Search

SM is grateful to the Carnegie Institution of Washington for funding this work through the bestowment of a Carnegie Postdoctoral Fellowship. SM also acknowledges the School of Earth and Environmental Science (St Andrews) for providing a start-up fund which assisted in the development of these data. DAS is grateful to grants from the Sloan Foundation through the Deep Carbon Observatory (Reservoirs and Fluxes, and Extreme Physics and Chemistry programs) and a community-building Officer Grant from the Sloan Foundation, as well as support from NSF grants EAR-1624325 and ACI-1550346, and a grant from the W.M. Keck Foundation (The Co-Evolution of the Geo- and Biosphere) Grant #10583-02 to Sverjensky. PHB’s contribution was supported in part by the NSF grant EAR-1144559 (A Petrological and N Isotope Study Of Crustal Recycling Through Time). Nitrogen is distributed throughout all terrestrial geological reservoirs (i.e., the crust, mantle, and core), which are in a constant state of disequilibrium due to metabolic factors at Earth’s surface, chemical weathering, diffusion, and deep N fluxes imposed by plate tectonics. However, the behavior of nitrogen during subduction is the subject of ongoing debate. There is a general consensus that during the crystallization of minerals from melts, monatomic nitrogen behaves like argon (highly incompatible) and ammonium behaves like potassium and rubidium (which are relatively less incompatible). Therefore, the behavior of nitrogen is fundamentally underpinned by its chemical speciation. In aqueous fluids, the controlling factor which determines if nitrogen is molecular (N2) or ammonic (inclusive of both NH4+ and NH30) is oxygen fugacity, whereas pH designates if ammonic nitrogen is NH4+ and NH30. Therefore, to address the speciation of nitrogen at high pressures and temperatures, one must also consider pH at the respective pressure–temperature conditions. To accomplish this goal we have used the Deep Earth Water Model (DEW) to calculate the activities of aqueous nitrogen from 1-5 GPa and 600-1000 °C in equilibrium with a model eclogite-facies mineral assemblage of jadeite + kyanite + quartz/coesite (metasediment), jadeite + pyrope + talc + quartz/coesite (metamorphosed mafic rocks), and carbonaceous eclogite (metamorphosed mafic rocks + elemental carbon). We then compare these data with previously published data for the speciation of aqueous nitrogen across these respective P-T conditions in equilibrium with a model peridotite mineral assemblage (Mikhail and Sverjensky, 2014). In addition, we have carried out full aqueous speciation and solubility calculations for the more complex fluids in equilibrium with jadeite + pyrope + kyanite + diamond, and for fluids in equilibrium with forsterite + enstatite + pyrope + diamond. Our results show that the pH of the fluid is controlled by mineralogy for a given pressure and temperature, and that pH can vary by several units in the pressure-temperature range of 1-5 GPa and 600-1000 °C. Our data show that increasing temperature stabilizes molecular nitrogen and increasing pressure stabilizes ammonic nitrogen. Our model also predicts a stark difference for the dominance of ammonic vs. molecular and ammonium vs. ammonia for aqueous nitrogen in equilibrium with eclogite-facies and peridotite mineralogies, and as a function of the total dissolved nitrogen in the aqueous fluid where lower N concentrations favor aqueous ammonic nitrogen stabilization and higher N concentrations favor aqueous N2. Overall, we present thermodynamic evidence for nitrogen to be reconsidered as an extremely dynamic (chameleon) element whose speciation and therefore behavior is determined by a combination of temperature, pressure, oxygen fugacity, chemical activity, and pH. We show that altering the mineralogy in equilibrium with the fluid can lead to a pH shift of up to 4 units at 5 GPa and 1000 °C. Therefore, we conclude that pH imparts a strong control on nitrogen speciation, and thus N flux, and should be considered a significant factor in high temperature geochemical modeling in the future. Finally, our modelling demonstrates that pH plays an important role in controlling speciation, and thus mass transport, of Eh-pH sensitive elements at temperatures up to at least 1000 °C. Postprint

This work was supported by the UK Natural Environment Research Council (award NE/I022973/1). The boron geochemistry of coral skeletons reflects the dissolved inorganic carbon (DIC) chemistry of the calcification fluid from which the skeletons precipitates and may be a valuable tool to investigate the effects of climate change on coral calcification. In this paper I calculate the predicted B/Ca of aragonite precipitating from seawater based fluids as a function of pH, [DIC] and [Ca2+]. I consider how different co-precipitating DIC species affect aragonite B/Ca and also estimate the impact of variations in the B(OH)4−/co-precipitating DIC aragonite partition coefficient (KD), which may be associated with changes in the DIC and Ca2+ chemistry of the calcification fluid. The coral skeletal B/Ca versus calcification fluid pH relationships reported previously can be reproduced by estimating B(OH)4− and co-precipitating DIC speciation as a function of pHCF and assuming that KD are constant i.e. unaffected by calcification fluid saturation state. Assuming that B(OH)4− co-precipitates with CO32−, then observed patterns can be reproduced by a fluid with approximately constant [DIC] i.e. increasing pHCF concentrates CO32−, as a function of DIC speciation. Assuming that B(OH)4− co-precipitates with HCO3− only or CO32− + HCO3− then the observed patterns can be reproduced if [DIC]CF and pHCF are positively related i.e. if DIC is increasingly concentrated in the calcification fluid at higher pHCF probably by CO2 diffusion into the calcification site. Publisher PDF

M.J. Heap acknowledges funding from an Initiative d’Excellence (IDEX) “Attractivité” grant (VOLPERM), funded by the University of Strasbourg. The disparate evolution of sibling planets Earth and Venus has left them markedly different. Venus’ hot (460 °C) surface is dry and has a hypsometry with a very low standard deviation, whereas Earth’s average temperature is 4 °C and the surface is wet and has a pronounced bimodal hypsometry. Counterintuitively, despite the hot Venusian climate, the rate of intraplate volcano formation is an order of magnitude lower than that of Earth. Here we compile and analyse rock deformation and atmospheric argon isotope data to offer an explanation for the relative contrast in volcanic flux between Earth and Venus. By collating high-temperature, high-pressure rock deformation data for basalt, we provide a failure mechanism map to assess the depth of the brittle–ductile transition (BDT). These data suggest that the Venusian BDT likely exists between 2–12 km depth (for a range of thermal gradients), in stark contrast to the BDT for Earth, which we find to be at a depth of ~25-27 km using the same method. The implications for planetary evolution are twofold. First, downflexing and sagging will result in the sinking of high-elevation structures, due to the low flexural rigidity of the predominantly ductile Venusian crust, offering an explanation for the curious coronae features on the Venusian surface. Second, magma delivery to the surface—the most efficient mechanism for which is flow along fractures (dykes; i.e., brittle deformation)—will be inhibited on Venus. Instead, we infer that magmas must stall and pond in the ductile Venusian crust. If true, a greater proportion of magmatism on Venus should result in intrusion rather than extrusion, relative to Earth. This predicted lower volcanic flux on Venus, relative to Earth, is supported by atmospheric argon isotope data: we argue here that the anomalously unradiogenic present-day atmospheric 40Ar/36Ar ratio for Venus (compared with Earth) must reflect major differences in 40Ar degassing, primarily driven by volcanism. Indeed, these argon data suggest that the volcanic flux on Venus has been three times lower than that on Earth over its 4.56 billion year history. We conclude that Venus’ hot climate inhibits volcanism. Postprint

This research is funded by NSF [OCE12-32987] to BH. The B/Ca ratio of planktic foraminiferal calcite, a proxy for the surface ocean carbonate system, displays large negative excursions during the Paleocene-Eocene Thermal Maximum (PETM, 55.9 Ma), consistent with rapid ocean acidification at that time. However, the B/Ca excursion measured at the PETM exceeds a magnitude that modern pH-calibrations can explain. Numerous other controls on the proxy have been suggested, including foraminiferal growth rate and the total concentration of Dissolved Inorganic Carbon (DIC). Here we present new calibrations for B/Ca vs. the combined effects of pH and DIC in the symbiont-bearing planktic foraminifer Orbulina universa, grown in culture solutions with simulated Paleocene seawater elemental composition (high [Ca], low [Mg], and low [B]T). We also investigate the isolated effects of low seawater total boron concentration ([B]T), high [Ca], reduced symbiont photosynthetic activity, and average shell growth rate on O. universa B/Ca in order to further understand the proxy systematics and to determine other possible influences on the PETM records. We find that average shell growth rate does not appear to determine B/Ca in high calcite saturation experiments. In addition, our “Paleocene” calibration shows higher sensitivity than the modern calibration at low [B(OH)4-]/DIC. Given a large DIC pulse at the PETM, this amplification of the B/Ca response can more fully explain the PETM B/Ca excursion. However, further calibrations with other foraminifer species are needed to determine the range of foraminifer species-specific proxy sensitivities under these conditions for quantitative reconstruction of large carbon cycle perturbations. Publisher PDF

This study was supported by funding from the Strategic Priority Research Program (B) of the Chinese Academy of Sciences (grant nos. XDB03010600 and XDB18020204), the National Natural Science Foundation of China (grant nos. 41202041, 41630208 and 41673033), the Key Program of the Chinese Academy of Sciences (QYZDJ-SSW-DQC026), the DREAM Program of China (No. 2016YFC0600407), talent project of Guangdong Province (2014TX01Z079), and GIG–CAS 135 project 135TP201601. PAC and CJH acknowledge support from the Natural Environment Research Council (grant NE/J021822/1). The senior author thanks the grant from the NSC, Taiwan, which supported his one-year academic visit at the NTU. This is contribution no. IS-2352 from GIG–CAS. Accretionary orogens are major sites of generation of continental crust but the spatial and temporal distribution of crust generation within individual orogens remains poorly constrained. Paleozoic (∼540–270 Ma) granitic rocks from the Alati, Junggar and Chinese Tianshan segments of the Central Asian Orogenic Belt (CAOB) have markedly bimodal age frequency distributions with peaks of ages at ∼400 Ma and 280 Ma for the Altai segment, and ∼430 Ma and 300 Ma for the Junggar and Chinese Tianshan segments. Most of the magma was generated in short time intervals (∼20–40 Ma), and variations in magma volumes and in Nd–Hf isotope ratios are taken to reflect variable rates of new crust generation within a long-lived convergent plate setting. The Junggar segment is characterized by high and uniform Nd–Hf isotope ratios (εNd(t) = +5 to +8; zircon εHf(t) = +10 to +16) and it appears to have formed in an intra-oceanic arc system. In the Altai and Chinese Tianshan segments, the Nd–Hf isotope ratios (εNd(t) = −7 to +8; zircon εHf(t) = −16 to +16) are lower, although they increase with decreasing age of the rock units. The introduction of a juvenile component into the Chinese Tianshan and Altai granitic rocks appears to have occurred in continental arc settings and it reflects a progressive reduction in the contributions from old continental lower crust and lithospheric mantle. Within the long-lived convergent margin setting (over ∼200 Ma), higher volumes of magma, and greater contributions of juvenile material, were typically emplaced over short time intervals of ∼20–40 Ma. These intervals were associated with higher Nb/La ratios, coupled with lower La/Yb ratios, in both the mafic and granitic rocks, and these episodes of increased magmatism from intraplate-like sources are therefore thought to have been in response to lithospheric extension. The trace element and Nd–Hf isotope data, in combination with estimates of granitic magma volumes, highlight that crust generation rates are strongly non-uniform within long-lived accretionary orogens. The estimated crust generation rates range from ∼0.1 to ∼40 km3/km/Ma for the Paleozoic record of the CAOB, and only comparatively short (20–40 Ma) periods of elevated magmatic activity had rates similar to those for modern intra-oceanic and continental arcs. Postprint

