Secondary Fluorescence Effects Research Articles

Microprobe Analysis of Titanium in Zircon: an Estimation of Secondary Fluorescence

Microprobe study of the effects of secondary fluorescence from high-titania glass (TiO2 ≈ 16 wt %) on apparent titanium content in Ti-free zircon was conducted. It was demonstrated that small crystals (10 µm) are not suitable for analysis. In boundary parts of large zircon crystals (20–30 µm) the error in Ti estimation may reach 10–23%. However, in central parts of large crystals ( 30 µm) the microprobe analysis gives practically undistorted titanium contents.

High precision measurement of trace F and Cl in olivine by electron probe microanalysis

Fluorine (F) and chlorine (Cl) are important volatiles in olivine and its high-pressure polymorphs, which would significantly affect olivine phase transition, melting temperature, and physical property of the mantle. F and Cl concentrations in olivine can be detected by electron probe microanalysis (EPMA). However, the analytical accuracy and precision can be impeded by severe peak overlaps, low peak intensities of traditional analytical crystals, and secondary fluorescence effects. In this study, we constructed an optimized analytical method with high accuracy and precision to analyze trace F and Cl in olivine. Key parameters of analytical crystals, beam conditions, peak overlaps, and secondary fluorescence effects were discussed. Variations in the levels of the analyzed trace elements fall within ± 10%. The detection limits (3σ) for F and Cl are lowered to 30 ppm and 5 ppm, respectively. This method can provide precise F and Cl analysis for natural olivine samples and help to provide significant information on its formation process.

Secondary fluorescence effect quantification of EPMA analyses of olivine grains embedded in basaltic glass

Trace element analysis of olivine is challenging but vital, since trace elements in olivine can potentially record crystallization conditions and, correspondingly, conditions of magma generation, evolution, and transport dynamics. Electron microprobe analysis (EPMA) is one of the most widely used methods for trace element analysis in olivine for many reasons including but not limited to high-spatial resolution and high precision. EPMA protocols with high-beam currents and long-counting times provide accurate trace element concentrations with low-detection limits. However, these protocols neglect the effect of secondary fluorescence (SF) across phase boundaries, which may lead to fictitious analytical results when analyses are performed near other phases. In these cases, obtaining accurate EPMA data requires correction of SF effects from the adjacent or surrounding phase. In this study, the contents of olivine trace elements Ca, Ni, Mn, Ti, Cr, and Al have been measured in run products of experimental high-temperature studies on mafic magmatic systems consisting of olivine grains embedded in basaltic glass. Olivine grain fragments with known composition, were embedded in basaltic powder, and heated to 1250 °C in 1-atm vertical gas-mixing furnace for a few minutes and quenched. EPMA analyses of the olivine grains before and after the experiments were used to quantify the effect of SF, which was found to be most significant for Ca and Ti, and to a lesser extend for Al, and to depend on the distance from the interface, olivine grain geometry, accelerating voltage, and olivine and glass compositions. By combining our experimental results with systematic SF calculations performed with the Monte Carlo simulation program PENEPMA, analytical expressions that give the apparent Ca, Ti, and Al concentrations due to SF in equant olivine grains embedded in basaltic glass were derived. These equations, which allow for a rapid correction of SF effects, are used to assess the average overestimation due to SF of olivine analyses included in current experimental databases, which might be the source of major discrepancies observed in petrological tools utilizing trace element contents in olivine.

Seeing through metamorphic overprints in Archean granulites: Combined high-resolution thermometry and phase equilibrium modeling of the Lewisian Complex, Scotland

Abstract The Lewisian Complex in northwest Scotland presents a record of the transition from the Neo-Archean to the Paleoproterozoic. However, this record is complicated by a long and varied history after peak metamorphism that has erased and/or partially reset much of the early history of the rocks. Such overprinting is a common feature of Archean granulites and poses a substantial problem when trying to understand the tectonic processes that were active prior to the onset of modern plate tectonics. By combining careful petrography with phase diagram modeling and a range of exchange thermometers we obtain the peak and retrograde temperature history of the Lewisian Complex from a single, well-preserved, representative sample of garnet-bearing mafic granulite. We present the application of high-resolution electron probe microanalysis (HR-EPMA) to characterize sub-micrometer orthopyroxene exsolution lamellae in clinopyroxene. We discuss ways to mitigate issues associated with HR-EPMA including surface contamination, beam drift, standards, and the need to correct for secondary fluorescence effects. The resulting compositions from our HR-EPMA analyses provide an independent measure of the retrograde temperature conditions and can also be used to back-calculate the compositions of clinopyroxene in the peak assemblage. We obtain peak metamorphic conditions for the Lewisian of >11 kbar and >1025 °C, and constrain subsequent metamorphic overprints to 850 °C (Grt-Cpx), 590 °C (Opx-Cpx), and 460 °C (Mag-Ilm). These peak and retrograde temperatures span the range of those found in the literature. Whereas recent phase equilibrium studies assume equilibrium among all preserved high-T minerals, this study considers microstructural and mineral-chemical evidence for corona formation that reflects post-peak decompression with partial equilibration at ~850 °C, as recognized in some earlier studies.

