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This work is a contribution to the HiTech AlkCarb project and was funded by the European Union's Horizon 2020 research and innovation programme under grant agreement No. 689909. W.H. also acknowledges support from a UKRI Future Leaders Fellowship (MR/S033505/1). A.J.B. is funded by the NERC National Environment Isotope Facility award (NE/S011587/1) and the Scottish Universities Environmental Research Centre. Alkaline igneous complexes are often rich in rare earth elements (REE) and other metals essential for modern technologies. Although a variety of magmatic and hydrothermal processes explain the occurrence of individual deposits, one common feature identified in almost all studies, is a REE-enriched parental melt sourced from the lithospheric mantle. Fundamental questions remain about the origin and importance of the mantle source in the genesis of REE-rich magmas. In particular, it is often unclear whether localized enrichments within an alkaline province reflect heterogeneity in the mantle source lithology (caused by prior subduction or plume activity) or variations in the degree of partial melting and differentiation of a largely homogeneous source. Sulfur isotopes offer a means of testing these hypotheses because they are unaffected by high temperature partial melting processes and can fingerprint different mantle sources. Although one must be careful to rule out subsequent isotope fractionation during magma ascent, degassing and crustal interactions. Here, we present new S concentration and isotope (δ34S) measurements, as well as a compilation of major and trace element data, for a suite of alkaline magmatic units and crustal lithologies from the Mesoproterozoic Gardar Province. Samples span all phases of Gardar magmatism (1330–1140 Ma) and include regional dykes, rift lavas and the alkaline complexes Motzfeldt and Ilímaussaq, which represent two of Europe's largest REE deposits. We show that the vast majority of our 115 samples have S contents >100 ppm and δ34S of −1 to 5‰. Only 8 samples (with low S contents

F.M. acknowledges funding from the European Research Council (ERC) under Horizon 2020 Framework Programme/ERC Grant Agreement 637503 (Pristine). F.M. and M.C. acknowledge the financial support of the UnivEarthS Labex Program at Sorbonne Paris Cité (Grants ANR-10-LABX-0023 and ANR-11-IDEX-0005-02). Parts of this work were supported by IPGP Plateau d’Analyse haute Résolution (PARI) and by Region Île-de-France Sesame Grant 12015908. Indirect evidence for the presence of a felsic continental crust, such as the elevated 49Ti/47Ti ratios in Archean shales, has been used to argue for ongoing subduction at that time and therefore plate tectonics. However, rocks of intermediate to felsic compositions can be produced in both plume and island arc settings. The fact that Ti behaves differently during magma differentiation in these two geological settings might result in contrasting isotopic signatures. Here, we demonstrate that, at a given SiO2 content, evolved plume rocks (tholeiitic) are more isotopically fractionated in Ti than differentiated island arc rocks (mainly calc-alkaline). We also show that the erosion of crustal rocks from whether plumes (mafic in average) or island arcs (intermediate in average) can all produce sediments having quite constant 49Ti/47Ti ratios being 0.1–0.3 per mille heavier than that of the mantle. This suggests that Ti isotopes are not a direct tracer for the SiO2 contents of crustal rocks. Ti isotopes in crustal sediments are still a potential proxy to identify the geodynamical settings for the formation of the crust but only if combined with additional SiO2 information. Postprint

International audience; We report on the effect of the end-Cretaceous impact event on the present-day deep microbial biosphere at the impact site. IODP-ICDP Expedition 364 drilled into the peak ring of the Chicxulub crater, México, allowing us to investigate the microbial communities within this structure. Increased cell biomass was found in the impact suevite, which was deposited within the first few hours of the Cenozoic, demonstrating that the impact produced a new lithological horizon that caused a long-term improvement in deep subsurface colonization potential. In the biologically impoverished granitic rocks, we observed increased cell abundances at impact-induced geological interfaces, that can be attributed to the nutritionally diverse substrates and/or elevated fluid flow. 16S rRNA gene amplicon sequencing revealed taxonomically distinct microbial communities in each crater lithology. These observations show that the impact caused geological deformation that continues to shape the deep subsurface biosphere at Chicxulub in the present day.

International audience; We present the first comprehensive P-T-deformation-time and kinematic constraints for HP/UHP eclogite, blueschist and greenschist-facies metavolcano-sedimentary rocks cropping out in the Chinese SW-Tianshan metamorphic complex (within the ~30 km wide N-S Akeyazi-Kebuerte area). We reappraise this HP/UHP “mélange”, which should be divided into three main tectonic units, from north to south, according to their discrepant lithologies and P-T-time-deformation histories. These three units crop out in a tectonic window beneath greenschist-facies metavolcanics. P-T estimates point to 1) UHP-LT conditions around 2.6–2.9 GPa at ~520 °C for the metavolcano-sedimentary rocks of the northern HP/UHP unit, 2) HP-LT conditions of 1.8–2.1 GPa and ~500 °C for the central blueschist horizon and 3) lower-blueschist facies conditions of 1.0–1.5 GPa at ~485 °C for the southern ultramafic-mafic unit. In situ laser probe Ar-Ar age constraints (with textural control) on recrystallized phengites from the HP/UHP unit cluster within 315 to 325 Ma. Phengite ages from the central blueschist horizon are 10–15 Ma older, at ~325–345 Ma. Laser-ICP-MS U-Pb dating on zircon from the south ultramafic-mafic unit yield ages around ~360 Ma for metamorphic overgrowths. In contrast, step-heating Ar-Ar phengite age constraints for the greenschist-facies metavolcano-sediments fall within 280–300 Ma. These new field and P-T-time data disclose an episodic exhumation of three main tectonic slices, respectively from ~85 km, ~65 km and ~45 km depths, and a progressive change of metamorphic gradients from ~12 to ~6–7 °C/km, which could reflect a cooling of the subduction system with time. Final juxtaposition at ~20 km was probably achieved around 300 Ma, prior to collision.

Joint International Ocean Discovery Program and International Continental Scientific Drilling Program Expedition 364 drilled into the peak ring of the Chicxulub impact crater. We present P-wave velocity, density, and porosity measurements from Hole M0077A that reveal unusual physical properties of the peak-ring rocks. Across the boundary between post-impact sedimentary rock and suevite (impact melt-bearing breccia) we measure a sharp decrease in velocity and density, and an increase in porosity. Velocity, density, and porosity values for the suevite are 2900–3700 m/s, 2.06–2.37 g/cm3, and 20–35%, respectively. The thin (25 m) impact melt rock unit below the suevite has velocity measurements of 3650–4350 m/s, density measurements of 2.26–2.37 g/cm3, and porosity measurements of 19–22%. We associate the low velocity, low density, and high porosity of suevite and impact melt rock with rapid emplacement, hydrothermal alteration products, and observations of pore space, vugs, and vesicles. The uplifted granitic peak ring materials have values of 4000–4200 m/s, 2.39–2.44 g/cm3, and 8–13% for velocity, density, and porosity, respectively; these values differ significantly from typical unaltered granite which has higher velocity and density, and lower porosity. The majority of Hole M0077A peak-ring velocity, density, and porosity measurements indicate considerable rock damage, and are consistent with numerical model predictions for peak-ring formation where the lithologies present within the peak ring represent some of the most shocked and damaged rocks in an impact basin. We integrate our results with previous seismic datasets to map the suevite near the borehole. We map suevite below the Paleogene sedimentary rock in the annular trough, on the peak ring, and in the central basin, implying that, post impact, suevite covered the entire floor of the impact basin. Suevite thickness is 100–165 m on the top of the peak ring but 200 m in the central basin, suggesting that suevite flowed downslope from the collapsing central uplift during and after peak-ring formation, accumulating preferentially within the central basin.

13 pages; International audience; Expedition 364 was a joint IODP and ICDP mission-specific platform (MSP) expedition to explore the Chicxulub impact crater buried below the surface of the Yucatán continental shelf seafloor. In April and May 2016, this expedition drilled a single borehole at Site M0077 into the crater's peak ring. Excellent quality cores were recovered from ∼505 to ∼1335 m below seafloor (m b.s.f.), and high-resolution open hole logs were acquired between the surface and total drill depth. Downhole logs are used to image the borehole wall, measure the physical properties of rocks that surround the borehole, and assess borehole quality during drilling and coring operations. When making geological interpretations of downhole logs, it is essential to be able to distinguish between features that are geological and those that are operation-related. During Expedition 364 some drilling-induced and logging-related features were observed and include the following: effects caused by the presence of casing and metal debris in the hole, logging-tool eccentering, drilling-induced corkscrew shape of the hole, possible re-magnetization of low-coercivity grains within sedimentary rocks, markings on the borehole wall, and drilling-induced changes in the borehole diameter and trajectory.