This study was supported financially by a Natural Environment Research Council Fellowship NE/H016805 (to A.Z.) and a Natural Environment Research Council Standard Grant NE/J023485 (to A.Z., M.C. and S.P.). Further financial support was generously provided via a SAGES Postdoctoral & Early Career Researcher Exchange grant and The Geological Society of London’s Alan and Charlotte Welch Fund (to G.I.). For his work performed at the Jet Propulsion Laboratory, California Institute of Technology, KHW acknowledges the support of a grant from the National Aeronautics and Space Administration. JF acknowledges funding from the NASA Exobiology program (NNX12AD91G). Emerging evidence suggests that atmospheric oxygen may have varied before rising irreversibly ∼2.4 billion years ago, during the Great Oxidation Event (GOE). Significantly, however, pre-GOE atmospheric aberrations toward more reducing conditions—featuring a methane-derived organic-haze—have recently been suggested, yet their occurrence, causes, and significance remain underexplored. To examine the role of haze formation in Earth’s history, we targeted an episode of inferred haze development. Our redox-controlled (Fe-speciation) carbon- and sulfur-isotope record reveals sustained systematic stratigraphic covariance, precluding nonatmospheric explanations. Photochemical models corroborate this inference, showing Δ36S/Δ33S ratios are sensitive to the presence of haze. Exploiting existing age constraints, we estimate that organic haze developed rapidly, stabilizing within ∼0.3 ± 0.1 million years (Myr), and persisted for upward of ∼1.4 ± 0.4 Myr. Given these temporal constraints, and the elevated atmospheric CO2 concentrations in the Archean, the sustained methane fluxes necessary for haze formation can only be reconciled with a biological source. Correlative δ13COrg and total organic carbon measurements support the interpretation that atmospheric haze was a transient response of the biosphere to increased nutrient availability, with methane fluxes controlled by the relative availability of organic carbon and sulfate. Elevated atmospheric methane concentrations during haze episodes would have expedited planetary hydrogen loss, with a single episode of haze development providing up to 2.6–18 × 1018 moles of O2 equivalents to the Earth system. Our findings suggest the Neoarchean likely represented a unique state of the Earth system where haze development played a pivotal role in planetary oxidation, hastening the contingent biological innovations that followed. Postprint

Financial support from National Science Foundation of China (41190073, 41372198 and 40490613), National Basic Research Program of China (2014CB440901 and 2016YFC0600303) and “the Fundamental Research Funds for the Central Universities to SYSU” are gratefully acknowledged. The basaltic rocks in NW Thailand belong to part of giant Southeast Asian igneous zone that delineates the extension of the Paleotethyan Ocean from SW China into NW Thailand. The Chiang Mai basaltic samples from the Chiang Dao, Fang, Lamphun and Ban Sahakorn sections are divisible into two groups of high-iron basalt. Group 1 has SiO2 of 38.30–49.18 wt.%, FeOt of 13.09–25.37 wt.%, MgO of 8.38–1.60 wt.%, TiO2 of 3.92–6.30 wt.%, which is rarely observed in nature. Group 2 shows SiO2 = 44.71–49.21 wt.%, FeOt = 10.88–14.34 wt.%, MgO = 5.24–16.11 wt.%, TiO2 = 2.22–3.07 wt.% and mg# = 44–70. Olivine and pyroxene are responsible for the fractionation of the Group 2 magma whereas low oxygen fugacity during the late-stage differentiation of the Group 1 magma prolonged fractionation of ilmenite and magnetite. The onset of ilmenite and magnetite fractionations controls the distinct differentiation commencing at MgO = ~ 7 wt.%. Both groups show similar REE and primitive mantle-normalized patterns with insignificant Eu, Nb-Ta and Zr-Hf anomalies. They have similar Nd isotopic compositions with εNd(t) values ranging from + 2.8 to + 3.7 and similar Nb/La, Nb/U, Th/La, Zr/Nb, Th/Ta, La/Yb, Nb/Th, Nb/Y and Zr/Y, resembling those of OIB-like rocks. The representative basaltic sample yields the argon plateau age of 282.3 ± 1.4 Ma, suggestive of early Permian origin. Our data argue for Group 1 and Group 2 are coeval in the intra-oceanic seamount setting within the Paleotethyan Ocean, which at least continued till 283 Ma. These data, along with other observations, suggest that the Inthanon zone defines the main Paleotethyan suture zone, which northerly links with the Changning-Menglian zone in SW China. Postprint

The work was supported by NERC grants NE/I006176/1 (Gavin L. Foster and Caroline H. Lear), NE/H006273/1 (Gavin L. Foster), NE/I006168/1 and NE/K014137/1 and a Royal Society Research Merit Award (Paul A. Wilson), a NERC Independent Research Fellowship NE/K00901X/1 (Mathis P. Hain) and a NERC studentship (Rosanna Greenop). The boron isotope composition (δ11B) of foraminiferal calcite reflects the pH and the boron isotope composition of the seawater the foraminifer grew in. For pH reconstructions, the δ11B of seawater must therefore be known, but information on this parameter is limited. Here we reconstruct Neogene seawater δ11B based on the δ11B difference between paired measurements of planktic and benthic foraminifera and an estimate of the coeval water column pH gradient from their δ13C values. Carbon cycle model simulations underscore that the ΔpH-Δδ13C relationship is relatively insensitive to ocean and carbon cycle changes, validating our approach. Our reconstructions suggest that δ11Bsw was ∼37.5‰ during the early and middle Miocene (roughly 23-12 Ma) and rapidly increased during the late Miocene (between 12 and 5 Ma) towards the modern value of 39.61 ‰. Strikingly, this pattern is similar to the evolution of the seawater isotope composition of Mg, Li and Ca, suggesting a common forcing mechanism. Based on the observed direction of change, we hypothesize that an increase in secondary mineral formation during continental weathering affected the isotope composition of riverine input to the ocean since 14 Ma. Publisher PDF

Nitrogen forms an integral part of the main building blocks of life, including DNA, RNA, and proteins. N2 is the dominant gas in Earth’s atmosphere, and nitrogen is stored in all of Earth’s geological reservoirs, including the crust, the mantle, and the core. As such, nitrogen geochemistry is fundamental to the evolution of planet Earth and the life it supports. Despite the importance of nitrogen in the Earth system, large gaps remain in our knowledge of how the surface and deep nitrogen cycles have evolved over geologic time. Here we discuss the current understanding (or lack thereof) for how the unique interaction of biological innovation, geodynamics, and mantle petrology has acted to regulate Earth’s nitrogen cycle over geologic timescales. In particular, we explore how temporal variations in the external (biosphere and atmosphere) and internal (crust and mantle) nitrogen cycles could have regulated atmospheric pN2. We consider three potential scenarios for the evolution of the geobiological nitrogen cycle over Earth’s history: two in which atmospheric pN2 has changed unidirectionally (increased or decreased) over geologic time; and one in which pN2 could have taken a dramatic deflection following the Great Oxidation Event. It is impossible to discriminate between these scenarios with the currently available models and datasets. However, we are optimistic that this problem can be solved, following a sustained, open-minded, and multidisciplinary effort between surface and deep Earth communities. Publisher PDF

The author acknowledges with gratitude financial assistance from Rhodes University and the National Research Foundation of South Africa (Grant UID74438). The kinetic analysis of thermoluminescence of beta-irradiated SrAl2O4:Eu2+,Dy3+ is reported. The glow-curve is dominated by an apparently-single peak. It has been demonstrated using a number of tests including partial dynamic-heating, isothermal heating, phosphorescence and, the effect of fading, that the peak and the glow-curve consists of a set of closely-spaced peaks. In view of the peak being complex, its first few components were abstracted and analysed and for comparison, the peak was also analysed assuming it is genuinely single. In the latter, the order of kinetics is calculated to be intermediate between first and second-order and not first-order as predicted by qualitative tests such as the Tm − Tstop or Tm − dose procedures. A model based on density of energy states has been used to account for and reconcile the qualitative and quantitative results. The activation energy is found as ∼1 eV, consistent with the value expected of Dy2+, the presumed electron trapping state of the Dy3+ electron trap. The thermoluminescence is subject to thermal quenching with an activation energy of 0.520 ± 0.002 eV. The luminescence is ascribed to 5d→4f7 Eu2+ transitions whereas the thermal quenching is presumed to occur from an alternative level of the degenerate 5d energy level of the Eu2+ cation. Postprint

Multiple sulphur (S) isotope ratios are powerful proxies to understand the complexity of S biogeochemical cycling through Deep Time. The disappearance of a sulphur mass independent fractionation (S-MIF) signal in rocks

