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Pollen preserved in caves provides a little-appreciated opportunity to study past vegetation and climate changes in regions where conventional wetland sediments are either unavailable, contain little organic matter, and/or are difficult to date accurately. Most palynology in caves has focused on clastic infill sediments, but pollen preserved in growing speleothems provides important new opportunities to develop vegetation and climatic records that can be dated accurately with radiometric methods. However, when pollen is present in speleothems, concentrations can vary by orders of magnitude, highlighting how little we know about the processes that transport pollen into caves and onto speleothem surfaces, and that determine the pollen's preservation probability. To explore these aspects of speleothem pollen taphonomy, we investigated the distribution of pollen and microscopic charcoal within several stalagmites from southwest Australia. We examined spatial patterns in pollen and charcoal preservation in order to distinguish whether observed gradients result from preservation or are products of systematic transport processes working along stalagmite surfaces. We find that pollen grains and charcoal fragments are located preferentially on the flanks of most stalagmites. This suggests that pollen grain and charcoal deposition on speleothems is influenced by transport and accumulation of detrital debris on growing surfaces. These insights will assist in future sampling campaigns focusing on speleothem pollen and charcoal contents.

Initial radioactive disequilibrium amongst intermediate nuclides of the U decay chains can have a significant impact on the accuracy of U–Pb ages, especially in young samples. For samples that can reasonably be assumed to have attained radioactive equilibrium at the time of analysis, a relatively straightforward correction may be applied. However, in younger materials where this assumption is unreasonable, it is necessary to replace the familiar U–Pb age equations with more complete expressions that account for growth and decay of intermediate nuclides through time. DQPB is software for calculating U–Pb ages while accounting for the effects of radioactive disequilibrium among intermediate nuclides of the U decay chains. The software is written in Python and distributed as both a pure Python package and a stand-alone graphical user interface (GUI) application that integrates with standard Microsoft Excel spreadsheets. The software implements disequilibrium U–Pb equations to compute ages using various approaches, including concordia intercept ages on a Tera–Wasserburg diagram, U–Pb isochron ages, Pb*/U ages based on single aliquots, and 207Pb-corrected ages. While these age-calculation approaches are tailored toward young samples that cannot reasonably be assumed to have attained radioactive equilibrium at the time of analysis, they may also be applied to older materials where disequilibrium is no longer analytically resolvable. The software allows users to implement a variety of regression algorithms based on both classical and robust statistical approaches, compute weighted average ages and construct customisable, publication-ready plots of U–Pb age data. The regression and weighted average algorithms implemented in DQPB may also be applicable to other (i.e. non-U–Pb) geochronological datasets.

Editor’s note: The aim of the Geology and Mining series is to introduce early-career professionals and students to various aspects of mineral exploration, development, and mining in order to share the experiences and insight of each author on the myriad of topics involved with the mineral industry and the ways in which geoscientists contribute to each. Abstract Artificial intelligence (AI), and machine learning (ML) have emerged in the last few years from relative obscurity in the mineral exploration sector and they now attract significant attention from people in both industry and academia. However, due to the novelty of AI and ML applications, their practical use and potential remain enigmatic to many beyond a relatively few expert practitioners. We introduce this subject for the nonexpert and review some of the current applications and evolving uses. For the most traditionally minded geologist, we argue that ML can be an invaluable new tool, contributing to topics that range from exploratory data analysis to automated core logging and mineral prospectivity mapping, such that it will have a substantial impact on how exploration is conducted in the future. However, ML algorithms perform best with a large amount of homogeneously distributed clean data for a well-constrained objective. For this reason, the application to exploration strategy, especially for optimizing target selection, will be a challenge where data are heterogeneous, multiscale, amorphous, and discontinuous. For the more tech-savvy geologist and data scientist, we provide notes of caution regarding the limitations of ML applied to geoscience data, and reasons to temper expectations. Nonetheless, we project that such technologies, if used in an appropriate manner, will eventually be part of the full range of exploration tasks, allowing explorers to do more with their data in less time. However, whether this will tip the scales in favor of higher discovery rates remains to be demonstrated.

For riverine fishes threatened by fragmentation and flow modification, effective management requires an understanding of when and where key life history processes (spawning, recruitment and movement) take place. The structural and chemical properties of otoliths provide a unique means to recount a fish’s life in time and space. We investigated the age structure of the migratory, pelagic-spawning golden perch (Macquaria ambigua) in the Murray River, Australia, and used water and otolith 87Sr/86Sr ratios to delineate the natal origin and movement of fish from discrete cohorts. Water 87Sr/86Sr was distinct among the Darling River (a major tributary) and lower and mid-Murray River. Otolith chemistry revealed golden perch collected in the lower Murray River were progeny of spawning in either the Murray or Darling rivers, during years characterised by within-channel rises in flow, or in both rivers in a year of overbank flooding. Movement of juvenile fish from the Darling River substantially influenced population structure in the lower Murray River, whereby post-flood population growth was largely due to the immigration of age-1+ fish. This study demonstrates the potential importance of tributary recruitment sources, dispersal and connectivity on main-stem population dynamics and the utility of otolith chemistry for spatially reconciling population structure and the life histories of freshwater fishes.

Tumours are abnormal growths of cells that reproduce by redirecting essential nutrients and resources from surrounding tissue. Changes to cell metabolism that trigger the growth of tumours are reflected in subtle differences between the chemical composition of healthy and malignant cells. We used LA-ICP-MS imaging to investigate whether these chemical differences can be used to spatially identify tumours and support detection of primary colorectal tumours in anatomical pathology. First, we generated quantitative LA-ICP-MS images of three colorectal surgical resections with case-matched normal intestinal wall tissue and used this data in a Monte Carlo optimisation experiment to develop an algorithm that can classify pixels as tumour positive or negative. Blinded testing and interrogation of LA-ICP-MS images with micrographs of haematoxylin and eosin stained and Ki67 immunolabelled sections revealed Monte Carlo optimisation accurately identified primary tumour cells, as well as returning false positive pixels in areas of high cell proliferation. We analysed an additional 11 surgical resections of primary colorectal tumours and re-developed our image processing method to include a random forest regression machine learning model to correctly identify heterogenous tumours and exclude false positive pixels in images of non-malignant tissue. Our final model used over 1.6 billion calculations to correctly discern healthy cells from various types and stages of invasive colorectal tumours. The imaging mass spectrometry and data analysis methods described, developed in partnership with clinical cancer researchers, have the potential to further support cancer detection as part of a comprehensive digital pathology approach to cancer care through validation of a new chemical biomarker of tumour cells., Digital pathology and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) imaging reveals a unique elemental signature of colorectal cancer.

