Detrital zircon in six surface samples of sandstone and contact metamorphic quartzite of the Magaliesberg and Rayton formations of the Pretoria Group (depositional age c. 2.20–2.06 Ga) show a major age fraction at 2.35–2.20 Ga, and minor early Palaeoproterozoic – Neoarchaean fractions. Trace-element concentrations vary widely, with Ti, Y and light rare earth elements (LREEs) spanning over three orders of magnitude. REE distribution patterns range from typical zircon patterns (LREE depletion, heavy REE enrichment, well-developed positive Ce and negative Eu anomalies) to patterns that are flat to concave downwards, with indistinct Ce and Eu anomalies. The change in REE pattern correlates with increases in alteration-sensitive parameters such as Ti concentration and (Dy/Sm) + (Dy/Nd), U–Pb discordance and content of common lead, and with a gradual washing-out of oscillatory zoning in cathodoluminescence images. U and Th concentrations also increase, but Th/U behaves erratically. Discordant zircon scatters along lead-loss lines to zero-age lower intercepts, suggesting that the isotopic and chemical variations are the results of disturbance long after deposition. The rocks sampled have been in a surface-near position (at least) since Late Cretaceous time, and exposed to deep weathering under intermittently hot and humid conditions. In this environment, even elements commonly considered as relatively insoluble could be mobilized locally, and taken up by radiation-damaged zircon. Such secondary alteration effects on U–Pb and trace elements can be expected in zircon in any ancient sedimentary rock that has been exposed to tropical–subtropical weathering, which needs to be considered when interpreting detrital zircon data.

The ab initio molecular dynamics (MD) simulations using an atom-centered density matrix propagation method are carried out in the first time to investigate the dissociative electron attachment (DEA) processes of adenine and its tautomer in the gas phase. Since the incoming electron are captured on the lowest π∗ anti-bond orbital, which is led to the different N–H bond, the C–H bond and the C–N bond are broken. The dominant anion observed in DEA dissociation process is the closed-shell dehydrogenated anion (Ade − H)−. The additional anions (Ade − NH2)− and (Ade − 2H)− are also obtained in ADMP simulation. The results are well consistent with the previous DEA experimental results. Thus, the ADMP method is used to gain a more intuitive and better understanding of the necessary dissociation process in the DEA experiment.

This review demonstrates that high-resolution transmission electron microscopy (HRTEM) imaging of clay minerals or phyllosilicates with an incident electron beam along the major zone axes parallel to the constituting layers, in which the contrast corresponds to individual cation columns in the images obtained, is indispensable for elucidating the enigmatic structures of these minerals. Several kinds of variables for layer stacking, including polytypes, stacking disorder and the interstratification of various kinds of unit layers or interlayer materials, are common in phyllosilicates. Local and rigorous determination of such variables is possible only with HRTEM, although examination as to whether the results obtained by the HRTEM images from limited areas represent the whole specimen should be made using other techniques, such as X-ray diffraction. Analysis of these stacking features in clay minerals provides valuable insights into their origin and/or formation processes. Recent state-of-the-art techniques in electron microscopy, including incoherent imaging, superior resolutions of ~0.1 nm and low-dose imaging using new recording media, will also contribute significantly to our understanding of the true structures of clay minerals.

The authors discuss the dipole vibrational modes that predominate in the energy-loss spectra of ionic materials below 1 eV, concentrating on thin-film specimens of typical transmission electron microscopy (TEM) thickness. The thickness dependence of the intensity is shown to be a useful guide to the bulk or surface character of vibrational peaks. The lateral and depth resolution of the energy-loss signal is investigated with the aid of finite-element calculations.

Single crystals of synthetic reidite and natural radiation-damaged zircon from Okueyama, Japan were investigated using X-ray diffraction. The pressure-induced zircon–reidite transition is described by the twisting and translations of SiO4 tetrahedra with disappearance of the SiO4–ZrO8 shared edges. The lattice of radiation-damaged zircons expands mainly from α-decays of radioactive elements such as U and Th. Although old radiation-damaged zircons show anomolous lattice distortion, young radiation-damaged zircons do not show such distortions. These distortions are caused by thermal recovery that suppresses the Si4+–Zr4+ repulsion between the SiO4 tetrahedron and ZrO8 dodecahedron. These changes in structure can be understood by considering the cation–cation repulsion between the SiO4–ZrO8 shared edges.