Copper, a native metal found in ores, is the principal metal in bronze and brass. It is a reddish metal with a density of 8920 kg m−3. All of copper’s compounds tend to be brightly colored: for example, copper in hemocyanin imparts a blue color to blood of mollusks and crustaceans. Copper has three oxidation states, with electronic configurations of Cu([Ar]3 d 104 s 1), Cu+([Ar]3 d 10), and Cu2+([Ar]3 d 9). Cu does not react with aqueous hydrochloric or sulfuric acids, but is soluble in concentrated nitric acid due to its lesser tendency to be oxidized. Cu(I) exists as the colorless cuprous ion, Cu+. Cu(II) is found as the sky-blue cupric ion, Cu2+. The Cu+ ion is unstable, and tends to disproportionate to Cu and Cu2+. Nevertheless, Cu(I) forms compounds such as Cu2O. Cu(I) bonds more readily to carbon than Cu(II), hence Cu(I) has an extensive chemistry with organic compounds. In aqueous solutions, Cu2+ ion occurs as an aquacomplex. There is no clearly predominant structure among the four-, five-, and six-fold coordinated Cu(II) species (Chaboy et al. 2006). Hydrated Cu(II) ion has been represented as the hexaaqua complex Cu(H2O)62+, which shows the Jahn–Teller distortion effect (Sherman 2001; Bersuker 2006), whereby the two Cu–O distances of the vertical axial bond (Cu–Oax) are longer than four Cu–O distances in the equatorial plane (Cu–Oeq). The Jahn–Teller effect lowers the symmetry of Cu(H2O)62+ from octahedral Th to D2h. The sixfold coordination of hydrated Cu(II) species is questioned by a finding of fivefold coordination (Pasquarello et al. 2001; Chaboy et al. 2006; Little et al. 2014b …

This study is financially supported by the National Natural Science Foundation of China (41502068). The Xiaoliugou W-Mo ore field lies within the mid-Paleozoic North Qilian Orogen, NW China, and hosts a W resource of 48.8 Mt @ 0.4% and 412.6 Mt of Mo @ 0.075%. It contains five deposits, including Xiaoliugou, Qiqing, Guishan, Qibao and Shiji. The main mineralization styles at Xiaoliugou are skarn and veins in which the mineral sequence is scheelite > molybdenite > chalcopyrite and occurs in the endo- and exo-contact zones of granite intrusions. The scheelite-dominated orebodies are overprinted by molybdenite-dominated quartz veins. Two molybdenite samples yielded Silurian Re-Os model ages of 427.4 ± 6.0 Ma and 428.2 ± 6.0 Ma. Three muscovite samples coexisting with molybdenite yielded Middle Devonian Ar-Ar ages of 392.0 ± 2.7 Ma, 391.1 ± 2.7 Ma and 391.4 ± 2.8 Ma. The Re-Os and Ar-Ar ages indicate that the W-Mo mineralization and alteration occurred at ca. 428–391 Ma, which corresponds with regional continental collision within the Qilian Orogen. δ34S for the sulfides molybdenite and pyrite are 7.70–11.67 ‰ and 4.98–13.17 ‰, respectively. The 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb of the sulfides are 17.98–21.73, 15.34–18.81, and 37.18–38.63, respectively. The granites yield similar corrected (206Pb/204Pb)i, (207Pb/204Pb)i and (208Pb/204Pb)i, ranging 16.14–19.35, 15.44–15.63, and 37.41–38.31, respectively. Calculated δ18O of the fluid inclusions in quartz range from -3.38–2.34 ‰, whereas the δD of the hydrothermal fluids ranges from -94 to -47 ‰. The S-, Pb-, O- and D-isotopic data imply that the metals originated from the granite intrusion with a minor component sourced from the host sediments, and that the ore-forming fluids were dominated by magmatic-hydrothermal fluids mixed with minor meteoric water. Postprint

TvdF and TS acknowledge financial support for a bursary by the Grantham Institute of Climate Change and the Environment and a Marie Curie Reintegration grant (IRG 230828), as well as funding from the Leverhulme Trust (RPG-398) and the NERC (NE/N001141/1). Additional financial support was provided to LFR by the USGS-WHOI Co-operative agreement, NSF-ANT grants 0636787 and 80295700, The European Research Council, the Leverhulme Trust and a Marie Curie Reintegration grant. LB was supported by a NOAA/UCAR Climate and Global Change Postdoctoral Fellowship and KJM acknowledges funding from a Marie Curie International Outgoing fellowship (IOF 236962). Cold-water corals (CWCs) are unique archives of mid-depth ocean chemistry and have been used successfully to reconstruct the neodymium (Nd) isotopic composition of seawater from a number of species. High and variable Nd concentrations in fossil corals however pose the question as to how Nd is incorporated into their skeletons. We here present new results on modern specimens of Desmophyllum dianthus, Balanophyllia malouinensis, and Flabellum curvatum, collected from the Drake Passage, and Madrepora oculata, collected from the North Atlantic. All modern individuals were either collected alive or uranium-series dated to be < 500 years old for comparison with local surface sediments and seawater profiles. Modern coral Nd isotopic compositions generally agree with ambient seawater values, which in turn are consistent with previously published seawater analyses, supporting small vertical and lateral Nd isotope gradients in modern Drake Passage waters. Two Balanophyllia malouinensis specimens collected live however deviate by up to 0.6 epsilon units from ambient seawater. We therefore recommend that this species should be treated with caution for the reconstruction of past seawater Nd isotopic compositions. Seventy fossil Drake Passage CWCs were furthermore analysed for their Nd concentrations, revealing a large range from 7.3 to 964.5 ng/g. Samples of the species D. dianthus and Caryophyllia spp. show minor covariation of Nd with 232Th content, utilised to monitor contaminant phases in cleaned coral aragonite. Strong covariations between Nd and Th concentrations are however observed in the species B. malouinensis and G. antarctica. In order to better constrain the source and nature of Nd in the cleaned aragonitic skeletons, a subset of sixteen corals was investigated for its rare earth element (REE) content, as well as major and trace element geochemistry. Our new data provide supporting evidence that the applied cleaning protocol efficiently removes contaminant lithogenic and ferromanganese oxyhydroxide phases. Mass balance calculations and seawater-like REE patterns rule out lithogenic and ferromanganese oxyhydroxide phases as a major contributor to elevated Nd concentrations in coral aragonite. Based on mass balance considerations, geochemical evidence, and previously published independent work by solid-state nuclear magnetic resonance (NMR) spectroscopy, we suggest authigenic phosphate phases as a significant carrier of skeletal Nd. Such a carrier phase could explain sporadic appearance of high Nd concentrations in corals and would be coupled with seawater-derived Nd isotopic compositions, lending further confidence to the application of Nd isotopes as a water mass proxy in CWCs. Publisher PDF

RFI is funded by NERC grant #NE/K008536/1. Numerical climate model simulations made use of the N8 HPC Centre of Excellence (N8 consortium and EPSRC Grant #EP/K000225/1). Collapse of ice sheets can cause significant sea-level rise and widespread climate change. We examine the climatic response to meltwater generated by the collapse of the Cordilleran-Laurentide ice saddle (North America) ~14.5 thousand years ago (ka) using a high-resolution drainage model coupled to an ocean-atmosphere-vegetation general circulation model. Equivalent to 7.26 m global mean sea-level rise in 340 years, the meltwater caused a 6 sverdrup weakening of Atlantic Meridional Overturning Circulation (AMOC) and widespread Northern Hemisphere cooling of 1-5 °C. The greatest cooling is in the Atlantic-sector high latitudes during Boreal winter (by 5-10 °C), but there is also strong summer warming of 1-3 °C over eastern North America. Following recent suggestions that the saddle collapse was triggered by the Bølling warming event ~14.7-14.5 ka, we conclude that this robust submillennial mechanism may have initiated the end of the warming and/or the Older Dryas cooling through a forced AMOC weakening. Publisher PDF

JP was partly supported by NERC fellowship NE/H01313X/2. AB was supported by a Janet Watson Earth Science and Engineering Departmental PhD studentship and MW was supported in part by an undergraduate research opportunity award from Imperial College London. Trace element analyses were supported from US NSF Grant EAR-1456814 to TP. Stable thallium (Tl) isotopes are an extremely sensitive tracer for the addition of small amounts of sediments or materials altered at low temperatures to the source(s) of mantle-derived melts. The ability of Tl to trace such materials is due to the large concentration contrast between the mantle (Tl < 2 ng/g) and possible exotic inputs (Tl ~ 100 ng/g to > μg/g), which also often display fractionated Tl isotope compositions. However, the magnitude of Tl isotope fractionation induced by igneous processes alone has not been systematically assessed. Here, two suites of co-genetic magmas, spanning a large range of differentiation, from Hekla, Iceland, and Anatahan, in the Mariana arc, are used to assess the behavior of thallium and its stable isotope variations during magmatic processes. Thallium behaves as a near-perfectly incompatible lithophile element throughout magmatic evolution, mirroring elements such as Rb, Cs, and K. Lavas from Hekla have restricted Cs/Tl ratios and stable Tl isotope compositions, which overlap with mantle estimates. Lavas from subduction-related Anatahan volcano also have a restricted range in Tl isotope composition, which overlaps with Hekla and MORB, demonstrating that fractional crystallisation and partial melting does not fractionate stable Tl isotopes. Subduction environments display variable Cs/Tl, indicating that the subduction process commonly fractionates these two elements. The immunity of thallium stable isotopes to fractionation by magmatic processes coupled with its extreme sensitivity for tracing pelagic sediments, FeMn crusts and low temperature altered oceanic crust highlight its value in elucidating the nature of mantle sources of both oceanic basalts and arc lavas. Critically, meaningful interpretation of thallium isotope compositions need not be restricted to primitive lavas. Postprint

This work was supported by NERC Isotope Geoscience Facility Steering Committee grant IP-1462-0514. The end-Cryogenian glaciation (Marinoan) is portrayed commonly as the archetype of snowball Earth, yet its duration and character remain uncertain. Here we report U-Pb zircon ages for two ash beds from widely separated localities of the Marinoan-equivalent Ghaub Formation in Namibia: 639.29 ± 0.26 Ma and 635.21 ± 0.59 Ma. These findings verify, for the first time, the key prediction of the snowball Earth hypothesis for the Marinoan glaciation, i.e., longevity, with a duration of ≥4 m.y. They also show that the nonglacial interlude of Cryogenian time spanned 20 m.y. or less and that glacigenic erosion and sedimentation, and at least intermittent open-water conditions, occurred 4 m.y. prior to termination of the Marinoan glaciation. Postprint

