The accuracy of boron isotope analysis by laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS), particularly when the mass bias correction utilises non-matrix-matched reference materials, is compromised by matrix- and mass-load induced biases and an interference from scattered Ca and Ar ions which can induce bias in excess of 20‰. Here we explore the first application to in situ boron isotope analysis of the Thermo Scientific Neoma MS/MS mass spectrometer, which combines a traditional MC-ICP mass spectrometer with a collision/reaction cell and pre-cell mass filtering technology. While operating in full transmission mode, i.e. without using the collision/reaction cell, the pre-cell mass filter successfully eradicates the interference from scattered ions seen on some pre-existing models of MC-ICP-MS and exhibits good analytical sensitivity (∼6-14 mV per μg per g of total boron is typically achieved here). Furthermore, when matching laser operating parameters for samples/secondary reference materials and bracketing reference materials, and limiting the mass of ablated material introduced to the plasma, matrix- and mass-load induced biases can be prevented without the need for instrument tune conditions that severely limit sensitivity. Mean values of 14 reference materials, varying in bulk chemical composition (carbonates and silicates) and boron concentration (c. 2-150 μg g-1), are within uncertainty of reference values when instrumental mass bias is normalised using bracketing analyses of NIST SRM612 glass, demonstrating the accuracy and utility of this approach. Internal precision and external reproducibility are primarily controlled by boron signal intensity and both are typically better than 1‰ when the 11B intensity is at least ∼40 mV. LA-MC-ICP-MS/MS therefore offers a new and exciting opportunity for accurate and precise matrix independent, in situ, boron isotope analysis of geological materials.

The fossil record provides the most powerful evidence of large-scale biodiversity change on Earth, but it does so at coarse and often idiosyncratic temporal scales. One critical problem that arises concerns the evolutionary consequences of individual environmental experience. Individuals respond to their environment instantaneously, whereas the resolution of most fossil records aggregates multiple paleoenvironments over time scales beyond individual lifespans. Therefore, the presence of phenotypic plasticity in deep time and the extent of its influence on macroevolution remain poorly understood. Using coupled computed tomography and laser ablation inductively coupled plasma mass spectrometry protocols, we studied the environmental dependence of developmental trajectories across three sister species of macroperforate planktonic foraminifera. A foraminiferal shell preserves all stages of the individual's ontogeny, as well as the environmental state experienced throughout its lifetime. Generalized additive mixed effect (GAMM) models show that somatic growth rates differ among the three Menardella species and that these are inversely correlated with calcification temperature, as reconstructed from Mg/Ca measurements through ontogeny. This environmental dependence varies among species: The thermal sensitivity of individual chamber-to-chamber growth rates of Menardella limbata and Menardella pertenuis is double that seen in Menardella exilis. In contrast, no such environmental signal was recovered for architectural shape traits. Our integrated approach is widely applicable and demonstrates that detecting developmental plasticity in the fossil record is feasible. Extrapolating these techniques in deep time promises to revolutionize our understanding of the ways in which environmentally associated trait variation drove the diversification of life on Earth.

U-Th dating of associated carbonate crusts has been applied to date parietal art in Maltravieso cave, Extremadura, Spain. Known for its large collection of red hand stencils (>= 60), one example previously dated to >66.7 ka was taken to suggest Neandertal authorship. Here we present a more detailed U-series study of hand stencils within the cave, and place the results in the context of the chronology of these motifs worldwide. Twenty-two carbonate samples overlying pigment of hand stencils were dated from the cave's Sala de las Pinturas and the Galeria de la Serpiente. Minimum ages for the art range from the Holocene to the Middle Palaeolithic. Alongside published dating results from other sites, this demonstrates that Neandertals as well as modern humans could create these motifs.

