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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 ~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.

Chemical heterogeneities along grain boundaries in garnet occur across a wide range of metamorphic conditions, yet the processes underlying their development remain poorly understood. Here we integrate electron backscattered diffraction (EBSD) and atom probe tomography (APT) to evaluate the mechanisms driving nanoscale trace element mobility to deformation microstructures in a granulite-facies garnet. This approach shows that low-angle boundaries can be enriched in Ca, Ti, P, Cu, K, Na, Cl, and H. Based on the correlation between EBSD and APT data, we propose that solute ions (Ca, Ti, P, and Cu) were segregated to the interface during the migration of dislocation associated with ductile deformation of the grain. In contrast, elements such as K, Na, Cl, and H are interpreted to reflect diffusion along the low-angle boundary from an externally derived fluid source. These results provide the missing link between chemical heterogeneity and deformation-related microstructures in garnet. Our approach shows that a combination of microstructural and nanoscale geochemical analyses can provide unprecedented insights into mechanisms of element transfer within minerals.

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.

Constraining precise ages for impact events is crucial in establishing Earth’s history, and several geochronometers have been developed to date impacts. We present electron backscatter diffraction (EBSD), sensitive high-resolution ion microprobe (SHRIMP) and atom probe tomography (APT) data from shocked xenotime [(Y,HREE)PO4] collected from two impact sites to investigate the potential of xenotime as an impact geochronometer. A detrital xenotime grain from the Vredefort dome (South Africa) contains planar fractures, planar deformation bands and {112} twinning, the latter of which are diagnostic shock microstructures. However, APT analysis from the twin domains and also from the host yielded no evidence of Pb mobility at the nanometer scale during the impact. SHRIMP analysis (n=24) on the grain yielded a discordia with an upper intercept of 3136 ± 110 Ma and an imprecise lower intercept of 1793 ± 280 Ma. These correspond, respectively, to the bedrock age and a post-impact, cryptic terrane-wide fluid infiltration event. Three neoblastic grains from the Araguainha dome (Brazil) experienced partial to complete recrystallisation. The least recrystallised grain yields the oldest 238U/206Pb age of 479 ± 26 Ma, whereas a completely recrystallised neoblastic grain gave an age of 257 ± 11 Ma. APT analysis on the latter grain showed different nanoscale features that shed light on Pb mobility during shock deformation and recrystallisation. Based on observations of nanoscale Pb mobility and the correlation between recrystallisation and isotopic resetting, and prior published ages, we interpret 257 ± 11 Ma to date the impact event. These data confirm that recrystallised neoblastic xenotime is a useful impact geochronometer.

Tellurium (Te) is a critical commodity, essential for renewable energies and high-tech applications. Most Te is currently recovered from copper smelters, but rising demand requires sourcing from alternative supplies. However, the mineralogy of Te-rich ores is poorly understood and hinders their economic potential. Here, we investigate the distribution of Te in pyrite from a high-grade Au-Ag-Te epithermal-type ore to inform metallurgical extraction methods, and secure future Te supply. We identified three distinct modes of Te incorporation in this pyrite, which challenge previous solubility models. (1) Te solid-solution, at concentrations (up to 285 ppma) that significantly exceed previous solubility limits. (2) Nano-telluride inclusions along cracks that formed by intra-grain remobilization. (3) Crystal defects, enriched in Te through pipe diffusion hosting up to 0.5 at.% Te. Our results therefore provide new fundamental insights into the chemical and structural coordination of Te in pyrite, which may guide future efforts for its direct recovery.

The emplacement of large igneous provinces (LIPs) has been linked to catastrophic mass extinctions in Earth's history, but some LIPs are only associated with less severe oceanic anoxic events, and others have negligible environmental effects. Although it is widely accepted that massive magma outpouring can affect the environment through volatile degassing, it remains debated what controls the severity of environmental crises. Here, we demonstrate that the second-most-voluminous Phanerozoic LIP, the Kerguelen LIP, may have contributed to the early Aptian oceanic anoxic event 1a, a global event previously believed to have been caused by the Ontong Java LIP. Geochronological data show that the earliest eruptions of the Kerguelen LIP preceded the onset of oceanic anoxic event 1a by at least ∼5 million years. Analyses of CO