Most countries intend to dispose of their high-level radioactive wastes by converting them into a solidified wasteform which is to be buried within the earth. SYNROC is a titanate ceramic wasteform which has been designed for this purpose on the basis of geochemical principles. It comprises essentially rutile TiO2, ‘hollandite’ Ba(Al,Ti)Ti6O16, zirconolite CaZrTi2O7, and perovskite CaTiO3. The latter three phases have the capacity to accept the great majority of radioactive elements occurring in high-level wastes into their crystal lattice sites. These minerals (or their close relatives) also occur in nature, where they have demonstrated their capacity to survive for many millions of years in a wide range of geological environments. The properties of SYNROC and the crystal chemistry of its constituent minerals are reviewed in some detail and current formulations of SYNROC are summarized. A notable property of SYNROC it its extremely high resistance to leaching by groundwaters, particularly above 100°C. In addition, it can be shown that the capacity of SYNROC minerals to immobilize high-level waste elements is not markedly impaired by high levels of radiation damage. Current investigations are focused on developing a satisfactory production technology for SYNROC and progress towards this objective is described. The high leach resistance of SYNROC at elevated temperatures increases the range of geological environments in which the waste may be finally interred; in particular, SYNROC is well adapted for disposal in deep drill-holes, both in continental and marine environments. The fact that SYNROC is comprised of minerals which have demonstrated long-term geological stability is significant in establishing public confidence in the ability of the nuclear industry to immobilize high-level wastes for the very long periods required.

The macroscopic behaviour of minerals is not always directly related to their crystalline structure at the atomic scale but often depends explicitly on mesoscopic (nanometer–micrometer) features. This paper reviews various cases where the macroscopic phenomena differ from those of the bulk, with structural and chemical variations related to: domain walls, leading to enhanced or reduced transport properties; surfaces controlling growth morphologies; and radiation-damaged minerals where the interface between the amorphous and crystalline phase is believed to play a key role in hydrothermal leaching behaviour. Minerals explicitly discussed are: quartz, agate, hydroxylapatite, cordierite and metamict zircon.

Natural onyx agate from Mali was investigated in an integrated mineralogical and chemical study to reveal the origin of the unusual black colouration. Detailed studies by polarizing microscopy, scanning electron microscopy and micro-Raman spectroscopy showed that the colour of the dark bands is related to the incorporation of small particles of carbon (low-crystalline graphite) up to 200 nm in size into the cryptocrystalline silica matrix. The dark bands have carbon contents of 1.88 wt.%. The location of the graphite particles is closely related to the primary structural banding in the chalcedony. Cathodoluminescence data shows that the banding is interrupted by small fissures containing secondary hydrothermal quartz. The carbon isotope composition (δ13C value of –31.1±0.2‰) of the carbonaceous material points to an organic precursor. Both the direct hydrothermal formation of graphite from methane under elevated temperature and the graphitization of organic precursors by secondary hydrothermal or metamorphic overprint are possible explanations for the colour of the dark bands. The graphitization of organic precursors results in an intense electron spin resonance line at geff = 2.0026.

A detailed understanding of the response of mineral phases to the radiation fields experienced in a geological disposal facility (GDF) is currently poorly constrained. Prolongued ion irradiation has the potential to affect both the physical integrity and oxidation state of materials and therefore may alter a structure's ability to react with radionuclides. Radiohalos (spheres of radiation damage in minerals surrounding radioactive (α-emitting) inclusions) provide useful analogues for studying long term α-particle damage accumulation. In this study, silicate minerals adjacent to Th- and U-rich monazite and zircon were probed for redox changes and long/short range disorder using microfocus X-ray absorption spectroscopy (XAS) and high resolution X-ray diffraction (XRD) at Beamline I18, Diamond Light Source. Fe3+ → Fe2+ reduction has been demonstrated in an amphibole sample containing structural OH– groups – a trend not observed in anhydrous phases such as garnet. Coincident with the findings of Pattrick et al. (2013), the radiolytic breakdown of OH– groups is postulated to liberate Fe3+ reducing electrons. Across all samples, high point defect densities and minor lattice aberrations are apparent adjacent to the radioactive inclusion, demonstrated by micro-XRD.