This work was done with the support of the CNPq, National Council for Technological and Scientific Development – Brazil [grant numbers 443355/2014-2, 200473/2015-8, 141587/2013-0]; Peter A. Cawood acknowledges support from the Australian Research Council [grant number FL160100168]. The Figueira Branca Suite is a layered mafic-ultramafic complex in the Jauru Terrane, southwest Amazon Craton. New lithological, geochemical, gamma-ray and potential field data, integrated with geological, isotope and paleomagnetic data are used to characterize this pulse of Mesoproterozoic extension-related magmatism. The Figueira Branca Suite formed through juvenile magma emplacement into the crust at 1425 Ma, coeval with the later stages of the Santa Helena Orogen. Gabbros and peridotite-gabbros display increasing enrichment of LREE, interpreted as evidence of progressive fractionation of the magma. Magnetic and gamma-ray data delimit the extent of magmatism within the suite to four bodies to the north of Indiavaí city. Modelling gravity and magnetic field data indicate that the anomalous sources are close to the surface or outcropping. These intrusions trend northwest over 8 km, with significant remanent magnetization that is consistent with published direction obtained through paleomagnetic data. The emplacement, mineralogy and geochemical signature point towards a back-arc extension tectonic framework in the later stages of the Santa Helena Orogen. Postprint

JY is funded by a Clarendon Scholarship and a Dr Bill Willetts Scholarship from the University of Oxford. The research leading to these results has received funding from the European Research Council under the European Union's Seventh Framework Programme (FP7/2007-2013) / ERC grant agreement No. 247422. This work has also supported by Science & Technology Facilities Council. This study reports Mo isotopic compositions for fifty-two Palaeozoic granitic rocks with contrasting source affinities (A-, I- and S-type) from the Lachlan Fold Belt (LFB) and the New England Batholith (NEB), both in SE Australia, and three compositionally zoned plutons (Loch Doon, Criffell, and Fleet) located in the South Uplands of Scotland. The results show relatively large variations in δ98Mo for igneous rocks ranging from -1.73‰ to 0.59‰ with significant overlaps between different types. No relationships between δ98Mo and δ18O or ASI (Alumina Saturation Index) are observed, indicating that Mo isotopes do not clearly distinguish igneous versus sedimentary source types. Instead, effects of igneous processes, source mixing, regional geology, as well as hydrothermal activity control the Mo isotope compositions in these granites. It is found that Mo is mainly accommodated in biotite and to a lesser extent in hornblende. Hornblende and Fe3+-rich minerals may preferentially incorporate light isotopes, as reflected by negative correlations between δ98Mo and K/Rb and [Fe2O3]. There is a positive correlation between initial 87Sr/86Sr and δ98Mo in I-type granitic rocks, reflecting the admixing of material from isotopically distinct sources. Granitic rocks from Scotland and Australia display strikingly similar curvilinear trends in δ98Mo vs. initial 87Sr/86Sr despite the differing regional geology. Localized hydrothermal effects on Mo isotopes in three samples from Loch Doon and Criffell can result in anomalously low δ98Mo of < -1‰. Based on this study, an estimate of δ98Mo = 0.14±0.07‰ (95% s.e.) for the Phanerozoic upper crust is proposed. This is slightly heavier than basalts indicating an isotopically light lower crust and / or a systematic change to the crust resulting from subduction of isotopically light dehydrated slab and / or pelagic sediment over time. Publisher PDF

International audience; The Chinese Southwestern Tianshan high- to ultra-high pressure low temperature (HP–UHP/LT) metamorphic belt exhibits well-preserved mafic layers, tectonic blocks/slices and boudins of different sizes and lithology embedded within dominant meta-volcanosedimentary rocks. Despite a wealth of previous studies on UHP relicts, P–T path estimates and age constraints for metamorphism, controversies still exist on P–T–t assessments and regional exhumation patterns (i.e., tectonic mélange versus internally coherent “sub-belt” model). This study focuses on a group of coesite-bearing eclogite samples from a thick (~ 5 m) layered metabasalt outcrop in order to unravel its detailed tectono-metamorphic evolution through space and time (both prograde, peak and exhumation). Using SIMS zircon U–Pb and oxygen isotope analyses, TIMS Sm–Nd multi-point isochron dating, in situ laser-ICP-MS trace-element analyses, classical thermobarometry and thermodynamic modeling, we link the multistage zircon growth to garnet growth and reconstruct a detailed P–T–time-isotopic evolution history for this UHP tectonic slice: from UHP peak burial ~ 2.95 ± 0.2 GPa, 510 ± 20 °C around 318.0 ± 2.3 Ma to HP peak metamorphism ~ 2.45 ± 0.2 GPa, 540 ± 20 °C at 316.8 ± 0.8 Ma, then, with eclogite-facies deformation ~ 2.0 ± 0.15 GPa, 525 ± 25 °C at 312 ± 2.5 Ma, exhumed to near surface within ca. 303 to ca. 280 Ma. Our P–T-time-isotopic results combined with the compilation of regional radiometric data and P–T estimates notably point to the existence of a short-lived period of rock detachment and exhumation (< 10 Ma, i.e. at ca. 315 ± 5 Ma) with respect to subduction duration.

This study was supported financially by NERC Fellowship NE/H016805/2 (to AZ), NERC Standard Grant NE/J023485/2 (to AZ and MC), NSFEAR-1455258 (to CJK). Samples were collected by RJT, who thanks G. Cuny and the Danish National Research Foundation for logistics and financial support. New high-resolution geochemical and sedimentological data from Fiskegrav, East Greenland, reveal fluctuations in marine redox conditions associated with the final disappearance of bioturbating organisms during the latest Permian mass extinction (LPME). Sedimentological observations imply a transgressive episode, and associated geochemical evidence for decreasing oxygen availability and the establishment of persistently ferruginous (Fe2 +-rich) conditions implies the shoreward migration of oxygen deficient waters. The long-term decline in dissolved oxygen (DO) availability could have been exacerbated by increasing water temperatures, reducing the solubility of oxygen and promoting thermal stratification. Mixing of the water column could have been further inhibited by freshwater influxes that could have generated salinity contrasts that reinforced thermal stratification. Enhanced runoff could also have increased the delivery of nutrients to the marine shelf, stimulating biological oxygen demand (BOD). During the transition to persistently ferruginous conditions we identify intervals of intermittent benthic meiofaunal recolonization, events that we attribute to small transient increases in DO availability. The mechanism controlling these fluctuations remains speculative, but given the possible centennial- to millennial-scale frequency of these changes, we hypothesise that the mid-latitude setting of Fiskegrav during the Late Permian was sensitive to changes in atmospheric circulation patterns, which may have influenced local precipitation and intermittently modulated some of the processes promoting anoxia. Publisher PDF

An ultrahigh-temperature (UHT) metapelitic granulite assemblage consisting of garnet(g)–spinel(sp)–orthopyroxene(opx)-sillimanite(sil)–cordierite(cd)–ilmenite(ilm)–biotite(bi)–plagioclase(pl)–quartz(q) occurs within migmatitic paragneiss near Kalasu in the Chinese Altai, NW China. Textural relations, mineral compositions and P-T estimates, indicate three stages of mineral assemblages: (1) pre-peak prograde stage (M1) consisting of a sp–sil-bearing or sp–opx-bearing inclusion assemblage, with low-Al2O3 contents (4–5 wt.%) in orthopyroxene and P-T conditions of ∼7 kbar and ∼890 °C, (2) peak UHT stage (M2) comprising a g–opx–cd-bearing coarse-grained assemblage, with high-Al2O3 contents (8–9 wt.%) in orthopyroxene and peak conditions of ∼8 kbar and ∼970 °C, and (3) post-peak HT stage (M3) containing an oriented opx–bi–sil-bearing assemblage in matrix, with moderate amounts of Al2O3 (6–7 wt.%) in orthopyroxene and P-T conditions of 8–9 kbar and ∼870 °C. The three discrete stages define an anticlockwise P-T path involving initial prograde heating and post-peak near isobaric cooling. Such a near isobaric cooling anticlockwise P-T path suggests that UHT metamorphism likely occurred in an overall extensional tectonic setting with associated underplating of mantle-derived mafic magma. A SHRIMP zircon U–Pb age of 278 ± 2 Ma obtained from the metapelitic granulite indicates UHT metamorphism in the Altai orogen occurred during the Permian, coeval with spacially associated mantle-derived mafic intrusions (∼280 Ma) and the Tarim mantle plume (∼275 Ma). Thus, the Permian UHT metamorphism of the Chinese Altai is likely associated with underplating and heating of mantle-derived mafic magma as a result of the Tarim mantle plume. Postprint

This research was supported by the University of St Andrews and the Natural Environment Research Council Steering Committee (IMF458/0512 and IP-1326-0512). The greenschist-facies late Mesoproterozoic Bandak succession in southern Norway consists of interlayered quartzites and meta-volcanic rocks with well preserved depositional and structural relations, which when combined provide important information on the late Mesoproterozoic continental margin of Baltica prior to the assembly of the supercontinent Rodinia. The timing of deposition of the Bandak succession is constrained by previously published tuff ages and new detrital zircon analyses reported here. The lower units of the Bandak succession (the Ofte and Røynstaul formations) display diverse detrital zircon age spectra implying derivation from a wide array of sources. The Morgedal and Gjuve formations have unimodal U-Pb age spectra, suggesting input from a single source and probably accumulation in restricted basins. The overlying Eidsborg Formation displays a wide range of detrital zircon age peaks indicative of input from more varied source regions. Hf and O isotopes in detrital zircons of the Bandak succession indicate derivation from typical Fennoscandian basement rocks with the youngest dominant population (∼1150 Ma) having been derived from sources formed by remelting of the pre-Sveconorwegian juvenile Gothian basement. Whole rock geochemistry and Nd isotopic signatures further imply that the rhyolite of the Dalaå Formation was formed from anatexis of c. 1500 Ma crust. In contrast, mafic volcanic rocks indicate a mantle source that had been previously enriched through subduction, and variable contamination from older continental crust, or melts derived from it (i.e. the Dalaå Formation). The mafic lithologies reveal decreasing amounts of crustal contamination higher in the section, compatible with increasing amounts of extension and a thinner crustal column. Age, sedimentological, and geochemical data for the volcanosedimentary units in the Bandak succession record an episode of intracontinental extension, associated with formation of a series of intermontane basins. We hypothesize that these localized basins were formed at different stages of extensional collapse following a pulse of regional orogenesis. The Ofte and Røynstaul formations accumulated during rifting and were followed by bimodal volcanism within the Morgedal, Dalaå, and Gjuve formations. The Eidsborg Formation, at the top of the succession, records post-extension transgressive sedimentation. This tectonic scenario represents a pre-Sveconorwegian stage of orogenesis that can be related to convergent margin processes. The surface expression of crustal growth during this time is relatively small; however, the volume of a postulated mafic underplate that accreted and intruded the lower crust in the Telemark region at this time is unknown. Crustal growth during syn-convergent extension in a retro-arc region may be significant if volumes of accreted mafic underplate are large. Postprint