Rubble piles asteroids consist of reassembled fragments from shattered monolithic asteroids and are much more abundant than previously thought in the solar system. Although monolithic asteroids that are a kilometer in diameter have been predicted to have a lifespan of few 100 million years, it is currently not known how durable rubble pile asteroids are. Here, we show that rubble pile asteroids can survive ambient solar system bombardment processes for extremely long periods and potentially 10 times longer than their monolith counterparts. We studied three regolith dust particles recovered by the Hayabusa space probe from the rubble pile asteroid 25143 Itokawa using electron backscatter diffraction, time-of-flight secondary ion mass spectrometry, atom probe tomography, and 40 Ar/ 39 Ar dating techniques. Our results show that the particles have only been affected by shock pressure of ca. 5 to 15 GPa. Two particles have 40 Ar/ 39 Ar ages of 4,219 ± 35 and 4,149 ± 41 My and when combined with thermal and diffusion models; these results constrain the formation age of the rubble pile structure to ≥4.2 billion years ago. Such a long survival time for an asteroid is attributed to the shock-absorbent nature of rubble pile material and suggests that rubble piles are hard to destroy once they are created. Our results suggest that rubble piles are probably more abundant in the asteroid belt than previously thought and provide constrain to help develop mitigation strategies to prevent asteroid collisions with Earth.

To test the potential of deformation twins to record the age of impact events, micrometre-scale size mechanical twins in shocked monazite grains from three impact structures were analyzed by atom probe tomography (APT). Shocked monazite from Vredefort (South Africa; ∼300 km crater diameter), Araguainha (Brazil; ∼40 km diameter), and Woodleigh (Australia; 60 to 120 km diameter) were studied, all from rocks which experienced pressures of ∼30 GPa or higher, but each with a different post-impact thermal history. The Vredefort sample is a thermally recrystallised foliated felsic gneiss and the Araguainha sample is an impact melt-bearing bedrock. Both Vredefort and Araguainha samples record temperatures > 900 °C, whereas the Woodleigh sample is a paragneiss that experienced lower temperature conditions (350–500 °C). A combined 208Pb/232Th age for common {1 2 ¯ 2 ¯ } twins and shock-specific ( 1 ¯ 01) twins in Vredefort monazite was defined at 1979 ± 150 Ma, consistent with the accepted impact age of ∼2020 Ma. Irrational η1 [ 1 ¯ 1 ¯ 0] shock-specific twins in Araguainha monazite yielded a 260 ± 48 Ma age, also consistent with the accepted 250–260 Ma impact age. However, the age of a common (001) twin in Araguainha monazite is 510 ± 87 Ma, the pre-impact age of igneous crystallisation. These results are explained by the occurrence of common (001) twins in tectonic deformation settings, in contrast to the ( 1 ¯ 01) and irrational η1 [ 1 ¯ 1 ¯ 0] twins, which have only been documented in shock-deformed rocks. In Woodleigh monazite, APT age data for all monazite twins [(001), ( 1 ¯ 01), newly identified 102°/ 4 ¯ 23> twin], and host monazite are within uncertainty at 1048 ± 91 Ma, which is interpreted as a pre-impact age of regional metamorphism. We therefore are able to further constrain the poorly known age of the Woodleigh impact to

To evaluate the mechanisms driving nanoscale trace element mobility in radiation-damaged zircon, we analyzed two well-characterized Archean zircons from the Kaapvaal Craton (southern Africa): one zircon remained untreated and the other was experimentally heated in the laboratory at 1450 °C for 24 h. Atom probe tomography (APT) of the untreated zircon reveals homogeneously distributed trace elements. In contrast, APT of the experimentally heated zircon shows that Y, Mg, Al, and Pb+Yb segregate to a set of two morphologically and crystallographically distinct cluster populations that range from 5 nm tori to 25 nm toroidal polyhedra, which are confirmed to be dislocation loops by transmission electron microscopy (TEM). The dislocation loops lie in {100} and {001} planes; the edges are aligned with , , and . The largest loops (up to 25 nm diameter) are located in {100} and characterized by high concentrations of Mg and Al, which are aligned with . The 207Pb/206Pb measured from Pb atoms located within all of the loops (0.264 ± 0.025; 1σ) is consistent with present-day segregation and confirms that the dislocation loops formed during our experimental treatment. These experimentally induced loops are similar to clusters observed in zircon affected by natural geologic processes. We interpret that differences in cluster distribution, density, and composition between experimentally heated and geologically affected zircon are a function of the radiation dose, the pressure-temperature-time history, and the original composition of the zircon. These findings provide a framework for interpreting the significance of clustered trace elements and their isotopic characteristics in zircon. Our findings also suggest that the processes driving cluster formation in zircon can be replicated under laboratory conditions over human timescales, which may have practical implications for the mineralogical entrapment of significant nuclear elements.