Snapshots of a rotary pump Vesicular- or vacuolar-type adenosine triphosphatases (V-ATPases) are ATP-hydrolysis–driven proton pumps. In neurons, V-ATPase activity generates a proton gradient across the membrane of synaptic vesicles so that neurotransmitters can be loaded into the vesicles. Abbas et al. developed a method to purify V-ATPase from rat brain and determined the structure of the entire complex by cryo–electron microscopy. Native mass spectrometry showed that the preparation was homogeneous and complemented structural studies by confirming the subunit composition. Three rotational states were resolved at better than 4-angstrom resolution, providing insight into the conformational changes that couple ATP hydrolysis to proton pumping. Science , this issue p. 1240

S- and I-type granites from the Lachlan Fold Belt, southeastern Australia, have been investigated to assess the role of disequilibrium melting in their petrogenesis. Differences between the median initial eHf compositions of magmatic zircon populations and the host bulk-rock (ΔeHfblk-zrc) range from −0.6 to +2.5 e units, providing evidence for intra-sample (and hence inter-phase) Hf-isotopic heterogeneity. Linear variations on Harker diagrams and O and Hf isotope compositions of magmatic zircon preserved in many I- and S-type granites are inconsistent with assimilation or simple mixing hypotheses. In contrast, isotopic disequilibrium between the melt and a restite assemblage can explain the bulk-rock versus zircon differences observed in these samples. Assuming that magmatic zircon records the melt composition, differences between the bulk-rock eHf and eHf of magmatic zircon (ΔeHfblk-zrc values) measured for I-type granites (0.4–2.5) can largely be explained by disequilibrium amphibole dehydration melting of meta-igneous protoliths that were either isotopically heterogenous at the time they were formed, or perfectly homogeneous before being aged in the crust for 0.4–1.0 billion years prior to partial melting. The Currowong Suite exhibits petrographic features and preserves geochemical and isotopic compositions that do not lend themselves to simple restite model or magma mixing explanations; however, these observations could be explained by the restite unmixing of magma batches generated from a single source rock if, as modelling has suggested, separate batches contain different melt compositions. By investigating the application of disequilibrium melting to granite genesis, this study demonstrates that isotopic heterogeneity at various sampling scales should actually be expected for the production of granites from a single source, rather than necessitating the involvement of multiple sources and mixing processes. As a result great care should be taken in the interpretation of isotope data from granitic bulk-rocks or their zircons.

Caves are important fossil repositories providing records extending back over million-year timescales. While the physical processes of cave formation are well understood, a more important parameter to studies of palaeontology, palaeoanthropology and archaeology — that of the timing of initial cave development and opening — has proved more difficult to constrain. The Naracoorte Cave Complex (NCC) in southern Australia is a World Heritage site with a rich record of Pleistocene vertebrate fossils, including extinct megafauna, and serves as a natural laboratory in which to investigate these fundamental cave processes. Using U-Th-Pb dating of speleothems we show that the NCC is at least 1.32 million years old, extending the current understanding of initial speleothem formation by ~70% and the antiquity of initial cave development at this site by at least ~20%. We use charcoal and pollen trapped in the same speleothems to place robust constraints on the timing and extent of subsequent cave opening. The findings of this study provide an important means for researchers working on the plethora of fossil-rich sites worldwide to assess the potential upper limit of vertebrate fossil records within caves.

Disorders of gastric function are highly prevalent, but diagnosis often remains symptom-based and inconclusive. Body surface gastric mapping is an emerging diagnostic solution, but current approaches lack scalability and are cumbersome and clinically impractical. We present a novel scalable system for non-invasively mapping gastric electrophysiology in high-resolution (HR) at the body-surface. The system comprises a custom-designed flexible HR sensor array and portable data-logger synchronized to an App, with automated analysis and visualization algorithms. The novel system underwent performance testing then validation in 24 healthy subjects. In all subjects, gastric electrophysiology and meal responses were successfully captured and mapped non-invasively (mean frequency 2.9 ± 0.3 cycles per minute; peak amplitude at mean 60 m postprandially with return to baseline in

Speleothems represent important archives of terrestrial climate variation that host a variety of proxy signals and are also highly amenable to radiometric age determination. Although speleothems have been forming on Earth for at least 400 million years, most studies rely upon the U-Th chronometer which extends only to the mid Pleistocene, leaving important questions over their longer-term preservation potential. To date, older records, exploiting the advantages of the U-Pb chronometer, remain fragmentary ‘snapshots in time’. Here we demonstrate the viability of speleothems as deep time climate archives by showing that a vast system of shallow caves beneath the arid Nullarbor plain of southern Australia, the world’s largest exposed karst terrain, formed largely within the Pliocene epoch, with a median age of 4.2 Ma, and that, in these caves, even the most delicate formations date from this time. The long-term preservation of regional-scale cave networks such as this demonstrates that abundant speleothem archives do survive to permit the reconstruction of climates and environments for much older parts of Earth history than the ~600 ka period to which most previous studies have been limited.

The utility of speleothems as environmental and geological archives has greatly expanded with recent advances in geochronology. Here we reevaluate their ability to constrain late Cenozoic uplift in karst terranes. Using combined U-Th and U-Pb speleothem chronologies for the Buchan karst along the passive margin of southeastern Australia, we calculate a maximum uplift rate of 76 ± 7 m m.y.−1 maintained over the past 3.5 m.y. The timing and extent of this process is consistent with independent constraints on Neogene uplift in Australia, possibly in response to increased plate-boundary strain with New Zealand. Speleothem chronologies provide highly precise age control on individual events and the potential for near-continuous records across long periods of geological time, complementing and expanding upon existing uplift proxies.

