Panama ́ Viejo, founded in 1519 by the Spanish explorer Pedrarias Da ́vila, was the first permanent European settlement on the Pacific Ocean, and became a city, by royal decree, in 1521. Shortly after its creation, the city became an important base for trade with Spain. In 1671, the English pirate Henry Morgan waged an attack on Panama ́ Viejo, which resulted in a fire that destroyed the entire city. A new settlement built a few miles west, called Casco Antiguo or San Felipe, is now the historic district of modern Panama City. The Pb isotopic compositions of the glazes on the surface of sixteenth to seventeenth century majolica pottery sherds from Panama Viejo and Casco Antiguo (both in Panama), and Lima (Peru) were determined via non-destructive laser ablation multi-collector ICP-MS (LA-MC-ICP-MS). The contrast in Pb isotopic compositions in the glazes on ceramics recovered in different locations demonstrate that early majolica pottery production during this period used Pb obtained from the Andes. However, the Pb used in later majolica production in Panama is of Spanish origin. After Panama ́ Viejo was burned to the ground, Panamanian majolica production ended.

Martian meteorite NWA 7533 is a regolith breccia that compositionally resembles the Martian surface measured by orbiters and landers. NWA 7533 contains monzonitic clasts that have zircon with U–Pb ages of 4.428 Ga. The Pb isotopic compositions of plagioclase and alkali feldspars, as well as U–Pb isotopic compositions of chlorapatitein the monzonitic clasts of NWA 7533 have been measured by Secondary Ion Mass Spectrometry (SIMS). The U–Pb isotopic compositions measured from the chlorapatitein NWA 7533 yield an age of 1.357 ±81Ga(2σ). The least radiogenic Pb isotopic compositions measured in plagioclase and K-feldspar lie within error of the 4.428 Ga Geochron. These data indicate that the monzonitic clasts in NWA 7533 are a product of a differentiation history that includes residence in areservoir that formed prior to 4.428 Ga with a μ-value (238U/204Pb) of at least 13.4 ±1.7 (2σ)and aκ-value (232Th/238U) of ∼4.3. This μ-value is more than three times higher than any other documented Martian reservoir. These results indicate either the Martian mantle is significantly more heterogeneous than previously thought (μ-value of 1–14 vs. 1–5) and/or the monzonitic clasts formed by the melting of Martian crust with a μ-value of at least 13.4. Therefore, NWA 7533 may contain the first isotopic evidence for an enriched, differentiated crust on Mars.

The Pb isotope composition of a nuclear fallout debris particle has been directly measured in post-detonation materials produced during the Trinity nuclear test by a secondary ion mass spectrometry (SIMS) scanning ion image technique (SII). This technique permits the visual assessment of the spatial distribution of Pb and can be used to obtain full Pb isotope compositions in user-defined regions in a 70 μm × 70 μm analytical window. In conjunction with backscattered electron (BSE) and energy-dispersive spectroscopy (EDS) mapping of the same particle, the Pb measured in this fallout particle cannot be from a major phase in the precursor arkosic sand. Similarly, the Pb isotope composition of the particle is resolvable from the surrounding glass at the 2σ uncertainty level (where σ represents the standard deviation). The Pb isotope composition measured in the particle here is in excellent agreement with that inferred from measurements of green and red trinitite, suggesting that these types of particles are responsible for the Pb isotope compositions measured in both trinitite glasses. 

Five Hadean (> 4 Ga) aged zircon grains from the Jack Hills metasedimentary belt have been investigated by a secondary ion mass spectrometry scanning ion image technique. This technique has the ability to obtain accurate and precise full U-Pb systematics on a scale < 5 μm, as well as document the spatial distribution of U, Th and Pb. All five of the grains investigated here have complex cathodoluminescence patterns that correlate to different U, Th, and Pb concentration domains. The age determinations for these different chemical zones indicate multiple reworking events that are preserved in each grain and have affected the primary crystalized zircon on the scale of < 10 μm, smaller than conventional ion microprobe spot analyses. In comparison to the spot analyses performed on these grains, these new scanning ion images and age determinations indicate that almost half of the spot analyses have intersected several age and chemical domains in both fractured and unfractured parts of the individual crystals. Some of these unfractured, mixed domain spot analyses have concordant ages that are inaccurate. Thus, if the frequency of spot analyses intersecting mixed domains here is even close to representative of all other studies of the Jack Hills zircon population, it makes the interpretation of any trace element, Hf, or O isotopic data present in the literature tenuous. Lastly, all of the grains analysed here preserve at least two distinguishable 207Pb/206Pb ages. These ages are preserved in core-rim and/or complex internal textural relationships in unfractured domains. These secondary events took place at ca. 4.3, 4.2, 4.1, 4.0, 3.7, and 2.9 Ga, which are coincident with previously determined statistically robust age peaks present in this zircon population.