The isotopic composition of water in Earth’s oceans is challenging to recreate using a plausible mixture of known extraterrestrial sources such as asteroids—an additional isotopically light reservoir is required. The Sun’s solar wind could provide an answer to balance Earth’s water budget. We used atom probe tomography to directly observe an average ~1 mol% enrichment in water and hydroxyls in the solar-wind-irradiated rim of an olivine grain from the S-type asteroid Itokawa. We also experimentally confirm that H+ irradiation of silicate mineral surfaces produces water molecules. These results suggest that the Itokawa regolith could contain ~20 l m−3 of solar-wind-derived water and that such water reservoirs are probably ubiquitous on airless worlds throughout our Galaxy. The production of this isotopically light water reservoir by solar wind implantation into fine-grained silicates may have been a particularly important process in the early Solar System, potentially providing a means to recreate Earth’s current water isotope ratios. Water and hydroxyl enrichment in the solar-wind-irradiated rim of an olivine grain from asteroid Itokawa suggests that its regolith could contain ~20 l m−3 of water from solar wind—a potential water source for airless planetary bodies.

Mining of “invisible gold” associated with sulfides in gold ores represents a significant proportion of gold production worldwide. Gold hosted in sulfide minerals has been proposed to be structurally bound in the crystal lattice as a sulfide-gold alloy and/or to occur as discrete metallic nanoparticles. Using a combination of microstructural quantification and nanoscale geochemical analyses on a pyrite crystal from an orogenic gold deposit, we show that dislocations hosted in a deformation low-angle boundary can be enriched in Ni, Cu, As, Pb, Sb, Bi, and Au. The cumulative trace-element enrichment in the dislocations is 3.2 at% higher compared to the bulk crystal. We propose that trace elements were segregated during the migration of the dislocation following the dislocation-impurity pair model. The gold hosted in nanoscale dislocations represents a new style of invisible gold.

Gold (Au) is largely hosted by pyrite in a variety of hydrothermal systems, but the incorporation of Au into pyrite under disequilibrium conditions remains poorly understood. We integrate synchrotron X-ray fluorescence microscopy, electron backscatter diffraction, nanoscale secondary ion mass spectrometry, and laser ablation–multicollector–inductively coupled plasma–mass spectrometry to constrain the processes that sequester Au into zoned pyrite in the hydrothermal cement of breccia ores from the world-class Daqiao orogenic Au deposit, central China. Euhedral pyrite cores with oscillatory and sector zoning, variable δ34S values, and lower Au-As contents than the mantles are attributed to crystallization during oxidation of metal-depleted ore fluids with local variation in fluid conditions. The isotopically uniform colloform mantles are formed by pyrite crystallites separated by low-angle boundaries and are characterized by unusual decoupling of Au and As. Mantle formation is attributed to rapid disequilibrium precipitation from a metal-rich FeS2-supersaturated fluid. Incorporation of Au into the pyrite mantles was facilitated by abundant lattice defects produced by rapid nucleation. Gold-As–poor pyrite rims were deposited from an evolved ore fluid or other metal-depleted fluids. These results show that chemical variations recorded by fine layering within minerals can provide valuable insights into disequilibrium mass transfer and ore formation. The decoupling between Au and As in pyrite mantles indicates that As is not always a reliable proxy for Au enrichment in rapidly crystallized porous pyrite.