Time-equivalent Early Permian sedimentary successions from high-latitude Gondwana basins and from equatorial accumulations in North China, covering the glacial to postglacial transition, display correlatable trends in continental weathering intensity based on chemical index of alteration (CIA) values. The successions display a pattern of CIA values that varies with latitude, similar to modern estuarine suspended sediments. Based on the modern-day CIA-temperature correlation, the glacial Early Permian low- to high-latitude land surface temperature gradient is estimated as ~ 20 ºC, slightly higher than the calculated values for the contemporaneous sea-surface temperature gradient. Postprint

International audience; The strong present-day Asian monsoons are thought to have originated between 25 and 22 million years (Myr) ago, driven by Tibetan-Himalayan uplift. However, the existence of older Asian monsoons and their response to enhanced greenhouse conditions such as those in theEocene period (55-34Myrago) are unknownbecause of the paucity of well-dated records. Here we show late Eocene climate records revealing marked monsoon-like patterns in rainfall and wind south and north of the Tibetan-Himalayan orogen. This is indicated by low oxygen isotope values with strong seasonality in gastropod shells and mammal teeth from Myanmar, and by aeolian dust deposition in northwest China. Our climate simulations support modern-like Eocene monsoonal rainfall and show that a reinforced hydrological cycle responding to enhancedgreenhouse conditions counterbalanced the negative effect of lowerTibetanrelief onprecipitation. These strong monsoons later weakened with the global shift to icehouse conditions 34Myr ago.

This research was funded through Natural Environment Research Council (grant NE/J021822/1) and the APC was paid through the RCUK OA block grant. Earth's middle age, extending from 1.7 to 0.75 Ga, was characterized by environmental, evolutionary, and lithospheric stability that contrasts with the dramatic changes in preceding and succeeding eras. The period is marked by a paucity of preserved passive margins, an absence of a significant Sr anomaly in the paleoseawater record and in the εHf(t) in detrital zircon, a lack of orogenic gold and volcanic-hosted massive sulfide deposits, and an absence of glacial deposits and iron formations. In contrast, anorthosites and kindred bodies are well developed and major pulses of Mo and Cu mineralization, including the world's largest examples of these deposits, are features of this period. These trends are attributed to a relatively stable continental assemblage that was initiated during assembly of the Nuna supercontinent by ca. 1.7 Ga and continued until breakup of its closely related successor, Rodinia, ca. 0.75 Ga. The overall low abundance of passive margins is consistent with a stable continental configuration, which also provided a framework for environmental and evolutionary stability. A series of convergent margin accretionary orogens developed along the edge of the supercontinent. Abundant anorthosites and related rocks developed inboard of the plate margin. Their temporal distribution appears to link with the secular cooling of the mantle, at which time the overlying continental lithosphere was strong enough to be thickened and to support the emplacement of large plutons into the crust, yet the underlying mantle was still warm enough to result in widespread melting of the lower thickened crust. Publisher PDF

This work was funded by a Natural Environment Research Council New Investigator Award (NE/C507529/1) to SAK. PPvS is funded by NERC Research Fellowship NE/1020571/1. A marked ocean acidification event and elevated atmospheric carbon dioxide concentrations following the extreme environmental conditions of the younger Cryogenian glaciation have been inferred from boron isotope measurements. Calcium and magnesium isotope analyses offer additional insights into the processes occurring during this time. Data from Neoproterozoic sections in Namibia indicate that following the end of glaciation the continental weathering flux transitioned from being of mixed carbonate and silicate character to a silicate-dominated one. Combined with the effects of primary dolomite formation in the cap dolostones, this caused the ocean to depart from a state of acidification and return to higher pH after climatic amelioration. Differences in the magnitude of stratigraphic isotopic changes across the continental margin of the southern Congo craton shelf point to local influences modifying and amplifying the global signal, which need to be considered in order to avoid overestimation of the worldwide chemical weathering flux. Postprint

This study was supported by China Natural Science Foundation (41190073 and 41372198), National Basic Research Program of China (2014CB440901) and Natural Environment Research Council (grant NE/J021822/1). Lenses of amphibolites occur along the Ailaoshan suture zone at the southwestern margin of the Yangtze Block, South China. Petrological, geochemical and zircon U-Pb geochronological data indicate that they are divisible into two coeval groups. Group 1, represented by the Jinping amphibolite, has mg-number of 71-76 and (La/Yb)cn ratios of 7.2-7.7, and displays a geochemical affinity to island arc volcanic rocks. Group 2 amphibolites occur at Yuanyang and are characterized by high Nb contents (14.3-18.4 ppm), resembling Nb-enriched basalts. The epsilon(Nd)(t) values for Group 1 range from -3.45 to -2.04 and for Group 2 from +4.08 to +4.39. A representative sample for Group 1 yields a U-Pb zircon age of 803 7 Ma, whereas two samples for Group 2 give U-Pb zircon ages of 813 +/- 11 Ma and 814 +/- 12 Ma. Petrogenetic analysis suggests that Group 1 originated from an orthopyroxene-rich source and Group 2 from a mantle wedge modified by slab-derived melt. In combination with other geological observations, these amphibolites are inferred to constitute part of an early Neoproterozoic (similar to 815-800 Ma) arc-back-arc basin system. The Neoproterozoic amphibolites and related rocks along the Ailaoshan zone may be the southward extension of the Neoproterozoic supra-subduction zone that developed along the western margin of the Yangtze Block. (C) 2014 Elsevier B.V. All rights reserved. Postprint

We present a new method to probe atmospheric pressure on Earthlike planets using (O2-O2) dimers in the near-infrared. We also show that dimer features could be the most readily detectable biosignatures for Earthlike atmospheres, and may even be detectable in transit transmission with the James Webb Space Telescope (JWST). The absorption by dimers changes more rapidly with pressure and density than that of monomers, and can therefore provide additional information about atmospheric pressures. By comparing the absorption strengths of rotational and vibrational features to the absorption strengths of dimer features, we show that in some cases it may be possible to estimate the pressure at the reflecting surface of a planet. This method is demonstrated by using the O2 A band and the 1.06 $\mu$m dimer feature, either in transmission or reflected spectra. It works best for planets around M dwarfs with atmospheric pressures between 0.1 and 10 bars, and for O2 volume mixing ratios above 50% of Earth's present day level. Furthermore, unlike observations of Rayleigh scattering, this method can be used at wavelengths longer than 0.6 $\mu$m, and is therefore potentially applicable, although challenging, to near-term planet characterization missions such as JWST. We have also performed detectability studies for JWST transit transmission spectroscopy and find that the 1.06 $\mu$m and 1.27 $\mu$m dimer features could be detectable (SNR$>$3) for an Earth-analog orbiting an M5V star at a distance of 5 pc. The detection of these features could provide a constraint on the atmospheric pressure of an exoplanet, and serve as biosignatures for oxygenic photosynthesis. We have calculated the required signal-to-noise ratios (SNRs) to detect and characterize O2 monomer and dimer features in reflected spectra and find that SNRs greater than 10 at a spectral resolving power of R=100 would be required., Comment: 39 pages, 24 figures and 2 tables. Accepted for publication in Astrobiology, Dec 2013

In situ Terrestrial Cosmogenic Nuclides (hereafter TCNs) are increasingly important for absolutely dating terrestrial events and processes. This study aimed at improving our knowledge of the production rate of Terrestrial Cosmogenic 3 He formed in situ in rock surfaces at low latitude and sea level as well as re-evaluation of the Canary Islands as a calibration site for TCNs. For this purpose, we sampled basaltic lava flows from some of the youngest and yet undated volcanic sites and used the 40 Ar/ 39 Ar incremental heating method on groundmass samples and in situ cosmogenic 3 He on olivine and clinopyroxene phenocrysts. 40 Ar/ 39 Ar analysis was done on a Hiden HAL Series 1000 triple filter quadrupole mass spectrometer with extraction furnace. Incremental heating data shows ages in the Late Pleistocene from 52.7 ± 21.6 ka to 398.6 ± 27.6 ka. We measured cosmogenic 3 He concentrations in olivine and clinopyroxene phenocrysts from flow top samples on a MAP 215-50 sector mass spectrometer with a crushing device and a diode laser extraction system. Exposure age calculations yielded ages in the range 38.9 ± 4.0 ka to 62.3 ± 6.7 ka for the youngest lava flow and the data series is in broad agreement with the argon data up to 250 ka and reveals a more continuous time line of volcanism during the late Pleistocene on the island. However, the dataset was not sufficient for calculation of production rates for in situ Terrestrial Cosmogenic 3 He as many samples showed signs of erosion. Calculated erosion rates range from none to as high as 7.3 mm/kyr assuming a rock density of 2.9 g/cm 2 . This finding puts a constraint on the use of Fuerteventura as a calibration site for exposure histories older than 50–100 ka. A comparison with cosmogenic 36 Cl data supports these findings and indicates substantial weathering.