Funding: SIMS analyses were supported by the Natural Environment Research Council, UK (IMF689/0519). Coral skeletal boron geochemistry offers opportunities to probe the pH of the calcification media (pHCM) of modern and fossil specimens, to estimate past changes in seawater pH and to explore the biomineralisation response to future ocean acidification. In this research we grew 2 Stylophora pistillata coral microcolonies over glass coverslips to allow analysis of the pH sensitive dye SNARF-1, in the extracellular calcification medium at the growing edge of colonies where the first aragonite crystals are formed, under both light and dark conditions. We use secondary ion mass spectrometry (SIMS) to measure the boron isotopic composition (δ11B) of the skeleton close to the growth edge after 2 to 3 days of additional calcification had enlarged the crystals until they joined, generating a continuous sheet of aragonite. Mean skeletal δ11B-pHCM estimates are higher than those of by SNARF-1 by 0.35 to 0.44 pH units. These differences either reflect real variations in the pH of the calcification media associated with each measurement technique or indicate other changes in the biomineralisation process which influence skeletal δ11B. SNARF-1 measures directly the pH of the extracellular calcification medium while skeletal δ11B analyses aragonite potentially formed via both extracellular and intracellular biomineralisation pathways. Analysis of a third coral specimen, also growing on a glass slide but with a 5 cm long branch, indicated good agreement between the δ11B value of the apex of the branch and the skeletal growth edge. The tissues overlying both these regions were transparent indicating they had low symbiont densities. This suggests that the biomineralisation process is broadly comparable between these sites and that studies growing corals over glass slides/coverslips provide representative data for the colony apex. Publisher PDF

Funding: T.C. acknowledges support from the Strategic Priority Research Program of Chinese Academy of Sciences (XDB40010200), Fundamental Research Funds for the Central Universities (020614380116) and National Natural Science Foundation of China (41991325, 41822603 and 42021001). L.F.R. acknowledges support from the Natural Environment Research Council (NE/S001743/1, NE/R005117/1, NE/N003861/1 and NE/X00127X/1). Proxy-based studies have linked the pre-industrial atmospheric pCO2 rise of ∼20 ppmv in the mid- to late Holocene to an inferred increase in the Southern Ocean overturning and associated biogeochemical changes. However, the history of polar ocean overturning and ventilation through the Holocene remains poorly constrained, leaving important gaps in the assessment of the feedbacks between changes in ocean circulation and the carbon cycle in a warm climate state. The deep-ocean radiocarbon content, which provides a measure of ventilation, responds to circulation changes on centennial to millennial time scales. Here we present absolutely dated deep-sea coral radiocarbon records from the Drake Passage, between South America and Antarctica, and Reykjanes Ridge, south of Iceland, over the Holocene. Our data suggest that ventilation in the Antarctic circumpolar waters and North Atlantic Deep Water is surprisingly invariant within proxy uncertainties at our sampling resolution. Our findings indicate that long-term, large-scale polar ocean overturning has not been disturbed to a level resolvable by radiocarbon and is probably not responsible for the millennial atmosphere pCO2 evolution through the Holocene. Instead, continuous nutrient and carbon redistribution within the water column following deglaciation, as well as changes in land organic carbon stock, might have regulated atmospheric CO2 budget during this period. Publisher PDF

The Chicxulub impact crater, known for its link to the demise of the dinosaurs, also provides an opportunity to study rocks from a large impact structure. Large impact craters have “peak rings” that define a complex crater morphology. Morgan et al. looked at rocks from a drilling expedition through the peak rings of the Chicxulub impact crater (see the Perspective by Barton). The drill cores have features consistent with a model that postulates that a single over-heightened central peak collapsed into the multiple-peak-ring structure. The validity of this model has implications for far-ranging subjects, from how giant impacts alter the climate on Earth to the morphology of crater-dominated planetary surfaces.Science, this issue p. 878; see also p. 836Large impacts provide a mechanism for resurfacing planets through mixing near-surface rocks with deeper material. Central peaks are formed from the dynamic uplift of rocks during crater formation. As crater size increases, central peaks transition to peak rings. Without samples, debate surrounds the mechanics of peak-ring formation and their depth of origin. Chicxulub is the only known impact structure on Earth with an unequivocal peak ring, but it is buried and only accessible through drilling. Expedition 364 sampled the Chicxulub peak ring, which we found was formed from uplifted, fractured, shocked, felsic basement rocks. The peak-ring rocks are cross-cut by dikes and shear zones and have an unusually low density and seismic velocity. Large impacts therefore generate vertical fluxes and increase porosity in planetary crust.

Funding information: DEJ acknowledges financial support by the German Sciences Foundation and the Australian Research Council (CE110001017). SM acknowledges financial support by a National Environmental Research Council standard grant (NE/P012167/1) and a UK Space Agency Aurora grant (ST/T001763/1). Postprint

Funding: Funding for this work was provided by a NERC GW4+ Doctoral Training Partnership studentship (NE/S007504/1) awarded to J.K., an Antarctic Bursary awarded to J.A.S, and NERC grants awarded to L.F.R. (NE/S001743/1; NE/R005117/1; NE/N003861/1). Cruise DY081 was funded by European Research Council starting grant ICY-LAB (Grant Agreement 678371). The concentration of dissolved barium in seawater ([Ba]SW) is influenced by both primary productivity and ocean circulation patterns. Reconstructing past subsurface [Ba]SW can therefore provide important information on processes which regulate global climate. Previous Ba/Ca measurements of scleractinian and bamboo deep-sea coral skeletons exhibit linear relationships with [Ba]SW, acting as archives for past Ba cycling. However, skeletal Ba/Ca ratios of the Stylasteridae – a group of widely distributed, azooxanthellate, hydrozoan coral – have not been previously studied. Here, we present Ba/Ca ratios of modern stylasterid (aragonitic, calcitic and mixed mineralogy) and azooxanthellate scleractinian skeletons, paired with published proximal hydrographic data. We find that [Ba]SW and sample mineralogy are the primary controls on stylasterid Ba/Ca, while seawater temperature exerts a weak secondary control. [Ba]SW also exerts a strong control on azooxanthellate scleractinian Ba/Ca. However, Ba-incorporation into scleractinian skeletons varies between locations and across depth gradients, and we find a more sensitive relationship between scleractinian Ba/Ca and [Ba]SW than previously reported. Paired Sr/Ca measurements suggest that this variability in scleractinian Ba/Ca may result from the influence of varying degrees of Rayleigh fractionation during calcification. We find that these processes exert a smaller influence on Ba-incorporation into stylasterid coral skeletons, a result consistent with other aspects of their skeletal geochemistry. Stylasterid Ba/Ca ratios are therefore a powerful, novel archive of past changes in [Ba]SW, particularly when measured in combination with temperature sensitive tracers such as Li/Mg or Sr/Ca. Indeed, with robust [Ba]SW and temperature proxies now established, stylasterids have the potential to be an important new archive for palaeoceanographic studies. Publisher PDF

Lipids may serve as energy reserves to support coral calcification, allow acclimation to higher temperatures, and are implicated in the control of CaCO3 precipitation. Here, we report the lipid composition of the soft tissues (including host and symbionts) of 7 massive Porites spp. coral colonies (4 × P. lutea and 3 × P. murrayensis), which were cultured under different pCO2 concentrations (180, 260, 400 and 750 µatm) and at two temperatures (25 ℃ and 28 ℃), below the thermal stress threshold. We report the fatty acid methyl esters (FAME), free fatty acid (FFA) to total fatty acid content, sterol and wax ester profiles, and identify two ketones (n-alkanone) and three long chain aldehyde (n-alkanal) derivatives. Increasing seawater temperature significantly increases the contributions of FFAs to the total lipids, of C18:2 and C20:0 to the total FFA pool, of C14:0 to total FAME, and of campesterol to total sterol. The temperature increase also reduces the contributions of unusual fatty acid derivatives to total lipids, of C14:0, C15:0, C16:0 and C17:0 saturated free fatty acids to total FFAs, and of C16:0 FA to total FAME. Fatty acids are implicated in the control of membrane structure fluidity and the observed changes may promote acclimation and thermostability as temperature varies. Seawater pCO2 has no significant effect on the composition of tissue lipids with the exception that the contribution of C14:0 FA to total lipid content is significantly lower at 180 µatm compared to 260 and 750 µatm. Decreased contribution of total sterols and unusual fatty acid derivatives and increased contribution of total FFAs to total lipids are observed in the fastest calcifying coral (a P. lutea specimen) compared to the other corals, under all pCO2 and temperature conditions. Although a rapid calcifier this genotype has been shown previously to exhibit pronounced abnormal changes in skeletal morphology in response to decreased seawater pCO2. Variations in tissue lipid composition between coral genotypes may influence their resilience to future climate change.

The Tonian–Cambrian Dalradian Supergroup in Scotland is a siliciclastic–carbonate succession that can be up to 10 km thick. The consensus view is that its lower part, the mid- to late Tonian Grampian and Appin groups, formed in rift basins: the deep marine turbidites of the Grampian Group infilled rift depocentres, whereas the shallow marine strata of the Appin Group mark basin-bounding palaeohighs. This scenario is used as a key line of evidence to infer the onset of the break-up of Rodinia between Laurentia and Baltica. However, deformation during the mid-Ordovician Caledonian Orogeny obscured the original depositional frameworks. Reconstructing these frameworks (and hypothesized rift basins) has relied on the trace and major element log-ratio geochemistry of minor carbonate rocks to assign the units to either the Grampian or Appin group – that is, to rift depocentres or basin-bounding palaeohighs, respectively. We report new carbon and oxygen isotope and geochemical data and use these to create a revised stratigraphic framework for the Grampian and Appin groups. Our findings show that the previous geochemical-based correlations are unreliable and that there is no evidence for palaeohighs or rift basins. Instead, the Grampian–Appin groups are a deeper marine flysch to a shallower marine molasse succession formed in response to the mid-Tonian Knoydartian Orogeny. From a Scottish perspective, evidence for the break-up of Rodinia is recorded higher in the Dalradian succession during the deposition of the early Cryogenian Argyll Group. Supplementary material: Geochemical analysis of samples is available at https://doi.org/10.6084/m9.figshare.c.6317830 Thematic collection: This article is part of the Caledonian Wilson cycle collection available at: https://www.lyellcollection.org/topic/collections/the-caledonian-wilson-cycle

