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Late Pleistocene ice-age climates are routinely characterized as having imposed moisture stress on low- to mid-latitude ecosystems1-5. This idea is largely based on fossil pollen evidence for widespread, low-biomass glacial vegetation, interpreted as indicating climatic dryness6. However, woody plant growth is inhibited under low atmospheric CO2 (refs. 7,8), so understanding glacial environments requires the development of new palaeoclimate indicators that are independent of vegetation9. Here we show that, contrary to expectations, during the past 350 kyr, peaks in southern Australian climatic moisture availability were largely confined to glacial periods, including the Last Glacial Maximum, whereas warm interglacials were relatively dry. By measuring the timing of speleothem growth in the Southern Hemisphere subtropics, which today has a predominantly negative annual moisture balance, we developed a record of climatic moisture availability that is independent of vegetation and extends through multiple glacial-interglacial cycles. Our results demonstrate that a cool-moist response is consistent across the austral subtropics and, in part, may result from reduced evaporation under cool glacial temperatures. Insofar as cold glacial environments in the Southern Hemisphere subtropics have been portrayed as uniformly arid3,10,11, our findings suggest that their characterization as evolutionary or physiological obstacles to movement and expansion of animal, plant and, potentially, human populations10 should be reconsidered.

Speleothems are increasingly valued as important paleoclimate archives and yet the removal of samples from caves can come at a cost to natural heritage, impacting delicate environments with limited mechanisms for repair. Conservation of cave environments is a key responsibility for scientists and, with this in mind, we are working to develop and implement techniques that allow us to extract valuable scientific data, with minimal impact. In this study, we demonstrate the utility of low-impact reconnaissance dating surveys on caves in southern Tasmania and southwest Western Australia as a precursor to the removal of stalagmites for paleoclimate reconstruction. Small flakes of calcite were discretely extracted from the base and tip of fallen stalagmites and dated using U-Th techniques. We specifically targeted stalagmites that have naturally fallen or been previously broken by human interference, to further reduce our impact on the caves. This approach provides maximum and minimum age constraints for each stalagmite and valuable information of growth frequencies without the need to remove whole samples from the cave. Selecting the most appropriate samples to analyze based on reconnaissance ages greatly reduces the quantity of speleothem material to be removed from a cave to locate a desired interval of past time, mitigating the impacts of the research. Moreover, the reconnaissance age data enable us to build an archive of speleothem ages from the cave for future scientific research and to provide information on the age and nature of cave development, useful for cave management purposes and other studies. To assess the accuracy of this method we compared the reconnaissance age with the results of a detailed age evaluation on a small number of stalagmites removed from the caves. We have found this method to be effective and has allowed us to successfully identify several stalagmites suitable for our scientific objectives.

Earth's carbon cycle is strongly influenced by subduction of sedimentary material into the mantle. The composition of the sedimentary subduction flux has changed considerably over Earth's history, but the impact of these changes on the mantle carbon cycle is unclear. Here, we show that the carbon isotopes of kimberlite magmas record a fundamental change in their deep-mantle source compositions during the Phanerozoic Eon. The 13C/12C of kimberlites before ~250 Ma preserves typical mantle values, whereas younger kimberlites exhibit lower and more variable ratios-a switch coincident with a recognized surge in kimberlite magmatism. We attribute these changes to increased deep subduction of organic carbon with low 13C/12C following the Cambrian Explosion when organic carbon deposition in marine sediments increased significantly. These observations demonstrate that biogeochemical processes at Earth's surface have a profound influence on the deep mantle, revealing an integral link between the deep and shallow carbon cycles.

Caves are important fossil repositories which provide records extending back over million-year timescales. While the physical processes of cave formation are well understood, the timing of initial cave development and opening—a more important parameter to studies of palaeontology, palaeoanthropology and archaeology—has proved more difficult to constrain. Here we investigate speleothems from the Naracoorte Cave Complex in southern Australia, with a rich record of Pleistocene vertebrate fossils (including extinct megafauna) and partly World Heritage-listed, using U-Th-Pb dating and analyses of their charcoal and pollen content. We find that, although speleothem formation began at least 1.34 million years ago, pollen and charcoal only began to be trapped within growing speleothems from 600,000 years ago. We interpret these two ages to represent the timing of initial cave development and the subsequent opening of the caves to the atmosphere respectively. These findings demonstrate the potential of U-Th-Pb dating combined with charcoal and pollen as proxies to assess the potential upper age limit of vertebrate fossil records found within caves.

