Nuclear Microprobe Analysis Research Articles

A scalable, resource-efficient process for synthesis of self-supporting germanium nanomembranes

The design of self-supporting membranes is gaining high interest in a broad range of applications, from nanodevices, optoelectronics, sensing, separation, and catalysis. In this report, we demonstrate a synthesis pathway for high quality ultrathin self-supporting germanium membranes using a highly scalable and resource-efficient process. We discuss the process flow, the compatibility between the materials and the processing chemicals, the important details for achieving the pure membranes and potential anomalies related to the etching process. Comprehensive characterization using SEM, EDX, TEM and nuclear microprobe analysis is employed for revealing the physical and structural properties of the synthesized membranes. The outcome of the fabrication process is large-area Ge nanomembranes with extremely flat and clean surfaces.

Novel Ca and Ca-Li Intercalated B/C and B/C/N Materials with Layered Structures

Abstract Boron/carbon/nitrogen (B/C/N) materials and boron/carbon (B/C) materials having graphite-like layered structures were synthesized by using a chemical vapor deposition (CVD) method. Calcium (Ca) was intercalated into the B/C materials by the reaction of Ca vapor with the host B/C film to form an intercalation compound with a second stage structure as a main product. Ca was also co-intercalated with lithium (Li) into the B/C/N materials by using a liquid-alloy method to form an intercalation compound. These are the first examples of syntheses of Ca and Ca-Li intercalated B/C and B/C/N materials. A nuclear microprobe analysis (NMA) indicated the compositions of the original host B/C/N and B/C materials to be BC2.6N0.55 and BC6.4, and the Ca-Li intercalated compound to be Ca0.67Li0.42(BC3.3N0.50) and suggested the homogeneity of these materials and the compound. We also found that the NMA is one of the most accurate methods for determining the compositions of air and water sensitive intercalation compounds as well as complex systems like B/C/N and B/C materials.

Lowering R3m Symmetry in Mg-Fe-Tourmalines: The Crystal Structures of Triclinic Schorl and Oxy-Dravite, and the Mineral luinaite-(OH) Discredited

Discreditation of the monoclinic tourmaline mineral species luinaite-(OH), ideally (Na,▯)(Fe2+,Mg)3Al6(BO3)3Si6O18(OH)4 was approved by the IMA-CNMNC (proposal 21-L) and is described. We analyzed two luinaite-(OH) samples: one from the type locality Cleveland tin mine, Luina, Waratah, Tasmania, Australia, and the other from Blue Mountain Saddle (Bald Hornet Claim), North Bend, King County, Washington, DC, USA. Biaxial (−) crystals representative of the studied samples were spectroscopically (Mössbauer, polarized Fourier transform infrared, optical absorption spectroscopy), chemically (nuclear microprobe analysis and electron microprobe analysis), and structurally characterized (single-crystal X-ray diffraction). Results show the occurrence of a triclinic structure for the studied luinaite-(OH) samples, which differs only in terms of a slight structural distortion from typical trigonal tourmaline structure (the topology of the structure is retained). As a result, following the IMA-CNMNC and tourmaline nomenclature rules, the triclinic luinaite-(OH) from the type locality (Australia) can be considered as the triclinic dimorph of schorl, as its chemical composition corresponds to schorl, and thus it should be referred as schorl-1A. Similarly, the triclinic sample from the USA can be considered as the triclinic dimorph of oxy-dravite, as its chemical composition corresponds to oxy-dravite, and then is referred to as oxy-dravite-1A.

Convergent patterns of tissue-level distribution of elements in different tropical woody nickel hyperaccumulator species from Borneo Island.

The Malaysian state of Sabah on the Island of Borneo has recently emerged as a global hotspot of nickel hyperaccumulator plants. This study focuses on the tissue-level distribution of nickel and other physiologically relevant elements in hyperaccumulator plants with distinct phylogenetical affinities. The roots, old stems, young stems and leaves of Flacourtia kinabaluensis (Salicaceae), Actephila alanbakeri (Phyllanthaceae), Psychotria sarmentosa (Rubiaceae) and young stems and leaves of Glochidion brunneum (Phyllanthaceae) were studied using nuclear microprobe (micro-PIXE and micro-BS) analysis. The tissue-level distribution of nickel found in these species has the same overall pattern as in most other hyperaccumulator plants studied previously, with substantial enrichment in the epidermal cells and in the phloem. This study also revealed enrichment of potassium in the spongy and palisade mesophyll of the studied species. Calcium, chlorine, manganese and cobalt were found to be enriched in the phloem and also concentrated in the epidermis and cortex of the studied species. Although hyperaccumulation ostensibly evolved numerous times independently, the basic mechanisms inferred from tissue elemental localization are convergent in these tropical woody species from Borneo Island.