The initial Pb compositions of one enriched shergottite, one intermediate shergottite, two depleted shergottites, and Nakhla have been measured by Secondary Ion Mass Spectrometry (SIMS). These values, in addition to data from previous studies using an identical analytical method performed on three enriched shergottites, ALH 84001, and Chassigny, are used to construct a unified and internally consistent model for the differentiation history of the Martian mantle and crystallization ages for Martian meteorites. The differentiation history of the shergottites and Nakhla/Chassigny are fundamentally different, which is in agreement with short-lived radiogenic isotope systematics. The initial Pb compositions of Nakhla/Chassigny are best explained by the late addition of a Pb-enriched component with a primitive, non-radiogenic composition. In contrast, the Pb isotopic compositions of the shergottite group indicate a relatively simple evolutionary history of the Martian mantle that can be modeled based on recent results from the Sm–Nd system. The shergottites have been linked to a single mantle differentiation event at 4504 Ma. Thus, the shergottite Pb isotopic model here reflects a two-stage history 1) pre-silicate differentiation (4504 Ma) and 2) post-silicate differentiation to the age of eruption (as determined by concordant radiogenic isochron ages). The μ-values (238U/204Pb) obtained for these two different stages of Pb growth are μ1 of 1.8 and a range of μ2 from 1.4–4.7, respectively. The μ1-value of 1.8 is in broad agreement with enstatite and ordinary chondrites and that proposed for proto Earth, suggesting this is the initial μ-value for inner Solar System bodies. When plotted against other source radiogenic isotopic variables (Sri, γ187Os, ε143Nd, and ε176Hf), the second stage mantle evolution range in observed mantle μ-values display excellent linear correlations (r2 > 0.85) and represent a spectrum of Martian mantle mixing-end members (depleted, intermediate, enriched).

The full U-Pb isotopic systematics in a complex lunar zircon ‘Pomegranate’ from lunar impact breccia 73235 have been investigated by the development of a novel Secondary Ion Mass Spectrometry (SIMS) scanning ion imaging (SII) technique. This technique offers at least a four-fold increase in analytical spatial resolution over traditional SIMS analyses in zircon. Results from this study confirm the hypothesis that the Pomegranate zircon crystallized at 4.302 ± 0.013 Ga and experienced an impact that formed, U-enriched zircon around primary zircon cores at 4.184 ± 0.007 Ga (2σ, all uncertainties). The increase in spatial resolution offered by this technique has facilitated targeting of primary zircon that was previously inaccessible to conventional spot analyses. This approach has yielded results indicating that individual grains with a diffusive distance of less than ~4 μm have been reset to the young impact age, while individual grains with a diffusive distance larger than ~6 μm have retained the old crystallization age. Assuming a broad range in cooling rate of 0.5–50 °C/year, which has been observed in a suite of similar lunar breccias, a maximum localized temperature generated by the impact that reset small prima- ry zircon and created new, high-U zircon is estimated to be between 1100 and 1280 °C.