A step-change in the utility of elemental imaging in the biological sciences can be achieved by the integration of quantitative elemental distributions with structural information, allowing novel insights into how tissue development is associated with a dynamic chemical environment. To demonstrate this potential, here we construct a 3D correlative map of biometal distribution and skeletal growth for the first time in a complex organism – in a mouse embryo at developmental stage E14. We achieved this by registering laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) data to micro-computerized tomography (μCT) imagery using endogenous fiducial markers. LA-ICP-MS compositional maps of Rb were used as fiducial markers of dense regions in the micro-CT dataset (e.g. skeletal structure). Results of image registration showed high spatial correlation between both datasets which improved with increasing contrast of the micro-CT images. When coupled with recent advances in analytical instrumentation promoting rapid LA-ICP-MS scanning, this technique promises an enhanced understanding of development in complex biological systems without the need for chemical pre-treatment.

The recent development of methods for in situ U–Pb age determination in carbonates has found widespread application, but the benefits and limitations of the method over bulk analysis (isotope dilution – ID) approaches have yet to be fully explored. Here we use speleothems – cave carbonates such as stalagmites and flowstones – to investigate the utility of in situ dating methodologies for “challenging” matrices with typically low U and Pb contents and predominantly late Cenozoic ages. Using samples for which ID data have already been published, we show that accurate ages can be obtained for many speleothem types by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). Consideration of our own and literature data suggest that most carbonates with >1 ppm uranium and a few hundred parts per billion of Pb should be good targets for in situ methodologies, regardless of age. In situ analysis often provides a larger spread in U∕Pb ratios, which can be advantageous for isochron construction, but isochron ages rarely achieve the ultimate precision of ID analyses conducted on the same samples simply because signal sizes are dramatically reduced. LA analysis is faster than ID and thus will play a significant role in reconnaissance studies. The major advantage of the in situ methodology appears to be the potential for successful dating outcomes in sample types requiring high spatial-resolution analysis or those with a high common-Pb component where LA approaches may facilitate identification of the most radiogenic regions for analysis.

Kimberlites are ultrabasic, Si-undersaturated, low Al, low Na rocks rich in CO2 and H2O. The distinctive geochemical character of kimberlite is strongly influenced by the nature of the local underlying lithospheric mantle. Despite this, incompatible trace element ratios and radiogenic isotope characteristics of kimberlites, filtered for the effects of crustal contamination and alteration, closely resemble rocks derived from the deeper, more primitive, convecting mantle. This suggests that the ultimate magma source is sub-lithospheric. Although the composition of primitive kimberlite melt remains unresolved, kimberlites are likely derived from the convecting mantle, with possible source regions ranging from just below the lithosphere, through the transition zone, to the core–mantle boundary.

The trace-element geochemistry of speleothems is becoming increasingly used for reconstructing palaeoclimate, with a particular emphasis on elements whose concentrations vary according to hydrological conditions at the cave site (e.g. Mg, Sr, Ba and U). An important step in interpreting trace-element abundances is understanding the underlying processes of their incorporation. This includes quantifying the fractionation between the solution and speleothem carbonate via partition coefficients (where the partitioning (D) of element X (D-X) is the molar ratio [X/Ca] in the calcite divided by the molar ratio [X/Ca] in the parent water) and evaluating the degree of spatial variability across time-constant speleothem layers. Previous studies of how these elements are incorporated into speleothems have focused primarily on stalagmites and their source waters in natural cave settings, or have used synthetic solutions under cave-analogue laboratory conditions to produce similar dripstones. However, dripstones are not the only speleothem types capable of yielding useful palaeoclimate information. In this study, we investigate the incorporation of Mg, Sr, Ba and U into a subaqueous calcite speleothem (CD3) growing in a natural cave pool in Italy. Pool-water measurements extending back 15 years reveal a remarkably stable geochemical environment owing to the deep cave setting, enabling the calculation of precise solution [X/Ca]. We determine the trace element variability of 'modern' subaqueous calcite from a drill core taken through CD3 to derive D-Mg, D-Sr, D-Ba and D-U then compare these with published cave, cave-analogue and seawater-analogue studies. The D-Mg for CD3 is anomalously high (0.042 +/- 0.002) compared to previous estimates at similar temperatures (similar to 8 degrees C). The D-Sr (0.100 +/- 0.007) is similar to previously reported values, but data from this study as well as those from Tremaine and Froelich (2013) and Day and Henderson (2013) suggest that [ Na/Sr] might play an important role in Sr incorporation through the potential for Na to outcompete Sr for calcite non-lattice sites. DBa in CD3 (0.086 +/- 0.008) is similar to values derived by Day and Henderson (2013) under cave-analogue conditions, whilst DU (0.013 +/- 0.002) is almost an order of magnitude lower, possibly due to the unusually slow speleothem growth rates (

The widely accepted paradigm of Earth's geochemical evolution states that the successive extraction of melts from the mantle over the past 4.5 billion years formed the continental crust, and produced at least one complementary melt-depleted reservoir that is now recognized as the upper-mantle source of mid-ocean-ridge basalts1. However, geochemical modelling and the occurrence of high 3He/4He (that is, primordial) signatures in some volcanic rocks suggest that volumes of relatively undifferentiated mantle may reside in deeper, isolated regions2. Some basalts from large igneous provinces may provide temporally restricted glimpses of the most primitive parts of the mantle3,4, but key questions regarding the longevity of such sources on planetary timescales—and whether any survive today—remain unresolved. Kimberlites, small-volume volcanic rocks that are the source of most diamonds, offer rare insights into aspects of the composition of the Earth’s deep mantle. The radiogenic isotope ratios of kimberlites of different ages enable us to map the evolution of this domain through time. Here we show that globally distributed kimberlites originate from a single homogeneous reservoir with an isotopic composition that is indicative of a uniform and pristine mantle source, which evolved in isolation over at least 2.5 billion years of Earth history—to our knowledge, the only such reservoir that has been identified to date. Around 200 million years ago, extensive volumes of the same source were perturbed, probably as a result of contamination by exogenic material. The distribution of affected kimberlites suggests that this event may be related to subduction along the margin of the Pangaea supercontinent. These results reveal a long-lived and globally extensive mantle reservoir that underwent subsequent disruption, possibly heralding a marked change to large-scale mantle-mixing regimes. These processes may explain why uncontaminated primordial mantle is so difficult to identify in recent mantle-derived melts.

