Probe Microanalysis of Nitrogen in Glasses and Glass Ceramics

 A homogeneous (phosphate glass) and a heterogeneous (glass ceramic) material were chosen to develop a method for electron microprobe analysis of nitrogen in glasses and glass ceramics. The metaphosphate (50 mole-% P₂O₅, 25 mole-% BaO, 25 mole-% Rb₂O) base glass and the silicate glass (composition of the base glass: 6.9 mole-% Al₂O₃, 21.3 mole-% MgO, 47.3 mole-% SiO₂, 5.1 mole-% CaO, 19.4 mole-% AlN) were melted and cooled down to room temperature. In a second step, the two materials were nitrided by applying dry NH₃ in a special tube furnace. Up to 5 wt.-% of nitrogen could be introduced. The ability of energy dispersive (EDX) as well as wavelength dispersive (WDX) electron probe microanalysis to analyze low contents of light elements in combination with highly concentrated heavy elements was tested both for glasses and for glass ceramics. Measuring conditions had to be optimized to get reliable analytical results as well as to avoid radiation damage of the glasses which may occur especially in the case of wavelength dispersive X-ray analysis. The results were compared with two different analytical methods: inductive coupled plasma analysis and a commercial nitrogen-oxygen-analyzer (the specimen is decomposed by heating and the released gases are analyzed spectroscopically (O) and electrically (N)).     

Determination of thickness distribution and composition of thin coatings by EPMA: Application in the field of steel sheet production

A new method for the investigation of surface coatings by EPMA is presented. It is based on a physical model which takes into account the X-ray intensity depth distribution, the absorption and the electron backscattering effects at the interface between film and substrate. When combined with the concentration mapping (CM) technique, a two-dimensional film thickness distribution and the film composition can be determined simultaneously. Only bulk standards are required for this method.With some examples in the field of steel sheet production and electrogalvanizing the versatility of the method as well as its high sensitivity are pointed out. Particularly important for practical work is the applicability to almost any combinations of film and substrate materials as well as the wide thickness range from almost the total X-ray emergence depth down to the monolayer range.Dedicated to Professor Günther Tölg on the occasion of his 60th birthday     

Application of Sputter-Assisted EPMA to Depth Profile Analysis

 A common problem in depth profile measurement is the calibration of the depth scale. The new technique of sputter assisted electron probe microanalysis offers the possibility of calculating the composition as well as the depth scale solely from the acquired X-ray intensity data without further information, e.g. sputter rates. To achieve a depth resolution that is smaller than the depth of information of the electron probe, i.e. 0.1–1 μm, special deconvolution algorithms must be applied to the acquired data. To assess the capabilities of this new technique it was applied to a Ti/Al/Ti multilayer on Si under different measurement conditions. Quantitative depth profiles were obtained by application of a deconvolution algorithm based on maximum entropy analysis. By comparison of these profiles with AES depth profiles and AFM roughness measurements, it was shown that the limiting factor to the achievable depth resolution is the occurrence of surface roughening induced by the sputtering process rather than the relatively large depth of information of the electron probe. We conclude that for certain applications sputter-assisted EPMA can be regarded as a valid depth profiling technique with a depth resolution in the nm range.     

Determination of Nitrogen in Duplex Stainless Steels by EPMA

 We describe the quantitative determination of low nitrogen contents (< 1 %wt) in highly-alloyed, duplex stainless steels by EPMA using a calibration curve. Five monophasic stainless steels with various nitrogen concentrations were used for the calibration curve, namely, three highly alloyed steels prepared in the laboratory, with nitrogen contents 0.066, 0.565 and 1.016 %wt and two industrial alloys with nitrogen concentrations 0.174 %wt and 0.023 %wt. For these samples, the plot of nitrogen X-ray intensities versus nitrogen contents exhibited an acceptable linear relationship. Average nitrogen contents of the analysed duplex alloys were found to vary in the range < 0.045–0.07 %wt in ferrite and 0.52–0.77 %wt in austenite. These results suggest that the nitrogen solubility limit in ferrite has been reached; on the other hand, nitrogen solubility in austenite increases due to the high manganese and low nickel contents.     