This paper reports a high-resolution isotopic study of medieval horse mobility, revealing their origins and in-life mobility both regionally and internationally. The animals were found in an unusual horse cemetery site found within the City of Westminster, London, England. Enamel strontium, oxygen, and carbon isotope analysis of 15 individuals provides information about likely place of birth, diet, and mobility during the first approximately 5 years of life. Results show that at least seven horses originated outside of Britain in relatively cold climates, potentially in Scandinavia or the Western Alps. Ancient DNA sexing data indicate no consistent sex-specific mobility patterning, although three of the five females came from exceptionally highly radiogenic regions. Another female with low mobility is suggested to be a sedentary broodmare. Our results provide direct and unprecedented evidence for a variety of horse movement and trading practices in the Middle Ages and highlight the importance of international trade in securing high-quality horses for medieval London elites.

Ocean Acidification (OA) arises from the increase in atmospheric carbon dioxide concentration following the industrial revolution. The ecological and socio-economic consequences of OA were first identified around 10-15 years ago but remain poorly understood. This is particularly true in coastal regions where local processes can have dramatic consequences on pH trends through time, obscuring and compounding the long-term effects from rising atmospheric CO2. Here we explore the possibility of generating long records of coastal ocean pH using the skeletons of widely distributed coralline algae (CA). The skeletons of these slow growing (<1 mm/year) taxa often contain micron-scale heterogeneities, making sampling for high-resolution climate reconstructions using bulk sampling techniques difficult. Here we use laser ablation coupled to inductively coupled plasma mass spectrometers to generate high-resolution 2D images of the element/calcium ratios and boron isotope composition (delta B-11) of a sample of Boreolithothamniom cf. soriferum from Loch Sween in Scotland, UK where we have been monitoring temperature since 2004 and pH during 2014. By carefully correlating the geochemical images with a scanning electron microscopy image we can segment them to remove the marginal portions of the skeleton, isolating the central growth axis to generate an age model and growth rate. The delta B-11-pH is significantly elevated above the seawater pH in Loch Sween (8.4 to 8.9 vs. 7.9 to 8.1) consistent with other CA that show internal pH elevation. On a seasonal scale, internal pH is negatively correlated with temperature and also exhibits a long-term decline. By removing this temperature effect, internal pH can be correlated to seawater pH during the 2014 monitoring period allowing us to reconstruct a seawater acidification trend from 2004 to 2018 of-0.018 pH units per year, 10x higher than open ocean trends but consistent with contemporaneous monitoring efforts of UK coastal waters. Reconstructed aqueous CO2 suggests that prior to similar to 2008 Loch Sween was a sink of CO2 but after this date, particularly during the early summer, it was a substantial CO2 source. Comparison of reconstructed aqueous CO2 with a record of calcification rate of our sample of Boreolithothamniom cf. soriferum suggests this acidification and associated rise in local seawater pCO(2) may have freed this sample from carbon limitation leading to a recent increase in calcification.

Serpentinised mantle rocks reflect the cumulative sum of multiple alteration events, but to date, identifying distinct serpentinisation episodes has remained challenging due to limited knowledge of the spatial distribution of tracers of fluid -rock exchange. Here we present novel high spatial resolution (-10 mu m) boron, nickel, calcium, and lithium concentration maps combined with in situ boron isotope analyses of strongly serpentinised mantle peridotites from the Troodos ophiolite, Cyprus. Our maps indicate strongly heterogenous boron concentrations with high boron concentrations in early formed serpentine replacing olivine but much lower boron contents in meshtextured serpentine and bastitic pyroxene. Late stage crosscutting serpentine veins have very low boron concentrations. In contrast, boron isotope measurements, made at coarser scales, are remarkably uniform (mean value thorn 11.9 +/- 3.2 parts per thousand, 1 sigma, n = 49). We interpret the high boron serpentine as reflecting the partial preservation of an early pervasive serpentinisation episode by fluids with high boron concentrations sourced from the dehydration of the subducting Cyprus slab. Subsequent serpentine phases with moderate to low boron reflect progressive recrystallisation and leaching by low boron concentration meteoric waters.