The Cl isotopic compositions and halogen (Cl, F, Br, and I) abundances in phosphates from eight Martian meteorites, spanning most rock types and ages currently available, have been measured in situ by Secondary Ion Mass Spectrometry (SIMS). Likewise, the distribution of halogens has been documented by x-ray mapping. Halogen concentrations range over several orders of magnitude up to some of the largest concentrations yet measured in Martian samples or on the Martian surface, and the inter-element ratios are highly variable. Similarly, Cl isotope compositions exhibit a larger range than all pristine terrestrial igneous rocks. Phosphates in ancient (>4 Ga) meteorites (orthopyroxenite ALH 84001 and breccia NWA 7533) have positive d³⁷Cl anomalies (+1.1 to +2.5 ‰).  These samples also exhibit explicit whole rock and grain scale evidence for hydrothermal or aqueous activity. In contrast, the phosphates in the younger basaltic Shergottite meteorites (<600 Ma) have negative d³⁷Cl anomalies (-0.2 to -5.6 ‰).  Phosphates with the largest negative d³⁷Cl anomalies display zonation where the rims of the grains are enriched in all halogens and have significantly more negative d³⁷Cl anomalies indicating interaction with the surface of Mars during the latest stages of basalt crystallization. The phosphates with no textural, major element, or halogen enrichment evidence for mixing with this surface reservoir have an average d³⁷Cl of -0.6 ‰, which suggests a similar Cl isotope composition between Mars, the Earth, and the Moon. The only process known to fractionate Cl isotopes, both positively and negatively, is formation of perchlorate, which has been detected in weight percent concentrations on the Martian surface. The age range and obvious mixing history of the phosphates studied here suggest perchlorate formation and halogen cycling via brines, which have also been observed on the Martian surface, has been active throughout Martian history. 

The formation of a primordial crust is a critical step in the evolution of terrestrial planets but the timing of this process is poorly understood. The mineral zircon is a powerful tool for constraining crust formation because it can be accurately dated with the uranium-to-lead (U–Pb) isotopic decay system and is resistant to subsequent alteration. Moreover, given the high concentration of hafnium in zircon, the lutetium-to-hafnium (176Lu–176Hf) isotopic decay system can be used to determine the nature and formation timescale of its source reservoir (1,2,3) Ancient igneous zircons with crystallization ages of around 4,430 million years (Myr) have been reported in Martian meteorites that are believed to represent regolith breccias from the southern highlands of Mars (4,5) These zircons are present in evolved lithologies interpreted to reflect re-melted primary Martian crust4, thereby potentially providing insight into early crustal evolution on Mars. Here, we report concomitant high-precision U–Pb ages and Hf-isotope compositions of ancient zircons from the NWA 7034 Martian regolith breccia. Seven zircons with mostly concordant U–Pb ages define 207Pb/206Pb dates ranging from 4,476.3 ± 0.9 Myr ago to 4,429.7 ± 1.0 Myr ago, including the oldest directly dated material from Mars. All zircons record unradiogenic initial Hf-isotope compositions inherited from an enriched, andesitic-like crust extracted from a primitive mantle no later than 4,547 Myr ago. Thus, a primordial crust existed on Mars by this time and survived for around 100 Myr before it was reworked, possibly by impacts (4,5) to produce magmas from which the zircons crystallized. Given that formation of a stable primordial crust is the end product of planetary differentiation, our data require that the accretion, core formation and magma ocean crystallization on Mars were completed less than 20 Myr after the formation of the Solar System. These timescales support models that suggest extremely rapid magma ocean crystallization leading to a gravitationally unstable stratified mantle, which subsequently overturns, resulting in decompression melting of rising cumulates and production of a primordial basaltic to andesitic crust (6,7).

Hadean (≥4.0 Ga) zircon grains provide the only direct record of the first half-billion years of Earth’s history. Determining accurate and precise crystallization ages of these ancient zircons is a prerequisite for any interpretation of crustal evolution, surface environment, and geodynamics on the early Earth, but this may be compromised by mobilization of radiogenic Pb due to subsequent thermal overprinting. Here we report a detrital zircon from the Jack Hills (Western Australia) with 4486–4425 Ma concordant ion microprobe ages that yield a concordia age of 4463 ± 17 Ma (2σ), the oldest zircon age recorded from Earth. However, scanning ion imaging reveals that this >4.4 Ga apparent age resulted from incorporation of micrometer-scale patches of unsupported radiogenic Pb with extremely high ²⁰⁷Pb/²⁰⁶Pb ratios and >4.5 Ga ²⁰⁷Pb/²⁰⁶Pb ages. Isotopic modeling demonstrates that these patches likely resulted from redistribution of radiogenic Pb in a ca. 4.3 Ga zircon during a ca. 3.8 Ga or older event. This highlights that even a concordia age can be spurious and should be carefully evaluated before being interpreted as the crystallization age of ancient zircon.