X-ray fluorescence elemental mapping of roots, stems and leaves of the nickel hyperaccumulators Rinorea cf. bengalensis and Rinorea cf. javanica (Violaceae) from Sabah (Malaysia), Borneo

There are major knowledge gaps in understanding the translocation leading from nickel uptake in the root to accumulation in other tissues in tropical nickel hyperaccumulator plant species. This study focuses on two species, Rinorea cf. bengalensis and Rinorea cf. javanica and aims to elucidate the similarities and differences in the distribution of nickel and physiologically relevant elements (potassium, calcium, manganese and zinc) in various organs and tissues. High-resolution X-ray fluorescence microscopy (XFM) of frozen-hydrated and fresh-hydrated tissue samples and nuclear microprobe (micro-PIXE) analysis of freeze-dried samples were used to provide insights into the in situ elemental distribution in these plant species. This study has shown that the distribution pattern of nickel hyperaccumulation is typified by very high levels of accumulation in the phloem bundles of roots and stems. In the leaves, nickel is preferentially located in epidermal cell region, whereas manganese is located mainly in the lower epidermis and zinc in the upper epidermis and palisade mesophyll. The abundant formation of calcium-oxalate crystals, lining the collenchyma, is a prominent feature of both Rinorea cf. bengalensis and Rinorea cf. javanica. Future investigations on Rinorea cf. bengalensis and Rinorea cf. javanica should focus on unravelling the mechanisms of nickel uptake in the root, specifically targeting the identification of nickelspecific membrane transporters.

Overview on the intercalation of gold into graphite

The intercalation of gold into graphite has been achieved thanks to a solid-liquid method using potassium metal-based molten alloys. Numerous syntheses have been performed varying the reactive alloy composition, the reaction temperature and the reaction time. The optimization of these parameters allowed to synthesize three novel ternary graphite intercalation compounds (GIC) containing poly-layered intercalated sheets, called alpha, beta and gamma. Thanks to a specific X-Ray diffraction study, the c-axis stacking sequence of the three compounds was determined. The α-GIC, which is a metastable compound, contains mixed potassium and gold two-layered intercalated sheets. The β-GIC and γ-GIC contain very thick well ordered three-layered and five-layered sheets respectively. The very high repeat distances of the latter compounds are clearly explained by the amount of intercalated metals, precisely determined using nuclear microprobe analyses.

Late magmatic controls on the origin of schorlitic and foititic tourmalines from late-Variscan peraluminous granites of the Arbus pluton (SW Sardinia, Italy): Crystal-chemical study and petrological constraints

Tourmalines from the late-Variscan Arbus pluton (SW Sardinia) and its metamorphic aureole were structurally and chemically characterized by single-crystal X-ray diffraction, electron and nuclear microprobe analysis, Mössbauer, infrared and optical absorption spectroscopy, to elucidate their origin and relationships with the magmatic evolution during the pluton cooling stages. The Arbus pluton represents a peculiar shallow magmatic system, characterized by sekaninaite (Fe-cordierite)-bearing peraluminous granitoids, linked via AFC processes to gabbroic mantle-derived magmas. The Fe2+-Al-dominant tourmalines occur in: a) pegmatitic layers and pods, as prismatic crystals; b) greisenized rocks and spotted granophyric dikes, as clots or nests of fine-grained crystals in small miaroles locally forming orbicules; c) pegmatitic veins and pods close to the contacts within the metamorphic aureole. Structural formulae indicate that tourmaline in pegmatitic layers is schorl, whereas in greisenized rocks it ranges from schorl to fluor-schorl. Tourmalines in thermometamorphosed contact aureole are schorl, foitite and Mg-rich oxy-schorl. The main substitution is Na + Fe2+ ↔ □ + Al, which relates schorl to foitite. The homovalent substitution (OH) ↔ F at the O1 crystallographic site relates schorl to fluor-schorl, while the heterovalent substitution Fe2+ + (OH, F) ↔ Al + O relates schorl/fluor-schorl to oxy-schorl.Tourmaline crystallization in the Arbus pluton was promoted by volatile (B, F and H2O) enrichment, low oxygen fugacity and Fe2+ activity. The mineralogical evolutive trend is driven by decreasing temperature, as follows: sekaninaite + quartz → schorl + quartz → fluor-schorl + quartz → foitite + quartz. The schorl → foitite evolution represents a distinct trend towards (Al + □) increase and unit-cell volume decrease. These trends are typical of granitic magmas and consistent with Li-poor granitic melts, as supported by the absence of elbaite and other Li-minerals in the Arbus pluton. Tourmaline-bearing rocks reflect the petrogenetic significance of contribution from a metapelitic crustal component during the evolution of magmas in the middle-upper crust.