Ocean-island basalts (OIB) are the products of intra-plate mantle melting above mantle plumes. These hot, buoyant upwellings rise from the deep mantle, possibly the core-mantle boundary, to the Earth's surface. Radiogenic isotope signatures of trace elements in OIB are consistent with a variety of crustally-derived recycled components in their source that are suggested to reside in the plume as eclogite or their pyroxenitic melt-reaction products. The global OIB compositional spectrum exhibits a continuum of radiogenic isotope characteristics (Sr-Nd-Pb-Hf) that indicate mixing of these plume components. However, the petrological mechanisms underpinning this mixing remain elusive. Here, we report stable Fe isotope data for plume-derived lavas of Pitcairn Island from the southwest Pacific. Iron isotope compositions, corrected for olivine fractionation, show a strong co-variation with radiogenic Nd-Sr-Pb isotopes. At Pitcairn, two isotopically distinct components have been identified, one being an enriched-mantle 1 (EM-1) component and the other being a more primitive component, which plots in multiple radiogenic isotope space in the so-called focal zone (FOZO), tentatively identified here as the plume matrix. We suggest a two-stage scenario in which Fe isotopes are first fractionated towards heavier values during formation of a reaction-zone pyroxenite. Partial silicate melt derived from a recycled crustal eclogite, assumed here to be of a subducted sediment origin, reacts with ambient peridotite to form an isotopically heavier Fe isotope pyroxenite with memory of its precursor in radiogenic isotopes. Subsequently, both, isolated and enriched reaction zone pyroxenites and ambient plume matrix reach their solidus and mixing of their partial melts to variable proportions create the spread in radiogenic and stable isotope systematics. This mixing of components is coherent with the widely observed disparity in trajectories between plume matrix and enriched components in long-lived (Sr-Nd-Pb-Hf) and extinct (W) radiogenic and stable (Fe-Mg) isotope systematics and marks a fundamental process for chemical diversity in OIB. It supports a model of isolated plume components in a primitive mantle matrix. Enriched components in the plume that contribute to this mixing appear to be solely pyroxenitic with no or very little direct contribution from the original eclogite. Timing and loci of pyroxenite formation remain to be elucidated.

Diadromy is a form of migration where aquatic organisms undergo regular movements between fresh and marine waters for the purposes of feeding and reproduction. Despite having arisen in independent lineages of fish, gastropod molluscs and crustaceans, the evolutionary drivers of diadromous migration remain contentious. We test a key aspect of the 'productivity hypothesis', which proposes that diadromy arises in response to primary productivity differentials between marine and freshwater habitats. Otolith chemistry and biochronology data are analysed in a facultatively catadromous tropical fish (barramundi, Lates calcarifer) to determine the effect of freshwater residence on growth rates. Individuals that accessed freshwater grew ~ 25% faster on average than estuarine residents in the year following migration, suggesting that catadromy provides a potential fitness advantage over non-catadromous (marine/estuarine) life histories, as predicted by the productivity hypothesis. Although diadromous barramundi exhibited faster growth than non-diadromous fish, we suggest that the relative reproductive success of diadromous and non-diadromous contingents is likely to be strongly influenced by local environmental variability such as temporal differences in river discharge, and that this may facilitate the persistence of diverse life history strategies within populations.

Globally distributed kimberlites with broadly chondritic initial (143)Nd-(176)Hf isotopic systematics may be derived from a chemically homogenous, relatively primitive mantle source that remained isolated from the convecting mantle for much of the Earth’s history. To assess whether this putative reservoir may have preserved remnants of an early Earth process, we report (182)W/(184)W and (142)Nd/(144)Nd data for “primitive” kimberlites from 10 localities worldwide, ranging in age from 1,153 to 89 Ma. Most are characterized by homogeneous μ(182)W and μ(142)Nd values averaging −5.9 ± 3.6 ppm (2SD, n = 13) and +2.7 ± 2.9 ppm (2SD, n = 6), respectively. The remarkably uniform yet modestly negative μ(182)W values, coupled with chondritic to slightly suprachondritic initial (143)Nd/(144)Nd and (176)Hf/(177)Hf ratios over a span of nearly 1,000 Mya, provides permissive evidence that these kimberlites were derived from one or more long-lived, early formed mantle reservoirs. Possible causes for negative μ(182)W values among these kimberlites include the transfer of W with low μ(182)W from the core to the mantle source reservoir(s), creation of the source reservoir(s) as a result of early silicate fractionation, or an overabundance of late-accreted materials in the source reservoir(s). By contrast, two younger kimberlites emplaced at 72 and 52 Ma and characterized by distinctly subchondritic initial (176)Hf/(177)Hf and (143)Nd/(144)Nd have μ(182)W values consistent with the modern upper mantle. These isotopic compositions may reflect contamination of the ancient kimberlite source by recycled crustal components with μ(182)W ≥ 0.

The end of the Younger Dryas (YD) was Earth’s last major abrupt climate event and is most vividly preserved in the water-isotope (ice δ18O), calcium (Ca2+) and methane-concentration (CH4) series of Greenland ice cores. Although numerous palaeoclimate records span this transition, surprisingly few have the dating precision necessary to test whether or not abrupt warming in Greenland was accompanied by synchronous climate changes beyond the Arctic. Speleothems, with their exceptional absolute chronologies, are well placed to conduct such a test.Here we apply a change-point detection algorithm to new and published speleothem δ18O records of the YD from the Indo-Australian summer monsoon and Asian summer monsoon domains to compare the synchronicity of hydroclimate changes across the YD termination. The algorithm, which identifies the age (and its uncertainty) of a regime shift in a time series, was applied to the 13 - 11 ka interval of each speleothem record. The results yield an error-weighted mean YD-termination age of 11.55 ± 0.02 ka BP (2σ), supporting the hypothesis of a closely coupled monsoon seesaw. Analysis of the Greenland NGRIP ice-core δ18O and Ca2+ records on the GICC05 chronology for the same interval produces a YD-termination age of 11.63 ± 0.10 ka BP. Although the NGRIP and speleothem ages overlap within uncertainties, this hints at a possible Arctic lead over the tropics. However, if we apply a correction to the GICC05 chronology based on recent ice-core 10Be and tree-ring 14C synchronisation, the change-point analysis gives a NGRIP termination age of 11.57 ± 0.02 ka BP. This revised timing is consistent with the Cariaco Basin greyscale record (11.56 ± 0.02 ka BP). It also brings the NGRIP and Antarctic WAIS Divide ice-core CH4 records into perfect alignment across the transition. This assemblage of ages from geographically dispersed regions suggests that hydroclimate changes associated with the YD termination were synchronous, at least to within a couple of decades. It also calls for a revision to the onset age of the Greenlandian Stage (the Pleistocene-Holocene boundary).