Funding: This work was supported by NSF EAR-1650033 (DT), NSF EAR-1751903 (DT) and NASA PC3 grant 80NSSC19M0069 (DT). Constraining the lithological diversity and tectonics of the earliest Earth is critical to understanding our planet’s evolution. Here we use detrital Jack Hills zircon (3.7 − 4.2 Ga) analyses coupled with new experimental partitioning data to model the silica content, Si+O isotopic composition, and trace element contents of their parent melts. Comparing our derived Jack Hills zircons’ parent melt Si+O isotopic compositions (−1.92 ≤ δ30SiNBS28 ≤ 0.53 ‰; 5.23 ≤ δ18OVSMOW ≤ 9.00 ‰) to younger crustal lithologies, we conclude that the chemistry of the parent melts was influenced by the assimilation of terrigenous sediments, serpentinites, cherts, and silicified basalts, followed by igneous differentiation, leading to the formation of intermediate to felsic melts in the early Earth. Trace element measurements also show that the formational regime had an arc-like chemistry, implying the presence of mobile-lid tectonics in the Hadean. Finally, we propose that these continental-crust forming processes operated uniformly from 4.2 to at least 3.7 Ga. Publisher PDF

Funding: Funding was provided by NSF Grants OCE1220600 and OCE1220302 awarded to JA and WB, respectively, MINECO PID2020-113526RB-I00, the Generalitat de Catalunya MERS (#2017 SGR-1588) awarded to PZ and NERC grant NE/N011716/1 awarded to JR. Planktonic calcifying organisms play a key role in regulating ocean carbonate chemistry and atmospheric CO2. Surprisingly, references to the absolute and relative contribution of these organisms to calcium carbonate production are lacking. Here we report quantification of pelagic calcium carbonate production in the North Pacific, providing new insights on the contribution of the three main planktonic calcifying groups. Our results show that coccolithophores dominate the living calcium carbonate (CaCO3) standing stock, with coccolithophore calcite comprising ~90% of total CaCO3 production, and pteropods and foraminifera playing a secondary role. We show that pelagic CaCO3 production is higher than the sinking flux of CaCO3 at 150 and 200 m at ocean stations ALOHA and PAPA, implying that a large portion of pelagic calcium carbonate is remineralised within the photic zone; this extensive shallow dissolution explains the apparent discrepancy between previous estimates of CaCO3 production derived from satellite observations/biogeochemical modeling versus estimates from shallow sediment traps. We suggest future changes in the CaCO3 cycle and its impact on atmospheric CO2 will largely depend on how the poorly-understood processes that determine whether CaCO3 is remineralised in the photic zone or exported to depth respond to anthropogenic warming and acidification. Publisher PDF

STFC are acknowledged for supporting the “Curation and Preliminary Examination of the Winchcombe Carbonaceous Chondrite Fall” project (ST/V000799/1), and Natural History Museum staff for curatorial support. Oxygen isotope studies at the Open University are funded by a consolidated grant from the Science and Technology Facilities Council (STFC), UK GRANT NUMBER: ST/T000228/1 (IAF, RCG, JM, MA), and STFC studentship NUMBER: ST/S505614/1 (RF). As part of an integrated consortium study, we have undertaken O, Cd, Cr, Si, Te, Ti, and Zn whole rock isotopic measurements of the Winchcombe CM2 meteorite. δ66Zn values determined for two Winchcombe aliquots are +0.29 ± 0.05‰ (2SD) and +0.45 ± 0.05‰ (2SD). The difference between these analyses likely reflects sample heterogeneity. Zn isotope compositions for Winchcombe show excellent agreement with published CM2 data. δ114Cd for a single Winchcombe aliquot is +0.29 ± 0.04‰ (2SD), which is close to a previous result for Murchison. δ130Te values for three aliquots gave indistinguishable results, with a mean value of +0.62 ± 0.01‰ (2SD) and are essentially identical to published values for CM2s. ε53Cr and ε54Cr for Winchcombe are 0.319 ± 0.029 (2SE) and 0.775 ± 0.067 (2SE), respectively. Based on its Cr isotopic composition, Winchcombe plots close to other CM2 chondrites. ε50Ti and ε46Ti values for Winchcombe are 3.21 ± 0.09 (2SE) and 0.46 ± 0.08 (2SE), respectively, and are in line with recently published data for CM2s. The δ30Si composition of Winchcombe is −0.50 ± 0.06‰ (2SD, n = 11) and is essentially indistinguishable from measurements obtained on other CM2 chondrites. In conformity with petrographic observations, oxygen isotope analyses of both bulk and micromilled fractions from Winchcombe clearly demonstrate that its parent body experienced extensive aqueous alteration. The style of alteration exhibited by Winchcombe is consistent with relatively closed system processes. Analysis of different fractions within Winchcombe broadly support the view that, while different lithologies within an individual CM2 meteorite can be highly variable, each meteorite is characterized by a predominant alteration type. Mixing of different lithologies within a regolith environment to form cataclastic matrix is supported by oxygen isotope analysis of micromilled fractions from Winchcombe. Previously unpublished bulk oxygen isotope data for 12 CM2 chondrites, when combined with published data, define a well‐constrained regression line with a slope of 0.77. Winchcombe analyses define a more limited linear trend at the isotopically heavy, more aqueously altered, end of the slope 0.77 CM2 array. The CM2 slope 0.77 array intersects the oxygen isotope field of CO3 falls, indicating that the unaltered precursor material to the CMs was essentially identical in oxygen isotope composition to the CO3 falls. Our data are consistent with earlier suggestions that the main differences between the CO3s and CM2s reflect differing amounts of water ice that co‐accreted into their respective parent bodies, being high in the case of CM2s and low in the case of CO3s. The small difference in Si isotope compositions between the CM and CO meteorites can be explained by different proportions of matrix versus refractory silicates. CMs and COs may also be indistinguishable with respect to Ti and Cr isotopes; however, further analysis is required to test this possibility. The close relationship between CO3 and CM2 chondrites revealed by our data supports the emerging view that the snow line within protoplanetary disks marks an important zone of planetesimal accretion. Publisher PDF

Funding: Samples NJH-16-39 and NJH-16-41 were collected during fieldwork associated with the HiTech AlkCarb project, which was supported by the European Union’s Horizon 2020 research and innovation programme under grant agreement No. 689909. NJH gratefully acknowledges PhD funding from the NERC SoS RARE consortium NE/M010856/1 and the University of St Andrews. The luminescence spectroscopy facility used in the present study was funded by NERC grant NE/H002715/1. EPMA data were collected at the University of Edinburgh, UK, with the assistance of Dr Chris Hayward. For the purpose of open access, the authors have applied a CC BY public copyright licence to any Accepted Author Manuscript version arising. Fluorite is one of the most common minerals in the crust and is of widespread economic importance. It shows strong UV-excited luminescence, variously attributed to defects within the fluorite structure and lanthanide substitutions. We present here a detailed chemical characterisation of a suite of natural fluorite samples, chosen to represent the range of compositions observed in nature. We perform X-ray excited luminescence spectroscopy on the samples as a function of temperature (20–673 K) in the wavelength range 250–800 nm to provide insights into physical defects in the lattice and their interactions with lanthanide substituents in natural fluorite. Most broad bands in the UV are attributed to electronic defects in the fluorite lattice, whereas sharp emissions are attributed to intra-ion energy cascades in trivalent lanthanides. Lanthanides are accommodated in fluorite by substitution for Ca2+ coupled with interstitial F−, O2− (substituting for F−) and a variety of electronic defect structures which provide local charge balance. The chondrite-normalised lanthanide profiles show that fluorite accommodates a greater proportion of heavy lanthanides (and Y) as the total Rare Earth Element (REE) concentration increases; whereas cell parameters decrease and then increase as substitution continues. Luminescence intensity also goes through a maximum and then decreases as a function of REE concentration. All three datasets are consistent with a model whereby lanthanides initially act as isolated centres, but, beyond a critical threshold (~ 1000 ppm), cluster into lanthanide-rich domains. Clustering results in shorter REE-O bond distances (favouring smaller heavier ions), a larger unit cell but more efficient energy transfer between lanthanides, thereby promoting non-radiative energy loss and a drop in the intensity of lanthanide emission. Publisher PDF

Funding: This research has been supported by the Leverhulme Trust (grant RPG-2015-246), by a Royal Society Professorship (grant no. RP/R/180003), and by a Marie Curie Career Integration Grant (CIG14-631752). Volcanic eruptions are the dominant cause of natural variability in climate forcing on timescales up to multidecadal. Large volcanic eruptions lead to global-scale climate effects and influence the carbon cycle on long timescales. However, estimating the frequency of eruptions is challenging. Here we assess the frequency at which eruptions with particular deposition fluxes are observed in the EPICA Dome C ice core over the last 200 kyr. Using S isotope analysis we confirm that most of the largest peaks recorded at Dome C are from stratospheric eruptions. The cumulative frequency through 200 kyr is close to linear, suggesting an approximately constant rate of eruptions. There is no evidence for an increase in the rate of events recorded in Antarctica at either of the last two deglaciations. Millennial variability is at the level expected from recording small numbers of eruptions, while multimillennial variability may be partly due to changes in transport efficiency through the Brewer–Dobson circulation. Our record of events with sulfate deposition rates > 20 and >50 mg m−2 contains 678 and 75 eruptions, respectively, over the last 200 kyr. Calibration with data on historic eruptions and analysis of a global Quaternary dataset of terrestrial eruptions indicates that sulfate peaks with deposition rates > 20 and >50 mg m−2 correspond to explosive eruptions of magnitude ≥ 6.5 and ≥7, respectively. The largest recorded eruption deposited just over 300 mg m−2. Publisher PDF