Mechanical twins form by the simple shear of the crystal lattice during deformation. In order to test the potential of narrow twins in monazite to record the timing of their formation, we investigated a ca. 1700 Ma monazite grain (from the Sandmata Complex, Rajasthan, India) deformed at ca. 980 Ma, by electron backscattered diffraction (EBSD), transmission electron microscopy (TEM), and atom probe tomography (APT). APT 208Pb/232Th ages indicate that the twin was entirely reset by radiogenic Pb loss during its formation at conditions far below the monazite closure temperature. The results are consistent with a model where Pb is liberated during rupture of rare earth element–oxygen (REE-O) bonds in the large [REE]O9 polyhedra during twinning. Liberated Pb likely migrated along fast diffusion pathways such as crystal defects. The combination of a quantitative microstructural investigation and nanogeochronology provides a new approach for understanding the history of accessory phases.

Carbonaceous matter (CM) plays a critical role in the formation of sediment-hosted ore deposits, but metal partitioning between CM and associated sulfides remains unclear. Here we use synchrotron X-ray fluorescence microscopy (SXRF), laser ablation–inductively coupled plasma–mass spectrometry (LA–ICP–MS), and nanoscale secondary ion mass spectrometry (NanoSIMS) to characterize the distribution and deportment of trace elements between CM and sulfides from the Daqiao orogenic gold deposit, China. Four types of CM co-existing with different generations of sulfides are recognized: sedimentary CM1 with pyrite polyframboids in black shale host; indigenous CM2 with early- to main-ore pyrite and marcasite; CM3 with main-ore pyrite; CM4 with pyrite porphyroblasts in underlying graphitic schists. The SXRF results reveal that As, Se, Ni, Pb, and Cu are enriched in pyrite polyframboids relative to CM1 in black shales, although a small proportion of As, Pb, Bi, and U is accommodated in the latter. NanoSIMS images show that Au and As are associated with the CM1 matrix within pyrite framboids that are overgrown by recrystallized pyrite rims. Most trace elements are enriched in the newly-formed aggregates of pyrite and marcasite relative to the CM2 rims that formed via the interactions between ore fluids and pre-existing CM2 cores. Gold, As, Tl, Se, and Hg are highly enriched in the main-ore pyrite relative to co-precipitated CM3 veinlets, and this deportment might reflect changes in fluid redox conditions in response to hydraulic fracturing that is the main mechanism of gold deposition. The pyrite porphyroblasts in the schists are enriched in As, Se, Ni, and Cu relative to CM4, but have lower Au, As, Co, Ni, and Pb than sedimentary pyrite framboids. Taken together, we suggest that biological activity causes accumulation of As and Au within CM interstitial to the framboidal pyrite, and that these elements are released during metamorphic recrystallization and hydrothermal replacement. Trace element deportment in hydrothermal CM and sulfides is controlled by a variety of factors such as the fluid chemistry and interaction between indigenous CM and fluids. Our quantitative results provide significant new insights into the complex processes that formed carbonaceous sediment-hosted ore systems worldwide.

Cristobalite is a low-pressure, high-temperature SiO2 polymorph that occurs as a metastable phase in many geologic settings, including as crystals deposited from vapor within the pores of volcanic rocks. Such vapor-phase cristobalite (VPC) has been inferred to result from silica redistribution by acidic volcanic gases but a precise mechanism for its formation has not been established. We address this by investigating the composition and structure of VPC deposited on plagioclase substrates within a rhyolite lava flow, at the micrometer to nanometer scale. The VPC contains impurities of the form [AlO4/Na+]0—coupled substitution of Al3+ charge-balanced by interstitial Na+—which are typical of cristobalite. However, new electron probe microanalysis (EPMA) element maps show individual crystals to have impurity concentrations that systematically decline from crystal cores-to-rims, and atom probe tomography reveals localized segregation of impurities to dislocations. Impurity concentrations are inversely correlated with degrees of crystallinity [observed by electron backscatter diffraction (EBSD), hyperspectral cathodoluminescence, laser Raman, and transmission electron microscopy (TEM)], such that crystal cores are poorly crystalline and rims are highly ordered tetragonal α-cristobalite. The VPC-plagioclase interfaces show evidence that dissolution-reprecipitation reactions between acidic gases and plagioclase crystals yield precursory amorphous SiO2 coatings that are suitable substrates for initial deposition of impure cristobalite. Successive layers of cubic β-cristobalite are deposited with impurity concentrations that decline as Al-bearing gases rapidly become unstable in the vapor cooling within pores. Final cooling to ambient temperature causes a displacive transformation from β→α cristobalite, but with locally expanded unit cells where impurities are abundant. We interpret this mechanism of VPC deposition to be a natural proxy for dopant-modulated Chemical Vapor Deposition, where halogen-rich acidic gases uptake silica, react with plagioclase surfaces to form suitable substrates and then deposit SiO2 as impure cristobalite. Our results have implications for volcanic hazards, as it has been established that the toxicity of crystalline silica is positively correlated with its purity. Furthermore, we note that VPC commonly goes unreported, but has been observed in silicic lavas of virtually all compositions and eruptive settings. We therefore suggest that despite being metastable at Earth's surface, cristobalite may be the most widely occurring SiO2 polymorph in extrusive volcanic rocks and a useful indicator of gas-solid reaction having occurred in cooling magma bodies.