Australia is the driest continent outside of Antarctica yet relatively little is known about its long-term moisture history. Many local palaeoclimate archives suffer preservation problems, particularly in the arid centre of the continent, where weathering and erosion leave behind an incomplete record. In an attempt to redress the paucity of arid-zone palaeoclimate records, we investigate ‘pendulites’, subaqueous speleothems that grow episodically according to fluctuations in local groundwater levels. At Mairs Cave (central Flinders Ranges, South Australia), pendulites have formed around stalactites. During the first sustained episode of drowning, the stalactite is veneered by subaqueous calcite, sealing it and preventing further stalactitic growth after water levels fall. Once sealed, the pendulites only record periods of persistent drowning, assumed to correspond to major pluvial episodes.Age data from two pendulite samples collected from close to the ceiling where the highest water levels have reached reveal two main groundwater ‘high-stand’ phases centred on ~67 and ~48 ka, coincident with Southern Hemisphere summer insolation maxima. This suggests that precession-driven southward migration of the ITCZ resulted in regular and persistent incursions of tropical air masses to the central Flinders Ranges. Trace element, stable isotope and growth-rate changes reveal that these orbitally controlled growth intervals are superimposed by regional climate responses to Dansgaard-Oeschger and Heinrich events. The results from Mairs Cave shed new light on the moisture history of central Australia, in particular the competing influences of tropical and middle-latitude circulation systems. This provides a precisely dated regional palaeoclimate template for reconstructing ecosystem changes, understanding human migration/dispersal patterns of the first Australians, and the progressive demise of megafauna. We also highlight the utility of subaqueous speleothems more generally as important archives for investigating arid-zone palaeoclimate.

Under the current rapid global warming, studying how environments responded to past climate change becomes increasingly important to better understand what impact climate variability has on regional flora and fauna. Our new multi-proxy study to the World Heritage Naracoorte Caves in southern Australia provides a unique window into the past climate as they are heavily decorated with speleothems but also contain in-fill deposits rich in Pleistocene vertebrate fossils including the extinct Australian megafauna. Until now, these speleothems have been dated using U-Th series and the fossil-bearing sediments with Optical Stimulated Luminescence and Electro Spin Resonance techniques, but only up to ca. 500 ka. We have U-Pb dated speleothems from the Naracoorte Caves for the first time and extended the record beyond 500 ka. We combined precise chronology with analyses of pollen and charcoal within the speleothems which allows us to better understand how southern Australia’s climate and its vegetation changed during the Quaternary. It also provides a unique insight into the timing and extent of cave opening with important potential for much older vertebrate fossil deposits than previously thought.

High-resolution U-Th and 14C dating of two calcite flowstones (RTf: Last Interglacial; RTy: Late Holocene) from the Re Tiberio – Monte Tondo karst system (North Italy) is presented to investigate the palaeoclimate potential of speleothems from gypsum caves. To date, there is a lack of information regarding the dating potential of calcite speleothems that have grown in such gypsum karst environment (e.g. no pseudokarst). High-resolution U-Th dating, aimed at establishing if these speleothems can provide robust radiometric age sequences, is first presented. Although both samples show promise for reliable radiometric dating, about 20% of the ages in the RTf dataset were excluded from the age-model as outliers. These outliers are best explained by post-depositional diagenetic processes affecting the U-Th system rather than anything specific to gypsum karst environment conditions. In contrast, outliers were not detected in the RTy sample, but U-Th analysis was not able to constrain its relatively young age (∼600 years before present, B.P.). Consequently, radiocarbon measurements were undertaken, and combined with the U-Th ages to build an age-model. The latter allowed the estimation of “dead carbon fraction” (DCF), which yields a constant value through time, and a magnitude comparable to other sites where climate is similar to Monte Tondo. Soils were considered the main source of carbon, because bedrock dissolution acted predominantly under open-system conditions, and soil organic matter (SOM) turnover rate appears above average compared to sites studied elsewhere.

International audience; Mangaia, an ocean island in the Cook-Austral volcanic chain, is the type locality for the HIMU mantle reservoir, and has also been shown to exhibit evidence for recycled sulfur with anomalous δ34S and ∆33S that has been attributed an Archean origin. Here we report bulk S isotope data from sulfide inclusions in olivine and pyroxene phenocrysts from one of the previously analyzed and four additional Mangaia basalts to further test for the prevalence of anomalous S in the HIMU mantle source feeding Mangaia. We document compositions that range from -5.13‰ to +0.21‰ (±0.3 2σ), +0.006‰ to +0.049‰ (±0.016 2σ), -0.81‰ to +0.69‰ (±0.3 2σ) for δ34S, Δ33S, and Δ36S respectively. These data extend the range of measured compositions and suggest S-isotope heterogeneity in the HIMU mantle source at Mangaia. We show that S-isotope compositions of bulk sulfide in olivine is not in isotopic equilibrium with bulk sulfide in pyroxene from the same samples and that samples from a confined area (M4,M10, M12, & M13) in the northern central part of the island show a distinct covariation for δ34S and Δ33S. This isotopic variation (forming an array) suggests mixing of sulfur from two sources that were captured at different stages of crystallization by phenocrysts in the Mangaia HIMU sulfur endmember.