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.

Radiometric dating of glacial terminations over the past 640,000 years suggests pacing by Earth's climatic precession, with each glacial-interglacial period spanning four or five cycles of ~20,000 years. However, the lack of firm age estimates for older Pleistocene terminations confounds attempts to test the persistence of precession forcing. We combine an Italian speleothem record anchored by a uranium-lead chronology with North Atlantic ocean data to show that the first two deglaciations of the so-called 100,000-year world are separated by two obliquity cycles, with each termination starting at the same high phase of obliquity, but at opposing phases of precession. An assessment of 11 radiometrically dated terminations spanning the past million years suggests that obliquity exerted a persistent influence on not only their initiation but also their duration.

The nature and duration of the Last Glacial Maximum (LGM) in Australia are poorly understood, with little regional agreement on the timing and direction of LGM climate changes. One reason for this is that Australian Late Pleistocene terrestrial sediments typically are both sparse and inorganic, inhibiting the development of detailed radiocarbon chronologies. To address this problem, we extracted fossil pollen from radiometrically dated stalagmites collected in southwest Western Australia. Our pollen record, supported by 30 U‐Th dates, reveals the vegetation response to Late Pleistocene climates between ~34 and 14 ka, through the body of the LGM. Before ~28 ka, sclerophyll forests were more open than today, but at ~28 ka forest cover was essentially eliminated, and treeless conditions were maintained until progressive reforestation at ~17.5 ka. This ~10‐ka‐long full glacial episode correlates with other mid‐high latitude Southern Hemisphere records, suggesting that LGM environmental changes were closely coordinated across the hemisphere.

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.

Climate projections1–3 and observations over recent decades4,5 indicate that precipitation in subtropical latitudes declines in response to anthropogenic warming, with significant implications for food production and population sustainability. However, this conclusion is derived from emissions scenarios with rapidly increasing radiative forcing to the year 21001,2, which may represent very different conditions from both past and future ‘equilibrium’ warmer climates. Here, we examine multi-century future climate simulations and show that in the Southern Hemisphere subtropical drying ceases soon after global temperature stabilizes. Our results suggest that twenty-first century Southern Hemisphere subtropical drying is not a feature of warm climates per se, but is primarily a response to rapidly rising forcing and global temperatures, as tropical sea-surface temperatures rise more than southern subtropical sea-surface temperatures under transient warming. Subtropical drying may therefore be a temporary response to rapid warming: as greenhouse gas concentrations and global temperatures stabilize, Southern Hemisphere subtropical regions may experience positive precipitation trends.

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 (DX) 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 DMg, DSr, DBa and DU then compare these with published cave, cave-analogue and seawater-analogue studies. The DMg for CD3 is anomalously high (0.042 ± 0.002) compared to previous estimates at similar temperatures (∼8 °C). The DSr (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

[This corrects the article DOI: 10.1039/C5SC02231B.].

Metals have a number of important roles within the brain. We used laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to map the three-dimensional concentrations and distributions of transition metals, in particular iron (Fe), copper (Cu) and zinc (Zn) within the murine brain. LA-ICP-MS is one of the leading analytical tools for measuring metals in tissue samples. Here, we present a complete data reduction protocol for measuring metals in biological samples, including the application of a pyramidal voxel registration technique to reproducibly align tissue sections. We used gold (Au) nanoparticle and ytterbium (Yb)-tagged tyrosine hydroxylase antibodies to assess the co-localisation of Fe and dopamine throughout the entire mouse brain. We also examined the natural clustering of metal concentrations within the murine brain to elucidate areas of similar composition. This clustering technique uses a mathematical approach to identify multiple 'elemental clusters', avoiding user bias and showing that metal composition follows a hierarchical organisation of neuroanatomical structures. This work provides new insight into the distinct compartmentalisation of metals in the brain, and presents new avenues of exploration with regard to region-specific, metal-associated neurodegeneration observed in several chronic neurodegenerative diseases.