Northwest Africa 7533, a polymict Martian breccia, consists of fine-grained clast- laden melt particles and microcrystalline matrix. While both melt and matrix contain medium-grained noritic-monzonitic material and crystal clasts, the matrix also contains lithic clasts with zoned pigeonite and augite plus two feldspars, microbasaltic clasts, vitrophyric and microcrystalline spherules, and shards. The clast-laden melt rocks contain clump-like aggregates of orthopyroxene surrounded by aureoles of plagioclase. Some shards of vesicular melt rocks resemble the pyroxene-plagioclase clump-aureole structures. Submicron size matrix grains show some triple junctions, but most are irregular with high intergranular porosity. The noritic-monzonitic rocks contain exsolved pyroxenes and perthitic intergrowths, and cooled more slowly than rocks with zoned-pyroxene or fine grain size. Noritic material contains orthopyroxene or inverted pigeonite, augite, calcic to intermediate plagioclase, and chromite to Cr-bearing magnetite; monzonitic clasts contain augite, sodic plagioclase, K feldspar, Ti-bearing magnetite, ilmenite, chlorapatite, and zircon. These feldspathic rocks show similarities to some rocks at Gale Crater like Black Trout, Mara, and Jake M. The most magnesian orthopyroxene clasts are close to ALH 84001 orthopyroxene in composition. All these materials are enriched in siderophile elements, indicating impact melting and incorporation of a projectile component, except for Ni-poor pyroxene clasts which are from pristine rocks. Clast-laden melt rocks, spherules, shards, and siderophile element contents indicate formation of NWA 7533 as a regolith breccia. The zircons, mainly derived from monzonitic (melt) rocks, crystallized at 4.43 ` 0.03 Ga (Humayun et al. 2013) and a 147Sm-143Nd isochron for NWA 7034 yielding 4.42 ` 0.07 Ga (Nyquist et al. 2016) defines the crystallization age of all its igneous portions. The zircon from the monzonitic rocks has a higher D17O than other Martian meteorites explained in part by assimilation of regolith materials enriched during surface alteration (Nemchin et al. 2014). This record of protolith interaction with atmosphere- hydrosphere during regolith formation before melting demonstrates a thin atmosphere, a wet early surface environment on Mars, and an evolved crust likely to have contaminated younger extrusive rocks. The latest events recorded when the breccia was on Mars are resetting of apatite, much feldspar and some zircons at 1.35–1.4 Ga (Bellucci et al. 2015), and formation of Ni-bearing pyrite veins during or shortly after this disturbance (Lorand et al. 2015).

Despite the wide utility of apatite, Ca5(PO4)3(F,Cl,OH), in the geosciences, including tracing volatile abundances on the Moon and Mars, little is known about how the mineral responds to the extreme temperatures and pressures associated with hypervelocity impacts. To address this deficiency, we here present the first microstructural analysis and chemical mapping of shocked apatite from a terrestrial impact crater. Apatite grains from the Paasselkä impact structure, Finland, display intragrain crystal-plastic deformation as well as pervasive recrystallization—the first such report in terrestrial apatite. A partially recrystallized grain offers the opportunity to investigate the effect of shock recrystallization on the chemical composition of apatite. The recrystallized portion of the fluorapatite grain is depleted in Mg and Fe relative to the remnant non-recrystallized domain. Strikingly, the recrystallized region alone hosts inclusions of (Mg,Fe)2(PO4)F, wagnerite or a polymorph thereof. These are interpreted to be a product of phase separation during recrystallization and to be related to the reduced abundances of certain elements in the recrystallized domain. The shock-induced recrystallization of apatite, which we show to be related to changes in the mineral’s chemical composition, is not always readily visible in traditional imaging techniques (such as backscattered electron imaging of polished interior surfaces), thus highlighting the need for correlated microstructural, chemical, and isotopic studies of phosphates. This is particularly relevant for extraterrestrial phosphates that may have been exposed to impacts, and we urge the consideration of microstructural data in the interpretation of the primary or secondary nature of elemental abundances and isotopic compositions.

