Search

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

Ruddons Point, on the Firth of Forth coastline, Scotland, is a laterally extensive terrace of glacial and marine sediment deposits raised above current sea-level, situated near to Kincraig Point, a key site that records a series of stepped erosional platforms carved into the local bedrock, interpreted as post Last Glacial Maximum palaeoshorelines. The deposits at Ruddons Point continue inland, with exposures of the raised sands and gravels cut by the local river, the Cocklemill Burn. The site provides an opportunity to examine the depositional history through the Late Devensian and Holocene. Geophysical survey aided in interpreting characteristics of subsurface sediments such as the transition between the younger saltmarsh sediments and older underlying sands and clays below, which slope in a northerly direction. A chronology obtained through optically stimulated luminescence (OSL) dating spans from c. 29 ka for sands and clays at an elevation of −0.66 mOD to surface windblown sands at c. 9.2 ka, formed prior to the Main Postglacial Transgression. Dating of inland raised marine deposits along the Cocklemill Burn records dates ranging from c. 8.9 to c. 4.3 ka. The raised marine deposits of Ruddons Point range from c. 8.1 to c. 2.9 ka, deposited unconformably on glacial tills and clays. This multidisciplinary field study builds depositional scenarios utilizing two dating methods, spanning the last c. 29 ka, to better understand coastal evolution for a region which has experienced complex relative sea-level variations. Supplementary material : Supplementary data related to this research article is available at https://doi.org/10.6084/m9.figshare.c.6080999 Thematic collection: This article is part of the Early Career Research collection available at: https://www.lyellcollection.org/topic/collections/early-career-research

Funding: The research was carried out as part of a project funded by the Malaysian Palm Oil Board (MPOB). L. K. K and E. R. are both employees of MPOB. The research was carried out with the support of Sarawak Oil Palm Berhard (SOPB) on whose land the research project was based. Need for regional economic development and global demand for agro‐industrial commodities has resulted in large‐scale conversion of forested landscapes to industrial agriculture across South East Asia. However, net emissions of CO2 from tropical peatland conversions may be significant and remain poorly quantified, resulting in controversy around the magnitude of carbon release following conversion. Here we present long term, whole ecosystem monitoring of carbon exchange from two oil palm plantations on converted tropical peat swamp forest. Our sites compare a newly converted oil palm plantation (OPnew) to a mature oil palm plantation (OPmature) and combine them in the context of existing emission factors. Mean annual net emission (NEE) of CO2 measured at OPnew during the conversion period (137.8 Mg CO2 ha‐1 yr ‐1) were an order of magnitude lower during the measurement period at OPmature (17.5 Mg CO2 ha‐1 yr‐1). However, mean water table depth (WTD) was shallower (0.26 m) than a typical drainage target of 0.6 m suggesting our emissions may be a conservative estimate for mature plantations, mean WTD at OPnew was more typical at 0.54 m. Reductions in net emissions were primarily driven by increasing biomass accumulation into highly productive palms. Further analysis suggested annual peat carbon losses of 24.9 Mg CO2‐C ha‐1 yr‐1 over the first 6 years, lower than previous estimates for this early period from subsidence studies, losses reduced to 12.8 Mg CO2‐C ha‐1 yr‐1 in the later, mature phase. Despite reductions in NEE and carbon loss over time, the system remained a large net source of carbon to the atmosphere after 12 years with the remaining 8 years of a typical plantation’s rotation unlikely to recoup losses. These results emphasise the need for effective protection of tropical peatlands globally and strengthening of legislative enforcement where moratoria on peatland conversion already exist. Publisher PDF

Mars today has no active volcanism and its atmosphere is oxidizing, dominated by the photochemistry of CO2 and H2O. Using a one-dimensional photochemical model, we consider whether plausible volcanic gas fluxes could have switched the redox-state of the past martian atmosphere to reducing conditions. In our model, the total quantity and proportions of volcanic gases depend on the water content, outgassing pressure, and oxygen fugacity of the source melt. We find that with reasonable melt parameters the past martian atmosphere (~3.5 Gyr to present) could have easily reached reducing and anoxic conditions with modest levels of volcanism, >0.14 km^3/yr, well within the range of prior estimates. Counter-intuitively we also find that more reducing melts with lower oxygen fugacity require greater amounts of volcanism to switch a paleo-atmosphere from oxidizing to reducing. The reason is that sulfur is more stable in such melts and lower absolute fluxes of sulfur-bearing gases more than compensate for increases in the proportions of H2 and CO. These results imply that ancient Mars should have experienced periods with anoxic and reducing atmospheres even through the mid-Amazonian whenever volcanic outgassing was sustained at sufficient levels. Reducing anoxic conditions are potentially conducive to the synthesis of prebiotic organic compounds, such as amino acids, and are therefore relevant to the possibility of life on Mars. Also, anoxic reducing conditions should have influenced the type of minerals that were formed on the surface or deposited from the atmosphere such as elemental polysulfur (S8) as a signature of past reducing atmospheres. Finally, our models allow us to estimate the amount of volcanically sourced atmospheric sulfate deposited over Mars' history, approximately 10^6 to 10^9 Tmol, with a spread depending on assumed outgassing rate history and magmatic source conditions., 6 Figures, 1 Table, 3 Appendices