[This corrects the article DOI: 10.1039/C5SC02231B.].

Kimberlites and orangeites (previously named Group-II kimberlites) are small-volume igneous rocks occurring in diatremes, sills and dykes. They are the main hosts for diamonds and are of scientific importance because they contain fragments of entrained mantle and crustal rocks, thus providing key information about the subcontinental lithosphere. Orangeites are ultrapotassic, H2O and CO2-rich rocks hosting minerals such as phlogopite, olivine, calcite and apatite. The major, trace element and isotopic compositions of orangeites resemble those of intensely metasomatized mantle of the type represented by MARID (mica-amphibole-rutile-ilmenite-diopside) xenoliths. Here we report new data for two MARID xenoliths from the Bultfontein kimberlite (Kimberley, South Africa) and we show that MARID-veined mantle has mineralogical (carbonate-apatite) and geochemical (Sr-Nd-Hf-O isotopes) characteristics compatible with orangeite melt generation from a MARID-rich source. This interpretation is supported by U-Pb zircon ages in MARID xenoliths from the Kimberley kimberlites, which confirm MARID rock formation before orangeite magmatism in the area.

Kimberlites and orangeites (previously named Group-II kimberlites) are small-volume igneous rocks occurring in diatremes, sills and dykes. They are the main hosts for diamonds and are of scientific importance because they contain fragments of entrained mantle and crustal rocks, thus providing key information about the subcontinental lithosphere. Orangeites are ultrapotassic, H2O and CO2-rich rocks hosting minerals such as phlogopite, olivine, calcite and apatite. The major, trace element and isotopic compositions of orangeites resemble those of intensely metasomatized mantle of the type represented by MARID (mica-amphibole-rutile-ilmenite-diopside) xenoliths. Here we report new data for two MARID xenoliths from the Bultfontein kimberlite (Kimberley, South Africa) and we show that MARID-veined mantle has mineralogical (carbonate-apatite) and geochemical (Sr-Nd-Hf-O isotopes) characteristics compatible with orangeite melt generation from a MARID-rich source. This interpretation is supported by U-Pb zircon ages in MARID xenoliths from the Kimberley kimberlites, which confirm MARID rock formation before orangeite magmatism in the area.

Sukhoi Log is one of the largest gold deposits in Russia (1100 t Au at 2.45 g/t). Like many other sediment-hosted gold deposits throughout the world, Sukhoi Log preserves textural, structural and geochemical evidence for multiple generations of Au enrichment and pyrite growth. The deposit is located in the Lena gold province of Siberia, on the edge of the Siberian Craton and occurs in the core of a recumbent anticline in a Neoproterozoic black shale and quartz-rich siltstone–sandstone turbidite succession. Temporal constraints on pyrite paragenesis at the deposit have been determined using laser ablation inductively coupled mass spectrometry (LA-ICPMS) measurements of U, Th and Pb isotopes in pyrite, monazite and zircon. LA-ICPMS age determinations on detrital zircons indicate the host rocks were deposited after 600 ± 10 Ma and derived from a mixture of Palaeoproterozoic and Neoproterozoic sources. The U, Th and Pb isotopic systematics indicate the cores of large monazite crystals, which predate obvious tectonic fabric development in the host rocks, began growing at 573 ± 12 Ma. The rims of the same monazite crystals formed at 516 ± 10 Ma, during peak metamorphism and deformation. Small monazite crystals also grew in the sedimentary rocks during the Devonian (374 ± 20 Ma) and the Carboniferous or Early Permian (288 ± 22 Ma), possibly in response to fluid movements triggered by synchronous granite intrusion in the area. Multi-collector and quadrupole LAICPMS Pb isotopic determination on pyrite, combined with overprinting criteria, show that the earliest (stratiform) Pb and Au-bearing pyrite formed prior to metamorphism—possibly during sedimentation or early diagenesis (575–600 Ma). Small Au-rich pyrite nodules preserved as cores to folded bedding-parallel pyrite–quartz veins probably grew during late diagenesis or early metamorphism. Large pyrite euhedra, which overgrow the strong axial planar cleavage in the host rocks, have more radiogenic Pb-isotopic compositions