Zircon survival in shallow asthenosphere and deep lithosphere

Abstract Zircon (ZrSiO4) is the most frequently used geochronometer of terrestrial and extraterrestrial processes. To shed light on question of zircon survival in the Earth's shallow asthenosphere, high-temperature experiments of zircon dissolution in natural mid-ocean ridge basaltic (MORB) and synthetic haplobasaltic melts have been performed at temperatures of 1250–1300 °C and pressures from 0.1 MPa to 0.7 GPa. Zirconium measurements were made in situ by electron probe microanalyses (EPMA) at high current. Taking into account secondary fluorescence effects in zircon-glass pairs during EPMA, a zirconium diffusion coefficient of 2.87E-08 cm2/s was determined at 1300 °C and 0.5 GPa. When applied to the question of zircon survival in asthenospheric melts of tholeiitic basalt composition, the data are used to infer that typical 100 mm zircon crystals dissolve rapidly (~10 h) and congruently upon reaction with basaltic melt at pressures of 0.2–0.7 GPa. We observed incongruent (to crystal ZrO2 and SiO2 in melt) dissolution of zircon in natural mid-ocean ridge the basaltic melt at low pressures <0.2 GPa and in the haplobasaltic melt at 0.7 GPa pressure. Our experimental data raise questions about the origin of zircon crystals in mafic and ultramafic rocks, in particular, in shallow oceanic asthenosphere and deep lithosphere, as well as the meaning of the zircon-based ages estimated from these minerals. The origin of zircon in shallow (ultra-) mafic chambers is likely related to the crystallization of intercumulus liquid. Large zircon megacrysts in kimberlites, peridotites, alkali basalts, and carbonatite magmas suggest fast transport and short interaction durations between zircon and melt. The origin of zircon megacrysts is likely related to metasomatic addition of Zr into the mantle as an episode of mantle melting should eliminate them on geologically short timescales.

Correction of Secondary Fluorescence Across Phase Boundaries in Electron Probe Microanalysis of Mineral Inclusions.

One of the limiting factors for the analysis of minor elements in multiphase materials by electron probe microanalysis is the effect of secondary fluorescence (SF), which is not accounted for by matrix corrections. Although the apparent concentration due to SF can be calculated numerically or measured experimentally, detailed investigations of this effect for fine-grained materials are scarce. In this work, we use the Monte Carlo simulation program PENEPMA to examine and correct the effect of SF affecting micron-sized mineral inclusions hosted by other minerals. A concentration profile across an olivine [(Mg,Fe)2SiO4] inclusion in chromite (Fe2+Cr2O4) is measured and used to assess the reliability of calculations, where different boundary geometries are examined. Three application examples are presented, which include the determination of Cr in olivine and serpentine [Mg3Si2O5(OH)4] inclusions hosted by chromite and of Fe in quartz (SiO2) inclusions hosted by almandine garnet (Fe3Al2Si3O12). Our results show that neglecting SF leads to concentrations that are overestimated by ~0.1–0.8 wt%, depending on inclusion size. In addition, assuming a straight boundary yields to an underestimation of SF effects by a factor of ~2–4. Because its long-range nature, SF severely compromises trace element analyses even for phases as large as 1 mm in size.

Environmental gas impact on the emission volume of X-rays near the interface in the variable pressure scanning electron microscopy

In this paper, our previously developed model to account for the secondary X-ray fluorescence and absorption effects near the interface of two adjacent materials in a high-vacuum scanning electron microscope (Zoukel & Khouchaf, 2014) is adapted and extended to experimental conditions of low-vacuum mode (in the presence of a gaseous environment in the SEM analysis chamber). The position shifting effect of the two Gaussian peaks issued from the first derivative equation that can fit the experimental low-vacuum EDS profiles is investigated. The impact of the medium gas on the emission volume of secondary X-rays near the interface is qualitatively discussed. Water vapour and helium are successively used as gas environment, in order to link the resolution of microanalysis profiles with the effects of the X-ray fluorescence and absorption phenomenon. A close agreement between Monte Carlo simulation and experimental results is found.