Rare earth elements (REE) are critical to the development of a sustainable hi-tech economy [1].Eudialyte-bearing nepheline syenites provide promising alternatives to currently mined REE deposits in China, and techniques for their economic and environmental friendly exploitation are being developed. Europe hosts substantial eudialyte deposits within three rift-related peralkaline complexes, i.e. Ilímaussaq (Greenland), Lovozero (Russia), and Norra Kärr (Sweden) [2,3]. Despite being relatively low grade (c. 2 wt% TREO) compared to conventionally exploited REE phases, eudialyte is attractive for exploitation because of its (1) associated enrichment in other critical metals e.g. Zr, Nb and Ta; (2) high proportions of heavy relative to light REE (up to 1:1), (3) low U and Th contents, and (4) easy magnetic separation. Publisher PDF Non

NJG acknowledges the Oxford University Fell Fund (Ref. DGD07260) and Highland Metals Pte Ltd. for financial support. Analytical support at NIGL was funded through NIGFSC grant IP-1554-0515. Myanmar is perhaps one of the world's most prospective but least explored minerals jurisdictions, containing important known deposits of tin, tungsten, copper, gold, zinc, lead, nickel, silver, jade and gemstones. A scarcity of recent geological mapping available in published form, coupled with an unfavourable political climate, has resulted in the fact that although characterized by several world-class deposits, the nation's mineral resource sector is underdeveloped. As well as representing a potential new search space for a range of commodities, many of Myanmar's known existing mineral deposits remain highly prospective. Myanmar lies at a crucial geologic juncture, immediately south of the Eastern Himalayan Syntaxis, however it remains geologically enigmatic. Its Mesozoic-Recent geological history is dominated by several orogenic events representing the closing of the Tethys Ocean. We present new zircon U-Pb age data related to several styles of mineralization within Myanmar. We outline a tectonic model for Myanmar from the Late Cretaceous onwards, and document nine major mineralization styles representing a range of commodities found within the country. We propose a metallogenetic model that places the genesis of many of these metallotects within the framework of the subduction and suturing of Neo-Tethys and the subsequent Himalayan Orogeny. Temporal overlap of favourable conditions for the formation of particular deposit types during orogenic progression permits the genesis of differing metallotects during the same orogenic event. We suggest the evolution of these favourable conditions and resulting genesis of much of Myanmar's mineral deposits, represents a single, evolving, mineral system: the subduction and suturing of Neo-Tethys. Postprint

This study was jointly funded by the National Science Foundation of China (41190073), National Basic Research Program of China (2014CB440901 and 2016YFC0600303) and the Fundamental Research Funds for the Central Universities to SYSU. New U-Pb geochronological, petrologic, elemental and Sr-Nd-Hf-O isotopic data for the granites from the Inthanon and Sukhothai zones in NW Thailand in conjunction with correlations with SW China are presented to constrain the age and position of the Paleotethys Ocean in this region and the associated assembly of Southeast Asia. The geochronological data show that the granitic rocks in the Inthanon and Sukhothai zones, herein named Group 1 and Group 2 granites, respectively, yield similar crystallization ages of 230-200 Ma. Group 1 samples are characterized by monzogranite and granite with I- and S-type geochemical affinity and Group 2 samples by I-type monzogranite and granodiorite. They have generally similar chondrite-normalized REE and PM- normalized multi-element patterns but distinct Sr-Nd-Hf-O isotopic compositions. Group 1 samples have slightly higher initial 87Sr/86Sr ratios (0.7111- 0.7293) but lower εNd(t) values (-11.1 ~ -14.1) than those of Group 2 samples (87Sr/86Sr(i)=0.7073-0.7278 and εNd(t)=-8.3 ~ -11.0). Group 1 samples show the lower εHf(t) values (-5.4 ~ -18.2), older TDM (1.62-2.40 Ga) and higher δ18O values (+ 7.95-+9.94) than those of Group 2 samples (εHf(t) of -11.1-+4.80, TDM of 0.96-1.95 Ga and δ18O of + 4.95 ~+7.98) for the Triassic crystallization zircons. These geochemical signatures are similar to the Kwangsian and Indosinian granites in the South China and Indochina blocks but distinct from those of the Gangdese I-type granite and Sibumasu Paleozoic granite. Our data suggest that Group 1 samples mainly originated from the early Paleozoic supracrustal rocks containing metapelite and metavolcanic components, which had previously experienced the surface weathering. Group 2 samples were derived from a hybridized source of an old metamorphic and a newly underplated mafic component. Synthesis of our data with available regional observations indicate that the Inthanon zone represents the main suture zone of the eastern Paleotethyan Ocean in NW Thailand and links with the Changning-Menglian suture zone in SW Yunnan (SW China). In NW Thailand, a switch from the eastward subduction of the Paleotethyan oceanic plate to the collision of the Sibumasu with Indochina blocks occurred at ~ 237 Ma, and syn- and post-collisional time being at ~ 237-230 Ma and ~ 200-230 Ma, respectively. The late Triassic granites in the Inthanon and Sukhothai zones are representative of the post-collisional magmatic products. Postprint

This study was supported by National Basic Research Program of China (2014CB440901), the Strategic Priority Research Program (B) of CAS (XDB18020104), National Science Foundation of China (41190073, 41372198 and 41304071), and NERC grant NE/J021822/1. Numerical experiments are used to investigate the thermo- mechanical controls for inducing flat subduction and why flat subduction is rare relative to normal/steep subduction. Our modeling results demonstrate that flat subduction is an end-member of a steady state subduction geometry and is characterized by a curved slab with a nearly-horizontal slab section. Intermediate cases between normal/steep and flat subduction appear to be transient in origin and evolve toward one of the stable end-members. Physical parameters inducing flat subduction can be classified into four categories: buoyancy of the subducting oceanic lithosphere (e.g., slab age, oceanic crustal thickness), viscous coupling between the overriding and downgoing plates (e.g., initial subduction angle), external kinematic conditions, and rheological properties of the subduction zone. On the basis of parameter sensitivity tests and the main characteristics of present-day flat subduction zones, positive buoyancy from either the young slab or the thickened oceanic crust are considered the primary controlling parameter. Our results show that the possibility of flat subduction is directly proportional to oceanic crustal thickness and inversely proportional to the slab age. Furthermore, oceanic crust must be thicker than 8 km to induce flat subduction, when the slab is older than 30 Ma with an initial subduction angle of ≥ 20°, and without absolute trenchward motion of the overriding plate. The lower the initial subduction angle or the thicker the overriding continental lithosphere, the more likelihood for flat subduction. The initial subduction angle is more influential for the development of flat subduction than the overriding lithospheric thickness, and a thick overriding lithosphere induces flat subduction only under the condition of an initial subduction angle of ≤ 25°, with a slab age of ≥ 30 Ma and without absolute trenchward motion of the overriding plate. However, when the initial subduction angle is increased to > 25°, no flat subduction is predicted. All the parameters are evaluated within the constraints of a mechanical framework in which the slab geometry is regarded as a result of a balance between the gravitational and hydrodynamic torque. Any factor that can sufficiently reduce gravitational torque or increase hydrodynamic torque will exert a strong effect on flat subduction development. Our results are consistent with the observations of modern flat subduction zones on Earth. Postprint

This study was funded by University of Washington Department of Earth and Space Sciences Harry Wheeler Scholarship and Jody Bourgeois Graduate Student Support Fund granted to MCK. Stephen Hillier acknowledges support of the Scottish Government's Rural and Environment Science and Analytical Services Division (RESAS). The late Ordovician is characterized by dramatic changes in global climate concurrent with a major mass extinction and possible changes in ocean redox. To further refine our understanding of these events, we present nitrogen and carbon isotope and abundance data from the Ordovician-Silurian (O-S) Global Boundary Stratotype Section and Point at Dob's Linn, Scotland. We show that this section experienced post-depositional ammonium migration from the organic-rich to the organic-poor horizons. However, our data suggest that isotopic fractionations from ammonium substitution into illitic clay minerals are small and can be corrected. Reconstructed primary nitrogen isotope ratios indicate that unlike in tropical continental shelf sections that were transiently enriched in nitrate during the Hirnantian glaciation, the sub-tropical continental slope setting at Dob's Linn experienced persistent limitation of fixed nitrogen across the O-S boundary. Shallow subpolar settings appear to be the only environment that shows persistent nitrate availability at that time. This pattern suggests that spatial trends in marine nitrate concentrations – which are observed in the modern ocean as a result of latitudinal temperature gradients – were already established during the Paleozoic. While the average marine O2 chemocline depth may have deepened during the Hirnantian glaciation, it probably did not lead to global ventilation of the deep ocean, which may have been delayed until the Carboniferous. Furthermore, carbonate data from this and other sections suggest a deepening of the carbonate compensation depth (CCD) during the Hirnantian. This observation indicates that Pacific-style responses of the CCD to glacial/interglacial periods were operational across the O-S boundary, and that the expansion of abiotic carbonate deposition and preservation beyond the shelf break could have in-part mediated changes to surface CO2 during these extreme changes in climate. Postprint

The application of optically stimulated luminescence (OSL) dating within glacial settings can be limited where sediments have not had their OSL signal fully reset by sunlight exposure. Heterogeneous bleaching can result in age overestimations, and although it is recognized that certain depositional settings are more likely to have experienced sufficient sunlight exposure to bleach the OSL signal, no comprehensive study has empirically investigated the processes of sediment bleaching, or the variability in bleaching between deposits of the same type and within the same glacial catchment. A suite of modern glacial and glaciofluvial sediments from Fabergstolsda- len, southern Norway, have been analysed to explore the controls that sedimentary processes and depositional setting have on bleaching of the OSL signal of quartz. There is considerable variability in the residual OSL ages of similar modern deposits, which reflects high sensitivity of the OSL signal to sediment source, sedimentary process, transport distance and depositional setting. Overdispersion values are greatest for the sediments which have been most heterogeneously bleached and these sediments have the lowest residual ages. Sampling strategies that incorporate sufficient consideration of the depositional framework of sample settings can minimize the effects of unbleached residuals on OSL age determinations. Copyright # 2013 The Authors. Journal of Quaternary Science published by John Wiley & Sons Ltd on behalf of Quaternary Research Association

Funding: Dean's Scholarship at the University of East Anglia. The potential habitability of newly discovered exoplanets is initially assessed by determining whether their orbits fall within the circumstellar habitable zone of their star. However, the habitable zone (HZ) is not static in time or space, and its boundaries migrate outward at a rate proportional to the increase in luminosity of a star undergoing stellar evolution, possibly including or excluding planets over the course of the star’s main sequence lifetime. We describe the time that a planet spends within the HZ as its ‘‘habitable zone lifetime.’’ The HZ lifetime of a planet has strong astrobiological implications and is especially important when considering the evolution of complex life, which is likely to require a longer residence time within the HZ. Here, we present results from a simple model built to investigate the evolution of the ‘‘classic’’ HZ over time, while also providing estimates for the evolution of stellar luminosity over time in order to develop a ‘‘hybrid’’ HZ model. These models return estimates for the HZ lifetimes of Earth and 7 confirmed HZ exoplanets and 27 unconfirmed Kepler candidates. The HZ lifetime for Earth ranges between 6.29 and 7.79 · 109 years (Gyr). The 7 exoplanets fall in a range between ∼1 and 54.72 Gyr, while the 27 Kepler candidate planets’ HZ lifetimes range between 0.43 and 18.8 Gyr. Our results show that exoplanet HD 85512b is no longer within the HZ, assuming it has an Earth analog atmosphere. The HZ lifetime should be considered in future models of planetary habitability as setting an upper limit on the lifetime of any potential exoplanetary biosphere, and also for identifying planets of high astrobiological potential for continued observational or modeling campaigns. Publisher PDF