Coral reef ecosystems are delicately balanced and are thus prone to disruption by stressors such as storms, disease, climate variability and natural disasters. Most tropical coral populations worldwide are now in rapid decline owing to additional anthropogenic pressures, such as global warming, ocean acidification and a variety of local stressors. One such problem is the addition of excess sediment and nutrients flux to reefs from increased soil erosion from land use changes. Here we present century-long Ba/Ca records from two Siderastrea siderea colonies as a proxy for local riverine discharge and sediment flux to the southern Mesoamerican Barrier Reef System (MBRS). The coral colonies have linear extension trends, which can be seen as a first-order indicator for coral health and response. The coral colony that exhibits a decline in linear extension rate from the forereef of the MBRS, mainly receives riverine input from Honduras, whilst the coral from the backreef, which does not exhibit a decline in extension rate, primarily receives riverine input from more sparsely populated regions of Belize. Coral Ba/Ca increased (>70%) through time in the forereef colony, while the backreef colony showed little long-term increase in Ba/Ca over the last century. Our results suggest that increasing sediment supply may have played a role in the decline of forereef skeletal extension in the southernmost MBRS region, likely stemming from increasing land-use changes in Honduras.

The chemical and isotopic composition of stony coral skeletons form an important archive of past climate. However, these reconstructions are largely based on empirical relationships often complicated by “vital effects” arising from uncertain physiological processes of the coral holobiont. The skeletons of deep-sea corals, such as Desmophyllum dianthus, are characterised by micron-scale or larger geochemical heterogeneity associated with: (1) centres of calcification (COCs) where nucleation of new skeleton begins, and (2) fibres that thicken the skeleton. These features are difficult to sample cleanly using traditional techniques, resulting in uncertainty surrounding both the causes of geochemical differences and their influence on environmental signals. Here we combine optical, and in-situ chemical and isotopic, imaging tools across a range of spatial resolutions (~ 100 nm to 10 s of μm) in a correlative multimodal imaging (CMI) approach to isolate the microstructural geochemistry of each component. This reveals COCs are characterised by higher organic content, Mg, Li and Sr and lower U, B and δ11B compared to fibres, reflecting the contrasting biomineralisation mechanisms employed to construct each feature. CMI is rarely applied in Environmental/Earth Sciences, but here we illustrate the power of this approach to unpick the “vital effects” in D. dianthus, and by extension, other scleractinian corals.

Many applications at the forefront of the study of the chemical composition of marine carbonates require in-situ micro-scale geochemical imaging. Such analyses are, however, challenging, requiring analytical techniques that are either expensive with limited accessibility (e.g. synchrotron X-Ray spectroscopy and secondary ion mass spectrometry), or time-consuming and able to only analyse a limited range of elements (e.g. electron microprobe). Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) as a tool for generating 2D images has grown in popularity, yet many analytical issues remain when generating high-spatial resolution geochemical images using this approach. Here we employ the imageGEO193 (ESL) fast wash-out laser ablation system coupled to the Nu Instruments Vitesse Time-of-Flight (TOF) ICP mass spectrometer, with its near-full mass spectra capabilities, to generate 2D geochemical images of a range of biogenic carbonates at <= 2 mu m pixel resolution (pixel widths of either 1 or 2 mu m) and at an unprecedented speed (200 pixels/s). We demonstrate sensitivity of similar to 100 cps/mu g g(-1) at low mass rising to similar to 1000 cps/mu g g(-1) at high mass based on analyses of reference materials JCp-1 (carbonate) and NIST SRM612 (silicate) with 1 mu m wide square laser beams, and accuracy of +/- 7 % for elements present at concentrations >0.5 mu g g(-1) based on analyses of carbonate reference material JCt-1. By applying our quantitative method to a range of biogenic carbonates (coral skeletons, coralline algae, foraminifera), we demonstrate that considerable but coherent micron-scale compositional variability is the norm for nearly all quantified elements, including: Mg, Sr, Ba and U. This approach therefore has great potential to provide valuable insights into biomineralisation mechanisms and "vital effects", ultimately facilitating more robust reconstructions of past environments.