Diamond Anvil Cell Partitioning Experiments for Accretion and Core Formation: Testing the Limitations of Electron Microprobe Analysis.

Metal-silicate partitioning studies performed in high-pressure, laser-heated diamond anvil cells (DAC) are commonly used to explore element distribution during planetary-scale core-mantle differentiation. The small run-products contain suitable areas for analysis commonly less than tens of microns in diameter and a few microns thick. Because high spatial resolution is required, quantitative chemical analyses of the quenched phases is usually performed by electron probe microanalysis (EPMA). Here, EPMA is being used at its spatial limits, and sample thickness and secondary fluorescence effects must be accounted for. By using simulations and synthetic samples, we assess the validity of these measurements, and find that in most studies DAC sample wafers are sufficiently thick to be characterized at 15 kVacc. Fluorescence from metal-hosted elements will, however, contaminate silicate measurements, and this becomes problematic if the concentration contrast between the two phases is in excess of 100. Element partitioning experiments are potentially compromised; we recommend simulating fluorescence and applying a data correction, if required, to such DAC studies. Other spurious analyses may originate from sources external to the sample, as exemplified by 0.5 to >1 wt% of Cu arising from continuum fluorescence of the Cu TEM grid the sample is typically mounted on.

Secondary fluorescence effects in microbeam analysis and their impacts on geospeedometry and geothermometry

Characteristic and bremsstrahlung X-ray emission during electron-specimen interactions in electron microprobe (EPMA) and scanning electron microscope (SEM) instruments causes secondary fluorescence X-ray effects from adjacent (boundary) phases. This is well-known, yet the impact of such effects in microbeam analysis of natural mineral-hosted inclusions and adjacent to mineral-mineral and mineral-glass boundaries are frequently neglected, especially in geospeedometry and geothermometry applications. To demonstrate the important influence of the secondary fluorescence effect on the measured concentration of elements and its consequences for geochemical applications, we consider the effect of mineral-mineral and mineral-glass boundaries in microanalysis of Cr, Zr and Ti both experimentally, using electron probe measurements on cold-pressed material couples, and computationally, using the software suite “CalcZAF/Standard” and its Graphical User Interface (GUI) for the semi-analytical model FANAL (Llovet et al., 2012). We demonstrate, for example, that apparent Cr contents of the order of ~3000 to 5000 ppm in chromite-hosted glass inclusions at 6 μm from the inclusion boundary can be entirely due to secondary fluorescence in the Cr-rich host phase. Because the spatial gradient in secondary fluorescence-induced X-ray emission superficially resembles a diffusion profile, we emphasize the need to quantitatively correct for such effects in any geospeedometry application involving measurement of diffusion profiles adjacent to grain boundaries with large concentration contrasts. We also provide a scheme for estimating analytical errors related to the secondary fluorescence effect when applying geothermometers such as Ti-in-zircon, Ti-in-quartz (TitaniQ) and Zr-in-rutile. Temperature estimates based on trace Ti, Zr and Cr contents in minerals and glasses affected by secondary fluorescence in nearby phases (e.g., rutile, zircon and chromite) can be severely overestimated, in some cases by hundreds of degrees Celsius.

An experimental study of Fe–Ni exchange between sulfide melt and olivine at upper mantle conditions: implications for mantle sulfide compositions and phase equilibria