Atom probe tomography (APT) is used to quantify atomic-scale elemental and isotopic compositional variations within a very small volume of material (typically µm3). The small analytical volume ideally contains specific compositional or microstructural targets that can be placed within the context of the previously characterized surface in order to facilitate a correct interpretation of APT data. In this regard, careful targeting and preparation are paramount to ensure that the desired target, which is often smaller than 100 nm, is optimally located within the APT specimen. Needle-shaped specimens required for atom probe analysis are commonly prepared using a focused ion beam scanning electron microscope (FIB-SEM). Here, we utilize FIB-SEM-based time-of-flight secondary ion mass spectrometry (ToF-SIMS) to illustrate a novel approach to targeting

The emplacement of large igneous provinces (LIPs) has been linked to catastrophic mass extinctions in Earth’s history, but some LIPs are only associated with less severe oceanic anoxic events, and others have negligible environmental effects. Although it is widely accepted that massive magma outpouring can affect the environment through volatile degassing, it remains debated what controls the severity of environmental crises. Here, we demonstrate that the second-most-voluminous Phanerozoic LIP, the Kerguelen LIP, may have contributed to the early Aptian oceanic anoxic event 1a, a global event previously believed to have been caused by the Ontong Java LIP. Geochronological data show that the earliest eruptions of the Kerguelen LIP preceded the onset of oceanic anoxic event 1a by at least ∼5 million years. Analyses of CO 2 abundances in melt inclusions combined with Monte Carlo simulations reveal that the volume and degassing rate of CO 2 emissions from the Kerguelen LIP are an order of magnitude lower compared to LIPs that caused severe mass extinctions. We propose that the severity of volcanism-related environmental and biotic perturbations is positively correlated with the volume and rate of CO 2 emissions. Our results highlight the significant importance of reducing and slowing down CO 2 emission in preventing future disastrous environmental consequences.

A 10- to 10 000-fold enrichment is required to form economic metal deposits. Such enrichment is achieved through the accumulation of metals transported in hydrothermal fluids from their source to the deposit. The contribution of gold nanoparticle suspensions in fluids is required to form bonanza gold grades. However, as the source of gold is spatially disconnected from the deposit location, it is not known how the transport of gold nanoparticles is achieved. Here we show that metal nanoparticles (Au, AgO, AuAg Cu) are stabilised by colloidal silica in nanoparticle emulsion and transported with the aid of low-density carbonic phases. We document systematic occurrence of metals nanoparticle in five deposits that show a previously unrecognized association with amorphous silica and carbon. Our results demonstrate that stabilisation of metal nanoparticles may be achieved over kilometres through the Earth’s upper crust and offers a step change in our understanding of metalliferous deposit formation.