Funding: This study was financially supported by a NERC research grant (NE/V010824/1), and Estonian Science Agency project PRG447 to K.K Hydrothermal vents are important targets in the search for life on other planets due to their potential to generate key catalytic surfaces and organic compounds for biogenesis. Less well studied, however, is the role of hydrothermal circulation in maintaining a biosphere beyond its origin. Here we explored this question with analyses of organic carbon, nitrogen abundances, and isotopic ratios from the Paleoproterozoic Zaonega Formation (2.0 Ga), NW Russia, which is composed of interbedded sedimentary and mafic igneous rocks. Previous studies have documented mobilization of hydrocarbons, likely associated with magmatic intrusions into unconsolidated sediments. The igneous bodies are extensively hydrothermally altered. Our data reveal strong nitrogen enrichments of up to 0.6 wt.% in these altered igneous rocks, suggesting that the hydrothermal fluids carried ammonium concentrations in the millimolar range, which is consistent with some modern hydrothermal vents. Further, large isotopic offsets of approximately 10 ‰ between organic-bound and silicate-bound nitrogen are most parsimoniously explained by partial biological uptake of ammonium from the vent fluid. Our results, therefore, show that hydrothermal activity in ancient marine basins can provide a locally high flux of recycled nitrogen. Hydrothermal nutrient recycling may thus be an important mechanism for maintaining a large biosphere on anoxic worlds. Postprint

Authors acknowledge the crew and researchers on board the research cruises JC142 (Tropic Seamount in 2016; project ‘MarineE-tech’; grants NE/M011186/1, awarded to B. Murton and NE/M011151/1, awarded to P. Lusty), JC094 (Equatorial Atlantic in 2013) and CE08-06 (Reykjanes Ridge in 2008) who obtained the samples for this study. We thank Christopher Coath, Carolyn Taylor and Yun-Ju Sun for their help with laboratory work. We thank the editors, Sophia Hines, and two other reviewers for their comments which considerably improved this manuscript. Funding was provided by NERC grants awarded to L.F.R. (NE/S001743/1 and NE/R005117/1) and by Schlumberger Foundation who provided the PhD scholarship “Faculty for the Future Fellowship”. M.V.K. acknowledges the support from the São Paulo Research Foundation (FAPESP #2017/50229-5) and from the National Council for Scientific and Technological Development (CNPq #301436/2018-5). Scleractinian cold-water corals are found across the Northeast Atlantic, providing structure for important habitats that support high biodiversity. Climate-driven perturbations on parameters such as carbonate chemistry, oxygen, bottom currents, productivity and temperature have the potential to impact the abundance and diversity of these cold-water coral communities. One way to explore the linkage between corals and climate is to examine historic coral distributions during times of past climate change. Previous coral dating efforts in the Northeast Atlantic (n ∼ 700) have focused on reef-forming colonial coral communities from shelf and slope areas. However, there are far fewer data from open-ocean settings or from solitary coral species, thus precluding assessment of basin-wide controls on coral occurrence. Here, we contribute >600 new U-series ages for both solitary and colonial coral species from open-ocean sites including the Reykjanes Ridge and seamounts in the mid and low latitudes to map the changing distribution of Northeast Atlantic cold-water corals over the last 150,000 years. The temporal occurrences of solitary and colonial corals from our offshore sites are broadly similar to the distributions along the nearer-shore sites at the same latitudes. In the cold-temperate and high-latitude Northeast Atlantic, corals are most abundant during warm climate intervals, with the Reykjanes Ridge (60°N) representing the northernmost limit of corals in the Northeast Atlantic during Marine Isotope Stage (MIS) 5, MIS 3 and Bølling-Allerød. This biogeographical distribution expanded northwards to the Norwegian margin at the onset of the Holocene when the ice sheets retreated and modern-like oceanographic conditions were established. We interpret the abundance of corals at these northerly sites to be linked with increased food supply and favourable hydrological conditions. By contrast, coral sites south of 45°N are characterised by glacial and deglacial occurrences, with a marked decline during the Holocene. This distribution is also linked to food supply, potentially driven by shifts in dust fertilization and upwelling, in addition to changes in dissolved oxygen concentration and temperature. Together, these findings emphasize the links between climate, oceanic processes, and cold-water coral distribution, pointing to low food supply and low oxygen concentration as limiting factors for cold-water coral populations. Both parameters are changing in the modern ocean, with implications for future coral communities. Publisher PDF

We measured the isotopic compositions and concentrations of He, Ne and Ar as well as the concentrations of cosmogenic ^Be, ^Al and ^Cl in 26 H-chondrites and 1 L-chondrite from a meteorite stranding area near the Frontier Mountain Range, East Antarctica. Based on the radionuclide concentrations and the noble gas signatures we conclude the 26 H-chondrite samples represent at least 13 different falls. The exposure ages of most H-chondrites are in the range of 4-10 million years (My). This age range encompasses the well-established exposure age peak at ∿7 My and an additional feature at ∿4 My. We determined the terrestrial ages on the basis of the ^Cl concentration as well as using the relation between the ^Cl/^Be ratio and the ^Be concentration. This relation also corrects for shielding effects and reduces the uncertainty in the age by ∿25% compared to simple ^Cl terrestrial ages. About 40% of the meteorites are older than 100 thousand years (ky), but none are older than 200ky. The relatively short terrestrial ages suggest that Frontier Mountain is a young meteorite stranding area. This seems to be supported by the bedrock exposure history, which shows a recent surface exposure≤70ky.

International audience; Water enters Earth's mantle via subduction of hydrated oceanic slab and largely returns to the ocean-atmosphere system through arc volcanism. However, the extent to which H 2O is transferred into the deep mantle is poorly constrained. Here, we address this question by combining mineral chemistry and bulk-rockgeochemistry data for aillikites related to the deep mantle plume which generated the Permian Tarim large igneous province (NW China). The water contents of olivine phenocrysts are 75–168 ppm H 2O and positively correlated with Ti contents. These results, combined with infrared hydroxyl peaks at 3,572 and 3,525 cm −1 , suggest that H is mainly present in the form of Ti-clinohumite-like point defects. Hydrogen concentration profiles across olivine reveal that H loss during decompression was limited to the outermost rims, and yield dehydration durations of 15–417 min. Based on the water contents of the highest-Fo olivine cores, the water contents of the primitive aillikite melts and their mantle source are estimated as 1.6–4.7 wt% and 150–1,200 ppm H 2O, respectively. 3He/ 4He ratios (5.31–5.84 Ra) of olivine phenocrysts are slightly lower than MORBs and suggest involvement of recycled slab containing U (and hence radiogenic 4He) in the plume source. This interpretation is consistent with Pb isotope compositions of the aillikites which are intermediate between PREMA (Prevalent Mantle) and EM (Enriched Mantle) compositions. These lines of evidence combined with the depleted Sr-Nd isotopes and moderately radiogenic Os isotopes of the aillikites suggest that water in these rocks derived from a plume source marginally contaminated by deeply subducted hydrated material.

Funding information: This work was supported by grants from the National Science Foundation (OCE-2015647 and OCE-2032340 to PAR; OCE- 2032343 to MPH); NERC grant NE/N011716/1 to JWBR and NERC grant NE/M004619/1 to AB. Using new and published marine fossil radiocarbon (14C/C) measurements, a tracer uniquely sensitive to circulation and air-sea gas exchange, we establish several benchmarks for Atlantic, Southern, and Pacific deep-sea circulation and ventilation since the last ice age. We find the most 14C-depleted water in glacial Pacific bottom depths, rather than the mid-depths as they are today, which is best explained by a slowdown in glacial deep-sea overturning in addition to a “flipped” glacial Pacific overturning configuration. These observations cannot be produced by changes in air-sea gas exchange alone, and they underscore the major role for changes in the overturning circulation for glacial deep-sea carbon storage in the vast Pacific abyss and the concomitant drawdown of atmospheric CO2. Publisher PDF

Present estimates of the biogeochemical cycles of calcium, strontium, and potassium in the ocean reveal large imbalances between known input and output fluxes. Using pore fluid, incubation, and solid sediment data from North Pacific multi‐corer cores we show that, contrary to the common paradigm, the top centimeters of abyssal sediments can be an active site of authigenic precipitation of clay minerals. In this region, clay authigenesis is the dominant sink for potassium and strontium and consumes nearly all calcium released from benthic dissolution of calcium carbonates. These observations support the idea that clay authigenesis occurring over broad regions of the world ocean may be a major buffer for ocean chemistry on the time scale of the ocean overturning circulation, and key to the long‐term stability of Earth's climate., Key Points: North Pacific red clay sediments are a sink for marine calcium, strontium, and potassium. Authigenic formation of clay minerals is prevalent in pelagic sediments throughout the North Pacific. The main mechanism for clay formation is recrystallization of aluminosilicates, neoformation can occur in biogenic silica rich sediments., EC H2020 PRIORITY “Excellent science” H2020 European Research Council http://dx.doi.org/10.13039/100010663, Blavatnik Family Foundation http://dx.doi.org/10.13039/100011643, Isaac Newton Trust http://dx.doi.org/10.13039/501100004815, Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659, National Science Foundation http://dx.doi.org/10.13039/100000001, https://doi.pangaea.de/10.1594/PANGAEA.946881

Recent advances in geochemical techniques mean that several robust proxies now exist to determine the past carbonate chemistry of the oceans. Foraminiferal δ11B and alkenone carbon isotopes allow us to reconstruct sea-surface pH and pCO2, respectively, and the ability to apply both proxies to the same sediment sample would give strongly paired datasets and reduce sample waste. However, no studies to date have examined whether the solvents and extraction techniques used to prepare alkenones for analysis also impact the geochemistry of foraminifera within those sediments. Here we examine six species pairs of planktic foraminifera, with half being taken from non-treated sediments and half being taken from sediments where alkenones have been extracted. We look for visual signs of contrasting preservation and compare analyses of δ18O, δ13C, δ11B and trace elements (Li, B, Na, Mn, Mg, Sr and U/Ca). We find no consistent geochemical offset between the treatments and excellent agreement in δ11B measurements between them. Our results show that boron isotope reconstructions of pH in foraminifera from alkenone-extracted sediments can be applied with confidence.