This article reviews the state of the art of speleogenetic investigations in gypsum karsts from numerous studies carried out over the past 50 years in Spain. A classification of gypsum karsts is proposed based on the hydrogeological, tectonic and stratigraphic criteria that decisively control the evolution of gypsum karsts. In this respect, lithological aspects of Messinian and Triassic-Permian gypsum series in south-eastern Spain are considered, such as the alternation of rhythmic levels of marl and gypsum, as well as geodynamic aspects. The influence of the hydrogeological characteristics of evaporite aquifers on gypsum cave speleogenesis is discussed; this includes speleogenetic processes in confined, semi-confined or free aquifers controlled by regional and local base levels. Also, the importance of intense saline diapiric uplift is examined. To illustrate our classification, examples of gypsum caves developed in Spain are presented. Their similarities and differences with gypsum karsts in other regions (Italy, Ukraine, and USA) are discussed. A first general division addresses: (1) caves controlled by stratigraphic factors and (2) caves controlled by tectonic factors. Several typologies can be described, including (A) multilayer caves with confined hydrogeological origin, (B) confined hypophreatic caves with linear or maze configurations, (C) caves controlled by the variation or remanence of regional or local base-levels, and (D) caves controlled by the halokinetic evolution of salt/gypsum diapirs. The proposed classification is flexible and adaptable to each case, because different genetic mechanisms can coincide in time and space. Likewise, most considerations stated in this work about gypsum karst are valid for speleogenesis in other rock types. Publisher PDF

We acknowledge the financial support by the Major State Research Development Program of China (Grant No. 2016YFC0600202), National Natural Science Foundation of China (Nos. 41330208 and 41572200) and State Key Laboratory for Mineral Deposits Research (Nanjing University) (ZZKT-201603). The Cathaysia Block of the South China Craton includes a Proterozoic basement that experienced a prolonged Precambrian crustal evolution but to date lacks evidence of Proterozoic metamorphic ages. At Lichuan and Jianning, in the Wuyi Domain of the eastern Cathaysia Block, Proterozoic rock units include migmatized paragneiss of the Wanyuan Group and minor amphibolite of the Tianjingping Formation, which are enveloped by schist of Mayuan Group, and all are intruded by Paleozoic and Mesozoic igneous rocks. Detrital zircon grains from the Wanyuan paragneiss display metamorphic rims that yield concordant weighted average 206Pb/238U ages of 860 ± 6 Ma and 435 ± 5 Ma, along with variably disconcordant ages with lower intercept ages of 442 ± 41 Ma. The zircon core ages range from 3015 Ma to 851 Ma, with three major age populations at 930–865 Ma, 1850–1200 Ma and 2650–2400 Ma. Detrital zircon grains from Mayuan schist samples at Jianning generally lack core-rim structures and yield three main age populations at 860–736 Ma, 1835–1775 Ma and 2720–2500 Ma. Metamorphic ages of ca. 860 Ma and ca. 435 Ma for the Wanyuan paragneiss along with the youngest detrital zircon constrain the depositional age of the protolith to ca. 865–860 Ma, whereas the Mayuan Group is younger and probably deposited after ca. 736 Ma. Characteristics of detrital zircon age populations along with regional geological data suggest accumulation of the Wanyuan Group in a convergent and/or collisional setting. Metamorphism and a possible subduction -collision process within the Cathaysia Block at around 860 Ma suggest it was not a unified block in early Neoproterozoic. The growth of ca. 440 Ma metamorphic rims is likely related to granitic magmatism, such as that exposed in the Lichuan region. The sparse evidence for early Neoproterozoic metamorphism likely reflects widespread overprinting by the Paleozoic tectonothermal event at around 440 Ma. Postprint

The authors would like to thank the support of the Fundamental Research Funds for the Central Universities of China (No.2-9-2015-191) and the National Nature Science Foundation of China (No.11205134). Thermoluminescence spectra of rare earth doped calcium fluoride samples, both powder and single crystal, were recorded over the temperature range from 25 K to 673 K. Although some broad band features exist, the spectra are dominated by the rare earth line transitions. The glow peak temperatures are slightly sensitive both to the ionic size of the dopants and the dopant concentration. By contrast, very considerable differences are generated by heat treatments, such as annealing followed by either fast or slow cooling. Comments are included on the reasons for such sensitivity in terms of association of dopant and intrinsic defect sites and why the results of dosimetry powder differ from those from single crystals. Postprint

The deep bedrock surroundings are an analog for extraterrestrial habitats for life. In this study, we investigated microbial life within anoxic ultradeep boreholes in Precambrian bedrock, including the adaptation to environmental conditions and lifestyle of these organisms. Samples were collected from Pyh&auml, salmi mine environment in central Finland and from geothermal drilling wells in Otaniemi, Espoo, in southern Finland. Microbial communities inhabiting the up to 4.4 km deep bedrock were characterized with phylogenetic marker gene (16S rRNA genes and fungal ITS region) amplicon and DNA and cDNA metagenomic sequencing. Functional marker genes (dsrB, mcrA, narG) were quantified with qPCR. Results showed that although crystalline bedrock provides very limited substrates for life, the microbial communities are diverse. Gammaproteobacterial phylotypes were most dominant in both studied sites. Alkanindiges -affiliating OTU was dominating in Pyh&auml, salmi fluids, while different depths of Otaniemi samples were dominated by Pseudomonas. One of the most common OTUs detected from Otaniemi could only be classified to phylum level, highlighting the uncharacterized nature of the deep biosphere in bedrock. Chemoheterotrophy, fermentation and nitrogen cycling are potentially significant metabolisms in these ultradeep environments. To conclude, this study provides information on microbial ecology of low biomass, carbon-depleted and energy-deprived deep subsurface environment. This information is useful in the prospect of finding life in other planetary bodies.