The behavior of nickel in the Earth’s mantle is controlled by sulfide melt–olivine reaction. Prior to this study, experiments were carried out at low pressures with narrow range of Ni/Fe in sulfide melt. As the mantle becomes more reduced with depth, experiments at comparable conditions provide an assessment of the effect of pressure at low-oxygen fugacity conditions. In this study, we constrain the Fe–Ni composition of molten sulfide in the Earth’s upper mantle via sulfide melt–olivine reaction experiments at 2 GPa, 1200 and 1400 °C, with sulfide melt \(X_{{{\text{Ni}}}}^{{{\text{Sulfide}}}}=\frac{{{\text{Ni}}}}{{{\text{Ni}}+{\text{Fe}}}}\) (atomic ratio) ranging from 0 to 0.94. To verify the approach to equilibrium and to explore the effect of \({f_{{{\text{O}}_{\text{2}}}}}\) on Fe–Ni exchange between phases, four different suites of experiments were conducted, varying in their experimental geometry and initial composition. Effects of Ni secondary fluorescence on olivine analyses were corrected using the PENELOPE algorithm (Baro et al., Nucl Instrum Methods Phys Res B 100:31–46, 1995), “zero time” experiments, and measurements before and after dissolution of surrounding sulfides. Oxygen fugacities in the experiments, estimated from the measured O contents of sulfide melts and from the compositions of coexisting olivines, were 3.0 ± 1.0 log units more reduced than the fayalite–magnetite-quartz (FMQ) buffer (suite 1, 2 and 3), and FMQ − 1 or more oxidized (suite 4). For the reduced (suites 1–3) experiments, Fe–Ni distribution coefficients \(K_{{\text{D}}}^{{}}=\frac{{(X_{{{\text{Ni}}}}^{{{\text{sulfide}}}}/X_{{{\text{Fe}}}}^{{{\text{sulfide}}}})}}{{(X_{{{\text{Ni}}}}^{{{\text{olivine}}}}/X_{{{\text{Fe}}}}^{{{\text{olivine}}}})}}\) are small, averaging 10.0 ± 5.7, with little variation as a function of total Ni content. More oxidized experiments (suite 4) give larger values of KD (21.1–25.2). Compared to previous determinations at 100 kPa, values of KD from this study are chiefly lower, in large part owing to the more reduced conditions of the experiments. The observed difference does not seem attributable to differences in temperature and pressure between experimental studies. It may be related in part to the effects of metal/sulfur ratio in sulfide melt. Application of these results to the composition of molten sulfide in peridotite indicates that compositions are intermediate in composition (\(X_{{{\text{Ni}}}}^{{{\text{sulfide}}}}\) ~ 0.4–0.6) in the shallow mantle at 50 km, becomes more Ni rich with depth as the O content of the melt diminishes, reaching a maximum (0.6–0.7) at depths near 80–120 km, and then becomes more Fe rich in the deeper mantle where conditions are more reduced, approaching (\(X_{{{\text{Ni}}}}^{{{\text{sulfide}}}}\) ~ 0.28) > 140 km depth. Because Ni-rich sulfide in the shallow upper mantle melts at lower temperature than more Fe-rich compositions, mantle sulfide is likely molten in much of the deep continental lithosphere, including regions of diamond formation.

FEG-EPMA of Solid State Redox Sensors - the Effect of Secondary Fluorescence on Analytical Precision

FEG-EPMA of Solid State Redox Sensors - the Effect of Secondary Fluorescence on Analytical Precision

Quantitative Mapping of and Secondary Fluorescence Effects in Olivine Hosted Melt Inclusions

Quantitative Mapping of and Secondary Fluorescence Effects in Olivine Hosted Melt Inclusions

On the accuracy of PLIF measurements in slender plumes

The purpose of this article was to assess the measurement uncertainty of the planar laser-induced fluorescence (PLIF) method and, as much as possible, to devise corrections for predictable biases. More specifically, we considered the measurement of concentration maps in cross sections parallel to and normal to the axis of a slender plume containing Rhodamine 6G as a passive scalar tracer and transported by a turbulent shear flow. In addition to previously examined sources of error related to PLIF, we also investigated several unexplored ones. First, we demonstrated that errors would arise if the laser sheet thickness was comparable to or larger than the thickness of the instantaneous plume. We then investigated the effect of secondary fluorescence, which was attributed to absorption and re-emission of primary fluorescence by dye both within and outside the laser sheet. We found that, if uncorrected, this effect would contaminate the calibration as well as the instantaneous concentration measurements of the plume, and proposed methods for the correction of these errors and for identifying the instantaneous boundaries of the in-sheet dye regions.

The secondary X-ray fluorescence and absorption near the interface of multi-material: Case of EDS microanalysis

A simple model is proposed to take into account secondary X-ray fluorescence and absorption effects near the interface. This model is based on the investigation of the shape change of the first derivative equation that can fit the sigmoidal EDS profile obtained when a high vacuum electron beam passes through the interface of two adjacent materials. The contribution of the photoelectric absorption of primary X-rays (characteristic and Bremsstrahlung) and the secondary fluorescence on the degradation of the X-ray spatial resolution can be easily quantified. The close agreement between the simulated (Monte Carlo simulation using the Casino software) and the experimental data serves to assess the reliability of this developed model.

Experimental study for the feasibility of using hard x-rays for micro-XRF analysis of multilayered metals

Application of polycapillary optical systems to improve a spatial resolution for the μ-XRF analysis by focusing a primary x-ray beam and/or by collecting fluorescence emission is well known. The challenge is to optimize them in combination with x-ray source for exciting K-lines above 20 keV that could allow characterization of many materials composed by heavy elements. To pursue this goal, preliminary studies on possible polycapillary lens employment in thickness determination for multilayer metal materials will be presented in this work. In this paper, the results of first attempts of integrating PyMCA with Monte Carlo simulation code (XMI-MSIM) that takes into account the secondary fluorescence effects on quantitative analysis of homogeneous matrices, in particular, metal alloys, are presented.

