Nanoscale gold clusters in arsenopyrite controlled by growth rate not concentration: Evidence from atom probe microscopy

Auriferous sulfides, most notably pyrite (FeS2) and arsenopyrite (FeAsS), are among the most important economic minerals on Earth because they can host large quantities of gold in many of the world's major gold deposits. Here we present the first atom probe study of gold distribution in arsenopyrite to characterize the three-dimensional (3D) distribution of gold at the nanoscale and provide data to discriminate among competing models for gold incorporation in refractory ores. In contrast to models that link gold distribution to gold concentration, gold incorporation in arsenopyrite is shown to be controlled by the rate of crystal growth, with slow growth rate promoting the formation of gold clusters and rapid growth rate leading to homogeneous gold distribution. This study yields new information on the controls of gold distribution and incorporation in sulfides that has important implications for ore deposit formation. More broadly this study reveals new information about crystal-fluid interface dynamics that determine trace element incorporation into growing mineral phases

Atomic worlds: Current state and future of atom probe tomography in geoscience

Atom Probe Tomography (APT) is rapidly finding new applications within the geosciences. Historically connected with materials science and semiconductor device applications, recent years have seen APT established as a useful tool for nanoscale geochemistry, offering unique capabilities when compared with conventional geoanalytical techniques. The ability to characterize 3D nanoscale chemistry with isotopic sensitivity has uncovered intricate details of complex trace element distributions within a variety of minerals. Already these advances are having an impact on long-standing questions within geochronology, planetary science and other fields. Future developments are likely to bring significant expansion in this research space

Mechanisms of deformation-induced trace element migration in zircon resolved by atom probe and correlative microscopy

The widespread use of zircon in geochemical and geochronological studies of crustal rocks is underpinned by an understanding of the processes that may modify its composition. Deformation during tectonic and impact related strain is known to modify zircon trace element compositions, but the mechanisms by which this occurs remain unresolved. Here we combine electron backscatter diffraction, transmission Kikuchi diffraction and atom probe microscopy to investigate trace element migration associated with a ~20 nm wide, 2° low-angle subgrain boundary formed in zircon during a single, high-strain rate, deformation associated with a bolide impact. The low-angle boundary shows elevated concentrations of both substitutional (Y) and interstitial (Al, Mg and Be) ions. The observed compositional variations reflect a dynamic process associated with the recovery of shock-induced vacancies and dislocations into lower energy low-angle boundaries. Y segregation is linked to the migration and localisation of oxygen vacancies, whilst the interstitial ions migrate in association with dislocations. These data represent the direct nanoscale observation of geologically-instantaneous, trace element migration associated with crystal plasticity of zircon and provide a framework for further understanding mass transfer processes in zircon

Behavior of molecules and molecular ions near a field emitter

The cold emission of particles from surfaces under intense electric fields is a process which underpins a variety of applications including atom probe tomography (APT), an analytical microscopy technique with near-atomic spatial resolution. Increasingly relying on fast laser pulsing to trigger the emission, APT experiments often incorporate the detection of molecular ions emitted from the specimen, in particular from covalently or ionically bonded materials. Notably, it has been proposed that neutral molecules can also be emitted during this process. However, this remains a contentious issue. To investigate the validity of this hypothesis, a careful review of the literature is combined with the development of new methods to treat experimental APT data, the modeling of ion trajectories, and the application of density-functional theory simulations to derive molecular ion energetics. It is shown that the direct thermal emission of neutral molecules is extremely unlikely. However, neutrals can still be formed in the course of an APT experiment by dissociation of metastable molecular ions

Developing atom probe tomography of phyllosilicates in preparation for extra-terrestrial sample return

Hydrous phyllosilicate minerals, including the serpentine subgroup, are likely to be major constituents of material that will be bought back to Earth by missions to Mars and to primitive asteroids Ryugu and Bennu. Small quantities (< 60 g) of micrometre sized, internally heterogeneous material will be available for study, requiring minimally destructive techniques. Many conventional methods are unsuitable for phyllosilicates as they are typically finely crystalline and electron beam sensitive resulting in amorphisation and dehydration. New tools will be required for nanoscale characterisation of these precious extra‐terrestrial samples. Here we test the effectiveness of atom probe tomography (APT) for this purpose. Using lizardite from the Ronda peridotite, Spain, as a terrestrial analogue, we outline an effective analytical protocol to extract nanoscale chemical and structural measurements of phyllosilicates. The potential of APT is demonstrated by the unexpected finding that the Ronda lizardite contains SiO‐rich nanophases, consistent with opaline silica that formed as a by‐product of the serpentinisation of olivine. Our new APT approach unlocks previously unobservable nanominerals and nanostructures within phyllosilicates owing to resolution limitations of more established imaging techniques. APT will provide unique insights into the processes and products of water/rock interaction on Earth, Mars and primitive asteroids

Lunar samples record an impact 4.2 billion years ago that may have formed the Serenitatis Basin

Impact cratering on the Moon and the derived size-frequency distribution functions of lunar impact craters are used to determine the ages of unsampled planetary surfaces across the Solar System. Radiometric dating of lunar samples provides an absolute age baseline, however, crater-chronology functions for the Moon remain poorly constrained for ages beyond 3.9 billion years. Here we present U–Pb geochronology of phosphate minerals within shocked lunar norites of a boulder from the Apollo 17 Station 8. These minerals record an older impact event around 4.2 billion years ago, and a younger disturbance at around 0.5 billion years ago. Based on nanoscale observations using atom probe tomography, lunar cratering records, and impact simulations, we ascribe the older event to the formation of the large Serenitatis Basin and the younger possibly to that of the Dawes crater. This suggests the Serenitatis Basin formed unrelated to or in the early stages of a protracted Late Heavy Bombardment

Atom-probe tomography characterization of the oxidation of stainless steel

Three-dimensional atomic characterization of oxidation in stainless steels under simulated nuclear reactor conditions has been achieved with atom-probe tomography (APT). By combining high spatial resolution and high chemical sensitivity, the ingress of oxygen and other trace elements has been studied on an "atom-by-atom" basis, together with their interaction with microstructural defects. APT has revealed how the highly dislocated microstructure in cold-worked stainless steels accelerates the oxidation and the formation of oxide precursors beyond the oxide-metal interface. © 2010 Acta Materialia Inc