We aim to assess net primary productivity (NPP) and carbon cycling in Andean tropical alpine grasslands (puna) and compare it with NPP of tropical montane cloud forests. We ask the following questions: (1) how do NPP and soil respiration of grasslands vary over the seasonal cycle? (2) how do burning and grazing affect puna productivity? (3) if the montane forest expands into the puna, what will be the resulting change in productivity? The study sites are located at the South-eastern Peruvian Andes; one grassland site and the forest sites are in Wayqecha biological station, and another grassland site in Manu National Park. At each grassland site, we selected a burnt and an unburnt area, installed unfenced and fenced transects in each area, and monitored above-ground productivity (NPPAG), below-ground productivity (NPPBG) and soil respiration (Rs) for 2 yr. In the forest, we monitored NPPAG, NPPBG and Rs for 2–4 yr. Grassland NPP varied between 4.6 ± 0.25 (disturbed areas) to 15.3 ± 0.9 Mg C ha-1 yr-1 (undisturbed areas) and cloud forest NPP was between 7.05 ± 0.39 and 8.0 ± 0.47 Mg C ha-1 yr-1, while soil carbon stocks were in the range of 126 ± 22 to 285 ± 31Mg C ha-1. There were no significant differences on NPP between the puna and forest sites. The most undisturbed site had significantly higher NPP than other grassland sites, but no differences were found when relating grazing and fire at other sites. There were lower residence times of above-ground biomass compared to below-ground biomass. There was a strong seasonal signal on grassland NPPAG and NPPBG, with a shift on allocation at the beginning of the austral summer. High elevation tropical grasslands can be as productive as adjacent cloud forests, but have very different carbon cycling and retention properties than cloud forests. S Online supplementary data available from stacks.iop.org/ERL/9/115011/mmedia Keywords: tropical alpine wetlands, above-ground productivity, below-ground productivity, fire, grazing, disturbances, puna

The Scottish pine network expansion has been an ongoing task since 2006 and funding must be acknowledged to the following projects: EU project ‘Millennium’ (017008-2), Leverhulme Trust project ‘RELiC: Reconstructing 8000 years of Environmental and Landscape change in the Cairngorms (F/00268/BG)’, the Native Oak and Pine project or ‘NOAP’ (Historic Scotland) and the NERC project ‘SCOT2K:Reconstructing 2000 years of Scottish climate from tree rings (NE/K003097/1)’. Further PhD funding for Milos Rydval is acknowledged from The Carnegie Trust. Dendroarchaeology almost exclusively uses ring-width (RW) data for dating historical structures and artefacts. Such data can be used to date tree-ring sequences when regional climate dominates RW variability. However, the signal in RW data can be obscured due to site specific ecological influences (natural and anthropogenic) that impact crossdating success. In this paper, using data from Scotland, we introduce a novel tree-ring parameter (Blue Intensity – BI) and explore its utility for facilitating dendro historical dating of conifer samples. BI is similar to latewood density as they both reflect the combined hemicellulose, cellulose and lignin content in the latewood cell walls of conifer species and the amount of these compounds is strongly controlled, at least for trees growing in temperature limited locations, by late summer temperatures. BI not only expresses a strong climate signal, but is also less impacted by site specific ecological influences. It can be concurrently produced with RW data from images of finely sanded conifer samples but at a significantly reduced cost compared to traditional latewood density. Our study shows that the probability of successfully crossdating historical samples is greatly increased using BI compared to RW. Furthermore, due to the large spatial extent of the summer temperature signal expressed by such data, a sparse multi-species conifer network of long BI chronologies across Europe could be used to date and loosely provenance imported material. Postprint