We report a new age for the Sääksjärvi impact structure, Finland, a 6 km diameter feature that formed in crystalline rocks of the Precambrian Baltic Shield. Two previous studies reported 40Ar/39Ar data for Sääksjärvi and suggested conflicting formation ages of ≤330 Ma or c. 560 Ma. The former age represents a possible complication for models which indicate that the region was covered by sediments of the Caledonian foreland basin throughout much of the Phanerozoic. We conducted a study combining imaging, microstructural analysis and U–Pb dating of shocked zircon from Sääksjärvi. The U–Pb dataset indicates a c. 600 Ma impact into predominantly c. 1850 Ma target rocks. A concordia age of 608 ± 8 Ma (2σ) confirms Sääksjärvi as the first known Ediacaran impact structure in the Baltic Shield and only the second worldwide. Our data indicate that the Sääksjärvi impact structure formed in exposed crystalline basement rocks of the Baltic Shield prior to the development of the Caledonian foreland basin. Given that most impact structures on Earth are relatively small features, radiometric dating of small impact structures in crystalline basement may place boundaries on the timing and spatial extent of palaeobasins that might otherwise be difficult to constrain.

The U-Th-Pb isotopic data from detrital zircon grains from five samples of Archean quartzite from the Mt. Alfred area of the Illaara greenstone belt in the Yilgarn Craton of Western Australia are presented in this study. The zircon grains are typically fractured and contain both irregular and oscillatory zoned internal structures as revealed by cathodoluminescence imaging. Concordant 207Pb/206Pb ages range between 3109 ± 17 and 3918 ± 16 Ma (2σ), with three main age peaks at ca. 3640, 3690 and 3760 Ma. Older 207Pb/206Pb ages up to 4067 ± 5 Ma are strongly affected by at least one recent disturbance event, however one single-grain discordia yields an upper intercept age of 4107 ± 12 (MSWD = 1.2). A further sixteen zircon grains with multiple analyses define discordia that suggest U-Pb disturbance events in the Neoarchean and the Mesozoic, the latter as a result of invasive low temperature weathering solutions. The notable lack of grains with ages less than ∼3.6 Ga in the Mt. Alfred detrital zircon population differentiates it from other quartzite samples from both the Illaara Formation and the Eoarchean zircon-bearing metasedimentary rocks of the Narryer Terrane. Also, the limited spread of zircon ages between 3640 and 3760 Ma suggests a relatively uniform and possibly local source region. However, no rocks of this age have been found in the Youanmi Terrane. This implies either the distal transport of similarly aged clastic sediments at 3.1 Ga from the Narryer Gneiss Complex (NGC) to the Mt. Alfred area, or the previous existence of NGC-like rocks near the Illaara greenstone belt that are either not currently recognised or have since been destroyed.

Pb-Pb isochron ages of ca. 3.92 Ga for three K-feldspar-rich clasts from Apollo 14 breccias 14303 and 14083 were determinedusing Secondary Ion Mass Spectrometry (SIMS). These ages are interpreted to represent the resetting of the U-Pb systemin the clasts as a result of brecciation during the Imbrium impact. One of the clasts contains zircon grains that record asignificantly older crystallization age (ca. 4.33–4.35 Ga) for the rock represented by that clast. Initial Pb compositions determinedfor the clasts, combined with the previously measured Pb isotopic compositions of K-feldspar grains from severalApollo 14 breccia samples, constrain a range of initial Pb compositions in the ca. 3.9 Ga Fra Mauro formation at the Apollo14 landing site. This range in initial Pb compositions indicates that the rocks represented by these clasts, or the sources ofthose rocks, evolved with a high ²³⁸U/²⁰⁴Pb (µ-value) for substantial periods of time, although the precise crystallization agesof the rocks represented by at least two of the clasts investigated here are unknown.