Geochemical proxies of sea surface temperature (SST) and seawater pH (pHsw) in scleractinian coral skeletons are valuable tools for reconstructing tropical climate variability. However, most coral skeletal SST and pHsw proxies are univariate methods that are limited in their capacity to circumvent non-climate-related variability. Here we present a novel multivariate method for reconstructing SST and pHsw from the geochemistry of coral skeletons. Our Scleractinian Multivariate Isotope and Trace Element (SMITE) method optimizes reconstruction skill by leveraging the covariance across an array of coral elemental and isotopic data with SST and pHsw. First, using a synthetic proxy experiment, we find that SMITE SST reconstruction statistics (correlation, accuracy, and precision) are insensitive to noise and variable calibration period lengths relative to Sr/Ca. While SMITE pHsw reconstruction statistics remain relative to δ11B throughout the same synthetic experiment, the magnitude of the long-term trend in pHsw is progressively lost under conditions of moderate-to-high analytical uncertainty. Next, we apply the SMITE method to an array of seven coral-based geochemical variables (B/Ca, δ11B, Li/Ca, Mg/Ca, Sr/Ca, U/Ca & Li/Mg) measured from two Bermudan Porites astreoides corals. Despite a <3.5 year calibration period, SMITE SST and pHsw estimates exhibit significantly better accuracy, precision, and correlation with their respective climate targets than the best single- and dual-proxy estimators. Furthermore, SMITE model parameters are highly reproducible between the two coral cores, indicating great potential for fossil applications (when preservation is high). The results shown here indicate that the SMITE method can outperform the most common coral-based SST and pHsw reconstructions methods to date, particularly in datasets with a large variety of geochemical variables. We therefore provide a list of recommendations and procedures for users to begin implementing the SMITE method as well as an open-source software package to facilitate dissemination of the SMITE method.

The skeletons of long-lived bamboo coral (Family Keratoisididae) are promising archives for deep-water palaeoceanographic reconstructions as they can record environmental variation at sub-decadal resolution in locations where in-situ measurements lack temporal coverage. Yet, detailed three dimensional (3D) characterisations of bamboo coral skeletal architecture are not routinely available and non-destructive investigations into microscale variations in calcification are rare. Here, we provide high-resolution micro-focus computed tomography (µCT) data of skeletal density for two species of bamboo coral (Acanella arbuscula: 5 specimens, voxel size, 15 µm (central branch scans) and 50 µm (complete structure scan); Keratoisis sp.: 4 specimens, voxel size, 15 µm) collected from the Labrador Sea and Baffin Bay deep-water basins, Eastern Canadian Arctic. These data provide reference models useful for developing methods to assess structural integrity and other fine-scale complexities in many biological, geological, and industrial systems. This will be of wider value to those investigating structural composition, arrangement and/or composition of complex architecture within the fields and subdisciplines of biology, ecology, medicine, environmental geology, and structural engineering.

Reindeer are part of the faunal suite that dominated central Europe during the last glacial cycle. Their importance to Late Gravettian hunters as prey and a source of raw materials (hide, bone, antler) is well attested, however the context of Late Gravettian reindeer predation is lesser understood. This paper presents an investigation of human and reindeer predator-prey interactions at the Late Gravettian kill-butchery site of Lubná VI, Czech Republic. We reconstruct seasonal mobility (87Sr/86Sr, δ18O), diet (δ13C, δ15N) and season of death (dental cementum) of up to nine reindeer prey, to inform on the strategic choices made by Late Gravettian hunters. Results indicate that most hunted reindeer lived year-round in the foothills of the Bohemian-Moravian highlands near where Lubná is located, at altitudes between 200–450 m above present sea level, while a smaller number showed evidence of seasonal migration between this area and the open plains of the Elbe river corridor (Bohemian Cretaceous basin). No evidence for long distance migration of reindeer was detected, indicating that productive local environments were supporting reindeer herds within a single annual territory. Meanwhile, areas higher than 450 m above present sea level were avoided entirely by all analysed individuals, consistent with these areas being topographic barriers to movement due to climate severity. We conclude that hunters visited Lubná as part of a logistically-organised subsistence strategy, deliberately targeting reindeer in late autumn when fat supplies, hides and antler are in prime condition knowing that they would reliably encounter their prey at this location.