We thank NSF EAR FESD grant #1338810 (RB), NASA grant NNX16AI37G (RB), the Agouron Institute (RB), the NASA Astrobiology Institute’s Virtual Planetary Laboratory (RB), the NSF Graduate Research Fellowship Program (MAK), and the Department of Earth and Space Sciences, University of Washington Goodspeed Geology Fellowship (MCK), Misch Fellowship (MCK), and the Kenneth C. Robbins Field Study Fellowship (2014, MCK) for funding. Fixed nitrogen is an essential nutrient for eukaryotes. As N2 fixation and assimilation of nitrate are catalyzed by metalloenzymes, it has been hypothesized that in Mesoproterozoic oceans nitrate was limited in offshore environments by low trace metal concentrations and high rates of denitrification in anoxic and episodically euxinic deep water masses, restricting eukaryotes to near-shore environments and limiting their evolutionary innovation. To date this hypothesis has only been tested in the Belt Supergroup (∼1.4 Ga), with results that support an onshore-offshore nitrate gradient as a potential control on eukaryote ecology. Here we present bulk nitrogen and organic carbon isotopic data from non-isochronous cross-basinal facies across the Bangemall (∼1.5 Ga) and the Roper (∼1.4-1.5 Ga) basins to better understand the extent and variability of onshore-offshore nitrogen isotope gradients in the Mesoproterozoic. Both basins show an average ∼1-2‰ enrichment in δ15Nbulk from deep to shallow facies, with a maximum range from -1‰ offshore to +7.5‰ onshore. Unlike the Belt basin, the Bangemall and Roper basins show some offshore δ15Nbulk values that are enriched beyond the isotopic range induced by biological N2 fixation alone. This suggests a mixture of aerobic and anaerobic metabolisms offshore. In shallow waters, where δ15Nbulk enrichment peaks, an aerobic nitrogen cycle was evidently operating vigorously. Even though isotopic signatures of aerobic nitrogen cycling are seen in all parts of the Bangemall and Roper basins, our data are consistent with a lateral gradient in nitrate availability within the photic zone, with higher concentrations in near-shore environments than offshore. The variability in δ15Nbulk values in each depositional environment and the consistently low δ15N values from Mesoproterozoic units compared to the Paleoproterozoic and Neoproterozoic suggest that nitrate concentrations in the global ocean were likely low. This trend is now seen in all three Mesoproterozoic basins so far examined, and contrasts with the Paleoproterozoic and Neoproterozoic where nearly all δ15Nbulk data plot above the N2 fixation window. Thus, we propose that the Mesoproterozoic ocean was characterized by a nitrate minimum between the Paleo- and Neoproterozoic, with the lowest concentrations in offshore environments. This inference is consistent with a Mesoproterozoic O2 decline following a temporary Paleoproterozoic O2 peak, and it further supports the idea that nitrate limitation offshore may have contributed to the restriction of photosynthetic eukaryotes to near-shore environments, delaying their rise to ecological dominance until the Neoproterozoic Era. Postprint

Funding during the compilation of this manuscript was provided by the NASA postdoctoral program. Postprint

EJH acknowledges funding from a NERC PhD studentship and the work was completed at the University of St Andrews, UK. The peralkaline to agpaitic Ilímaussaq Complex, S. Greenland, displays spectacular macrorhythmic (> 5 m) layering via the kakortokite (agpaitic nepheline syenite), which outcrops as the lowest exposed rocks in the complex. This study applies crystal size distribution (CSD) analyses and eudialyte-group mineral chemical compositions to study the marker horizon, Unit 0, and the contact to the underlying Unit − 1. Unit 0 is the best-developed unit in the kakortokites and as such is ideal for gaining insight into processes of crystal formation and growth within the layered kakortokite. The findings are consistent with a model whereby the bulk of the black and red layers developed through in situ crystallisation at the crystal mush–magma interface, whereas the white layer developed through a range of processes operating throughout the magma chamber, including density segregation (gravitational settling and flotation). Primary textures were modified through late-stage textural coarsening via grain overgrowth. An open-system model is proposed, where varying concentrations of halogens, in combination with undercooling, controlled crystal nucleation and growth to form Unit 0. Our observations suggest that the model is applicable more widely to the layering throughout the kakortokite series and potentially other layered peralkaline/agpaitic rocks around the world. Publisher PDF

This research was financially supported by the MOST of China (No. 2016YFC0600304 and No. 2016YFC0600407), the Strategic Priority Research Program (B) of the Chinese Academy of Sciences (XDB03010301), the National Science Foundation of China (41225006 and 41472061), and the MOST Special Fund from the State Key Laboratory of Geological Processes and Mineral Resources (China University of Geosciences). The surface uplift of mountain belts is in large part controlled by the effects of crustal thickening and mantle dynamic processes (e.g., lithospheric delamination or slab breakoff). Understanding the history and driving mechanism of uplift of the southern Tibetan Plateau requires accurate knowledge on crustal thickening over time. Here we determine spatial and temporal variations in crustal thickness using whole-rock La/Yb ratios of intermediate intrusive rocks from the Gangdese arc. Our results show that the crust was likely of normal thickness prior to ca. 70 Ma (~37 km) but began to thicken locally at ca. 70 − 60 Ma. The crust reached (58 − 50) ± 10 km at 55 − 45 Ma extending over 400 km along the strike of the arc. This thickening was likely due to magmatic underplating as a consequence of rollback and then breakoff of the subducting Neo-Tethyan slab. The crust attained a thickness of 68 ± 12 km at ca. 20 − 10 Ma, as a consequence of underthrusting of India and associated thrust faulting. The Gangdese Mountains in southern Tibet broadly attained an elevation of >4000 m at ca. 55 − 45 Ma as a result of isostatic surface uplift driven by crustal thickening and slab breakoff, and reached their present-day elevation by 20 − 10 Ma. Our paleoelevation estimates are consistent not only with the C − O isotope-based paleoaltimetry but also with the carbonate clumped isotope paleothermometer, exemplifying the promise of reconstructing paleoelevation in time and space for ancient orogens through a combination of magmatic composition and Airy isostatic compensation. Publisher PDF