As clinopyroxene is the main host of most lithophile elements in the lithospheric mantle, the trace element and radiogenic isotope systematics of this mineral have frequently been used to characterise mantle metasomatic processes. To further our understanding of mantle metasomatism, both solution-mode Sr-Nd-Hf-Pb and in situ trace element and Sr isotopic data have been acquired for clinopyroxene grains from a suite of peridotite (lherzolites and wehrlites), MARID (Mica-Amphibole-Rutile-Ilmenite-Diopside), and PIC (Phlogopite-Ilmenite-Clinopyroxene) rocks from the Kimberley kimberlites (South Africa). The studied mantle samples can be divided into two groups on the basis of their clinopyroxene trace element compositions, and this subdivision is reinforced by their isotopic ratios. Type 1 clinopyroxene, which comprises PIC, wehrlite, and some sheared lherzolite samples, is characterised by low Sr (~100–200 ppm) and LREE concentrations, moderate HFSE contents (e.g., ~40–75 ppm Zr; La/Zr < 0.04), and restricted isotopic compositions (e.g., 87Sr/86Sri = 0.70369–0.70383; εNdi = +3.1 to +3.6) resembling those of their host kimberlite magmas. Available trace element partition coefficients can be used to show that Type 1 clinopyroxenes are close to equilibrium with kimberlite melt compositions, supporting a genetic link between kimberlites and these metasomatised lithologies. Thermobarometric estimates for Type 1 samples indicate equilibration depths of 135–155 km within the lithosphere, thus showing that kimberlite melt metasomatism is prevalent in the deeper part of the lithosphere beneath Kimberley. In contrast, Type 2 clinopyroxenes occur in MARID rocks and coarse granular lherzolites, which derive from shallower depths (~0.05. The isotopic compositions of Type 2 clinopyroxenes are more variable and extend from compositions resembling the “enriched mantle” towards those of Type 1 rocks (e.g., εNdi = -12.7 to -4.4). To constrain the source of these variations, in situ Sr isotope analyses of clinopyroxene were undertaken, including zoned grains in Type 2 samples. MARID and lherzolite clinopyroxene cores display generally radiogenic but variable 87Sr/86Sri values (0.70526–0.71177), which might be explained by the interaction between peridotite and melts from different enriched sources with the lithospheric mantle. In contrast, the rims of these Type 2 clinopyroxenes trend towards compositions similar to those of the host kimberlite and Type 1 clinopyroxene from PIC and wehrlites. These results are interpreted to represent clinopyroxene overgrowth during late-stage (shortly before/during entrainment) metasomatism by kimberlite magmas. Our study shows that an early, pervasive, alkaline metasomatic event caused MARID and lherzolite genesis in the lithospheric mantle beneath the Kimberley area, which was followed by kimberlite metasomatism during Cretaceous magmatism. This latter event is the time at which discrete PIC, wehrlite, and sheared lherzolite lithologies were formed, and MARID and granular lherzolites were partly modified.

The standard classical statistics approach to isochron calculation assumes that the distribution of uncertainties on the data arising from isotopic analysis is strictly Gaussian. This effectively excludes datasets that have more scatter from consideration, even though many appear to have age significance. A new approach to isochron calculations is developed in order to circumvent this problem, requiring only that the central part of the uncertainty distribution of the data defines a “spine” in the trend of the data. This central spine can be Gaussian but this is not a requirement. This approach significantly increases the range of datasets from which age information can be extracted but also provides seamless integration with well-behaved datasets and thus all legacy age determinations. The approach is built on the robust statistics of Huber (1981) but using the data uncertainties for the scale of data scatter around the spine rather than a scale derived from the scatter itself, ignoring the data uncertainties. This robust data fitting reliably determines the position of the spine when applied to data with outliers but converges on the classical statistics approach for datasets without outliers. The spine width is determined by a robust measure, the normalised median absolute deviation of the distances of the data points to the centre of the spine, divided by the uncertainties on the distances. A test is provided to ascertain that there is a spine in the data, requiring that the spine width is consistent with the uncertainties expected for Gaussian-distributed data. An iteratively reweighted least squares algorithm is presented to calculate the position of the robust line and its uncertainty, accompanied by an implementation in Python.

Felsic magmas from the Izu-Bonin rear arc have compositions that resemble average continental crust in some respects. In order to understand their origin, we studied 1.1–4.4 Ma tephras in a rear-arc drill core from International Ocean Discovery Program Expedition 350, Site U1437. They provide a well-dated record of changing magmatic compositions during the early stages of the most recent episode of Izu-Bonin arc rifting. Based on our comprehensive recontextualization of published analyses of

We present a new approach to laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) U‐Pb dating of carbonates based on selection and pooling of pixels from 2‐D elemental and isotopic ratio maps. This image mapping technique is particularly useful for targeting subdomains in samples with complex geological histories. Key major and trace elements that are sensitive to detrital components, postformational fluid ingress, mineralogical changes, or diagenetic overprinting are measured along with the Pb and U isotopic data. Laser sampling is undertaken along successive linear rasters that are compiled into maps using the Monocle add‐on for Iolite, with one pixel in the map corresponding to one time slice of the time‐resolved signal. These element, element ratio, and isotope ratio maps can be overlain over photomicrographs or scanning electron microscopy images to spatially link compositional data to textural and structural features. The pixels corresponding to likely homogeneous age domains can be isolated by applying appropriate selection criteria (e.g., Th < 0.3 ppm, Mg/Ca < 0.004) and pooled into pseudo‐analyses using a proxy for the parent/daughter ratio (e.g., 207Pb/235U, 238U/208Pb) to retrieve the largest possible spread of the data points on isochron diagrams. The approach is best suited for analytical setups capable of rapidly or simultaneously scanning over a large mass range and can yield a precision of ±1% or better on quadrupole instruments depending on U concentration, 238U/204Pb, and age of the sample. The sample‐specific filtering criteria for selection and rejection of data and their rationale can be reported, resulting in more transparency with regard to data processing.