In Situ Detection and Single Cell Quantification of Metal Oxide Nanoparticles Using Nuclear Microprobe Analysis.

Micro-analytical techniques based on chemical element imaging enable the localization and quantification of chemical composition at the cellular level. They offer new possibilities for the characterization of living systems and are particularly appropriate for detecting, localizing and quantifying the presence of metal oxide nanoparticles both in biological specimens and the environment. Indeed, these techniques all meet relevant requirements in terms of (i) sensitivity (from 1 up to 10 µg.g-1 of dry mass), (ii) micrometer range spatial resolution, and (iii) multi-element detection. Given these characteristics, microbeam chemical element imaging can powerfully complement routine imaging techniques such as optical and fluorescence microscopy. This protocol describes how to perform a nuclear microprobe analysis on cultured cells (U2OS) exposed to titanium dioxide nanoparticles. Cells must grow on and be exposed directly in a specially designed sample holder used on the optical microscope and in the nuclear microprobe analysis stages. Plunge-freeze cryogenic fixation of the samples preserves both the cellular organization and the chemical element distribution. Simultaneous nuclear microprobe analysis (scanning transmission ion microscopy, Rutherford backscattering spectrometry and particle induced X-ray emission) performed on the sample provides information about the cellular density, the local distribution of the chemical elements, as well as the cellular content of nanoparticles. There is a growing need for such analytical tools within biology, especially in the emerging context of Nanotoxicology and Nanomedicine for which our comprehension of the interactions between nanoparticles and biological samples must be deepened. In particular, as nuclear microprobe analysis does not require nanoparticles to be labelled, nanoparticle abundances are quantifiable down to the individual cell level in a cell population, independently of their surface state.

Methods of local analysis for study of carbon in silicates: Nuclear microprobe analysis and secondary ion mass spectrometry

New approaches are proposed to analyze the content, distribution, and diffusion of carbon in silicates using nuclear microprobe analysis and secondary-ion mass spectrometry (SIMS). Techniques based on the nuclear reaction 12C(d,p)13C were developed to determine the coefficients of radiation-enhanced carbon diffusion in olivine at 300–370 K and deuteron doses that are comparable in terms of defect formation with those of α-particles generated by the decay of uranium and thorium isotopes for ~400 Ma (olivine age). The coefficients of thermal (Dth) and radiation-enhanced (Drad) carbon diffusion in synthetic forsterite were compared to those of natural olivines from alkaline basalt nodule (Shevaryn Tsaram volcano, Mongolia). It is demonstrated that the diffusion coefficients strongly depends on the migration mechanisms of carbon atoms in crystals. The developed techniques and software package for SIMS determination of carbon distribution in silicates allowed us to study simultaneously the carbon and hydrogen distribution in a glass vein of the Chelyabinsk meteorite. The possible presence of hydrocarbons in the studied silicate glass of meteorite is suggested.

In situ titanium dioxide nanoparticles quantitative microscopy in cells and in C. elegans using nuclear microprobe analysis

Detecting and tracking nanomaterials in biological systems is challenging and essential to understand the possible interactions with the living. In this context, in situ analyses were conducted on human skin cells and a multicellular organism (Caenorhabditiselegans) exposed to titanium dioxide nanoparticles (TiO2 NPs) using nuclear microprobe. Coupled to conventional methods, nuclear microprobe was found to be suitable for accurate description of chemical structure of biological systems and also for detection of native TiO2 NPs. The method presented herein opens the field to NPs exposure effects analyses and more generally to toxicological analyses assisted by nuclear microprobe. This method will show applications in key research areas where in situ imaging of chemical elements is essential.