The geologic records associated with the formation of the supercontinents Rodinia and Gondwana have markedly different seawater Sr and zircon Hf isotopic signatures. Rodinia-related (Grenville-Sveconorwegian-Sunsas) orogens display significantly less enriched crustal signatures than Gondwana-related (Pan-African) orogens. Seawater Sr isotope ratios also exhibit a more pronounced crustal signal during the span of the Gondwana supercontinent than at the time of Rodinia. Such isotopic differences are attributed to the age and nature of the continental margins involved in the collisional assembly, and specifically to the depleted mantle model ages, and hence the isotope ratios of the material weathered into the oceans. In our preferred model the isotopic signatures of Rodinia-suturing orogens reflect the closure of ocean basins with dual subduction zones verging in opposite directions, analogous to the modern Pacific basin. This would have resulted in the juxtaposition of juvenile continental and island arc terrains on both margins of the colliding plates, thus further reworking juvenile crust. Conversely, the assembly of Gondwana was accomplished primarily via a number of single-sided subduction zones that involved greater reworking of ancient cratonic lithologies within the collisional sutures. The proposed geodynamic models of the assembly of Rodinia and Gondwana provide a connection between the geodynamic configuration of supercontinent assembly and its resulting isotopic signature. Postprint

This study reveals that in the SE Carpathians terrace development and fluvial incision during the Middle Pleistocene-Holocene are predominantly controlled by tectonic uplift as shown by terrace distributions and uplift amounts and rates. The work focuses on a transect from the internal nappes and Braşov intramontane basin (western domain) to the external nappes and Focşani foredeep basin (eastern domain). New infrared stimulated luminescence ages were obtained and minimum terrace formation ages were determined to derive fluvial incision rates, and thereby, to constrain tectonic uplift. In the eastern domain, non-uniform terrace distributions in adjacent sub-parallel more active Punta and less active Şuşiţa rivers and an eastward migrated fluvial incision from the orogen to the foredeep basin indicate tectonic uplift as dominant control on terrace development. Strath-terraces in the western and eastern domains indicate repeated events of vertical fluvial incision and lateral erosion during the early Middle Pleistocene and late Middle Pleistocene-Holocene, respectively. These events imply successive recurrent disturbances of equilibrium conditions due to pulses of increased tectonic uplift. Fill-terraces in the western domain show that initial aggradation periods were followed by uplift-driven vertical incision during the late Middle-Late Pleistocene. As fill-terraces show a wide-spread development, climatic change and complex response cannot be excluded as contributing factors. Synchronous to terrace development, loess deposition periods during the late Middle-Late Pleistocene and Latest Pleistocene and intercalated episodes of palaeosol formation during the Late Pleistocene imply comparable climatic conditions across the SE Carpathians. Dominant strath-terraces of the eastern domain indicate stronger fluvial incision (~. 240. m) since the late Middle Pleistocene, whereas older strath- and younger dominant fill-terraces of the western domain designate a lower amount (~. 90. m) since the early Middle Pleistocene. Middle Pleistocene-Holocene fluvial incision rates document higher tectonic uplift in the external nappes and lower towards the western intramontane and eastern foredeep basins. © 2013 Elsevier B.V.

We have investigated the use of current amplifiers equipped with 10 12 ohm feedback resistors in thermal ionisation mass spectrometry (TIMS) analyses of sub-nanogram sample aliquots for Nd and Sr isotope ratios. The results of analyses using the 1012 ohm resistors were compared to those obtained with the conventional 1011 ohm amplifiers. We adopted a method where long baselines were measured before and after data acquisition to save time during sample analysis. The noise level on the new design 10 12 ohm resistors is 3-5 fold lower compared to the 1011 ohm resistors, which results in a two fold better analytical precision on 143Nd/144Nd and 87Sr/86Sr analyses for beam intensities of 10 mV for the 143Nd and 87Sr masses, respectively. Reproducibility of 87Sr/86Sr on repeat analyses of 1 ng Sr sample loads is better using 1012 ohm resistors compared to 1011 ohm resistors and is a factor of 2 better compared to previous studies. The external reproducibility of 143Nd/144Nd for 1 ng Nd sample loads is a factor of 1.4 better compared to previously published Nd+ results and is similar to those obtained using the more time-consuming NdO+ techniques. Reproducibility tests on 100 pg Nd and Sr samples of reference materials yield 176 ppm of 143Nd/144Nd and 92 ppm of 87Sr/ 86Sr. These data suggest that we can resolve variability in the fourth decimal place of Nd and Sr isotope ratios in geological samples as small as 100 pg. © The Royal Society of Chemistry.

JP was funded by NERC postdoctoral fellowship NE/H01313X/2, with support of the Oxford laboratories from an Advanced ERC grant (NEWISOTOPEGEOSCIENCE) to ANH. PAS by an APA PhD scholarship and ANU Vice-Chancellor’s Scholarship. Recycling pathways of multivalent elements, that impact our understanding of diverse geological processes from ore formation to the rise of atmospheric oxygen, depend critically on the spatial and temporal variation of oxygen fugacity (fO2) in the Earth’s interior. Despite its importance, there is currently no consensus on the relative fO2 of the mantle source of mid-ocean ridge basalts compared to the sub-arc mantle, regions central to the mediation of crust-mantle mass balances. Here we present the first stable vanadium isotope measurements of arc lavas, complemented by non-arc lavas and two co-genetic suites of fractionating magmas, to explore the potential of V isotopes as a redox proxy. Vanadium isotopic compositions of arc and non-arc magmas with similar MgO overlap with one another. However, V isotopes display strikingly large, systematic variations of ~2 ‰ during magmatic differentiation in both arc and non-arc settings. Calculated bulk V Rayleigh fractionation factors (1000 lnαmin-melt of -0.4 to -0.5 ‰) are similar regardless of the oxidation state of the evolving magmatic system, which implies that V isotope fractionation is most influenced by differences in bonding environment between minerals and melt rather than changes in redox conditions. Thus, although subtle fO2 effects may be present, V isotopes are not a direct proxy for oxygen fugacity in magmatic systems. Publisher PDF

This work was part-funded by a Research Incentive Grant from The Carnegie Trust (REF: 70335) and a Royal Society of Edinburgh Research Fellowship to C. Cousins. J, Harris acknowledges funding from STFC (consolidated grant ST/N000528/1). Salt minerals are an important natural resource. The ability to quickly and remotely identify and quantify salt deposits and salt contaminated soils and sands is therefore a priority goal for the various industries and agencies that utilise salts. The advent of global hyperspectral imagery from instruments such as Hyperion on NASA’s Earth-Observing 1 satellite has opened up a new source of data that can potentially be used for just this task. This study aims to assess the ability of Visible and Near Infrared (VNIR) spectroscopy to identify and quantify salt minerals through the use of spectral mixture analysis. The surface and near-surface soils of the Atacama Desert in Chile contain a variety of well-studied salts, which together with low cloud coverage, and high aridity, makes this region an ideal testbed for this technique. Two forms of spectral data ranging 0.35 – 2.5 μm were collected: laboratory spectra acquired using an ASD FieldSpec Pro instrument on samples from four locations in the Atacama desert known to have surface concentrations of sulfates, nitrates, chlorides and perchlorates; and images from the EO-1 satellite’s Hyperion instrument taken over the same four locations. Mineral identifications and abundances were confirmed using quantitative XRD of the physical samples. Spectral endmembers were extracted from within the laboratory and Hyperion spectral datasets and together with additional spectral library endmembers fed into a linear mixture model. The resulting identification and abundances from both dataset types were verified against the sample XRD values. Issues of spectral scale, SNR and how different mineral spectra interact are considered, and the utility of VNIR spectroscopy and Hyperion in particular for mapping specific salt concentrations in desert environments is established. Overall, SMA was successful at estimating abundances of sulfate minerals, particularly calcium sulfate, from both hyperspectral image and laboratory sample spectra, while abundance estimation of other salt phase spectral end-members was achieved with a higher degree of error. Publisher PDF

This work was supported by the Natural Environment Research Council (NERC grants NE/J021822/1 and NE/K008862/1) and by the Leverhulme Trust (grant RPG-2015–422). Most crustal rocks derive from preexisting crust, and so the composition of newly generated (juvenile) continental crust, and hence the tectonic settings of its formation, have remained difficult to determine, especially for the first billion years of Earth’s evolution. Modern primitive mantle–derived magmas have distinct U/Pb ratios, depending on whether they are generated in intraplate (mean U/Pb = 0.37) or in subduction settings (mean U/Pb = 0.10). The U/Pb ratio can therefore be used as a proxy for the tectonic settings in which juvenile continental crust is generated. This paper presents a new way to see back to the U/Pb ratios of juvenile continental crust that formed hundreds to thousands of millions of years ago, based on ion probe analysis of Pb isotopes in alkali feldspar and plagioclase inclusions within well-dated zircons. Pb isotope data are used to calculate the time-integrated U/Pb ratios (i.e., 238U/204Pb = µ) for the period between the Hf model age and the U-Pb crystallization age of the zircons. These time-integrated ratios reflect the composition of the juvenile continental crust at the time it was extracted from the mantle, and so they can be used as a proxy for the tectonic setting of formation of that crust. Two test samples with Proterozoic Hf model ages and Paleozoic crystallization ages have feldspar inclusions with measured Pb isotope ratios that overlap within analytical error for each sample. Sample Z7.3.1 from Antarctica has Pb isotope ratios (mean 206Pb/204Pb = 16.88 ± 0.08, 1σ) that indicate it was derived from source rocks with low U/Pb ratios (∼0.11), similar to those found in subduction-related settings. Sample Temora 2 from Australia has more radiogenic Pb isotope ratios (mean 206Pb/204Pb = 19.11 ± 0.23, 1σ) indicative of a source with higher U/Pb ratios (∼0.36), similar to magmas generated in intraplate settings. Analysis of detrital populations with a range of Hf model ages (e.g., Hadean to Phanerozoic), and for which zircons and their inclusions represent the only archive of their parent magmas, should ultimately open new avenues to our understanding of the formation and the evolution of the continental crust through time. Postprint Postprint

his work was financially co-supported by the National Natural Science Foundation of China (grants 41190073, 41176041, 91128211), the National Basic Research Program of China (grant 42014CB440901), the Fundamental Research Funds for the Central Universities to SYSU and the GIGCAS 135 Project (grant Y234031001). The Kenting Mélange on the Hengchun Peninsula, Taiwan, formed through tectonic shearing of subduction complex lithologies, probably within the plate boundary subduction channel between the Eurasian and Philippine Sea plates, with further deformation and exhumation in the Pliocene-Pleistocene during arc-continent collision. Field relations reveal a structural gradation from normal stratified turbidite sequence (Mutan Formation) through broken formation to highly sheared Kenting Mélange containing allochthonous polygenic blocks. This gradation is consistent with an increase of average vitrinite reflection values from ~ 0.72% in the Mutan Formation through ~ 0.93% in the broken formation to ~ 0.99% in the mélange, suggesting temperatures of at least 140 °C during formation of the Kenting Mélange. Zircons from gabbro in the Kenting Mélange are dated as 25.46 ± 0.18 Ma, which together with geochemical data constrains the source to South China Sea oceanic lithosphere. In combination with the field relationships, vitrinite reflectance values, microfossil stratigraphy and offshore geophysical data from S and SE Taiwan, we propose that the Kenting Mélange initially formed at the subduction plate boundary from offscraped trench deposits. Minor Plio-Pleistocene microfossils (< 5%) occur within the mélange in proximity to slope basin of equivalent age and were likely sheared into the mélange during out-of-sequence thrusting associated with active arc-continent collision, which in the Hengchun Peninsula commenced after 6.5 Ma. Postprint

