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Highly siderophile elements (HSEs), including Re and Os, are used extensively as geochemical tracers and geochronometers to investigate the formation and evolution of Earth's crust and mantle. Mantle rocks are commonly serpentinized, but the effect of serpentinization on the distribution of HSEs is controversial because HSEs are commonly hosted by rare, micrometer to sub-micrometer-scale grains of platinum group minerals (PGMs) of ambiguous origin that are challenging to identify, characterize, and interpret. In this study, atom probe tomography (APT) is used to characterize two spatially close PGM grains hosted by a partially serpentinized harzburgite from Macquarie Island, Australia. The APT data reveal an extraordinary level of detail that provides insights into the origin of a complex Cu-Pt alloy grain (average composition similar to Cu4Pt). The grain hosts Fe-, Ni-, and Pt-rich sub-grains associated with Rh, variably overlapping networks of Pd-and Cd-enrichment, and OH-rich volumes identified as fluid inclusions. Osmium and Ru are hosted by an idioblastic laurite (RuS2) grain. Compositional, textural, and phase-diagram constraints are consistent with a modified pre-serpentinization origin for the PGMs, and a comparison between observed and calculated grain distributions indicate that while Os isotope ratios were probably unaffected by serpentinization, whole-rock and grain-scale HSE and isotopic ratios may have been decoupled during serpentinization.

The trace-element composition of rutile is commonly used to constrain P–T–t conditions for a wide range of metamorphic systems. However, recent studies have demonstrated the redistribution of trace elements in rutile via high-diffusivity pathways and dislocation-impurity associations related to the formation and evolution of microstructures. Here, we investigate trace-element migration in low-angle boundaries formed by dislocation creep in rutile within an omphacite vein of the Lago di Cignana unit (Western Alps, Italy). Zr-in-rutile thermometry and inclusions of quartz in rutile and of coesite in omphacite constrain the conditions of rutile deformation to around the prograde boundary from high pressure to ultra-high pressure (~2.7 GPa) at temperatures of 500–565°C. Crystal-plastic deformation of a large rutile grain results in low-angle boundaries that generate a total misorientation of ~25°. Dislocations constituting one of these low-angle boundaries are enriched in common and uncommon trace elements, including Fe and Ca, providing evidence for the diffusion and trapping of trace elements along the dislocation cores. The role of dislocation microstructures as fast-diffusion pathways must be evaluated when applying high-resolution analytical procedures as compositional disturbances might lead to erroneous interpretations for Ca and Fe. In contrast, our results indicate a trapping mechanism for Zr.

Effective capture of fugitive actinides and daughter radionuclides constitutes a major remediation challenge at legacy or nuclear accident sites globally. The ability of double-layered, anionic clay minerals known as hydrotalcites (HTC) to contemporaneously sequester a range of contaminants from solution offers a unique remedy. However, HTC do not provide a robust repository for actinide isolation over the long term. In this study, we formed HTC by in-situ precipitation in a barren lixiviant from a uranium mine and thermally transformed the resulting radionuclide-laden, nanoscale HTC. Atomic-scale forensic examination of the amorphized/recrystallised product reveals segregation of U to nanometre-wide mineral interfaces and the local formation of interface-hosted mineral grains. This U-phase is enriched in rare earth elements, a geochemical analogue of actinides such as Np and Pu, and represents a previously unreported radionuclide interfacial segregation. U-rich phases associated with the mineral interfaces record a U concentration factor of ~ 50,000 relative to the original solute demonstrating high extraction and concentration efficiencies. In addition, the co-existing host mineral suite of periclase, spinel-, and olivine-group minerals that equate to a lower mantle, high P–T mineral assemblage have geochemical and geotechnical properties suitable for disposal in a nuclear waste repository. Our results record the efficient sequestering of radionuclides from contaminated water and this novel, broad-spectrum, nanoscale HTC capture and concentration process constitutes a rapid solute decontamination pathway and solids containment option in perpetuity.

A potential record of Earth’s magnetic field going back 4.2 billion years (Ga) ago is carried by magnetite inclusions in zircon grains from the Jack Hills. This magnetite may be secondary in nature, however, meaning that the magnetic record is much younger than the zircon crystallization age. Here, we use atom probe tomography to show that Pb-bearing nanoclusters in magnetite-bearing Jack Hills zircons formed during two discrete events at 3.4 and <2 Ga. The older population of clusters contains no detectable Fe, whereas roughly half of the younger population of clusters is Fe bearing. This result shows that the Fe required to form secondary magnetite entered the zircon sometime after 3.4 Ga and that remobilization of Pb and Fe during an annealing event occurred more than 1 Ga after deposition of the Jack Hills sediment at 3 Ga. The ability to date Fe mobility linked to secondary magnetite formation provides new possibilities to improve our knowledge of the Archean geodynamo.

A potential record of Earth’s magnetic field going back 4.2 billion years (Ga) ago is carried by magnetite inclusions in zircon grains from the Jack Hills. This magnetite may be secondary in nature, however, meaning that the magnetic record is much younger than the zircon crystallization age. Here, we use atom probe tomography to show that Pb-bearing nanoclusters in magnetite-bearing Jack Hills zircons formed during two discrete events at 3.4 and <2 Ga. The older population of clusters contains no detectable Fe, whereas roughly half of the younger population of clusters is Fe bearing. This result shows that the Fe required to form secondary magnetite entered the zircon sometime after 3.4 Ga and that remobilization of Pb and Fe during an annealing event occurred more than 1 Ga after deposition of the Jack Hills sediment at 3 Ga. The ability to date Fe mobility linked to secondary magnetite formation provides new possibilities to improve our knowledge of the Archean geodynamo.

Diverse assemblages of metal alloys occur within ultramafic rocks from a wide range of tectonic settings and geological environments. Alloys are typically small and can be difficult to find and identify, but they can host Re and Os, which are significant for geochronology, as well as other elements of economic interest, and can act as catalysts that help to form organic compounds. The alloys typically form from elements that show chalcophile and siderophile characteristics, indicating that alloys generally form under reducing, S-poor conditions. These conditions can be generated by a range of mechanisms that differ amongst alloy-forming environments, but include desulfidation during melting, exsolution from magmatic S-bearing phases during melt crystallisation, auto-hydrothermal, and sub-solidus processes involving a reduction in fS2, and electron transfer processes related to serpentinisation. Alloy formation during serpentinisation is typically associated with the formation of a companion phase that hosts Fe3+, such as Fe3+-bearing serpentine, magnetite, ferrit-chromite, or andradite, recording disproportionation of Fe2+ released by olivine alteration to form Fe0 and Fe3+. An additional source of electrons for alloy formation is provided by the reduction of H+ in water to H2, and the reduction of water activity couples with a reduction in fS2, driving desulfidation reactions and facilitating alloy formation. Other electron donors, such as methane, may also contribute to alloy formation. Alloy-forming serpentinites are strongly internally-buffered, but can follow a range of trajectories through compositional space. Serpentinite-hosted alloys offer opportunities to better understand a range of geological processes with applications within earth and material sciences. However, these advances require new thermodynamic data and activity composition models for all but the most common alloys, and better characterisation of alloy compositions.