The Cradle of Humankind (Cradle) in South Africa preserves a rich collection of fossil hominins representing Australopithecus, Paranthropus and Homo1. The ages of these fossils are contentious2-4 and have compromised the degree to which the South African hominin record can be used to test hypotheses of human evolution. However, uranium-lead (U-Pb) analyses of horizontally bedded layers of calcium carbonate (flowstone) provide a potential opportunity to obtain a robust chronology5. Flowstones are ubiquitous cave features and provide a palaeoclimatic context, because they grow only during phases of increased effective precipitation6,7, ideally in closed caves. Here we show that flowstones from eight Cradle caves date to six narrow time intervals between 3.2 and 1.3 million years ago. We use a kernel density estimate to combine 29 U-Pb ages into a single record of flowstone growth intervals. We interpret these as major wet phases, when an increased water supply, more extensive vegetation cover and at least partially closed caves allowed for undisturbed, semi-continuous growth of the flowstones. The intervening times represent substantially drier phases, during which fossils of hominins and other fossils accumulated in open caves. Fossil preservation, restricted to drier intervals, thus biases the view of hominin evolutionary history and behaviour, and places the hominins in a community of comparatively dry-adapted fauna. Although the periods of cave closure leave temporal gaps in the South African fossil record, the flowstones themselves provide valuable insights into both local and pan-African climate variability.

MARID (Mica-Amphibole-Rutile-Ilmenite-Diopside) and PIC (Phlogopite-Ilmenite-Clinopyroxene) xenoliths are thought to be formed by intense “primary” mantle metasomatism. These rocks also display secondary features, such as cross-cutting veins and geochemical zonation of matrix minerals, which probably reflect later metasomatic events. To investigate the nature and origin(s) of these secondary features, 28 MARID and PIC xenoliths from southern African kimberlites and orangeites have been studied. MARID-hosted veins contain both carbonate and Ti-rich phases (e.g., titanite, phlogopite), suggesting that they formed by the infiltration of a carbonated silicate melt. Elevated TiO2 contents in MARID matrix mineral rims are spatially associated with carbonate-dominated veins, suggesting a genetic relationship between vein formation and geochemical zonation. Spongy rims around primary MARID and PIC clinopyroxene are depleted in Na2O and Al2O3 relative to their cores, possibly reflecting mineral dissolution in the xenoliths during ascent and emplacement of the entraining kimberlite. The preservation of compositional differences between primary and secondary phases in MARID and PIC xenoliths indicates that metasomatism occurred shortly before, or broadly coeval with, kimberlite/orangeite magmatism; otherwise, at typical mantle temperatures, such features would have quickly re-equilibrated. Increased Na2O in some mineral rims (e.g., K-richterite) may therefore reflect equilibration with a more Na-enriched primitive kimberlite melt composition than is commonly suggested. Vein-hosted clinopyroxene 87Sr/86Sri (0.70539 ± 0.00079) in one MARID sample is intermediate between primary clinopyroxene in the sample (0.70814 ± 0.00002) and the host Bultfontein kimberlite (0.70432 ± 0.00005), suggesting that vein minerals are derived from interactions between primary MARID phases and kimberlite-related melts/fluids. Sulfur isotope compositions of barite (δ34SVCDT = +4.69 ‰) and sulfides (δ34SVCDT = −0.69 ‰) in carbonate veins reflect equilibration at temperatures of 850–900 °C, consistent with sulfur-rich melt/fluid infiltration in the lithospheric mantle. In contrast, vein carbonate C-O isotope systematics (δ13CVPDB = −9.18 ‰; δ18OVSMOW = +17.22 ‰) are not typical of kimberlites or other mantle carbonates (δ13CVPDB = −3 to −8 ‰; δ18OVSMOW = 6 to 9 ‰), and may represent post-emplacement hydrothermal interactions of the cooling kimberlite with crustal fluids. These constraints suggest protracted metasomatism of MARID rocks shortly before and during entrainment by the host kimberlite.

Radiogenic isotope variations unrelated to radiogenic ingrowth are common between minerals found in metasomatised mantle xenoliths entrained in kimberlite, basalts and related magmas. As the metasomatic minerals are assumed to have been in isotopic equilibrium originally, such variations are typically attributed to contamination by the magma host and/or interaction with mantle fluids during or before xenolith transport to surface. However, the increasing evidence of metasomatism by multiple, compositionally distinct fluids permeating the lithospheric mantle, coeval with specific magmatic events, suggests that isotopic disequilibrium might be a consequence of discrete, though complex, metasomatic events. Here we provide clear evidence of elemental and Sr isotope heterogeneity between coeval Ti-rich LIMA (lindsleyite–mathiasite) minerals at the time of their formation in the mantle. LIMA minerals occur in close textural association with clinopyroxene and phlogopite in low-temperature (∼800–900 °C), strongly metasomatised mantle xenoliths from the ∼84 Ma Bultfontein kimberlite (South Africa). Previous U/Pb dating of the LIMA phases was used to argue that each xenolith recorded a single event of LIMA crystallisation at ∼180–190 Ma, coeval with the emplacement of Karoo magmas. SEM imaging reveals that up to four types of LIMA phases coexist in each xenolith, and occasionally in a single LIMA grain. Major element and in situ Sr isotope analyses of the different LIMA types show that each phase has a distinct elemental composition and initial 87Sr/86Sr ratio (e.g., 0.7068–0.7086 and 0.7115–0.7129 for two LIMA types in a single xenolith; 0.7053-0.7131 across the entire sample suite). These combined age and isotopic constraints require that multiple fluids metasomatised these rocks at broadly the same time (i.e. within a few thousands to millions of years), and produced similar mineralogical features. Elemental and isotopic variations between different LIMA types could be due to interaction between one (or more) Karoo-related Ti-rich silicate melts and previously metasomatised, phlogopite-rich lithospheric mantle. This study demonstrates that mantle metasomatic assemblages seemingly generated in a single event may instead result from the infiltration of broadly coeval fluids with variable compositions. This in turn implies that the isotopic variations recorded in mantle rocks may be an inherent feature of metasomatism, and that hot fluids infiltrating a rock do not necessarily cause equilibration at the cm scale, as has been assumed previously. Simple modelling of solid-state diffusion in mantle minerals shows that isotopic disequilibrium may be preserved for up to hundreds of Myr at mantle lithosphere temperatures (≤1100–1200 °C), unless subsequently affected by transient heating and/or fluid infiltration events. Radiogenic isotope disequilibrium associated with mantle metasomatism may therefore be a common feature of mantle xenoliths.