In this contribution we describe the influx of non-formula elements (Fe, Ca, Al, Y, U and Th) into fractures and selected zone lamellae in zircons from Jack Hills during recent weathering and discuss the effects of this on overlapping SIMS U-Th-Pb and oxygen isotope analyses. Previous research has recognised the importance of fractures in the generation of anomalous U-Th-Pb and oxygen isotope systems. In this report we show that besides fractures specific zones in euhedrally zoned zircon can act as pathways for the influx of weathering solutions and contain a similar range of trace element materials as do the fractures. Whereas zero-age discordant U-Pb systems of Jack Hills zircons have been explained by many authors in terms of Pb loss, present results confirm conclusions of our previous study that the main discordance mechanism of Jack Hills zircons is U-Th gain, due to overlap of SIMS analyses with mineralized fractures and zone lamellae with excess weathering-fluid-deposited U and Th. We explain the anomalously light and heavy oxygen isotopes and significant OH in SIMS analyses that overlap fractures and mineralized zones as due to the presence in the fractures of Ca, Fe, Al oxides and hydroxides with complexly fractionated oxygen isotopic systems. There is a suggestion in some of the elemental maps that there has been minor dispersion of trace elements away from fractures. But SIMS U-Th-Pb and oxygen isotope analyses on parts of the zircon away from fractures and mineralized zones show no evidence of interaction with weathering-fluid, indicating that penetration of weathering fluids into the body of the zircon at the location of the SIMS spots has not occurred. Results of this study have implications for other SIMS U-Th-Pb and oxygen isotope studies of zircons from rocks that have been subjected to weathering and also for early TIMS U-Pb measurements of bulk zircon samples that show zero Ma U-Pb discordance.

Lunar meteorites provide a potential opportunity to expand the study of ancient (>4000 Ma) basaltic volcanism on the Moon, of which there are only a few examples in the Apollo sample collection. Secondary Ion Mass Spectrometry (SIMS) was used to determine the Pb isotopic compositions of multiple mineral phases (Ca-phosphates, baddeleyite K-feldspar, K-rich glass and plagioclase) in two lunar meteorites, Miller Range (MIL) 13317 and Kalahari (Kal) 009. These data were used to calculate crystallisation ages of 4332 ± 2 Ma (95% confidence level) for basaltic clasts in MIL 13317, and 4369 ± 7 Ma (95% confidence level) for the monomict basaltic breccia Kal 009. From the analyses of the MIL 13317 basaltic clasts, it was possible to determine an initial Pb isotopic composition of the protolith from which the clasts originated, and infer a 238 U/204 Pb ratio (μ-value) of 850 ± 130 (2σ uncertainty) for the magmatic source of this basalt. This is lower than μ-values determined previously for KREEP-rich (an acronym for K, Rare Earth Elements and P) basalts, although analyses of other lithological components in the meteorite suggest the presence of a KREEP component in the regolith from which the breccia was formed and, therefore, a more probable origin for the meteorite on the lunar nearside. It was not possible to determine a similar initial Pb isotopic composition from the Kal 009 data, but previous studies of the meteorite have highlighted the very low concentrations of incompatible trace elements and proposed an origin on the farside of the Moon. Taken together, the data from these two meteorites provide more compelling evidence for widespread ancient volcanism on the Moon. Furthermore, the compositional differences between the basaltic materials in the meteorites provide evidence that this volcanism was not an isolated or localised occurrence, but happened in multiple locations on the Moon and at distinct times. In light of previous studies into early lunar magmatic evolution, these data also imply that basaltic volcanism commenced almost immediately after Lunar Magma Ocean (LMO) crystallisation, as defined by Nd, Hf and Pb model ages at about 4370 Ma.

The basaltic suites collected at the Apollo 12 landing site have been interpreted as representing a stratigraphic sequence of volcanic flows emplaced in the Oceanus Procellarum region between approximately 3100–3300 Ma. This study presents Secondary Ion Mass Spectrometry (SIMS) Pb isotopic analyses of samples from each of the basaltic suites, which have been used to constrain precise crystallisation ages and initial Pb isotopic composi- tions. The new crystallisation ages are consistent with the three main basaltic suites (olivine, pigeonite and ilmenite) being emplaced over a period of approximately 60 million years, and the improved precision of these ages has made it possible to reinterpret the stratigraphic sequence of basalt flows underlying the Apollo 12 landing site. Contrary to previous studies, the three ilmenite basalts are determined as having the oldest ages (with a weighted average of 3187 ± 6 Ma; 2σ) and are, therefore, interpreted as representing the lowest unit in the sequence, underlying the olivine and pigeonite basalts (with an age range constrained by the oldest and youngest pigeonite basalts; 3176 ± 6 Ma and 3129 ± 10 Ma; 2σ). The initial Pb isotopic compositions have been compared with recalculated initial Sr and Nd isotopic compositions, and are consistent with the three main basaltic suites originating from magmatic sources that incorporated different proportions of a common primitive mafic cumulate and the residual trapped liquid fraction remaining after a majority of the lunar magma ocean had crystallised. Our data also demonstrate that the feldspathic basalt (12038) is unique, both in terms of its crys- tallisation age (3242 ± 13 Ma) and its derivation from a distinct mantle reservoir.