The first author acknowledges funding from an Initiative d’Excellence (IDEX) “Attractivité” grant (VOLPERM), funded by the University of Strasbourg. M.H. also acknowledges support from the CNRS (INSU 2016-TelluS-ALEAS). Surface gravitational acceleration (surface gravity) on Mars, the second-smallest planet in the Solar System, is much lower than that on Earth. A direct consequence of this low surface gravity is that lithostatic pressure is lower on Mars than on Earth at any given depth. Collated published data from deformation experiments on basalts suggest that, throughout its geological history (and thus thermal evolution), the Martian brittle lithosphere was much thicker but weaker than that of present-day Earth as a function solely of surface gravity. We also demonstrate, again as a consequence of its lower surface gravity, that the Martian lithosphere is more porous, that fractures on Mars remain open to greater depths and are wider at a given depth, and that the maximum penetration depth for opening-mode fractures (i.e., joints) is much deeper on Mars than on Earth. The result of a weak Martian lithosphere is that dykes—the primary mechanism for magma transport on both planets—can propagate more easily and can be much wider on Mars than on Earth. We suggest that this increased the efficiency of magma delivery to and towards the Martian surface during its volcanically active past, and therefore assisted the exogeneous and endogenous growth of the planet's enormous volcanoes (the heights of which are supported by the thick Martian lithosphere) as well as extensive flood-mode volcanism. The porous and pervasively fractured (and permeable) nature of the Martian lithosphere will have also greatly assisted the subsurface storage of and transport of fluids through the lithosphere throughout its geologically history. And so it is that surface gravity, influenced by the mass of a planetary body, can greatly modify the mechanical and hydraulic behaviour of its lithosphere with manifest differences in surface topography and geomorphology, volcanic character, and hydrology. Postprint

The facility is being developed under the auspices of the National Resource Sciences Precinct (NRSP) – a collaboration between CSIRO, Curtin University and The University of Western Australia – and is supported by the Science and Industry Endowment Fund (SIEF RI13-01). SMR acknowledges support from the ARC Core to Crust Fluid System COE (CE11E0070). The widespread use of zircon in geochemical and geochronological studies of crustal rocks is underpinned by an understanding of the processes that may modify its composition. Deformation during tectonic and impact related strain is known to modify zircon trace element compositions, but the mechanisms by which this occurs remain unresolved. Here we combine electron backscatter diffraction, transmission Kikuchi diffraction and atom probe microscopy to investigate trace element migration associated with a ∼20 nm wide, 2° low-angle subgrain boundary formed in zircon during a single, high-strain rate, deformation associated with a bolide impact. The low-angle boundary shows elevated concentrations of both substitutional (Y) and interstitial (Al, Mg & Be) ions. The observed compositional variations reflect a dynamic process associated with the recovery of shock-induced vacancies and dislocations into lower energy low-angle boundaries. Y segregation is linked to the migration and localization of oxygen vacancies, whilst the interstitial ions migrate in association with dislocations. These data represent the direct nanoscale observation of geologically-instantaneous, trace element migration associated with crystal plasticity of zircon and provide a framework for further understanding mass transfer processes in zircon. Postprint

This research was supported by the Open Fund (PLC201404) of State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation (Chengdu University of Technology), the National Natural Science Foundation of China (41502109), Project funded by China Postdoctoral Science Foundation (2015 M582528) and the Fundamental Research Funds for the Central Universities, Chengdu University of Technology. Claystone beds directly below and above the Emeishan basalts in SW China formed around the Guadalupian-Lopingian (G-L) boundary. Zircons from both levels give U–Pb ages of ~ 260 Ma, and are identical within-error to ages reported for the Emeishan Large Igneous Province (LIP). The claystones lack Nb-Ta anomalies on primitive mantle normalized elemental diagrams; zircons from these claystones have a geochemical affinity to within-plate-type magmas. These features, combined with the strong negative Eu anomalies in the zircons and high Al2O3/TiO2 ratios, indicate that claystones around the G-L boundary have a silicic volcanic component related to Emeishan LIP. Zircons from the underlying claystone bed have much higher U/Yb and Th/Nb ratios and lower εHf(t) values than those overlying the LIP, suggesting that early-stage silicic volcanic rocks had a higher crustal contamination or assimilation during magmatic processes. In terms of stratigraphic correlation, our data demonstrate that silicic eruptions occurred not only at the end, but also at the beginning of the Emeishan LIP, and the overall duration of the main basaltic phase was short (< 1 m.y). Postprint