Mapping ion beam induced current changes in a commercial MOSFET

We demonstrate a novel nuclear microprobe imaging and analysis modality for micrometre-scale field effect transistor devices probed with focused beams of MeV ions. By recording the drain current as a function of time during ion irradiation it is possible to identify current transients induced by the passage of single ions through the sensitive structures of the device. This modality takes advantage of the fact that the ionization produced by the passage of a single ion acts in an equivalent way to a transient change in the gate bias which therefore modulates the drain current as a function of time. This differs from the traditional ion beam induced charge technique where the ionization drifts in an internal electric field and induces a single charge pulse in an electrode applied to the device. Instead a richer variety of phenomena are observed, with different time constants which depend on the proximity of the ion strike to the channel of the device. The signals may be used to examine device function, radiation sensitivity or to count ion impacts within the channel.

Stained glasses under the nuclear microprobe: A window into history

Stained glass fragments from the 15th, 16th and 20th centuries, belonging to Mosteiro de Santa Maria da Vitória, Batalha (Portugal), were characterised non-destructively in a nuclear microprobe. The work aimed at finding the composition of the glasses and glass paintings and relating these with the corresponding production periods. The elemental compositions of the glass fragments were obtained by means of scanning micro-beam Particle Induced X-ray Emission (μ-PIXE) spectrometry in selected cross-sections. These were complemented by micro X-Ray fluorescence spectrometry. Characterisation of colour was performed by optical absorption spectroscopy in the UV–vis range, while the corrosion products were identified by optical microscopy and μ-FTIR (Fourier Transform Infra Red) spectroscopy in combination with the data generated by μ-PIXE. Nuclear microprobe analysis allowed unveiling the compositions and structures, in particular of glass paintings and corrosion products. While it is not surprising that Fe, Cu and Pb were the main elements identified in the grisaille paintings of all studied periods, as well as Ag and Cu found in the glasses decorated with yellow silver painting, their distribution gave important clues on the materials and techniques used to manufacture these stained glasses. Furthermore, it allowed establishing a definite relation between the compositions found and the periods of production, with the added bonus of correctly reassigning the manufacturing period of some samples.

The skin barrier function: a micro‐PIXE study

AbstractHuman body is perpetually subjected to environmental exposures as sun, natural, urban or industrial pollutions and societal exposures. Skin is the main physiological barrier facing to these different stresses; however its response mechanisms are still not well understood. Skin models are thus necessary to understand skin physiology and behavior in normal conditions or under stress. Because of the large natural interindividual variability and of some difficulties in obtaining human skin biopsies, we have been developing and characterizing different skin models such as reconstructed epidermis in vitro, native pigskin and human keratinocyte cells. These models allow us to study the mechanisms involved in ion homeostasis in correlation with structural organization and biological responses. In the present study, we have characterized the pig ear skin model using micro‐particle induced x‐ray emission (PIXE) analysis with the aim of evaluating the distribution of inorganic ions under normal or stress conditions together with the transepidermal penetration of external agents, such as aluminum oxides. The nuclear microprobe analysis allowed us to validate the culture conditions of the tissue and we have shown an alteration of the inorganic ion patterns after exposure to a chemical compound (sodium dodecyl sulfate) known for its deleterious effects on the barrier function. Finally, we have shown no transepidermal penetration of aluminum oxides after different exposures to cosmetic formulations. Copyright © 2009 John Wiley & Sons, Ltd.