Kimberlites and orangeites (previously named Group-II kimberlites) are small-volume igneous rocks occurring in diatremes, sills and dykes. They are the main hosts for diamonds and are of scientific importance because they contain fragments of entrained mantle and crustal rocks, thus providing key information about the subcontinental lithosphere. Orangeites are ultrapotassic, H2O and CO2-rich rocks hosting minerals such as phlogopite, olivine, calcite and apatite. The major, trace element and isotopic compositions of orangeites resemble those of intensely metasomatized mantle of the type represented by MARID (mica-amphibole-rutile-ilmenite-diopside) xenoliths. Here we report new data for two MARID xenoliths from the Bultfontein kimberlite (Kimberley, South Africa) and we show that MARID-veined mantle has mineralogical (carbonate-apatite) and geochemical (Sr-Nd-Hf-O isotopes) characteristics compatible with orangeite melt generation from a MARID-rich source. This interpretation is supported by U-Pb zircon ages in MARID xenoliths from the Kimberley kimberlites, which confirm MARID rock formation before orangeite magmatism in the area.

Kimberlites and orangeites (previously named Group-II kimberlites) are small-volume igneous rocks occurring in diatremes, sills and dykes. They are the main hosts for diamonds and are of scientific importance because they contain fragments of entrained mantle and crustal rocks, thus providing key information about the subcontinental lithosphere. Orangeites are ultrapotassic, H2O and CO2-rich rocks hosting minerals such as phlogopite, olivine, calcite and apatite. The major, trace element and isotopic compositions of orangeites resemble those of intensely metasomatized mantle of the type represented by MARID (mica-amphibole-rutile-ilmenite-diopside) xenoliths. Here we report new data for two MARID xenoliths from the Bultfontein kimberlite (Kimberley, South Africa) and we show that MARID-veined mantle has mineralogical (carbonate-apatite) and geochemical (Sr-Nd-Hf-O isotopes) characteristics compatible with orangeite melt generation from a MARID-rich source. This interpretation is supported by U-Pb zircon ages in MARID xenoliths from the Kimberley kimberlites, which confirm MARID rock formation before orangeite magmatism in the area.

Sukhoi Log is one of the largest gold deposits in Russia (1100 t Au at 2.45 g/t). Like many other sediment-hosted gold deposits throughout the world, Sukhoi Log preserves textural, structural and geochemical evidence for multiple generations of Au enrichment and pyrite growth. The deposit is located in the Lena gold province of Siberia, on the edge of the Siberian Craton and occurs in the core of a recumbent anticline in a Neoproterozoic black shale and quartz-rich siltstone–sandstone turbidite succession. Temporal constraints on pyrite paragenesis at the deposit have been determined using laser ablation inductively coupled mass spectrometry (LA-ICPMS) measurements of U, Th and Pb isotopes in pyrite, monazite and zircon. LA-ICPMS age determinations on detrital zircons indicate the host rocks were deposited after 600 ± 10 Ma and derived from a mixture of Palaeoproterozoic and Neoproterozoic sources. The U, Th and Pb isotopic systematics indicate the cores of large monazite crystals, which predate obvious tectonic fabric development in the host rocks, began growing at 573 ± 12 Ma. The rims of the same monazite crystals formed at 516 ± 10 Ma, during peak metamorphism and deformation. Small monazite crystals also grew in the sedimentary rocks during the Devonian (374 ± 20 Ma) and the Carboniferous or Early Permian (288 ± 22 Ma), possibly in response to fluid movements triggered by synchronous granite intrusion in the area. Multi-collector and quadrupole LAICPMS Pb isotopic determination on pyrite, combined with overprinting criteria, show that the earliest (stratiform) Pb and Au-bearing pyrite formed prior to metamorphism—possibly during sedimentation or early diagenesis (575–600 Ma). Small Au-rich pyrite nodules preserved as cores to folded bedding-parallel pyrite–quartz veins probably grew during late diagenesis or early metamorphism. Large pyrite euhedra, which overgrow the strong axial planar cleavage in the host rocks, have more radiogenic Pb-isotopic compositions