Funding was provided by the University of Edinburgh, the Royal Society (grant NIF\R1\191527), National Science Foundation (grants DEB 1654949 and EAR 1654952), European Research Council (ERC) starting grants (nos. 756226 and 805246) under the European Union’s Horizon 2020 Research and Innovation Programme, a Philip Leverhulme Prize and a SNSF Mobility Fellowship (grant P2EZP2_199923). After the end-Cretaceous extinction, placental mammals quickly diversified , occupied key ecological niches and increased in size , but this last was not true of other therians. The uniquely extended gestation of placental young may have factored into their success and size increase, but reproduction style in early placentals remains unknown. Here we present the earliest record of a placental life history using palaeohistology and geochemistry, in a 62 million-year-old pantodont, the clade including the first mammals to achieve truly large body sizes. We extend the application of dental trace element mapping by 60 million years, identifying chemical markers of birth and weaning, and calibrate these to a daily record of growth in the dentition. A long gestation (approximately 7 months), rapid dental development and short suckling interval (approximately 30-75 days) show that Pantolambda bathmodon was highly precocial, unlike non-placental mammals and known Mesozoic precursors. These results demonstrate that P. bathmodon reproduced like a placental and lived at a fast pace for its body size. Assuming that P. bathmodon reflects close placental relatives, our findings suggest that the ability to produce well-developed, precocial young was established early in placental evolution, and that larger neonate sizes were a possible mechanism for rapid size increase in early placentals. Postprint

This study was supported by a UK Natural Environment Research Council grant (NERC; number NE/R000670/1 to AG). MG is also grateful for support from an Ifremer Postdoctoral Fellowship. Alvinella samples were collected with the help of a NERC Small Grant (number NE/C000714/1 to CTSL). S isotopic analyses were undertaken under NERC Facility awards IP-1755-1117 and IMF672/1118. Symbioses between metazoans and microbes involved in sulfur cycling are integral to the ability of animals to thrive within deep‐sea hydrothermal vent environments; the development of such interactions is regarded as a key adaptation in enabling animals to successfully colonize vents. Microbes often colonize the surfaces of vent animals and, remarkably, these associations can also be observed intricately preserved by pyrite in the fossil record of vent environments, stretching back to the lower Paleozoic (Ordovician‐early Silurian). In non‐vent environments, sulfur isotopes are often employed to investigate the metabolic strategies of both modern and fossil organisms, as certain metabolic pathways of microbes, notably sulfate reduction, can produce large sulfur isotope fractionations. However, the sulfur isotopes of vent fossils, both ancient and recently mineralized, have seldom been explored, and it is not known if the pyrite‐preserved vent organisms might also preserve potential signatures of their metabolisms. Here, we use high‐resolution secondary ion mass spectrometry (SIMS) to investigate the sulfur isotopes of pyrites from recently mineralized and Ordovician‐early Silurian tubeworm fossils with associated microbial fossils. Our results demonstrate that pyrites containing microbial fossils consistently have significantly more negative δ34S values compared with nearby non‐fossiliferous pyrites, and thus represent the first indication that the presence of microbial sulfur‐cycling communities active at the time of pyrite formation influenced the sulfur isotope signatures of pyrite at hydrothermal vents. The observed depletions in δ34S are generally small in magnitude and are perhaps best explained by sulfur isotope fractionation through a combination of sulfur‐cycling processes carried out by vent microbes. These results highlight the potential for using sulfur isotopes to explore biological functional relationships within fossil vent communities, and to enhance understanding of how microbial and animal life has co‐evolved to colonize vents throughout geological time. Publisher PDF

Funding: This work was supported by the Swiss National Science Foundation (MHV fellowship to A.N.M.); the European Research Council (starting grant 638467 to A.N.M. and starting grant 805246 to J.W.B.R.); the Trond Mohn Foundation (starting grant BFS2015REK01 to A.N.M.); the Norwegian Research Council (infrastructure grant 245907 to A.N.M.); the Natural Environment Research Council (NERC grant NE/P019331/1 to P.F.S.); the Dutch Research Council (NWO VIDI project 016.161.365 to M.Z.); the Heising Simons Foundation (grant 2022-3314 to A.T.); and the Netherlands Earth System Science Centre (NESSC) (L.J.L.). Characterizing past climate states is crucial for understanding the future consequences of ongoing greenhouse gas emissions. Here, we revisit the benchmark time series for deep ocean temperature across the past 65 million years using clumped isotope thermometry. Our temperature estimates from the deep Atlantic Ocean are overall much warmer compared with oxygen isotope-based reconstructions, highlighting the likely influence of changes in deep ocean pH and/or seawater oxygen isotope composition on classical oxygen isotope records of the Cenozoic. In addition, our data reveal previously unrecognized large swings in deep ocean temperature during early Eocene acute greenhouse warmth. Our results call for a reassessment of the Cenozoic history of ocean temperatures to achieve a more accurate understanding of the nature of climatic responses to tectonic events and variable greenhouse forcing. Postprint

Funding: This work was supported by the Leverhulme Trust (Research project grant 2015-268 to NA, RK, and KP) and the UK Natural Environment Research Council (NE/S001417/1) to NA, KP, RK, MC and AF. The Raman Microscope is supported by the EPSRC (Light Element Analysis Facility Grant EP/T019298/1 and Strategic Equipment Resource Grant EP/R023751/1). Resolving how factors such as temperature, pH, biomolecules and mineral growth rate influence the geochemistry and structure of biogenic CaCO3, is essential to the effective development of palaeoproxies. Here we optimise a method to precipitate the CaCO3 polymorph aragonite from seawater, under tightly controlled conditions that simulate the saturation state (Ω) of coral calcification fluids. We then use the method to explore the influence of aspartic acid (one of the most abundant amino acids in coral skeletons) on aragonite structure and morphology. Using ≥200 mg of aragonite seed (surface area 0.84 m2), to provide a surface for mineral growth, in a 330 mL seawater volume, generates reproducible estimates of precipitation rate over Ωaragonite = 6.9-19.2. However, unseeded precipitations are highly variable in duration and do not provide consistent estimates of precipitation rate. Low concentrations of aspartic acid (1-10 µM) promote aragonite formation, but high concentrations (≥ 1 mM) inhibit precipitation. The Raman spectra of aragonite precipitated in vitro can be separated from the signature of the starting seed by ensuring that at least 60% of the analysed aragonite is precipitated in vitro (equivalent to using a seed of 200 mg and precipitating 300 mg aragonite in vitro). Aspartic acid concentrations ≥ 1mM caused a significant increase in the full width half maxima of the Raman aragonite v1 peak, reflective of increased rotational disorder in the aragonite structure. Changes in the organic content of coral skeletons can drive variations in the FWHM of the Raman aragonite ν1 peak, and if not accounted for, may confuse the interpretation of calcification fluid saturation state from this parameter. Publisher PDF

This research was supported in part by a Royal Society Newton International postdoctoral Fellowship to SZ from the Royal Society of London. JWBR acknowledges funding from the European Research Council under the European Union’s Horizon 2020 research and innovation program (grant agreement 805246). We also acknowledge support from U.K. NERC Grant (PUCCA) NE/V011049/1. The mass of well-preserved calcite in planktonic foraminifera shells provides an indication of the calcification potential of the surface ocean. Here we report the shell weight of 8 different abundant planktonic foraminifera species from a set of core-to sediments along the Mid-Atlantic Ridge. The analyses showed that near the equator, foraminifera shells of equivalent size weigh on average 1/3 less than those from the middle latitudes. The carbonate preservation state of the samples was assessed by high resolution X-ray microcomputed tomographic analyses of Globigerinoides ruber and Globorotalia truncatulinoides specimens. The specimen preservation was deemed good and does not overall explain the observed shell mass variations. However, G. ruber shell weights might be to some extent compromised by residual fine debris internal contamination. Deep dwelling species possess heavier tests than their surface-dwelling counterparts, suggesting that the weight of the foraminifera shells changes as a function of the depth habitat. Ambient seawater carbonate chemistry of declining carbonate ion concentration with depth cannot account for this interspecies difference. The results suggest a depth regulating function for plankton calcification, which is not dictated by water column acidity. Publisher PDF

S.W.P. acknowledges support from a Leverhulme Research Fellowship and a Royal Society Wolfson Research Merit Award. A.B. acknowledges support from the University of Johannesburg in the form of a Distinguished Visiting Professorship. D.T.J. acknowledges support from a NASA Exobiology award (NNX15AP58G). The rise of atmospheric oxygen fundamentally changed the chemistry of surficial environments and the nature of Earth’s habitability1. Early atmospheric oxygenation occurred over a protracted period of extreme climatic instability marked by multiple global glaciations2,3, with the initial rise of oxygen concentration to above 10−5 of the present atmospheric level constrained to about 2.43 billion years ago4,5. Subsequent fluctuations in atmospheric oxygen levels have, however, been reported to have occurred until about 2.32 billion years ago4, which represents the estimated timing of irreversible oxygenation of the atmosphere6,7. Here we report a high-resolution reconstruction of atmospheric and local oceanic redox conditions across the final two glaciations of the early Palaeoproterozoic era, as documented by marine sediments from the Transvaal Supergroup, South Africa. Using multiple sulfur isotope and iron–sulfur–carbon systematics, we demonstrate continued oscillations in atmospheric oxygen levels after about 2.32 billion years ago that are linked to major perturbations in ocean redox chemistry and climate. Oxygen levels thus fluctuated across the threshold of 10−5 of the present atmospheric level for about 200 million years, with permanent atmospheric oxygenation finally arriving with the Lomagundi carbon isotope excursion at about 2.22 billion years ago, some 100 million years later than currently estimated. Postprint