Bioimaging of cells and tissues using accelerator-based sources

A variety of techniques exist that provide chemical information in the form of a spatially resolved image: electron microprobe analysis, nuclear microprobe analysis, synchrotron radiation microprobe analysis, secondary ion mass spectrometry, and confocal fluorescence microscopy. Linear (LINAC) and circular (synchrotrons) particle accelerators have been constructed worldwide to provide to the scientific community unprecedented analytical performances. Now, these facilities match at least one of the three analytical features required for the biological field: (1) a sufficient spatial resolution for single cell (< 1 mum) or tissue (<1 mm) analyses, (2) a temporal resolution to follow molecular dynamics, and (3) a sensitivity in the micromolar to nanomolar range, thus allowing true investigations on biological dynamics. Third-generation synchrotrons now offer the opportunity of bioanalytical measurements at nanometer resolutions with incredible sensitivity. Linear accelerators are more specialized in their physical features but may exceed synchrotron performances. All these techniques have become irreplaceable tools for developing knowledge in biology. This review highlights the pros and cons of the most popular techniques that have been implemented on accelerator-based sources to address analytical issues on biological specimens.

Cell–metal interactions: A comparison of natural uranium to other common metals in renal cells and bone osteoblasts

Uranium acute intoxication has been documented to induce nephrotoxicity. Kidneys are the main target organs after short term exposures to high concentrations of the toxic, while chronic exposures lead to its accumulation in the skeleton. In this paper, chemical toxicity of uranium is investigated for rat osteoblastic bone cells and compared to results previously obtained on renal cells. We show that bone cells are less sensitive to uranium than renal cells. The influence of the chemical form on U cytotoxicity is demonstrated. For both cell types, a comparison of uranium toxicity with other metals or metalloids toxicities (Mn, Ni, Co, Cu, Zn, Se and Cd) permits classification of Cd, Zn, Se IV and Cu as the most toxic and Ni, Se VI, Mn and U as the least toxic. Chemical toxicity of natural uranium proves to be far less than that of cadmium. To try to explain the differences in sensitivities observed between metals and different cell types, cellular accumulations in cell monolayers are quantified by inductively coupled plasma-mass spectroscopy (ICP-MS), function of time or function of dose: lethal doses which simulate acute intoxications and sub-lethal doses which are more realistic with regard to environmentally metals concentrations. In addition to being more resistant, bone cells accumulated much more uranium than did renal cells. Moreover, for both cell models, Mn, U-citrate and U-bicarbonate are strongly accumulated whereas Cu, Zn and Ni are weakly accumulated. On the other hand, a strong difference in Cd behaviour between the two cell types is shown: whereas Cd is very weakly accumulated in bone cells, it is very strongly accumulated in renal cells. Finally, elemental distribution of the toxics is determined on a cellular scale using nuclear microprobe analysis. For both renal and osteoblastic cells, uranium was accumulated in as intracellular precipitates similar to those observed previously by SEM/EDS.

Factors to consider for trace element deposition biomonitoring surveys with lichen transplants

A trace element deposition biomonitoring experiment with transplants of the fruticose lichen Evernia prunastri was developed, aimed at monitoring the effects of different exposure parameters (exposure orientation and direct rain) and to the elements Ti, V, Cr, Co, Cu, Zn, Rb, Cd, Sb and Pb. Accumulations were observed for most of the elements, confirming the ability of Evernia transplants for atmospheric metal deposition monitoring. The accumulation trends were mainly affected by the exposure orientation and slightly less so by the protection from rain. The zonation of the trace elements inside the thallus was also studied. It was concluded that trace element concentrations were not homogeneous in Evernia, thus imposing some cautions on the sampling approach. A nuclear microprobe analysis of an E. prunastri transplanted thallus in thin cross-sections concluded that the trace elements were mainly concentrated on the cortex of the thallus, except Zn, Ca and K which were also present in the internal layers. The size of the particles deposited or entrapped on the cortex surface averaged 7 microm. A list of key parameters to ensure the comparability of surveys aiming at observing temporal or spatial deposition variation is presented.

A study of transport phenomena in the corrosion products of ferrous archaeological artefacts using 18O tracing and nuclear microprobe analysis

Studies of ferrous archaeological artefacts corroded in soil are of great interest for the cultural heritage community and for the prediction of very long term corrosion behaviour of low alloy steels. One important hypothesis of recent studies is that corrosion mechanisms seem to be controlled by oxygen diffusion that is solved in the soil water and in the porosities of the corrosion products. Consequently, cathodic and anodic corrosion reactions should happen at the metal/oxide interface. In order to verify this assertion, several experiments were done using 18O tracers, to visualize where the corrosion reactions take place in the system. Samples collected on archaeological ferrous artefacts were put with their already formed corrosion products in water previously deoxygenised and equilibrated with 18O at a pressure of 1.2atm. After various exposition periods, samples were removed and transverse sections were made. The distribution of the remaining18O precipitated product in the ancient corrosion products was mapped by means of the 18O(p,α)15N reaction. Indeed, this 18O presence seems to reveal the precipitation of new oxidation products and confirm the location of the cathodic reaction at the metal/oxide interface.