We present an overview of the performance of the Neutralized Drift Compression Experiment-II (NDCX-II) accelerator at Berkeley Lab, and report on recent target experiments on beam-driven melting and transmission ion energy loss measurements with nanosecond and millimeter-scale ion beam pulses and thin tin foils. Bunches with around 1011 ions, 1 mm radius, and 2–30 ns full width at half maximum duration have been created with corresponding fluences in the range of 0.1–0.7 J/cm2. To achieve these short pulse durations and mm-scale focal spot radii, the 1.1 MeV [megaelectronvolt (106 eV)] He+ ion beam is neutralized in a drift compression section, which removes the space charge defocusing effect during final compression and focusing. The beam space charge and drift compression techniques resemble necessary beam conditions and manipulations in heavy ion inertial fusion accelerators. Quantitative comparison of detailed particle-in-cell simulations with the experiment plays an important role in optimizing accelerator performance.

Beam damage is a major limitation in electron microscopy that becomes increasingly severe at higher resolution. One possible route to circumvent radiation damage, which forms the basis for single-particle electron microscopy and related techniques, is to distribute the dose over many identical copies of an object. For the acquisition of low-dose data, ideally no dose should be applied to the region of interest before the acquisition of data. We present an automated approach that can collect large amounts of data efficiently by acquiring images in a user-defined area-of-interest with atomic resolution. We demonstrate that the stage mechanics of the Nion UltraSTEM, combined with an intelligent algorithm to move the sample, allow the automated acquisition of atomically resolved images from micron-sized areas of a graphene substrate. Moving the sample stage automatically in a regular pattern over the area-of-interest enables the collection of data from pristine sample regions without exposing them to the electron beam before recording an image. Therefore, it is possible to obtain data with minimal dose (no prior exposure during focusing), which is only limited by the minimum signal needed for data processing. This enables us to minimize beam-induced damage in the sample and to acquire large data sets within a reasonable amount of time.

Whole cells can be studied in their native liquid environment using electron microscopy, and unique information about the locations and stoichiometry of individual membrane proteins can be obtained from many cells thus taking cell heterogeneity into account. Of key importance for the further development of this microscopy technology is knowledge about the effect of electron beam radiation on the samples under investigation. We used environmental scanning electron microscopy (ESEM) with scanning transmission electron microscopy (STEM) detection to examine the effect of radiation for whole fixed COS7 fibroblasts in liquid. The main observation was the localization of nanoparticle labels attached to epidermal growth factor receptors (EGFRs). It was found that the relative distances between the labels remained mostly unchanged (<1.5%) for electron doses ranging from the undamaged native state at 10 e−/Å2 toward 103 e−/Å2. This dose range was sufficient to determine the EGFR locations with nanometer resolution and to distinguish between monomers and dimers. Various different forms of radiation damage became visible at higher doses, including severe dislocation, and the dissolution of labels.

Recent studies have shown that chemical immiscibility is important to achieve enhanced radiation tolerance in metallic multilayers as immiscible layer interfaces are more stable against radiation induced mixing than miscible interfaces. However, as most of these immiscible systems have incoherent interfaces, the influence of coherency on radiation resistance of immiscible systems remains poorly understood. Here, we report on radiation response of immiscible Cu/Fe multilayers, with individual layer thickness h varying from 0.75 to 100 nm, subjected to He ion irradiation. When interface is incoherent, the peak bubble density decreases with decreasing h and reaches a minimum when h is 5 nm. At even smaller h when interface is increasingly coherent, the peak bubble density increases again. However, void swelling in coherent multilayers with smaller h remains less than those in incoherent multilayers. Our study suggests that the coherent immiscible interface is also effective to alleviate radiation induced damage.

The effect of gamma radiation in vacuum on the isothermal crystallization kinetics of syndiotactic polystyrene (sPS) was investigated via differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and x-ray diffraction (XRD). Amorphous sPS samples were irradiated in vacuum, heated to 310 °C, cooled down to crystallization temperatures (Tcs) from 220 to 260 °C, and annealed for different times. Upon reheating, overlapping endothermic melting peaks depicted the various crystallization forms, α, β, and β′. The endotherms were resolved using Gaussian functions relating enthalpy changes to the endothermic envelope. Isothermal crystallization kinetic data were analyzed using Avrami's model with Gaussian functions. The extent of crystallization of β and β′ forms increased with increasing crystallization time and temperature, while that of α form decreased. Crystallization half-time followed a modified Arrhenius equation. Crystallization activation energies for the β and β′ forms of sPS increased with increasing radiation doses. The results are compared to those of air irradiated sPS reported in the literature.