The impact of warming, acidification, and deoxygenation on deep-sea environments is a growing concern. Historical records are sparse, particularly at high latitudes, making climate change projections challenging. Indirect proxies, such as trace element composition of marine carbonates, such as coral skeletons, can offer an alternative method to fill data gaps but have not been realised. Here, using Laser Ablation Triple-Quadrupole Inductively Coupled Plasma Mass Spectrometry (LA-QQQ-ICP-MS), we examined micrometre-scale element variation within and between individual colonies of the bamboo coral Keratoisis sp. obtained from the Eastern Canadian Arctic. These data are used to assess the influence of biological variability on geochemical tracers for reconstructing past environmental conditions (temperature: Mg/Ca, Li/Mg, Sr/Ca, Ba/Ca, U/Ca; [Ba](SW): Ba/Ca). We place these data into context, based on a survey of literature data, using refined calibrations for high-Mg calcitic Octocorals. We find reproducible (2 sigma relative coefficient of variation) values of Mg/Ca (3%) and Ba/Ca (6%) along the radial growth axis of all colonies and internodes of Keratoisis sp., indicating that these signals are likely suitable for environmental reconstructions. After revising the available multi-taxa calibrations for Mg/Ca (0.316 +/- 0.026 degrees C/mmol/mol, R-2 = 0.87, p < 0.001) and Ba/Ca ([Ba/Ca mu mol/mol] = 0.148 +/- 0.005 [Ba-SW nmol/kg], R-2 = 0.97, p < 0.001), we show that vital effects within and among Keratoisis sp. colonies strongly influence reconstructed temperature and [Ba](SW), but this can be somewhat mitigated by combining multiple internode transects from one colony into a single composite series. Despite the ontogenetic variability, all colonies reveal a gradual deep-water cooling trend since the early 21st century and synchronised, multi-year spikes in Ba/Ca (and hence [Ba](SW)) that suggest substantial and coherent barium inputs to the seafloor. Our study confirms the reliability of Mg/Ca and Ba/Ca proxies in high-Mg bamboo corals for detecting multi-annual temperature and seawater barium variations in cold-water environments, but further investigation into micro-scale element behaviour influenced by biotic processes in these corals is needed to enhance confidence in reconstructions at finer spatial and temporal resolutions. We conclude that employing empirical calibrations based on multi-taxa approaches can increase the certainty of capturing regional changes in the environment more accurately than a single species calibration, while leveraging multiple element series to account for biological-induced variability improves single colony reconstructions.

This study introduces a novel methodology for utilizing historic built environments as reliable long-term geochemical archives, addressing a gap in the reconstruction of past anthropogenic pollution levels in urban settings. For the first time, we employ high-resolution laser ablation mass spectrometry for lead isotope (206Pb/207Pb and 208Pb/206Pb) analysis on 350-year-old black crust stratigraphies found on historic built structures, providing insights into past air pollution signatures. Our findings reveal a gradual shift in the crust stratigraphy toward lower 206Pb/207Pb and higher 208Pb/206Pb isotope ratios from the older to the younger layers, indicating changes in lead sources over time. Mass balance analysis of the isotope data shows black crust layers formed since 1669 primarily contain over 90% Pb from coal burning, while other lead sources from a set of modern pollution including but not limited to leaded gasoline (introduced after 1920) become dominant (up to 60%) from 1875 onward. In contrast to global archives such as ice cores that provide integrated signals of long-distance pollution, our study contributes to a deeper understanding of localized pollution levels, specifically in urban settings. Our approach complements multiple sources of evidence, enhancing our understanding of air pollution dynamics and trends, and the impact of human activities on urban environments.