Distribution analysis of trace elements in low alloy steel by means of EPMA,SIMS, and TEM

A combination of chemical analysis, EPMA, SIMS, and TEM was applied to gain information on the bulk values, the microstructure and the microdistribution of contaminants. The limitations of classical chemical analysis were overcome by the application of highly sophisticated analytical techniques. Optimized measurement conditions were worked out for SIMS analysis and basic data such as relative sensitivity factors were gained for further investigations. A correlation between the microdistribution of contaminants and mechanical data could not be established so far, since only two samples were investigated.List of acronyms used BAS British Association of Standardisation (UK) - CGHE carrier gas hot extraction - DL detection limit - ED energy discrimination - EPMA electron probe micro analysis - E ₀ energy of primary ions - HMR high mass resolution - I _B primary ion beam current - NBS National Bureau of Standards (USA) - OES optical emission spectroscopy - PI primary ions - RSF relative sensitivity factor - SI secondary ions - SIMS secondary ion mass spectrometry - SKF SKF Analytica Taeby (Sweden) - TEM transmission electron microscopy - XRFA X-ray fluorescence analysis - d _A diameter of analyzed area     

吸毒患者身体状况与微量元素水平关系研究

分析测定了３０例吸毒时间２年以上的吸毒患者血清中元素锌、铜、铁、钙、锶、镁的含量以及谷丙转氨酶（ＡＬＴ）、乙肝病毒表面抗原（ＨＢｓＡｇ）、尿素氮（ＢＵＮ）、尿八联。结果显示ＡＬＴ、ＢＵＮ的均值明显高于对照组，ＨＢｓＡｇ和尿八联中尿蛋白阳性率明显高于对照组，微量元素锌的含量明显低于对照组。说明吸毒时间较长的患者严重缺锌，应在戒毒同时及时补充适量的微量元素。     

Depth Profile Analysis on the Nanometer Scale by a Combination of Electron Probe Microanalysis (EPMA) and Focused Ion Beam Specimen Preparation (FIB)

Electron probe microanalysis (EPMA) offers high sensitivity and high accuracy in quantitative measurements of chemical compositions and mass coverages. Owing to the low detection limits of the wavelength-dispersive technique, monolayers with mass coverages of about 0.05µgcm^–2 can be detected. Assuming a density of 5gcm^–3 this corresponds to a thickness of 0.1nm. With these advantages in mind, EPMA was extended to depth profile analysis in the sub-micron range using a surface removal technique.The present paper shows how depth profile analysis can be improved by combining EPMA and the focused ion beam (FIB) technique. The focused ion beam system uses a Ga⁺ ion beam. The ion beam allows the milling of defined geometries on the nanometer scale, so that very shallow bevels with exactly defined angles in relation to the surface can be obtained. Low surface damage is expected due to low sputtering effects. Calibrated WDX measurements along the bevel deliver quantitative concentration depth profiles. First results obtained with this new combination of methods will be presented for a multilayered sample used in optical data storage.     

Light-Lithophile Element Metasomatism of Finero Peridotite (W ALPS): A Secondary-Ion Mass Spectrometry Study

The high sensitivity of Secondary-Ion Mass Spectrometry (SIMS) in determining very low trace-element concentrations (down to few ppb wt) has been used to address the important issue of the Light-Lithophile Element (LLE) signatures of mantle peridotites and their potential utility as tracers of transfer of subducted material into the overlying mantle wedge operated either by slab-related fluids or melts. The effects of such metasomatic agents have been described and interpreted on the basis of geochemical and isotopic characteristics of peridotites. However, direct observation of metasomatic processes occurring in the mantle is limited because the most highly metasomatised peridotites are usually found as xenoliths which do not allow large-scale chemical information. In this context, the Finero phlogopite-peridotite massif (Ivrea-Verbano Zone, western Italian Alps) offers a unique opportunity because it contains hydrous mineral assemblages (amphibole + phlogopite ± apatite) and trace element enrichments, supposed to be related to the pervasive migration of slab-derived melts. In this study we report the results of texture-related SIMS investigations performed on a wide range of trace elements such as Li, B, Large-Ion Lithophile Elements (LILE), Rare Earth Elements (REE), Nb, Zr, Ti on clinopyroxenes from the Finero peridotite. SIMS analyses revealed unusual LLE signatures that highlight the role of crust-derived components and open new perspectives on the timing of metasomatic processes.     