The authors acknowledge financial support from the National Science Foundation: EAR-1226741 (to M.B.S.) and EAR-1225630 (to J.D.B.), and from the REG Trust (to M.B.S.). The biogeochemical cycling of metals and other contaminants in river-floodplain corridors is controlled by microbial activity responding to dynamic redox conditions. Riverine flooding thus has the potential to affect speciation of redox-sensitive metals such as mercury (Hg). Therefore, inundation history over a period of decades potentially holds information on past production of bioavailable Hg. We investigate this within a Northern California river system with a legacy of landscape-scale 19th century hydraulic gold mining. We combine hydraulic modeling, Hg measurements in sediment and biota, and first-order calculations of mercury transformation to assess the potential role of river floodplains in producing monomethylmercury (MMHg), a neurotoxin which accumulates in local and migratory food webs. We identify frequently inundated floodplain areas, as well as floodplain areas inundated for long periods. We quantify the probability of MMHg production potential (MPP) associated with hydrology in each sector of the river system as a function of the spatial patterns of overbank inundation and drainage, which affect long-term redox history of contaminated sediments. Our findings identify river floodplains as periodic, temporary, yet potentially important, loci of biogeochemical transformation in which contaminants may undergo change during limited periods of the hydrologic record. We suggest that inundation is an important driver of MPP in river corridors and that the entire flow history must be analyzed retrospectively in terms of inundation magnitude and frequency in order to accurately assess biogeochemical risks, rather than merely highlighting the largest floods or low-flow periods. MMHg bioaccumulation within the aquatic food web in this system may pose a major risk to humans and waterfowl that eat migratory salmonids, which are being encouraged to come up these rivers to spawn. There is a long-term pattern of MPP under the current flow regime that is likely to be accentuated by increasingly common large floods with extended duration. Postprint

We acknowledge support from our respective funding agencies (NERC grant NE/J021822/1, and NSERC Canada). Periodic assembly and dispersal of continental fragments has been a characteristic of the solid Earth for much of its history. Geodynamic drivers of this cyclic activity are inferred to be either top-down processes related to near surface lithospheric stresses at plate boundaries or bottom-up processes related to mantle convection and, in particular, mantle plumes, or some combination of the two. Analysis of the geological history of Rodinian crustal blocks suggests that internal rifting and breakup of the supercontinent were linked to the initiation of subduction and development of accretionary orogens around its periphery. Thus, breakup was a top-down instigated process. The locus of convergence was initially around north-eastern and northern Laurentia in the early Neoproterozoic before extending to outboard of Amazonia and Africa, including Avalonia–Cadomia, and arcs outboard of Siberia and eastern to northern Baltica in the mid-Neoproterozoic (∼760 Ma). The duration of subduction around the periphery of Rodinia coincides with the interval of lithospheric extension within the supercontinent, including the opening of the proto-Pacific at ca. 760 Ma and the commencement of rifting in east Laurentia. Final development of passive margin successions around Laurentia, Baltica and Siberia was not completed until the late Neoproterozoic to early Paleozoic (ca. 570–530 Ma), which corresponds with the termination of convergent plate interactions that gave rise to Gondwana and the consequent relocation of subduction zones to the periphery of this supercontinent. The temporal link between external subduction and internal extension suggests that breakup was initiated by a top-down process driven by accretionary tectonics along the periphery of the supercontinent. Plume-related magmatism may be present at specific times and in specific places during breakup but is not the prime driving force. Comparison of the Rodinia record of continental assembly and dispersal with that for Nuna, Gondwana and Pangea suggests grouping into two supercycles in which Nuna and Gondwana underwent only partial or no break-up phase prior to their incorporation into Rodinia and Pangea respectively. It was only after this final phase of assembly that the supercontinents then underwent full dispersal. Publisher PDF

We thank the Natural Environment Research Council (grants NE/J021822/1 and NE/K008862/1) for funding. The continental crust is the archive of Earth's history. Its rock units record events that are heterogeneous in time with distinctive peaks and troughs of ages for igneous crystallization, metamorphism, continental margins, and mineralization. This temporal distribution is argued largely to reflect the different preservation potential of rocks generated in different tectonic settings, rather than fundamental pulses of activity, and the peaks of ages are linked to the timing of supercontinent assembly. Isotopic and elemental data from zircons and whole rock crustal compositions suggest that the overall growth of continental crust (crustal addition from the mantle minus recycling of material to the mantle) has been continuous throughout Earth's history. A decrease in the rate of crustal growth ca. 3.0 Ga is related to increased recycling associated with the onset of plate tectonics. We recognize five stages of Earth's evolution: (1) initial accretion and differentiation of the core/mantle system within the first few tens of millions of years; (2) generation of crust in a pre-plate tectonic regime in the period prior to 3.0 Ga; (3) early plate tectonics involving hot subduction with shallow slab breakoff over the period from 3.0 to 1.7 Ga; (4) Earth's middle age from 1.7 to 0.75 Ga, characterized by environmental, evolutionary, and lithospheric stability; (5) modern cold subduction, which has existed for the past 0.75 b.y. Cycles of supercontinent formation and breakup have operated during the last three stages. This evolving tectonic character has likely been controlled by secular changes in mantle temperature and how that impacts on lithospheric behavior. Crustal volumes, reflecting the interplay of crust generation and recycling, increased until Earth's middle age, and they may have decreased in the past ∼1 b.y. Publisher PDF