High-resolution mapping of uranium and other trace elements in recrystallized aragonite–calcite speleothems from caves in the Pyrenees (France): Implication for U-series dating

Aragonite and calcite speleothems were sampled in the cave of Pierre Saint-Martin (Pyrénées-Atlantiques, France). These speleothems contain significant amounts of uranium and strontium, which were measured spatially and chemically by nuclear microprobe analysis. Sr and U distributions are highly varied, with a marked contrast between aragonite and calcite because the aragonite concentrates Sr and U. On the other hand, Zn is preferentially located in calcite and in layers of organic matter trapped in CaCO 3. Sr contents ranged from 440 to 1100 μg/g in the calcite and 4900 to 18,500 μg/g in the aragonite. U concentrations show remarkably high values from 11 to 19 μg/g in the calcite and 89 to 350 μg/g in the aragonite. These U and Sr concentrations are amongst the highest measured in supergene speleothems deposited by infiltrating meteoric waters. X-ray absorption experiments with synchrotron radiation suggested that uranium was incorporated in its hexavalent oxidation state in both aragonite and calcite. Recrystallization from aragonite into calcite was indicated by micromorphological observations for some of the samples. This recrystallization process may explain the uranium loss in neogenic calcite deposits and consequently the opening of the geochemical system, which can lead to errors in age dating with the U-series dating method. Uranium loss in recrystallized calcite is one of the important aspects to be considered in U-series dating and more generally for U geochemical stability in CaCO 3.

Morphologic characterisation and elemental distribution of Octopus vulgaris Cuvier, 1797 vestigial shell

The elemental composition of mineral structures in marine organisms can provide useful information to reconstruct environmental histories of individuals and distinguish populations or stocks. In cephalopods, as Octopus vulgaris, morpho-physiological description of vestigial shells may contribute to a better understanding of the physiology, of the process involved in the increment growth and may eventually provide important and useful tools for the validation of age determination methods. Nuclear microprobe analysis was used to map chemical elements in O. vulgaris vestigial shell. The maps contain elemental and morphological information, and enabled especially through Cl and Ca distributions to classify bands of concentric rings. The levels of P, Ca and Sr decrease from central region to external rings, while those of S and Cl showed an inverse tendency. Enhanced concentrations of Fe, Cu and Zn were found in external rings, and no significant variations were detected in the K and Br contents. The results indicate that three regions can be established on the basis of the elemental contents distributions. Specially, the P and Ca variability can distinguish rings from central and external regions. The differential incorporation of elements in the vestigial shell observed may reflect environmental and physiological factors that are affecting the life cycle of this species.

Cellular distribution of uranium after acute exposure of renal epithelial cells: SEM, TEM and nuclear microscopy analysis

The major health effect of uranium exposure has been reported to be chemical kidney toxicity, functional and histological damages being mainly observed in proximal tubule cells. Uranium enters the proximal tubule as uranyl-bicarbonate or uranyl-citrate complexes. The aim of our research is to investigate the mechanisms of uranium toxicity, intracellular accumulation and repartition after acute intoxication of rat renal proximal tubule epithelial cells, as a function of its chemical form.Microscopic observations of renal epithelial cells after acute exposure to uranyl-bicarbonate showing the presence of intracellular precipitates as thin needles of uranyl-phosphate localized in cell lysosomes have been published. However the initial site of precipitates formation has not been identified yet: they could either be formed outside the cells before internalization, or directly inside the cells.Uranium solubility as a function and initial concentration was specified by ICP-MS analysis of culture media. In parallel, uranium uptake and distribution in cell monolayers exposed to U-bicarbonate was investigated by nuclear microprobe analyses. Finally, the presence of uranium precipitates was tested out by scanning electron microscopic observations (SEM), while extracellular and/or intracellular precipitates were observed on thin sections of cells by transmission electron microscopy (TEM).