Glassy melt inclusions are unique geological repositories that preserve evidence of the formation and evolution of mantle and crustal-derived magmas. However, the mechanisms responsible for their preservation in slowly cooled crustal rocks remain contentious, in some part due to their small size (commonly

The geometry and composition of deformation-related low-angle boundaries in naturally deformed olivine were characterized by electron backscattered diffraction (EBSD) and atom probe tomography (APT). EBSD data show the presence of discrete low-angle tilt boundaries, which formed by subgrain rotation recrystallisation associated with the (100)[001] slip system during fluid-catalysed metamorphism and deformation. APT analyses of these interfaces show the preferential segregation of olivine-derived trace elements (Ca, Al, Ti, P, Mn, Fe, Na and Co) to the low-angle boundaries. Boundaries with 2°), the interfaces become more ordered and linear enrichment of trace elements coincides with the orientation of dislocations inferred from the EBSD data. These boundaries show a systematic increase of trace element concentration with disorientation angle. Olivine-derived trace elements segregated to the low-angle boundaries are interpreted to be captured and travel with dislocations as they migrate to the subgrain boundary interfaces. However, the presence of exotic trace elements Cl and H, also enriched in the low-angle boundaries, likely reflect the contribution of an external fluid source during the fluid-present deformation. The observed compositional segregation of trace elements has significant implications for the deformation and transformation of olivine at mantle depth, the interpretation of geophysical data and the redistribution of elements deep in the Earth. The observation that similar features are widely recognised in manufactured materials, indicates that the segregation of trace elements to mineral interfaces is likely to be widespread.

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.

Supplemental geological context, analytical methods, and supporting data.

Impact cratering on the Moon and the associated size-frequency distribution of impact craters has been used to determine the ages of the lunar and planetary surfaces across the Solar System1,2. Radiometric age-dating of lunar samples plays a critical role in this endeavour3. However, due to paucity of pristine samples and challenges associated with interpreting the isotopic data, the lunar crater-chronology function remains poorly constrained above 3.9 billion years (Gyr), and with only a handful of craters with ages < 1 Gyr4. Additionally, much of the timescale for the earliest lunar cratering history hinges on the formation age of the Serenitatis basin – a topic of vigorous debate5–9. Here we report on U-Pb isotopic data and nanoscale observation of phosphate minerals within shocked lunar norites from the Apollo 17 Station 8 boulder that record a discordant array between an older event at ~4.2 Gyr, and a younger disturbance at ~0.5 Gyr. Based on available lunar cratering records and new impact modelling, we propose that the Station 8 boulder was likely ejected when the Dawes crater, located on the southeastern rim of the Serenitatis basin, formed ~0.5 Gyr ago10. Formation of the Dawes crater excavated the highly-shocked noritic basement, which had also recorded a ~4.2 Gyr impact event – an age we ascribe to the formation of the Serenitatis basin. Implications of ancient (pre-Nectarian), ~4.2 Gyr age of the Serenitatis basin are far-reaching, challenging the paradigm of the Late Heavy Bombardment and setting important constraints on the older segment of the crater size-frequency function.

Goethite (α-FeOOH) is dispersed throughout the earth's surface, and its propensity to recrystallize in aqueous solutions determines whether this mineral is a source or sink for critical trace elements in the environment. Under reducing conditions, goethite commonly coexists with aqueous Fe(II) (Fe(II)aq), which accelerates recrystallization by coupled electron transfer and atom exchange. Quantifying the amount of the mineral phase that exchanges its structural Fe(III) atoms with Fe(II)aq is complicated by recrystallization models with untested assumptions of whether, and to what extent, the recrystallized portion of the mineral continues to interact with the solution. Here, we reacted nanoparticulate goethite with 57Fe-enriched Fe(II)aq and used atom probe tomography (APT) to resolve the three-dimensional distribution of Fe isotopes in goethite at the sub nm scale. We found that the 57Fe tracer isotope is enriched in the bulk structure (tens of nanometers deep), with some samples having 57Fe penetration throughout at a level that is similar to the isotopic composition of Fe(II)aq. This suggests that some particles undergo near-complete recrystallization. In other cases, however, the distribution of 57Fe is more heterogeneous and generally concentrates near the particle periphery. Nanoparticle encapsulation and subsequent APT can hence capture hidden recrystallization mechanisms which are critical to predicting mineral reactivity in aqueous solutions.