The authors acknowledge the financial support provided by the National Basic Research Program of China (973 Program, 2012CB416701) and the National Natural Science Foundation of China (41330208 and 41572200). The Neoproterozoic Jiangnan orogenic belt delineates the suture zone between the Cathaysia and Yangtze blocks of the South China Craton. The western part of the belt, in the Longsheng region, consists of a disrupted mafic-ultramafic assemblage of pillow basalt, gabbro, diabase, and peridotite along with siliceous marble, ophicalcite, and jasper mixed with basalt. Significant talc deposits occur on the margins of the ultramafic bodies as well as in the transition zone between marble and basalt. Primary rock relations are largely overprinted by pervasive shearing, resulting in disruption of the assemblage into series of discontinuous blocks within a phyllite matrix. West-dipping thrust faults mark the eastern contact of blocks, and the overall succession has the appearance of a tectonic mélange. U-Pb zircon age data from the gabbros and diabases yield crystallization ages of 867 ± 10, 863 ± 8, and 869 ± 9 Ma, with positive εHf(t) values. The gabbro, basalt, serpentinite, and some talc samples display minor light rare earth element?enriched patterns with obvious depletion of Nb and Ta, indicating a subduction-related setting. The tuffaceous phyllite shows similar geochemical features. A few mafic rocks and the altered ultramafic rocks display mid-ocean ridge basalt (MORB) affinity. Overall lithostratigraphic relationships, age data, and geochemical signatures suggest a forearc setting that was imbricated and disrupted within an accretionary prism environment to form an ophiolitic mélange. The pillow basalt, red jasper, and MORB-type mafic-ultramafic rocks within the mélange occur as exotic blocks derived from the subducting oceanic plate, whereas the arc-type mafic rocks occur as autochthonous blocks, which are all exposed in a matrix of sandy and tuffaceous phyllite. Publisher PDF

This work was supported by NERC Grants NE/D012996/1 and NER/B/S/2002/00540 and NIGFSC IP/1024/0508. New geological and geochronological data define four episodes of volcanism for the Lake Tana region in the northern Ethiopian portion of the Afro–Arabian Large Igneous Province (LIP): pre-31 Ma flood basalt that yielded a single 40Ar/39Ar age of 34.05 ± 0.54/0.56 Ma; thick and extensive felsic ignimbrites and rhyolites (minimum volume of 2-3 x 103km3) erupted between 31.108 ± 0.020/0.041 Ma and 30.844 ± 0.027/0.046 Ma (U–Pb CA-ID-TIMS zircon ages); mafic volcanism bracketed by 40Ar/39Ar ages of 28.90 ± 0.12/0.14 Ma and 23.75 ± 0.02/0.04 Ma; and localised scoraceous basalt with an 40Ar/39Ar age of 0.033 ± 0.005/0.005 Ma. The felsic volcanism was the product of super eruptions that created a 60–80 km diameter caldera marked by km-scale caldera-collapse fault blocks and a steep-sided basin filled with a minimum of 180 m of sediment and the present-day Lake Tana. These new data enable mapping, with a finer resolution than previously possible, Afro–Arabian LIP volcanism onto the timeline of the Eocene–Oligocene transition and show that neither the mafic nor silicic volcanism coincides directly with perturbations in the geochemical records that span that transition. Our results reinforce the view that it is not the development of a LIP alone but its rate of effusion that contributes to inducing global-scale environmental change. Postprint

This work was supported by the UK Natural Environment Research Council (award NE/I022973/1). Coral skeletal Sr/Ca is a palaeothermometer commonly used to produce high resolution seasonal sea surface temperature (SST) records and to investigate the amplitude and frequency of ENSO and interdecadal climate events. The proxy relationship is typically calibrated by matching seasonal SST and skeletal Sr/Ca maxima and minima in modern corals. Applying these calibrations to fossil corals assumes that the temperature sensitivity of skeletal Sr/Ca is conserved, despite substantial changes in seawater carbonate chemistry between the modern and glacial ocean. We present Sr/Ca analyses of 3 genotypes of massive Porites spp. corals (the genus most commonly used for palaeoclimate reconstruction), cultured under seawater pCO2 reflecting modern, future (year 2100) and last glacial maximum (LGM) conditions. Skeletal Sr/Ca is indistinguishable between duplicate colonies of the same genotype cultured under the same conditions, but varies significantly in response to seawater pCO2 in two genotypes of Porites lutea, whilst Porites murrayensis is unaffected. Within P. lutea, the response is not systematic: skeletal Sr/Ca increases significantly (by 2-4%) at high seawater pCO2 relative to modern in both genotypes, and also increases significantly (by 4%) at low seawater pCO2 in one genotype. This magnitude of variation equates to errors in reconstructed SST of up to -5°C. Publisher PDF

The refurbishment of the RLTLCL system and the establishment of it as a facility at St. Andrews were funded by NERC Grant NE/H002715/1. The luminescence spectra of a suite of natural sodium framework silicates including four different sodalite variants and tugtupite have been collected during X-ray irradiation as a function of temperature between 20 and 673 K. The origin of the emission bands observed in these samples is attributed to F-centres (360 nm), paramagnetic oxygen defects (400 and 450 nm), S2 − ions (620 nm) and tetrahedral Fe3+ (730 nm). Luminescence in the yellow (550 nm) is tentatively attributed to Mn2+, and red luminescence in Cr-rich pink sodalite is possibly from Cr3+ activation. Sudden reduction in luminescence intensities of emission centres was observed for all minerals in the 60–120 K range. Since it is common to all the sodalite-group minerals, we infer it is a feature of the aluminosilicate framework. Sodalite luminescence has responses from substitutions on the framework (e.g. paramagnetic oxygen defects, Fe3+) which give sodalite properties akin to other framework silicates such as feldspar and quartz. However, the presence of the sodalite cage containing anions (such as F-centres, S2 − ions) imparts additional properties akin to alkali halides. The possibility of coupling between Fe3+ and S2 − is discussed. The overall luminescence behaviour of sodalite group can be understood in terms of competition between these centre types. Publisher PDF

This work was aided by a Nuffield Summer Studentship granted to MJH, a U.S. Science Support Program (USSSP) Post-Expedition Activity award for IODP Exp. 342 to PMH, a Flint Postdoctoral Fellowship to DEP, a NERC PhD Studentship granted to JWBR, and a URF and Wolfson merit award to DNS. Pelagic ecosystem function is integral to global biogeochemical cycling, and plays a major role in modulating atmospheric CO2 concentrations (pCO2). Uncertainty as to the effects of human activities on marine ecosystem function hinders projection of future atmospheric pCO2. To this end, events in the geological past can provide informative case studies in the response of ecosystem function to environmental and ecological changes. Around the Cretaceous–Palaeogene (K–Pg) boundary, two such events occurred: Deccan large igneous province (LIP) eruptions and massive bolide impact at the Yucatan Peninsula. Both perturbed the environment, but only the impact coincided with marine mass extinction. As such, we use these events to directly contrast the response of marine biogeochemical cycling to environmental perturbation with and without changes in global species richness. We measure this biogeochemical response using records of deep-sea carbonate preservation. We find that Late Cretaceous Deccan volcanism prompted transient deep-sea carbonate dissolution of a larger magnitude and timescale than predicted by geochemical models. Even so, the effect of volcanism on carbonate preservation was slight compared with bolide impact. Empirical records and geochemical models support a pronounced increase in carbonate saturation state for more than 500 000 years following the mass extinction of pelagic carbonate producers at the K–Pg boundary. These examples highlight the importance of pelagic ecosystems in moderating climate and ocean chemistry. Postprint

This study was financially supported by the National Natural Science Foundation of China (grants 41302083, 41572078), the National Basic Research Program of China (grant 2011CB808800), and the Fundamental Research Funds for the Central Universities (grant CUGL140402), China University of Geosciences (Wuhan). P.A. Cawood acknowledges support from NERC grant NE/J021822/1. Paleoflora studies suggest that continental drying occurred associated with the Early Permian deglaciation in southern North America, but not in North China. Both regions occupied tropical latitudes during the Early Permian, but they were separated by the Tethys Ocean. To further constrain the tropical paleoclimate conditions during the Early Permian glacial to deglacial transition, we undertook a weathering geochemistry study on Early Permian mudstone and siltstone samples from southeastern North China and evaluated the climate impact on regional weathering patterns. Whole-rock major- and trace-element geochemistry, and X-ray diffraction mineralogy data suggest that sample compositions, and resultant calculated values of most weathering indices, are dominated by chemical weathering from a source akin to the average upper continental crust (UCC) of the adjoining southern North China craton. Values of the chemical index of alteration (CIA) and other well-correlated weathering indices, including the index of sodium depletion fraction (τNa), indicate high chemical weathering intensity (e.g., CIA > 80 and τNa < −0.80) in the southern North China craton source region related to intense climate forcing. Based on modern surface weathering data from granitic landscapes, we propose that the dependence of land surface soil chemical weathering intensity on the air temperature can be described by a τNa-MAT (mean annual temperature) transfer function, where humidity control is demonstrated by the consistently high τNa values of surface soils at sites with low annual precipitation rates (