Metal–silicate partitioning experiments in the diamond anvil cell: A comment on potential analytical errors

We have performed simulations of the electron microbeam analysis of metal–silicate partitioning experiments in which a small (∼50μm) ball of metal is embedded in a silicate matrix. This geometry approximates that found in many high pressure diamond-cell experiments aimed at determining the partition coefficients (Di) of elements between metal and silicate. The simulations involved using the (publicly available) Monte Carlo simulation package PENEPMA which is based on the general-purpose electron–photon transport code PENELOPE. The code allows complex geometrical structures to be defined by quadric surfaces, which enclose homogeneous materials specified by the user. The package simulates both electron and photon transport, keeps track of the X-ray production mechanism and includes the continuum contribution.Our principal results came from simulating the effects of secondary fluorescence on the apparent metal–silicate partition coefficient of Ni for the case of an Ni-rich metal (26.8% Ni, 73.2% Fe) embedded in a silicate matrix. If, as is frequently the case, analysis of the silicate is performed 5–10μm from the silicate–metal interface then secondary fluorescence of Ni in the metal will increase the apparent NiO concentration in the silicate by ∼1000ppm. In the case considered, this is 25% of the Ni content of the silicate and the fluorescence effect decreases the apparent DNi from 110 to 84. For this type of experiment, therefore, the fluorescence effect reduces the apparent partition coefficient.We performed similar simulations of the analysis of the centre of a 10μm diameter metal ball embedded in the silicate matrix to determine apparent Si and O concentrations in the metal. In this case, because the electrons do not penetrate so far into the metal, the fluorescence effect is very small and can be neglected.Finally, we show that focused ion beam (FIB) sections, while providing the potential physically to separate metal from silicate present additional, but not insurmountable, problems of standardisation. The best results would be obtained with a section >3μm in thickness.We recommend that, in general, experimentalists consider simulating analysis of a typical experimental product before publication of results which may be affected by secondary fluorescence.

Targeting Ion Beam Analysis techniques for gold artefacts

The present study discusses the best experimental conditions for the quantitative analysis of gold jewellery artefacts by ion beam techniques (PIXE, RBS, PIGE and NRA). Special attention is given to the detection of enhancement or depletion below the surface, down to 10 microns, without any sampling or destruction. PIXE is certainly the most interesting technique for this purpose and the optimal geometrical arrangement of the experiment is described: orientation of the incident beam relative to sample surface, selection of the characteristic signals, use of reference material, choice of the detector and incident particle energy and type, computation of absorption and secondary fluorescence effects.

Secondary Fluorescence Enhancement in Confocal X-ray Microscopy Analysis

In the present work, the influence of the secondary fluorescence enhancement in confocal X-ray microscopy analysis is studied when stratified type of materials are examined. Through a proper mathematical formalism, an exact global theoretical model is presented which accounts for the secondary fluorescence enhancement when either particle (3D-Micro particle induced X-ray emission) or photon (3D-Micro X-ray fluorescence) microbeams are used in the excitation channel. The contribution of the secondary fluorescence effect to the confocal X-ray intensity profiles was calculated for some typical representative cases. In addition, the influence of several experimental parameters was examined in terms of their influence in the absolute intensity and shape of the secondary fluorescence intensity profile.

Numerical Calculation of Secondary Fluorescence Effects Near Phase Boundaries in EPMA

Extended abstract of a paper presented at Microscopy and Microanalysis 2008 in Albuquerque, New Mexico, USA, August 3 – August 7, 2008

Correction of secondary X-ray fluorescence near grain boundaries in electron microprobe analysis: Application to thermobarometry of spinel lherzolites

A correction procedure is proposed to account for the effect of secondary X-ray fluorescence near grain boundaries in electron microprobe analysis. The procedure is based on the Monte Carlo simulation method, which is used to calculate the X-ray spectrum emitted by the mineral couple (i.e., the mineral of interest with the neighboring mineral). The contribution of secondary fluorescence from the neighboring mineral, which appears in the simulated spectrum in a natural way, is then subtracted from the measured k-ratio and thereafter conventional matrix corrections are applied. The Monte Carlo simulation algorithm used is largely based on the general-purpose simulation package PENELOPE. In order to assess the reliability of this code, simulated “apparent” element profiles are compared with electron microprobe measurements found in the literature, in which the effect of secondary fluorescence was characterized and the reliability of the different assumptions underlying the proposed procedure is discussed.