Funding for SM, ERM, and MR is provided by NERC standard grant (NE/P012167/1) and UK Space Agency Aurora grant (ST/T001763/1). Funding for DAS is provided by the US DOE (DE-FG-02-96ER-14616) and the US NSF (EAR 1624325 and ACI 1550346). Diamond inclusions sample the otherwise inaccessible archive of Earth’s deep interior. The geochemical and petrological diversity of diamond inclusions reflects either pre-metasomatic upper mantle heterogeneity or metasomatism coeval with diamond formation. We focus on the origin of lithospheric garnet and clinopyroxene inclusions by simulating metasomatic reactions between eclogitic fluids and mantle peridotites at 5 GPa, 1000 °C, and across a range of redox conditions (logfO2 = −1 to −6 ΔFMQ). Our results demonstrate that fluid-rock interaction can result in the formation of eclogitic, websteritic, and peridotitic silicates from a single fluid during a single diamond-forming metasomatic event. Ergo, the petrogenesis of diamond and their inclusions can be syngenetic, and the petrological diversity of diamond inclusions can reflect metasomatism coeval with diamond formation. Furthermore, during the metasomatism, refractory peridotite can be converted to fertile websterite which could become a pyroxenitic mantle source for oceanic basalts. Publisher PDF

The scope of the present study was to develop an empirical kinetic model predicting, over the whole range of reactant conversions (0–100%), the yield of CH 4 generated from the thermal degradation of 1,2,4-trimethylbenzene, a model compound for methylated mono-aromatic hydrocarbons present in oil. Most of the chemical equations of the model were constrained by our previous mechanistic model ( Fusetti et al., 2010 ). The resulting reaction scheme was composed of four CH 4 generation pathways: ( P a ) dimerization of 1,2,4-trimethylbenzene, ( P b ) demethylation of 1,2,4-trimethylbenzene into xylenes, ( P c ) condensation reactions of dimers and C 18+ products into (prechar + char) components and ( P d ) dimerization of xylenes and their demethylation into toluene. Associated activation energies were in the range 52–61 kcalmol -1 and frequency factors were all in the neighborhood of 10 12 s −1 . Below 5% conversion, P b and P c governed CH 4 generation, followed by P a . Above 5% conversion, P c was the main source of CH 4 , followed by P b and P a , respectively. P d showed negligible CH 4 yields up to 95% conversion. Above 100% conversion, the degradation of (prechar + char) components seemed the most likely new source of gas which was not accounted for in the model. Using a unique chemical equation with a maximum CH 4 yield of 7.6 wt% per CH 3 group and an associated set of kinetic parameters E a = 58.5 kcalmol -1 and A = 10 11.96 s −1 , we demonstrated CH 4 generation kinetics from the thermal degradation of 1,2,4-trimethylbenzene to be similar to CH 4 generation kinetics previously reported from the thermal degradation of methylated polyaromatic hydrocarbons. Eventually, the four-equation empirical model was used to perform simulations under temperature conditions usually encountered in deeply buried reservoirs (DBR). Under these conditions, the simulations revealed the CH 4 prone character of methylated mono-aromatic hydrocarbons. Moreover, these simulations demonstrated that the thermal stability increased as follows: methylated polyaromatics

This work was supported by PhD funding to MM by the University of St Andrews School of Earth and Environmental Sciences and the Handsel scheme, as well as by NERC grant NE/R002134/1 to PS and NSF grant EAR-1321954 to RR and RG. Twenty-four composite samples of the fine-grained matrix of glacial diamictites deposited from the Mesoarchaean to Palaeozoic have been analysed for their silicon isotope composition and used to establish, for the first time, the long-term secular Si isotope record of the compositional evolution of upper continental crust (UCC). Diamictites with Archaean and Palaeoproterozoic Nd model ages show greater silicon isotope heterogeneity than those with younger model ages (irrespective of depositional age). We attribute the anomalously light Si isotope compositions of some diamictites with Archaean model ages to the presence of glacially milled banded iron formation (BIF), substantiated by the high iron content and Ge/Si in these samples. We infer that relatively heavy Si isotope signatures in some Palaeoproterozoic diamictites (all of which have Archaean Nd model ages) are due to contribution from tonalite-trondhjemite-granodiorites (TTGs), evidenced by the abundance of TTG clasts. By the Neoproterozoic (with model ages ranging from 2.3 to 1.8 Ga), diamictite Si isotope compositions exhibit a range comparable to modern UCC. This reduced variability through time is interpreted as reflecting the decreasing importance of BIF and TTG in post-Archaean continental crust. The secular evolution of Si isotopes in the diamictites offers an independent test of models for the emergence of stable cratons and the onset of horizontal mobile-lid tectonism. The early Archaean UCC was heterogeneous and incorporated significant amounts of isotopically light BIF, but following the late Archaean stabilisation of cratons, coupled with the oxygenation of the atmosphere that led to the reduced neoformation of BIF and diminishing quantities of TTGs, the UCC became increasingly homogeneous. This homogenisation likely occurred via reworking of preexisting crust, as evidenced by Archaean Nd model ages recorded in younger diamictites. Publisher PDF

Key Points: - High resolution carbonate chemistry, δ13C-DIC, and particle flux measurements in the NE Pacific sheds light on the upper oceancalcium carbonate and alkalinity cycles. - Based on this sampling campaign, there isevidence for substantial CaCO3 dissolution in the mesopelagic zone above the saturation horizon. - Dissolution experiments, observations, and modeling suggest that shallow CaCO3 dissolutionis coupled to the consumption of organic carbon, through a combination of zooplankton grazing and oxic respiration within particle microenvironments. The cycling of biologically produced calcium carbonate (CaCO3) in the ocean is a fundamental component of the global carbon cycle. Here, we present experimental determinations of in situcoccolith and foraminiferal calcite dissolution rates.We combine these rates with solid phase fluxes,dissolved tracers, and historical data to constrain the alkalinity cycle in the shallow North Pacific Ocean.The in situ dissolution rates of coccolithophores demonstrate a nonlinear dependence on saturation state. Dissolution ratesof all three major calcifying groups (coccoliths, foraminifera, and aragonitic pteropods)aretoo slow to explainthe patternsofboth CaCO3sinking fluxand alkalinity regenerationin the NorthPacific.Usinga combination of dissolved and solid-phase tracers, we document a significant dissolution signal in seawater supersaturated for calcite. Driving CaCO3dissolutionwith acombination of ambient saturation state and oxygen consumption simultaneously explainssolid-phase CaCO3flux profiles and patterns of alkalinity regeneration across the entire N. Pacific basin. Wedo not need to invokethe presence ofcarbonate phases with higher solubilities.Instead, biomineralization and metabolic processesintimately associatethe acid (CO2) and the base (CaCO3) in the same particles,driving the coupled shallow remineralization of organic carbonand CaCO3.The linkage of these processes likely occurs through a combination of dissolution due to zooplankton grazing and microbial aerobic respiration withindegrading particle aggregates.The coupling of these cyclesacts as a major filter on the export of both organic and inorganic carbon to the deep ocean.

Funding: Natural Environment Research Council (Grant Number(s): NE/V010824/1; Grant recipient(s): Eva Stüeken). Nitrogen isotopes and abundances in sedimentary rocks have become an important tool for reconstructing biogeochemical cycles in ancient ecosystems. There are two archives of nitrogen in the rock record, namely kerogen-bound amines and silicate-bound ammonium, and it is well documented that the isotopic ratios of these two archives can be offset from one another. This offset has been observed to increase with metamorphic grade, suggesting that it may be related to the bonding environment in differing nitrogen host phases and associated equilibrium isotope fractionation. However, theoretical bounds for this effect have not been established, and it remains possible that some isotopic offsets predate metamorphism. In support of this hypothesis, we report an unexpectedly large isotopic offset of 4–5‰ in siltstones of very low metamorphic grade from the late Mesoproterozoic Diabaig Formation in NW Scotland (1.0 Ga). Carbon to nitrogen ratios of bulk rocks are 2–3 times lower than in other Mesoproterozoic sections. The rocks also contain early-formed phosphate concretions and display wrinkled surfaces on bedding planes, indicative of fossilised microbial mats. Collectively, these data are most parsimoniously interpreted as evidence of diagenetic ammonium release from microbial mats into porewaters, followed by partial oxidation to nitrite or nitrate at the sediment–water interface. This process would render residual ammonium in clays isotopically heavy, while the resulting nitrite or nitrate would be relatively lighter and captured in new biomass, leading to the observed isotopic divergence. The same diagenetic degradation pathway likely also liberated phosphate that was trapped within concretions. Diagenetic release of nutrients is known to occur in modern settings, and our data suggest that nitrogen isotopes may be a way to track this local sedimentary nutrient source in past environments. Lastly, we speculate that diagenetic nutrient recycling within Proterozoic microbial mats may have created a favourable niche for eukaryotic organisms in shallow waters. Publisher PDF

This work was financially supported by the National Key R&D Program of China (2018YFA0702600) and National Science Foundation of China (41890831). Here we report the Si isotope compositions of four potential reference materials, including one fused quartz glass (Glass-Qtz), one natural quartz (Qinghu-Qtz), and two natural zircons (Qinghu-Zir and Penglai-Zir), suitable for in-situ Si isotopic microanalysis. Repeated SIMS (Secondary Ion Mass Spectrometry) analyses demonstrate that these materials are more homogeneous in Si isotopes (with the spot-to-spot uncertainty of 0.090-0.102‰), compared with the widely used NIST RM 8546 (previously NBS-28) quartz standard (with the spot-to-spot uncertainty poorer than 0.16‰). Based on the solution-MC-ICP-MS determination, the recommended δ30Si values are −0.10 ± 0.04 ‰ (2SD), −0.03 ± 0.05 ‰ (2SD), −0.45 ± 0.06 ‰ (2SD), and −0.34 ± 0.06 ‰ (2SD), for Glass-Qtz, Qinghu-Qtz, Qinghu-Zir, and Penglai-Zir, respectively. Our results reveal no detectable matrix effect on SIMS Si isotopic microanalysis between the fused quartz glass (Glass-Qtz) and natural quartz (Qinghu-Qtz) standards. Therefore, we propose that this synthetic quartz glass may be used as an alternative, more homogenous standard for SIMS Si isotopic microanalysis of natural quartz samples. Publisher PDF

