Atom probe tomography (APT) is an analytical technique that provides quantitative three‐dimensional elemental and isotopic analyses at sub‐nanometre resolution across the whole periodic table. Although developed and mostly used in the materials science and semiconductor fields, recent years have seen increasing development and application in the geoscience and planetary science disciplines. Atom probe studies demonstrate compositional complexity at the nanoscale and provide fundamental new insights into the atom‐scale mechanisms taking place in minerals over geological time. Here, we provide an overview of APT, including the historical development and technical aspects of the instrumentation, and the fundamentals of data acquisition, data processing and data reconstruction. We also review previous studies and highlight the potential future applications of nanoscale geochemical studies of natural materials.

Since the introduction of laser-assisted atom probe, analysis of nonconductive materials by atom probe tomography (APT) has become more routine. To obtain high-quality data, a number of acquisition variables needs to be optimized for the material of interest, and for the specific question being addressed. Here, the rutile (TiO2) reference material ‘Windmill Hill Quartzite,’ used for secondary ion mass spectrometry U–Pb dating and laser-ablation inductively coupled plasma mass spectrometry, was analyzed by laser-assisted APT to constrain optimal running conditions. Changes in acquisition parameters such as laser energy and detection rate are evaluated in terms of their effect on background noise, ionization state, hit-multiplicity, and thermal tails. Higher laser energy results in the formation of more complex molecular ions and affects the ionization charge state. At lower energies, background noise and hit-multiplicity increase, but thermal tails shorten. There are also correlations between the acquisition voltage and several of these metrics, which remain to be fully understood. The results observed when varying the acquisition parameters will be discussed in detail in the context of utilizing APT analysis of rutile within geology.

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The geochemical analysis of trace elements in rutile (e.g., Pb, U, and Zr) is routinely used to extract information on the nature and timing of geological events. However, the mobility of trace elements can affect age and temperature determinations, with the controlling mechanisms for mobility still debated. To further this debate, we use laser-ablation–inductively coupled plasma–mass spectrometry and atom probe tomography to characterize the micro- to nanoscale distribution of trace elements in rutile sourced from the Capricorn orogen, Western Australia. At the >20 μm scale, there is no significant trace-element variation in single grains, and a concordant U-Pb crystallization age of 1872 ± 6 Ma (2σ) shows no evidence of isotopic disturbance. At the nanoscale, clusters as much as 20 nm in size and enriched in trace elements (Al, Cr, Pb, and V) are observed. The 207Pb/206Pb ratio of 0.176 ± 0.040 (2σ) obtained from clusters indicates that they formed after crystallization, potentially during regional metamorphism. We interpret the clusters to have formed by the entrapment of mobile trace elements in transient sites of radiation damage during upper amphibolite facies metamorphism. The entrapment would affect the activation energy for volume diffusion of elements present in the cluster. The low number and density of clusters provides constraints on the time over which clusters formed, indicating that peak metamorphic temperatures are short-lived, <10 m.y. events. Our results indicate that the use of trace elements to estimate volume diffusion in rutile is more complex than assuming a homogeneous medium.

Well-defined reconstruction parameters are essential to quantify the size, shape, and distribution of nanoscale features in atom probe tomography (APT) datasets. However, the reconstruction parameters of many minerals are difficult to estimate because intrinsic spatial markers, such as crystallographic planes, are not usually present within the datasets themselves. Using transmission and/or scanning electron microscopy imaging of needle-shaped specimens before and after atom probe analysis, we test various approaches to provide best-fit reconstruction parameters for voltage-based APT reconstructions. The results demonstrate that the length measurement of evaporated material, constrained by overlaying pre- and post-analysis images, yields more consistent reconstruction parameters than the measurement of final tip radius. Using this approach, we provide standardized parameters that may be used in APT reconstructions of 11 minerals. The adoption of standardized reconstruction parameters by the geoscience APT community will alleviate potential problems in the measurement of nanoscale features (e.g., clusters and interfaces) caused by the use of inappropriate parameters.