Granite petrogenesis is an important component of crustal growth and evolution; however, the isotope systems commonly applied to investigations of such processes (Sr, Nd, Pb and Hf) may behave in a more complex manner during partial melting and crystallization than is often assumed in petrogenetic models. Using a range of experimentally determined melting reactions and accessory mineral dissolution equations, the Sr-, Nd- and Hf-isotopic compositions of melt, source (protolith), and restite (residual source material including peritectic phases) have been calculated for a variety of hypothetical melting scenarios, in which the protoliths have acquired an isotopically heterogeneous mineral assemblage by aging in the crust prior to melting. It is shown that the disequilibrium amphibole dehydration melting of meta-igneous protoliths that have resided in the crust for 1·0 Gyr can generate differences between protolith and melt compositions of -4·2 to +7·2 eHf units. This implies that bulk-rock (particularly mafic, restite-rich) samples may have Hf isotope compositions significantly different from the melt-precipitated zircons within them. The modelling also predicts differences between protolith and melt Sr and Nd isotope compositions and decoupling between these systems. Furthermore, we demonstrate that simple restite separation from a single protolith can produce magmas exhibiting a range of Sr-Nd-Hf isotope compositions; that is, producing within-suite isotopic heterogeneity independent of source variation. The results imply that great care should be taken in the interpretation of the isotopic compositions of zircons in granites, and that bulk-rock compositions of mafic samples from granitic suites, not zircons, may provide the most reliable constraint on the protolith isotopic composition.

The geological setting of extensive ~3.5 Ga greenstone sequences in the Pilbara Craton (Australia) has been controversial for many years. Models range from a purely oceanic origin to emplacement over a pre-existing, possibly Hadean, sialic basement. Here we present new isotopic (Nd Hf) and trace element and data for a geographically extensive suite of komatiitic-tholeiitic metavolcanic rocks which comprise much of the Pilbara Supergroup. Most of the samples have flat to mildly enriched normalised trace element patterns, often associated with a slight Nb Ta depletion. A small subset of samples, represented throughout the stratigraphy, show strong LREE enrichment and pronounced HFSE anomalies (low Nb/Th, high La/Nb and Zr/Y) either requiring a different magma source or the addition of an enriched component (possibly pre-existing continental crust). Despite this compositional diversity, the Sm Nd and Lu Hf data for all samples define ~3.5 Ga isochrons and yield homogeneous initial ratios (eNd = 1.15 ± 0.19; eHf = 2.29 ± 0.65) suggesting a magma source — or sources — slightly more depleted than the putative primitive (chondritic) mantle but consistent with recent observations of other primordial, deep mantle reservoirs. Published Sm Nd data for the Dresser Formation obtained during the Pilbara Drilling Project appear to be affected by alteration processes and are considered unreliable for the estimation of an accurate initial isotopic composition. The data for the enriched samples are inconsistent with assimilation of known examples of locally exposed continental crust as a mechanism responsible for their trace element characteristics. If an alternate crustal contaminant is invoked it cannot be much older than the basaltic magmatism itself. As a consequence, we see no evidence for an extensive Hadean (>4.0 Ga) sialic basement in the region.

At subduction zones, sinking of the downgoing lithosphere is thought to enable a return flow of asthenospheric mantle around the slab edges, so that the asthenosphere from underneath the slab invades the ambient mantle flowing underneath the volcanic arc and the backarc basin. For instance at the northern end of the Lau Basin, trench retreat and slab rollback enable toroidal return flow of Samoan mantle beneath a transform margin to provide a supply of fresh, undepleted Indian mantle that feeds the backarc spreading center. Questions, however, arise about the sense of mantle flow when plate kinematics predict that the trench is advancing, as seen in the Mariana convergent margin. Does the mantle flow in or does it escape outward through slab tears or gaps? Here, we address the origin and sense of asthenospheric mantle flow supplying the southern Mariana convergent margin, a region of strong extension occurring above the subducting Pacific plate. Does the asthenosphere flow northward, from underneath the Pacific plate and Caroline hotspot through a slab tear or gap, or does it flow outward from the Mariana Trough, which possesses a characteristic Indian Ocean isotopic signature? To address these questions, we integrate geodetic data along with new Hf–Nd isotopic data for fresh basaltic lavas from three tectonic provinces in the southernmost Marianas: the Fina Nagu volcanic complex, the Malaguana–Gadao backarc spreading ridge and the SE Mariana forearc rift. Our results indicate that Indian mantle flows outward and likely escapes through slab tears or gaps to accommodate shrinking of the Philippine Sea plate. We thus predict that asthenospheric flow around the Pacific slab at the southern Mariana Trench is opposite to that predicted by most subduction-driven mantle flow models.

The Richards Spur locality, Oklahoma, USA, represents an Early Permian infill in a series of Ordovician limestone and dolostone karst fissures. It exhibits the most diverse terrestrial Palaeozoic community currently known, with > 40 distinct tetrapod taxa. Speleothems intimately associated with the site indicate that Richards Spur is a cave system, suggesting a preservational environment that is distinct from those of more typical Early Permian lowland deltaic/fluvial localities. Fossil material obtained from the caves is often found in disarticulation, although articulated material is not uncommon. This suggests that there were several factors that affected how animal remains became deposited within the caves. Many animals that died outside the caves were likely disarticulated on the surface and then washed in during rainfall events, resulting in mostly disarticulated remains. Alternatively, animals could be washed in before being disarticulated and some probably fell into the caves, resulting in less chance for their remains to become disarticulated. Supporting evidence for these preservational hypotheses comes in the form of wear caused by attritional processes. Disarticulated elements can exhibit high levels of wear, likely due to water transport that would carry them into the caves from the surface, as well as reworking within the caves. The partially and completely articulated remains are normally unworn, presumably due to a lesser degree of transport and reworking. X-ray diffraction and stable isotope analysis of cave infill further supports the interpretations made from fossil material. The results of this study provide a much-improved understanding of the preservational environment at Richards Spur, and will be useful in integrating information from this unique upland locality with that from the more extensively studied lowland localities of the Early Permian.