The expedition was funded by the Mining Institute of Scotland Trust, the Institute of Materials, Minerals and Mining, the Society of Economic Geologists Hickok-Radford Fund, the Edinburgh Geological Society, the Augustine Courtauld trust and the Scott Polar Research Institute. Igneous sheet intrusions are a fundamental component of volcano plumbing systems. Identifying how sheet intrusion emplacement and geometry controls later magmatic processes is critical to understanding the distribution of volcanic eruptions and magma-related ore deposits. Using the Younger Giant Dyke Complex, a Mesoproterozoic suite of large (< 800 m wide) mafic dykes in southern Greenland, we assess the influence sheet of emplacement and geometry on subsequent magma flow and mush evolution. Through structural mapping, petrographic observations, and anisotropy of magnetic susceptibility fabric analyses, we show that the Younger Giant Dyke Complex was emplaced as a series of individual dyke segments, which following coalescence into a sheet intrusion remained largely isolated during their magmatic evolution. Through petrographic evidence for liquid-rich growth of cumulus phases, concentric magnetic fabrics, and the detailed study layered zones within the Younger Giant Dyke Complex, we infer magma convection occurred within the cores of each dyke element. We particularly relate layering to hydrodynamic sorting processes at a magma-mush boundary towards the base of each convection cell. Overall, our work demonstrates that the initial geometry of sheet intrusions can constrain magma flow patterns and affect the distribution of crystallisation regimes. Publisher PDF

This project was supported by the European Union’s Horizon 2020 research and innovation programme under grant agreement No. 689909. W.H. also acknowledges support from a UKRI Future Leaders Fellowship (MR/S033505/1). A.J.B. is funded by the NERC National Environment Isotope Facility award (NE/S011587/1) and the Scottish Universities Environmental Research Centre. Metal-rich fluids that circulate in magmatic-hydrothermal environments form a wide array of economically significant ore deposits. Unravelling the origins and evolution of these fluids is crucial for understanding how Earth’s metal resources form and one of the most widely used tools for tracking these processes is sulfur isotopes. It is well established that S isotopes record valuable information about the source of the fluid, as well as its physical and chemical evolution (i.e. changing pH, redox and temperature), but it is often challenging to unravel which of these competing processes drives isotopic variability. Here we use thermodynamic models to predict S isotope fractionation for geologically realistic hydrothermal fluids and attempt to disentangle the effects of fluid sources, physico-chemical evolution and S mineral disequilibrium. By modelling a range of fluid compositions, we show that S isotope fingerprints are controlled by the ratio of oxidised to reduced S species (SO42−/H2S), and this is most strongly affected by changing temperature, fO2 and pH. We show that SO42−/H2S can change dramatically during cooling and our key insight is that S isotopes of individual sulfide or sulfate minerals can show large fractionations (up to 20 ‰) even when pH is constant and fO2 fixed to a specific mineral redox buffer. Importantly, while it is commonly assumed that SO42−/H2S is constant throughout fluid evolution, our analysis shows that this is unlikely to hold for most natural systems. We then compare our model predictions to S isotope data from porphyry and epithermal deposits, seafloor hydrothermal vents and alkaline igneous bodies. We find that our models accurately reproduce the S isotope evolution of porphyry and high sulfidation epithermal fluids, and that most require magmatic S sources between 0 and 5 ‰. The S isotopes of low sulfidation epithermal fluids and seafloor hydrothermal vents do not fit our model predictions and reflect disequilibrium between the reduced and oxidised S species and, for the latter, significant S input from seawater and biogenic sources. Alkaline igneous fluids match model predictions and confirm magmatic S sources and a wide range of temperature and redox conditions. Of all these different ore deposits, porphyry and alkaline igneous systems are particularly well-suited to S isotope investigation because they show relationships between redox, alteration and ore mineralogy that could be useful for exploration and prospecting. Ultimately, our examples demonstrate that S isotope forward models are powerful tools for identifying S sources, flagging disequilibrium processes, and validating hypotheses of magmatic fluid evolution. Publisher PDF

The study was supported from Estonian Research Agency grant PRG447 to KK, AL and KB. The Paleoproterozoic Francevillian succession of Gabon has figured prominently in concepts about Earth’s early oxygenation and genesis of a large positive excursion in carbon-isotope values, the Lomagundi-Jatuli event (LJE). Here we present a detailed study of a 139-m-long core of Francevillian rocks marked by carbonate δ13C (δ13Ccarb) values of 5‰–9‰ that decline upsection to near 0‰, a trend inferred by many workers as a fingerprint of the LJE and its termination. However, we show that the shift in δ13Ccarb values coincides with a facies change: shallow-marine facies are marked by the strongly positive values, whereas deeper-marine facies (below storm wave base) are at ~0‰. The most circumspect interpretation of such facies dependence of δ13Ccarb is that shallow-marine settings record the isotope effects of local physical and biochemical processes driving the ambient dissolved inorganic carbon (DIC) pool to heavier values, and the lighter values (~0‰) in deeper-water facies track the DIC of the open-marine realm where δ13C was largely unaffected by fractionations occurring in shallow-water settings. Further, a transgressing redoxcline created conditions for precipitation of Mn-bearing minerals and chemotrophic microbial biota, including methane cycling communities evident by organic δ13C (δ13Corg) values of –4‰ and Δδcarb-org values as high as 46‰. Thus, the Francevillian C-isotope profile reflects basin-specific conditions and is not a priori an indicator of global C-cycle disturbances nor of the termination of the LJE. Postprint

This research was funded by European Research Council (ERC) under the European Union’s Horizon 2020 Research and Innovation Programme (Grant Agreement 678812) (to MWC). JS also acknowledges support from the China Scholarship Council (CSC). The hyperarid Atacama Desert is a unique Mars-analog environment with a large near-surface soil nitrate reservoir due to the lack of rainfall leaching for millennia. We investigated nitrogen (N) cycling and organic matter dynamics in this nitrate-rich terrestrial environment by analyzing the concentrations and isotopic compositions of nitrate, organic C, and organic N, coupled with microbial pathway-enzyme inferences, across a naturally occurring rainfall gradient. Nitrate deposits in sites with an annual precipitation of 15 mm annual precipitation. Metagenomic analyses suggest that the Atacama Desert harbors a unique biological nitrogen cycle driven by nitrifier denitrification, nitric oxide dioxygenase-driven alternative nitrification, and organic N loss pathways. Nitrate assimilation is the only nitrate consumption pathway available in the driest sites, although some hyperarid sites also support organisms with ammonia lyase- and nitric oxide synthase-driven organic N loss. Nitrifier denitrification is enhanced in the "transition zone" desert environments, which are generally hyperarid but see occasional large rainfall events, and shifts to nitric oxide dioxygenase-driven alternative nitrifications in wetter arid sites. Since extremophilic microorganisms tend to exploit all reachable nutrients, both N and O isotope fractionations during N transformations are reduced. These results suggest that N cycling on the more recent dry Mars might be dominated by nitrate assimilation that cycles atmospheric nitrate and exchanges water O during intermittent wetting, resulting stable isotope biosignatures could shift away from martian atmospheric nitrate endmember. Early wetter Mars could nurture putative life that metabolized nitrate with traceable paleoenvironmental isotopic markers similar to microbial denitrification and nitrification stored in deep subsurface. Publisher PDF

This work was supported by funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement 820047 to M.Si.), the Malcolm H. Wiener Foundation (Interdisciplinary Chronology of Civilizations Project to C.P.) and a UKRI Future Leader Fellowship (MR/S035478/1 to P.A). Decades of research have focused on establishing the exact year and climatic impact of the Minoan eruption of Thera, Greece (c.1680–1500 BCE). Ice cores offer key evidence to resolve this controversy, but attempts have been hampered by a lack of multi-volcanic event synchronization between records. In this study, Antarctic and Greenland ice-core records are synchronized using a double bipolar sulfate marker and calendar dates are assigned to each eruption revealed within the ‘Thera period’. From this global scale sequence of volcanic sulfate loading, we derive indications towards each eruption’s latitude and potential to disrupt the climate system. Ultra-fine sampling for sulfur isotopes and tephra conclusively demonstrate a colossal eruption of Alaska’s Aniakchak II as the source of stratospheric sulfate in the now precisely dated 1628 BCE ice layer. These findings end decades of speculation that Thera was responsible for the 1628 BCE event, and place Aniakchak II (52 ± 17 Tg S) and an unknown volcano at 1654 BCE (50 ± 13 Tg S) as two of the largest Northern Hemisphere sulfur injections in the last 4000 years. This opens possibilities to explore widespread climatic impacts for contemporary societies and, in pinpointing Aniakchak II, confirms that stratospheric sulfate can be globally distributed from eruptions outside the tropics. Dating options for Thera are reduced to a series of precisely dated, constrained stratospheric sulfur injection events at 1611 BCE, 1562-1555 BCE and c.1538 BCE which are all below 14 ± 5 Tg S, indicating a climatic forcing potential for Thera well below that of Tambora (1815 CE). Publisher PDF