The impact of changing nutrient conditions on scleractinian coral-based geochemical proxies is poorly understood, despite the nutrient balance in many coral reefs being disturbed by anthropogenic activity. Here, the geochemical responses of tropical corals Acropora polystoma and Porites lichen to nutrient enrichment and depletion are examined following growth under cultured conditions, to assess the impact of nutrients on traditional geochemical proxies for both temperature and the coral internal carbonate system. The corals were exposed to four different nutrient treatments over a period of 140 days: (1) a replete treatment with optimal levels of nitrate (-4.5 mu M) and phosphate (-0.6 mu M), (2) a nutrient depleted treatment with negligible nitrate and phosphate, (3) a treatment with high nitrate (-73 mu M) and negligible phosphate, and (4) a treatment with high phosphate (-5.7 mu M) and negligible nitrate. Results suggest nutrients play a hitherto under-appreciated role in coral skeleton elemental (Li/Ca, B/Ca, Mg/Ca, Sr/Ca, Li/Mg) and isotopic (611B) composition, with the internal carbonate chemistry also impacted. For example, Mg/Ca and Sr/Ca are lower, and Li/Mg higher, in the nutrient imbalanced and deplete treatments compared to the replete treatment for both species. Disruption to the carbonate system in corals cultured under imbalanced nutrient conditions is best explained by a decrease in dissolved inorganic carbon flux to the extracellular calcifying medium. Variations in nutrient concentration - or nutrient imbalance - can have dramatic consequences on both reconstructed sea surface temperatures and ocean or calcification pH, with reconstructed temperatures varying from - 7 degrees C to +52 degrees C, and 611B-derived pH by up to 0.13 pH units. The impact from anthropogenically-induced nutrient disturbances should therefore be considered when generating temporal records of environments using coral skeletal archives.

Variation among individuals within species is a biological precondition for co‐existence. Traditional geochemical analysis based on bulk averages facilitates rapid data gathering but necessarily means the loss of large amounts of potentially crucial information into variability within a given sample. As the sensitivity of geochemical analysis improves, it is now feasible to build sufficiently powerful datasets to investigate paleoclimatic variation at the level of individual specimens. Here, we investigate geochemical and morphological variation among the sensu stricto, sensu lato and sensu lato extreme subspecies of the workhorse extant planktic foraminifera Globigerinoides ruber . Our experimental design distinguishes between subspecies and intraspecific variability as well as the repeatability of laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS). We show that geochemical variability in Mg/Ca ratios is driven by differences in subspecies depth habitat and that ontogenetic trends in Mg/Ca ratios are evident in the final whorl, with the final chamber consistently showing depleted Mg/Ca. These ontogenetic trends are not driven by individual chamber or test size. The Mg/Ca value variance among individuals is ∼100 times higher than the variance among repeated laser spot analyses of single chambers, directing laboratory protocols towards the need to sample ecologically and environmentally homogeneous samples. Our results emphasize that we can use LA‐ICP‐MS to quantify how individual variability aggregates to bulk results, and highlights that, with sufficient sample sizes, it is possible to reveal how intraspecific variability alters geochemical inference.

Excavated over two centuries ago, the Upton Lovell G2a ‘Wessex Culture’ burial has held a prominent place in research on Bronze Age Britain. In particular, was it the grave of a ‘shaman’ or a metalworker? We take a new approach to the grave goods, employing microwear analysis and scanning electron microscopy to map a history of interactions between people and materials, identifying evidence for the presence of Bronze Age gold on five artefacts, four for the first time. Advancing a new materialist approach, we identify a goldworking toolkit, linking gold, stone and copper objects within a chaîne opératoire, concluding that modern categorisations of these materials miss much of their complexity.