In our study we explore the applicability of rutile as a pathfinder for orogenic gold deposits, which are an important source of this metal worldwide. We analysed rutile associated with orogenic Au deposits from three different Precambrian terranes, the Capricorn Orogen, the Barberton Greenstone Belt and the Ashanti Belt, all of which formed under greenschist conditions and share similarities in the style of mineralisation. Microtextural evidence from scanning electron microscopy and electron back-scatter diffraction indicates that rutile formed during the main deformation and alteration stage in these rocks, and is therefore related to mineralisation. We used electron microprobe and laser ablation ICP-MS to investigate the trace element compositions of rutile and we compared our results to other gold deposits. We find that hydrothermal rutile from gold deposits contains certain trace element characteristics, in particular high Sb concentrations (up to ∼1500 ppm in Au deposits of the Capricorn Orogen), that are distinct from rutile from non-mineralised rocks of various petrogenetic origin. Other elements, such as W and Sn, are found to be more enriched in rutile from other rock types, namely felsic magmatic rocks and hydrothermal veins, and are therefore not diagnostic of Au mineralisation in this type of deposits. We also find that the presence of sub-µm-scale inclusions – in particular Zr-(Si, Th)-bearing phases, sulfide minerals and native Au – can severely affect analyses of this type of rutile and compromise the applicability of Zr-in-rutile geothermometry.

In a hypervelocity impact event, the temperatures and pressures generated by the shock waves far exceed the values produced by endogenic processes. The shock-induced processes can modify the distribution of trace elements in zircon grains located in target rocks, potentially affecting the geochemical reliability of zircon, but also providing an opportunity to better understand the mechanisms of shock deformation. The formation of reidite lamellae by the shock-induced phase change of zircon has previously been proposed to be a diffusionless, martensitic transformation, with no associated atomic mobility over nanometre length scales. However, nanoscale characterization of the zircon–reidite interface and a low-angle boundary within the reidite by atom probe tomography, transmission electron microscopy and correlative analytical techniques, shows localised enrichment of particular trace elements (Y, Al, Ca, Be, Mg, Mn, and Ti). These observations indicate the presence of additional short-range diffusional components to explain the local compositional variations observed at the nanoscale for the high-pressure transformation of zircon to reidite lamellae. A new model for this transformation is proposed that consists of two stages: 1) the early stage of the impact event where the shock waves induce defects in the zircon grain and trigger a phase transformation, resulting in trace element segregation by interface migration; and 2) the recovery stage where the trace elements and shock induced defects migrate to areas of lower energy.

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.

The West Qinling Orogen (WQO) in Central China Orogenic Belt contains numerous metasedimentary rock-hosted gold deposits (>2000 t Au), which mainly formed during two pulses: one previously recognized in the Late Triassic to Early Jurassic (T3–J1) and one only recently identified in the Late Jurassic to Early Cretaceous (J3–K1). Few studies have focused on the origin and geotectonic setting of the J3–K1 gold deposits.Textural relationships, LA-ICP-MS trace element and sulfur isotope compositions of pyrites in hydrothermally altered T3 dykes within the J3–K1 Daqiao deposit were used to constrain relative timing relationships between mineralization and pyrite growth in the dykes, and to characterize the source of ore fluid. These results are integrated with an overview of the regional geodynamic setting, to advance understanding of the tectonic driver for J3–K1 hydrothermal gold systems. Pyrite in breccia- and dyke-hosted gold ores at Daqiao have similar chemical and isotopic compositions and are considered to be representative of J3–K1 gold deposits in WQO. Co/Ni and sulfur isotope ratios suggest that ore fluids were derived from underlying Paleozoic Ni- and Se-rich carbonaceous sedimentary rocks. The geochemical data do not support the involvement of magmatic fluids. However, in the EQO (East Qinling Orogen), J3–K1 deposits are genetically related to magmatism. Gold mineralization in WQO is contemporaneous with magmatic deposits in the EQO and both are mainly controlled by NE- and EW-trending structures produced by changes in plate motion of the Paleo-Pacific plate as it was subducted beneath the Eurasian continent. We therefore infer that the J3–K1 structural regime facilitated the ascent of magma in the EQO and metamorphic fluids in the WQO with consequent differences in the character of contemporaneous ore deposits. If this is correct, then the far-field effects of subduction along the eastern margin of NE Asia extended 1000's of km into the continental interior. Keywords: Pyrite LA-ICP-MS, Sulfur isotopes, Daqiao gold deposit, West Qinling Orogen, Paleo-Pacific plate, Jurassic–Cretaceous