Recent in situ Secondary Ion Mass Spectrometry (SIMS) Pb isotope analyses of lunar basalts have provided precise crystallisation ages and initial Pb isotopic compositions for these samples. In this study, the same approach has been tested in the Apollo 16 impact melt breccia 66095, referred to as the “Rusty Rock” due to its enrichments in volatile elements, including Pb. Based on these analyses of the breccia, a Pb-Pb isochron age of 3909±17 Ma (at the 95% confidence level) and an initial Pb composition for 66095 have been determined. This age is interpreted as representing the time of breccia formation that, when combined with recent studies of lunar breccias, can be linked to the Imbrium basin forming impact. The directly measured initial Pb composition of the breccia from this work is similar a modelled compositions presented previously, and likely reflects an average value for the lithologies present at the Apollo 16 landing site at the time that the Imbrium ejecta was emplaced. The 66095 initial Pb isotopic composition is compared with the compositions in other lunar samples and the nature of the endmember lithologies in this mixture has been discussed within the framework of a multiple stage model of Pb isotope evolution on the Moon. This study demonstrates the effectiveness of this technique beyond its application in crystalline basalts, opening up the possibility of obtaining precise geochronological and Pb isotopic compositions from a broader sample set than was previously recognised.

Despite more than 40 years of studying Apollo samples, the age and early evolution of the Moon remain contentious. Following the formation of the Moon in the aftermath of a giant impact, the resulting Lunar Magma Ocean (LMO) is predicted to have generated major geochemically distinct silicate reservoirs, including the sources of lunar basalts. Samples of these basalts, therefore, provide a unique opportunity to characterize these reservoirs. However, the precise timing and extent of geochemical fractionation is poorly constrained, not least due to the difficulty in determining accurate ages and initial Pb isotopic compositions of lunar basalts. Application of an in situion microprobe approach to Pb isotope analysis has allowed us to obtain precise crystallization ages from six lunar basalts, typically with an uncertainty of about ±10Ma, as well as constrain their initial Pb-isotopic compositions. This has enabled construction of a two-stage model for the Pb-isotopic evolution of lunar silicate reservoirs, which necessitates the prolonged existence of high-μreservoirs in order to explain the very radiogenic compositions of the samples. Further, once firm constraints on U and Pb partitioning behaviour are established, this model has the potential to help distinguish between conflicting estimates for the age of the Moon. Nonetheless, we are able to constrain the timing of a lunar mantle reservoir differentiation event at 4376 ±18Ma, which is consistent with that derived from the Sm–Nd and Lu–Hf isotopic systems, and is interpreted as an average estimate of the time at which the high-μurKREEP reservoir was established and the Ferroan Anorthosite (FAN) suite was formed.

The U-Pb systems of apatite and merrillite grains within four separate Apollo 14 impact melt breccia samples were analysed by secondary ion mass spectrometry. No systematic difference was identified between the ²⁰⁷Pb/²⁰⁶Pb ages of the apatites and merrillites. A combined ²⁰⁷Pb/²⁰⁶Pb age of 3927±2 Ma (95% conf.) is determined for three of these samples (14305,103: 3926±4 Ma; 14306,150: 3926±6 Ma; 14314,13: 3929±4 Ma). By combining these data with the ages previously obtained for zircons in Apollo 12 impact melt breccia fragments and the lunar meteorite SaU 169, a weighted average age of 3926±2 Ma (95% conf.) is obtained, which is attributed to the formation of the Imbrium basin. An age of 3943±5 Ma is determined for the fourth breccia (14321,134), which is similar to ages of 3946±15 Ma and 3958±19 Ma, obtained from several older phosphates in 14305,103 and 14314,13. The weighted average of these three older ages is 3944±4 Ma (95% conf.). This is indistinguishable to the age (3938±4 Ma; 2σ) obtained for a different Apollo 14 impact melt breccia in a previous study. After investigating likely sources for this older ~3940 Ma age, we conclude that the Humorum or Serenitatis basin forming events are likely candidates. The potential identification of two large impact events within ~15 Myrs has important implications for the rate of lunar bombardment around 3.95-3.92 Ga. This study demonstrates the importance of high-precision age determinations for interpreting the impact record of the Moon, as documented in lunar samples.