EPMA Major and Trace Element Analysis in Garnet and its Petrological Application

 A comparison between major and trace element concentrations in garnet performed by electron microprobe (EPMA) technique is reported. Quantitative spot analyses and X-ray maps of major elements (Fe, Mg, Mn, Ca) and the trace element yttrium in garnets from metamorphic rocks are presented. The selected garnet samples come from meta-pelitic and meta-basic specimens belonging to the tectonic unit of the Monte Rosa Nappe (Western Alps). In the metapelites, the quantitative Y distribution maps display a prominent increase at the core, the Y abundance varying by over two orders of magnitude, from about 80 ppm (rim) to over 2100 ppm (core). The Y profiles show well defined patterns with sharp features that do not correlate with major element distributions. A roughly comparable pattern can be supposed only with Mn. The Y distribution suggests that the diffusion of Y through the garnet is very slow compared to the major elements, thus the Y results are suitable for geothermometric estimates. In the metabasites, the Y spatial distribution is characterised by an increasing content from the core to the rim, displaying a zoning pattern opposite to the metapelite garnet. Quantitative EPMA analyses range from 1100 ppm at the rim to values lower than the detection limit at the core. Therefore, the Y content in the garnet can be related to several chemical and physical variables such as the bulk rock composition and the phase assemblage. In particular, in the xenotime-bearing metapelitic system the Y distribution seems to be correlated with metamorphic peak temperature.     

WDXRF, EPMA and SEM/EDX Quantitative Chemical Analyses of Small Glass Samples

Quantitative chemical analysis is a powerful tool for the classification and discrimination of small glass fragments in forensic and archaeometric analytical issues. In the choice of the analytical method the small dimensions and the irregular shape of the fragments must be accounted for. Several accurate and highly sensitive instrumental techniques successfully employed for the chemical analysis of small glass samples (AAS, ICP-AES and FAAS) are destructive, and therefore unacceptable for these applications. X-ray analytical techniques such as WDXRF, EPMA and SEM/EDX provide means for rapid, non destructive and sensitive multi-elemental analysis of glass fragments. In this study the analytical sensitivity and accuracy of WDXRF, EPMA and SEM/EDX for the analysis of small commercial glass fragments are investigated. The results are compared and discussed in order to establish a relation between the minimum size of glass samples and the accuracy and sensitivity of the analytical methods.     

Microanalysis of Hydrogen, Boron and Fluorine in Vesuvianite by Means of SIMS, EPMA and FTIR

Vesuvianite, a complex sorosilicate, often contains variable (from trace-to-minor-element) amounts of H, B and F. We describe a microanalytical study of H, B and F in vesuvianite by means of Electron Probe Microanalysis (EPMA), Secondary Ion Mass Spectrometry (SIMS), and single-crystal Fourier-Transform InfraRed (FTIR) spectroscopy. Most crystals investigated are B- (up to 3.67 wt% B₂O₃) and F-rich (up to 2.38 wt%); H₂O ranges from 0.243 to 0.665 wt%. The H data obtained by SIMS allowed us to calibrate the quantitative analysis of H₂O by FTIR spectroscopy. The resulting molar absorption coefficient (ɛ _i = 100 000 ± 2000 L · mol⁻¹ · cm⁻²) is in excellent agreement with working curves available from the literature. Moreover, the SIMS data allowed us to obtain the calibration curve to estimate the B₂O₃ content on the basis on the FTIR absorbance: a _i = 34000 ± 1400 · B₂O₃ (wt%).     

Electron probe microanalysis of SiO2-coated minerals: Subsurface phases in quartz

Crystal fragments of biotite, garnet, and spinel were mounted together in one block which afterwards was sawn into several pieces; each piece was coated with SiO₂ of varying thickness, up to 7.9m. Electron probe microanalysis was carried out at various accelerating voltages of the major elements present, using the non-SiO₂-coated minerals as reference standard.Calibration curves, depth below the surface versus ratios of X-ray yields, have been established with the ultimate goal to use them for a (semi)-quantification of elements present in subsurface phases in quartz, a common host mineral in rocks.     

Minor and Trace Element Analysis in Breast Milk Using Inductively Coupled Plasma Mass Spectrometry (ICP-MS)

 Thirty-two breast milk samples provided voluntarily by healthy women living in the Dongting Lake area were investigated by Inductively Coupled Plasma Mass Spectrometry (ICP/MS). Eleven minor and trace elements (Na, Mg, K, Ca, Mn, Fe, Cu, Zn, As, Se and Pb) were quantified and compared with literature reports. The results provide useful data for further studies in the nutritional field. Author for correspondence. E-mail: zhengmh@mail. rcees.ac.cn Received September 4, 2002; accepted February 11, 2003 Published online May 15, 2003