This study is financially supported by the National Natural Science Foundation of China (Grant Nos. 41272209, 41472165, 41502179, 41530207) and the Central University Basic Scientific Research Business Expenses of China University of Geosciences (Beijing) (Grant No. 2652015038). The North China Craton (NCC), dominated by ∼2.6-2.5 Ga tectonothermal events, provides a natural laboratory to study Neoarchean crustal growth and geodynamic evolution. Late Neoarchean granitoid gneisses are well exposed in the Northern Liaoning Province, located north of the ancient Anshan-Benxi terrane along the northeastern margin of the Eastern Block (EB) of the NCC. LA-ICPMS zircon U-Pb isotopic dating reveal that granitoid gneisses in the Qingyuan area can be grouped into two major episodes, i.e., ∼2559-2534 Ma strongly gneissic quartz dioritic and tonalitic to trondhjemitic gneisses; and ∼2529-2495 Ma weakly gneissic to massive quartz monzodioritic and monzogranitic gneisses, with subordinate tonalitic to trondhjemitic gneisses. The late magmatic episode was accompanied by regionally high-grade metamorphism (∼2510-2495 Ma). Most granitoid gneisses display highly depleted zircon εHf(t2) values (+4.2-+8.1), whereas one monzogranitic gneiss shows negative values of -4.7 to -1.0, indicating late Neoarchean crustal growth with minor involvement of ancient continental materials probably sourced from the Anshan-Benxi terrane. Geochemical and petrogenetic studies reveal that the quartz dioritic magmas were derived from partial melting of plagioclase-poor garnet amphibolites or eclogites metamorphosed from oceanic slab materials, with slab melts contaminated by mantle wedge peridotites during ascent. The tonalitic to trondhjemitic magmas stemmed from partial melting of mainly juvenile metabasaltic rocks with minor metagreywackes of lower arc crust. In comparison, the quartz monzodioritic and monzogranitic magmas were derived respectively from partial melting of depleted mantle sources metasomatized by slab-derived fluids and metagreywackes with different crustal resident ages at middle to lower crustal levels. Combined with previous studies of metavolcanic rocks, the Northern Liaoning Province records late Neoarchean crustal growth, evolving from mid-ocean ridge, through initiation and maturation of an intra-oceanic arc, to arc-continent collision. Arc-continent accretion and possibly slab rollback processes may have triggered reworking of both juvenile arc crust and minor ancient continental margin materials, generating the magmatic precursors for the monzogranitic gneisses. Overall, the intense late Neoarchean crustal growth of the EB was controlled mainly by arc-continent accretion, possibly linked to global assembly of cratonic fragments. Postprint

The authors acknowledge financial support from ICDP for the drilling programme. AEF, ATB and ARP thank NERC for financial support through NE/G00398X/1. VAM, AEC, and AL thank the Norwegian Research Council for financial support through 191530/V30. A variety of carbonates of different geneses, as indicated by petrography and geochemistry, are found throughout 400m of the volcano-sedimentary rocks of the Zaonega Formation of Palaeoproterozoic age in the Onega Basin of Fennoscandia. Following intensive sampling and analysis of varied calcites from drillcore recovered during the ICDP FAR-DEEP program, we report a highly unusual depth distribution of calcite oxygen isotope values (δ18Ocal). Unprecedentedly for such rocks, the δ18Ocal values over the full depth interval of 400m are strongly linearly correlated with depth (r2 = 0.9015, n=178). We propose that this is the result of major oxygen isotope resetting through water-rock interaction with a fluid of relatively constant oxygen isotopic composition (δ18Ow). In this model, the observed linear δ18Ocal-depth relationship is then a consequence of the increase in temperature with depth because of the background geothermal gradient. Minor deviations from the overall linear trend are likely due to bed-scale geological factors including locally high impermeability, and oxygen isotope modification of δ18Ow by comparatively intense water-rock interaction. Were the observed δ18Ocal values to have been reset during the greenschist facies Svecofennian metamorphism which affected the rocks at c. 1800Ma, the implied geothermal gradient of ∼ 560°C km-1 is geologically unreasonable and, accordingly, this hypothesis is ruled out. Rather, the δ18Ocal variation of 5‰ over 400m implies a near-surface depth for the rocks during fluid interaction, and this is consistent with a surface-derived origin of the infiltrating fluid (δ18Ow ∼ -13.6‰ for a surface temperature of 15°C and geothermal gradient of ∼ 52 °C km-1). It is speculated that the fluid accessed the carbonates from the basin edge by bed-parallel rather than cross-formational flow. There is an intriguing distribution of Na in the sedimentary rocks of the Zaonega Formation. Sodium is relatively abundant in rocks below a certain depth (the Lowermost Dolostone at ∼258m), but rare in shallower sequences. It is argued that this distribution did not originate with the basin-scale fluid-rock interaction documented above, but may rather be the result of evaporite dissolution, and subsequent redistribution of soluble elements during fluid flow associated with the syndepositional emplacement of basin-wide igneous rocks. Postprint