Apollo 12 breccia 12013 is composed of two portions, one grey in colour, the other black. The grey portion of the brecciaconsists mainly of felsite thought to have formed during a single crystallisation event, while the black part is characterized bypresence of lithic fragments of noritic rocks and individual plagioclase crystals. In this study, U-Pb analyses of Ca-phosphateand zircon grains were conducted in both portions of the breccia. The zircon grains within the grey portion yielded a largerange of ages (4154 ± 7 to 4308 ± 6 Ma, 2r) and show decreasing U and Th concentrations within the younger grains. Moreover,some grains exhibit recrystallisation features and potentially formation of neoblasts. The latter process requires hightemperatures above 1600–1700 C leading to the decomposition of the primary zircon grain and subsequent formation ofnew zircon occurring as neoblasts. As a result of the high temperatures, the U-Pb system of the remaining original zircongrains was most likely open for Pb diffusion causing partial resetting and the observed range of 207Pb/206Pb ages. The eventthat led to the Pb loss in zircon could potentially be dated by the U-Pb system in Ca-phosphates, which have a weighted average207Pb/206Pb age across both lithologies of 3924 ± 3 Ma (95% conf.). This age is identical within error to the combinedaverage 207Pb/206Pb age of 3926 ± 2 Ma that was previously obtained from Ca-phosphates within Apollo 14 breccias, zircongrains in Apollo 12 impact melt breccias, and the lunar meteorite SaU 169. This age was interpreted to date the Imbriumimpact. The zircon grains located within the black portion of the breccia yielded a similar range of ages (4123 ± 13 to4328 ± 14 Ma, 2r) to those in the grey portion. Given the brecciated nature of this part of the sample, the interpretationof these ages as representing igneous crystallisation or resetting by impact events remains ambiguous since there is no directlink to their source rocks via textural relationships or crystal chemistry. Similarly, the currently available zircon data set for alllunar samples may be distorted by partial Pb loss, resulting in meaningless and misleading age distribution patterns. Therefore,it is crucial to fully understand and recognize the processes and conditions that may lead to partial resetting of the U-Pbsystem in zircon in order to better constrain the magmatic and impact history of the Moon.

Secondary ion mass spectrometry (SIMS) U-Pb ages of Ca-phosphates from four texturally distinct breccia samples (72255, 76055, 76015, 76215) collected at the Apollo 17 landing site were obtained in an attempt to identify whether they represent a single or several impact event(s). The determined ages, combined with inferences from petrologic relationships, may indicate two or possibly three different impact events at 3920±3 Ma, 3922±5 Ma and 3930±5 Ma (all errors 2σ). Searching for possible sources of the breccias by calculating the continuous ejecta radii of impact basins and large craters as well as their expected ejecta thicknesses, we conclude that Nectaris, Crisium, Serenitatis and Imbrium are likely candidates. If the previous interpretation that the micropoikilitic breccias collected at the North Massif represent Serenitatis ejecta is correct, then the average ²⁰⁷Pb/²⁰⁶Pb age of 3930±5 Ma (2σ) dates the formation of the Serenitatis basin. The occurrence of zircon in the breccias sampled at the South Massif, which contain Ca-phosphates yielding an age of 3922±5 Ma (2σ), may indicate that the breccia originated from within the Procellarum KREEP terrane (PKT) and the Imbrium basin appears to be the only basin that could have sourced them. However, this interpretation implies that all basins suggested to fall stratigraphically between Serenitatis and Imbrium formed within a short (<11 Ma) time interval, highlighting serious contradictions between global stratigraphic constraints, sample interpretation and chronological data. Alternatively, the slightly older age of the two micropoikilitic breccias may be a result of incomplete resetting of the U-Pb system preserved in some phosphate grains. Based on the currently available dataset this possibility cannot be excluded.