Funding: This research was supported by American Chemical Society – Petroleum Research Fund (ACS-PRF #50755-ND2), Natural Science and Engineering Research Council (NSERC) - Discovery Grants Program (386188-2010), Ontario Ministry of Research and Innovation - Ontario Research Fund (MRI-ORF #28001), Canada Foundation for Innovation - Leaders Opportunity Fund (CFI-LOF #28001) to S.-T. Kim. Boron isotope ratios – as measured in marine calcium carbonate – are an established tracer of past seawater and calcifying fluid pH, and thus a powerful tool for probing marine calcifier physiology and reconstructing past atmospheric CO2 levels. For such applications, understanding the inorganic baseline upon which foraminiferal vital effects or coral pH upregulation are superimposed should be an important prerequisite. Yet, investigations into boron isotope fractionation in synthetic CaCO3 polymorphs have often reported variable and even conflicting results, implying our understanding of the pathways of boron incorporation into calcium carbonate is incomplete. Here we address this topic with experimental data from synthetic calcite and aragonite precipitated across a range of pH in the presence of both Mg and Ca. We observe coherent patterns in B/Ca and Na/Ca ratios that, we suggest, point to paired substitution of Na and B into the carbonate lattice to achieve local charge balance. In addition, we confirm the results of previous studies that the boron isotope composition of inorganic aragonite precipitates closely reflects that of aqueous borate ion, but that inorganic calcites display a higher degree of scatter, and diverge from the boron isotope composition of aqueous borate ion at low pH. With reference to the simultaneous incorporation of other trace and minor elements, we put forward possible explanations for the observed variability in the concentration and isotopic composition of boron in synthetic CaCO3. In particular, we highlight the potential importance of interface electrostatics in driving variability in our own and published synthetic carbonate datasets. Importantly for palaeo-reconstruction, however, these electrostatic effects are unlikely to play as important a role during natural precipitation of biogenic carbonates. Postprint

Development of renewable energy infrastructure requires critical raw materials, such as the rare earth elements (REEs, including scandium) and niobium, and is driving expansion and diversification in their supply chains. Although alternative sources are being explored, the majority of the world’s resources of these elements are found in alkaline-silicate rocks and carbonatites. These magmatic systems also represent major sources of fluorine and phosphorus. Exploration models for critical raw materials are comparatively less well developed than those for major and precious metals, such as iron, copper, and gold, where most of the mineral exploration industry continues to focus. The diversity of lithologic relationships and a complex nomenclature for many alkaline rock types represent further barriers to the exploration and exploitation of REE-high field strength element (HFSE) resources that will facilitate the green revolution. We used a global review of maps, cross sections, and geophysical, geochemical, and petrological observations from alkaline systems to inform our description of the alkaline-silicate REE + HFSE mineral system from continental scale (1,000s km) down to deposit scale (~1 km lateral). Continental-scale targeting criteria include a geodynamic trigger for low-degree mantle melting at high pressure and a mantle source enriched in REEs, volatile elements, and alkalies. At the province and district scales, targeting criteria relate to magmatic-system longevity and the conditions required for extensive fractional crystallization and the residual enrichment of the REEs and HFSEs. A compilation of maps and geophysical data were used to construct an interactive 3-D geologic model (25-km cube) that places mineralization within a depth and horizontal reference frame. It shows typical lithologic relationships surrounding orthomagmatic REE-Nb-Ta-Zr-Hf mineralization in layered agpaitic syenites, roof zone REE-Nb-Ta mineralization, and mineralization of REE-Nb-Zr associated with peralkaline granites and pegmatites. The resulting geologic model is presented together with recommended geophysical and geochemical approaches for exploration targeting, as well as mineral processing and environmental factors pertinent for the development of mineral resources hosted by alkaline-silicate magmatic systems. Development of renewable energy infrastructure requires critical raw materials, such as the rare earth elements (REEs, including scandium) and niobium, and is driving expansion and diversification in their supply chains. Although alternative sources are being explored, the majority of the world’s resources of these elements are found in alkaline-silicate rocks and carbonatites. These magmatic systems also represent major sources of fluorine and phosphorus. Exploration models for critical raw materials are comparatively less well developed than those for major and precious metals, such as iron, copper, and gold, where most of the mineral exploration industry continues to focus. The diversity of lithologic relationships and a complex nomenclature for many alkaline rock types represent further barriers to the exploration and exploitation of REE-high field strength element (HFSE) resources that will facilitate the green revolution. We used a global review of maps, cross sections, and geophysical, geochemical, and petrological observations from alkaline systems to inform our description of the alkaline-silicate REE + HFSE mineral system from continental scale (1,000s km) down to deposit scale (~1 km lateral). Continental-scale targeting criteria include a geodynamic trigger for low-degree mantle melting at high pressure and a mantle source enriched in REEs, volatile elements, and alkalies. At the province and district scales, targeting criteria relate to magmatic-system longevity and the conditions required for extensive fractional crystallization and the residual enrichment of the REEs and HFSEs. A compilation of maps and geophysical data were used to construct an interactive 3-D geologic model (25-km cube) that places mineralization within a depth and horizontal reference frame. It shows typical lithologic relationships surrounding orthomagmatic REE-Nb-Ta-Zr-Hf mineralization in layered agpaitic syenites, roof zone REE-Nb-Ta mineralization, and mineralization of REE-Nb-Zr associated with peralkaline granites and pegmatites. The resulting geologic model is presented together with recommended geophysical and geochemical approaches for exploration targeting, as well as mineral processing and environmental factors pertinent for the development of mineral resources hosted by alkaline-silicate magmatic systems. ispartof: Economic Geology vol:118 issue:1 pages:177-208 status: published

How does the brain process sensory stimuli, and decide whether to initiate locomotor behaviour? To investigate this question we develop two whole body computer models of a tadpole. The “Central Nervous System” (CNS) model uses evidence from whole-cell recording to define 2300 neurons in 12 classes to study how sensory signals from the skin initiate and stop swimming. In response to skin stimulation, it generates realistic sensory pathway spiking and shows how hindbrain sensory memory populations on each side can compete to initiate reticulospinal neuron firing and start swimming. The 3-D “Virtual Tadpole” (VT) biomechanical model with realistic muscle innervation, body flexion, body-water interaction, and movement is then used to evaluate if motor nerve outputs from the CNS model can produce swimming-like movements in a volume of “water”. We find that the whole tadpole VT model generates reliable and realistic swimming. Combining these two models opens new perspectives for experiments., Author summary Animals constantly receive sensory signals, make decisions and generate behaviours. We see a red light at a pedestrian crossing, stop, and only walk across at a green light. Two systems control this behaviour: the nervous system processes sensory signals and commands the musculoskeletal system to generate motor responses. Most nervous and musculoskeletal systems are too complex to be able to understand even simple behaviours step by step. To simplify the problem, we study responses to touch in young frog tadpoles. Here, detailed information is available on 12 types of brain and spinal cord neurons controlling swimming. To explore how these neurons work, we create two biologically realistic computational models: a CNS model of the nervous system with approximately 2300 neurons generates motor nerve activity and is fed to a virtual tadpole biomechanical model of the whole-body musculoskeletal system to produce movements. Our results suggest that we understand the essence of how simple behaviour is generated. We propose that a simple sensory memory process in the brain, which extends the brief sensory nerve activity, forms the basis for a decision process. This also generates unpredictability in behaviour.

P.K.B. acknowledges support from North Carolina State University. Funding for S.M. was provided by NERC standard grant NE/PO12167/1 and UK Space Agency Aurora grant ST/T001763/1. M.J.H. thanks the Institut Universitaire de France (IUF) for support. The thickness of the brittle lithosphere—the outer portion of a planetary body that fails via fracturing—plays a key role in the geological processes of that body. The properties of both a planet and its host star can influence that thickness, and the potential range of those properties exceeds what we see in the Solar System. To understand how planetary and stellar parameters influence brittle lithospheric thickness generally, we modeled a comprehensive suite of combinations of planetary mass, surface and mantle temperature, heat flux, and strain rate. Surface temperature is the dominant factor governing the thickness of the brittle layer: smaller and older planets generally have thick brittle lithospheres, akin to those of Mercury and Mars, whereas larger, younger planets have thinner brittle lithospheres that may be comparable to the Venus lowlands. But certain combinations of these parameters yield worlds with exceedingly thin brittle layers. We predict that such bodies have little elevated topography and limited volatile cycling and weathering, which can be tested by future telescopic observations of known extrasolar planets. Publisher PDF

Funding was provided by an Antarctic Bursary awarded to J.A.S., ERC and NERC grants awarded to L.F.R. (278705, NE/S001743/1, NE/R005117/1) and L.F.R. and J.W.B.R. (NE/N003861/1). The Antarctic Cold Reversal (ACR; 14.7 to 13 thousand years ago; ka) phase of the last deglaciation saw a pause in the rise of atmospheric CO2 and Antarctic temperature, that contrasted with warming in the North. A re-expansion of sea ice and a northward shift in the position of the westerly winds in the Southern Ocean are well-documented, but the response of deep-sea biota and the primary drivers of habitat viability remain unclear. Here we present a new perspective on ecological changes in the deglacial Southern Ocean, including multi-faunal benthic assemblage (foraminifera and cold-water corals) and coral geochemical data (Ba/Ca and δ11B) from the Drake Passage. Our records show that, during the ACR, peak abundances of thick-walled benthic foraminifera Uvigerina bifurcata and corals are observed at shallow depths in the sub-Antarctic (∼300 m), while coral populations at greater depths and further south diminished. Our ecological and geochemical data indicate that habitat shifts were dictated by (i) a northward migration of food supply (primary production) into the Subantarctic Zone and (ii) poorly oxygenated seawater at depth during this Antarctic cooling interval. Publisher PDF