The Pb isotopic composition of rocks is widely used to constrain the sources and mobility of melts and hydrothermal fluids in the Earth's crust. In many cases, the Pb isotopic composition appears to represent mixing of multiple Pb reservoirs. However, the nature, scale and mechanisms responsible for isotopic mixing are not well known. Additionally, the trace element composition of sulphide minerals are routinely used in ore deposit research, mineral exploration and environmental studies, though little is known about element mobility in sulphides during metamorphism and deformation. To investigate the mechanisms of trace element mobility in a deformed Witwatersrand pyrite (FeS2), we have combined electron backscatter diffraction (EBSD) and atom probe microscopy (APM). The results indicate that the pyrite microstructural features record widely different Pb isotopic compositions, covering the entire range of previously published sulphide Pb compositions from the Witwatersrand basin. We show that entangled dislocations record enhanced Pb, Sb, Ni, Tl and Cu composition likely due to entrapment and short-circuit diffusion in dislocation cores. These dislocations preserve the Pb isotopic composition of the pyrite at the time of growth (∼3 Ga) and show that dislocation intersections, likely to be common in deforming minerals, limit trace element mobility. In contrast, Pb, As, Ni, Co, Sb and Bi decorate a high-angle grain boundary which formed soon after crystallisation by sub-grain rotation recrystallization. Pb isotopic composition within this boundary indicates the addition of externally-derived Pb and trace elements during greenschist metamorphism at ∼2 Ga. Our results show that discrete Pb reservoirs are nanometric in scale, and illustrate that grain boundaries may remain open systems for trace element mobility over 1 billion years after their formation. Keywords: Atom probe microscopy, Nanoscale, Nanogeochronology, Microstructure, Isotope geochemistry, Common Pb

Mineral-scale episodic replacement of auriferous pyrite by texturally-complex pyrite, marcasite and minor arsenopyrite occurred in breccia ores from the Daqiao epizonal orogenic gold deposit, West Qinling Orogen, China. This study uses a novel combination of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), Nanoscale secondary ion mass spectrometry (NanoSIMS), and secondary ion mass spectrometry (SIMS) to investigate the remobilization and re-concentration of gold and other trace elements during this complex replacement process and the probable mechanism. Several lines of evidence including some degree of preservation of external morphology, sharp contacts and compositional differences between the parent pyrite and product pyrite and marcasite, and reaction-induced porosity suggest that the replacement of parent pyrite proceeds via a two-step replacement via a dissolution and reprecipitation mechanism, plus an additional marcasite overgrowth. During the replacement of euhedral pyrite, depletion of gold and other trace elements (Te, Se, Zn, Co, Tl, Ni, W, and As) in porous product pyrite relative to its precursor indicate exsolution and remobilization of these metals from crystal lattice of the original pyrite. In the subsequent replacement of porous pyrite by two types of marcasite and minor arsenopyrite, euhedral product marcasite contains low contents of trace elements, possibly due to high metal solubility in the acidic fluids favorable for marcasite precipitation. The complex-zoned marcasite significantly enriched in gold and other metals relative to porous pyrite (W, Tl, As, Sb, Ag, Se, and Zn) is thought to have formed via precipitation triggered by further oxidation and/or immediate reduction in threshold supersaturation. Dissolution of the impurity-rich pyrite and precipitation of new pyrite and marcasite generations could have occurred at low pH plus high concentrations of dissolved Fe2+ condition caused by partial oxidation of aqueous H2S and/or S2− in ore fluids. The fluid oxidation is evidenced by a general decreasing trend of δ34S values from the parent euhedral pyrite, to product porous pyrite, euhedral marcasite, and complex-zoned marcasite. The isotopic results are consistent with ore fluid oxidation controlled by pressure fluctuations during multistage hydraulic fracturing in a fault-valve regime at Daqiao deposit. This quantitative study emphasizes that the pressure-driven hydrothermal process plays a key role in the micron- to nano-scale redistribution and re-enrichment of gold and other trace metals during episodic replacement of auriferous pyrite in brittle rheological zones from epizonal orogenic gold systems.