Kimberlites and orangeites (previously named Group-II kimberlites) are small-volume igneous rocks occurring in diatremes, sills and dykes. They are the main hosts for diamonds and are of scientific importance because they contain fragments of entrained mantle and crustal rocks, thus providing key information about the subcontinental lithosphere. Orangeites are ultrapotassic, H2O and CO2-rich rocks hosting minerals such as phlogopite, olivine, calcite and apatite. The major, trace element and isotopic compositions of orangeites resemble those of intensely metasomatized mantle of the type represented by MARID (mica-amphibole-rutile-ilmenite-diopside) xenoliths. Here we report new data for two MARID xenoliths from the Bultfontein kimberlite (Kimberley, South Africa) and we show that MARID-veined mantle has mineralogical (carbonate-apatite) and geochemical (Sr-Nd-Hf-O isotopes) characteristics compatible with orangeite melt generation from a MARID-rich source. This interpretation is supported by U-Pb zircon ages in MARID xenoliths from the Kimberley kimberlites, which confirm MARID rock formation before orangeite magmatism in the area.

Sukhoi Log is one of the largest gold deposits in Russia (1100 t Au at 2.45 g/t). Like many other sediment-hosted gold deposits throughout the world, Sukhoi Log preserves textural, structural and geochemical evidence for multiple generations of Au enrichment and pyrite growth. The deposit is located in the Lena gold province of Siberia, on the edge of the Siberian Craton and occurs in the core of a recumbent anticline in a Neoproterozoic black shale and quartz-rich siltstone–sandstone turbidite succession. Temporal constraints on pyrite paragenesis at the deposit have been determined using laser ablation inductively coupled mass spectrometry (LA-ICPMS) measurements of U, Th and Pb isotopes in pyrite, monazite and zircon. LA-ICPMS age determinations on detrital zircons indicate the host rocks were deposited after 600 ± 10 Ma and derived from a mixture of Palaeoproterozoic and Neoproterozoic sources. The U, Th and Pb isotopic systematics indicate the cores of large monazite crystals, which predate obvious tectonic fabric development in the host rocks, began growing at 573 ± 12 Ma. The rims of the same monazite crystals formed at 516 ± 10 Ma, during peak metamorphism and deformation. Small monazite crystals also grew in the sedimentary rocks during the Devonian (374 ± 20 Ma) and the Carboniferous or Early Permian (288 ± 22 Ma), possibly in response to fluid movements triggered by synchronous granite intrusion in the area. Multi-collector and quadrupole LAICPMS Pb isotopic determination on pyrite, combined with overprinting criteria, show that the earliest (stratiform) Pb and Au-bearing pyrite formed prior to metamorphism—possibly during sedimentation or early diagenesis (575–600 Ma). Small Au-rich pyrite nodules preserved as cores to folded bedding-parallel pyrite–quartz veins probably grew during late diagenesis or early metamorphism. Large pyrite euhedra, which overgrow the strong axial planar cleavage in the host rocks, have more radiogenic Pb-isotopic compositions

Kimberlites and orangeites (previously named Group-II kimberlites) are small-volume igneous rocks occurring in diatremes, sills and dykes. They are the main hosts for diamonds and are of scientific importance because they contain fragments of entrained mantle and crustal rocks, thus providing key information about the subcontinental lithosphere. Orangeites are ultrapotassic, H2O and CO2-rich rocks hosting minerals such as phlogopite, olivine, calcite and apatite. The major, trace element and isotopic compositions of orangeites resemble those of intensely metasomatized mantle of the type represented by MARID (mica-amphibole-rutile-ilmenite-diopside) xenoliths. Here we report new data for two MARID xenoliths from the Bultfontein kimberlite (Kimberley, South Africa) and we show that MARID-veined mantle has mineralogical (carbonate-apatite) and geochemical (Sr-Nd-Hf-O isotopes) characteristics compatible with orangeite melt generation from a MARID-rich source. This interpretation is supported by U-Pb zircon ages in MARID xenoliths from the Kimberley kimberlites, which confirm MARID rock formation before orangeite magmatism in the area.