Irradiation is one of the characteristic conditions that nuclear wasteforms must withstand to assure integrity during their service life. This study investigates gamma irradiation resistance of an early age slag cement-based grout, which is of interest for the nuclear industry as it is internationally used for encapsulation of low and intermediate level radioactive wastes. The slag cement-based grout withstands a gamma irradiation dose of 4.77 MGy over 256 h without reduction in its compressive strength; however, some cracking of irradiated samples was identified. The high strength retention is associated with the fact that the main hydration product forming in this binder, a calcium aluminum silicate hydrate (C–A–S–H) type gel, remains unmodified upon irradiation. Comparison with a heat-treated sample was carried out to identify potential effects of the temperature rise during irradiation exposure. The results suggested that formation of cracks is a combined effect of radiolysis and heating upon irradiation exposure.

It is demonstrated that energy-filtered transmission electron microscope enables following of in situ changes of the Ca-L2,3 edge which can originate from variations in both local symmetry and bond lengths. Low accelerating voltages of 20 and 40 kV slow down radiation damage effects and enable study of the start and finish of phase transformations. We observed electron beam-induced phase transformation of single crystalline calcite (CaCO3) to polycrystalline calcium oxide (CaO) which occurs in different stages. The coordination of Ca in calcite is close to an octahedral one streched along the <111> direction. Changes during phase transformation to an octahedral coordination of Ca in CaO go along with a bond length increase by 5 pm, where oxygen is preserved as a binding partner. Electron loss near-edge structure of the Ca-L2,3 edge show four separated peaks, which all shift toward lower energies during phase transformation at the same time the energy level splitting increases. We suggest that these changes can be mainly addressed to the change of the bond length on the order of picometers. An important pre-condition for such studies is stability of the energy drift in the range of meV over at least 1 h, which is achieved with the sub-Ångström low-voltage transmission electron microscope I prototype microscope.

Taking advantage of previous measurements by Geiger and co-workers, we discuss the possibilities and problems of measuring vibrational modes of energy loss in a transmission electron microscope fitted with a monochromator and a high-resolution energy-loss spectrometer. The tail of the zero-loss peak is seen to be a major limitation, rather than its full-width at half-maximum. Because of the low oscillator strengths and small cross-sections involved, radiation damage will limit the spatial resolution if this technique is applied to organic specimens. Delocalization of the inelastic scattering may also be a limitation, if a dipole description of the scattering process is valid.

The structure of the metal–organic framework (MOF) compound [{Ca(H2O)6}{CaGd(oxydiacetate)3}2]·4H2O was determined by single-crystal X-ray diffraction and refined using conventional single-crystal X-ray diffraction data. In addition, the structure was refined using powder diffraction data collected from two sources, a conventional X-ray diffractometer in Bragg–Brentano geometry and a 12-detector high resolution synchrotron-based diffractometer in transmission geometry. Data from the latter were processed in three different ways to account for crystalline decay or radiation damage. One dataset was obtained by averaging the multiple detector patterns, another dataset was obtained by cutting the non-overlapping portions of each detector to consider only the first few minutes of data collection and a dose-corrected dataset was obtained by fitting the independent peaks in every dataset and extrapolating the intensity and peak position to the initial time of data collection or to zero-absorbed dose. The compared structural models obtained show that special processing of powder diffraction data produced a much accurate model, close to the single-crystal-based model for this particular compound with heavy atoms in high symmetry positions that do not contribute to a significant number of diffraction intensities.

Due to α radioactive decay Pu is vulnerable to aging. The behavior of He in Pu is the foundation for understanding Pu self-radiation damage aging. Molecular dynamics technique is performed to investigate the behavior of defects, the interaction between He and defects, the processes of initial nucleation and growth of He bubble and the dependence of He bubble on the macroscopical properties of Pu. Modified embedded atom method, Morse pair potential and the Lennard-Jones pair potential are used for describing the interactions of Pu-Pu, Pu-He and He-He, respectively. The main calculated results show that He atoms can combine with vacancies to form Hevacancy cluster (i.e., the precursor of He bubble) during the process of self-radiation as a result of high binding energy of an interstitial He atom to vacancy; He bubble’s growth can be dominated by the mechanism of punching out of dislocation loop; the swelling induced by He bubble is very small; grain boundaries give rise to an energetically more favorable zone for the interstitial He atom and self-interstitial atom accumulation than for vacancy accumulation; the process of He release can be identified as the formation of release channel induced by the cracking of He bubble and surface structure.