Astrobiology is the science that seeks to understand the story of life in our universe. Astrobiology includes investigation of the conditions that are necessary forlife to emerge and flourish, the origin of life, the ways that life has evolved and adaptedto the wide range of environmental conditions here on Earth, the search for life beyondEarth, the habitability of extraterrestrial environments, and consideration of the future oflife both here on Earth and elsewhere. It therefore requires knowledge of physics,chemistry and biology, and many more specialized scientific areas including astronomy,geology, planetary science, microbiology, atmospheric science and oceanography. Fil: Domagal Goldman, Shawn D.. National Aeronautics And Space Administration; Estados Unidos Fil: Wright, Katherine. University Of Bristol; Reino Unido Fil: Adamala, Katarzyna. University Of Minnesota; Estados Unidos Fil: Antonio, Marina. Washington State University. School Of Earth & Environmental Sciences; Estados Unidos Fil: Arino de la Rubia, Leigh. University Of New South Wales; Australia Fil: Carter Bond, Jade. University Of New South Wales; Australia Fil: Dartnell, Lewis. University Of Leicester; Reino Unido Fil: Goldman, Aaron. Oberlin College; Reino Unido Fil: Paulino Lima, Ivan Glaucio. National Aeronautics And Space Administration; Estados Unidos Fil: Lynch, Kennda. Colorado School; Estados Unidos Fil: Naud, Marie Eve. Université Du Québec A Montreal; Canadá Fil: Singer, Kelsi. Southwest Research Institute; Estados Unidos Fil: Abrevaya, Ximena Celeste. Consejo Nacional de Investigaciónes Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Astronomía y Física del Espacio. - Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Astronomía y Física del Espacio; Argentina Fil: Anderson, Rika. University of Washington; Estados Unidos Fil: Arney, Giada. University of Washington; Estados Unidos Fil: Atri, Dimitra. International Centre Of Theoretical Science. Tata Institute Of Fundamental Research; España Fil: Azua Bustos, Armando. Pontificia Universidad Católica de Chile; Chile Fil: Bowman, Jeff. Lamont Doherty Earth Observatory; Estados Unidos Fil: Brazelton, William. University of Utah; Estados Unidos Fil: Brennecka, Gregory. Westfalische Wilhelms Universitat; Alemania Fil: Carns, Regina. University of Washington; Estados Unidos Fil: Chopra, Adytia. Australian National University; Australia Fil: Collangelo Lillis, Jess. McGill University; Estados Unidos Fil: Crockett, Christopher. University Of Carnegie Mellon; Estados Unidos Fil: DeMarines, Julia. University Of Carnegie Mellon; Estados Unidos Fil: Frank, Elizabeth. University Of Carnegie Mellon; Estados Unidos Fil: Frantz, Carie. University of Washington; Estados Unidos Fil: Galante, Douglas. Brazilian Synchrotron Light Laboratory; Brasil Fil: Glass, Jennifer. Georgia Institute Of Techology; Estados Unidos Fil: Gleeson, Damhait. Instituto Nacional de Tecnica Aeroespacial; España

This work was funded in part by Historic Environment Scotland. The World Heritage Sites of Orkney, Scotland contain iconic examples of Neolithic monumentality that have provided significant information about this period of British prehistory. However, currently, a complete understanding of the sites remains to be achieved. This is, in part, because the monuments lack an adequate context within the broader palaeolandscape. Recent investigations (seismic geophysical survey, microfossil analysis and 14C dating) in and around the Brodgar Isthmus, both onshore and offshore, are used to reconstruct the landscapes at a time when sea-level, climate and vegetation were different to that experienced today. Results show that in the early Neolithic the isthmus between the Ring of Brodgar and Stones of Stenness was broader with a smaller loch to the west. Furthermore this landscape contained sandstone outcrops that would have provided a potential source of stone for monument construction. Microfossil analysis and radiocarbon dates demonstrate that the Loch of Stenness was transformed from freshwater to brackish during the early Neolithic, perhaps immediately preceding construction of the major monuments. Finally, the analysis of our data suggests that sediment influx to the loch shows a tenfold increase coincident with widespread vegetation change that straddles the Mesolithic/Neolithic transition at c. 8 ka cal. B.P. These results provide, for the first time, a landscape context for the Neolithic sites on the isthmus. Postprint

There is considerable controversy over the nature of geophysically recognized low-velocity–high-conductivity zones (LV–HCZs) within the Tibetan crust, and their role in models for the development of the Tibetan Plateau. Here we report petrological and geochemical data on magmas erupted 4.7–0.3 Myr ago in central and northern Tibet, demonstrating that they were generated by partial melting of crustal rocks at temperatures of 700–1,050 °C and pressures of 0.5–1.5 GPa. Thus Pliocene-Quaternary melting of crustal rocks occurred at depths of 15–50 km in areas where the LV–HCZs have been recognized. This provides new petrological evidence that the LV–HCZs are sources of partial melt. It is inferred that crustal melting played a key role in triggering crustal weakening and outward crustal flow in the expansion of the Tibetan Plateau., The role of the low velocity-high conductivity zones (LV–HCZs) in developing the Tibetan Plateau has remained controversial. Here, Wang et al. present new geochemical and petrological data that show the LV–HCZs are sources of partial melt thus giving insight into the development of the Tibetan Plateau.

MS, AF and FW acknowledge the support of the NERC SoS:RARE consortium grant (NE/M011267/1). D. Kavecsanszki acknowledges the support of a postgraduate fellowship from the College of Engineering, Mathematics and Physical Sciences at the University of Exeter. The rare earth elements are unusual when defining giant-sized ore deposits, as resources are often quoted as total rare earth oxide, but the importance of a deposit may be related to the grade for individual, or a limited group of, the elements. Taking the total REE resource, only one currently known deposit (Bayan Obo) would class as giant (>1.7×107 tonnes contained metal), but a range of others classify as large (>1.7×106 tonnes). With the exception of unclassified resource estimates from the Olympic Dam IOCG deposit, all of these deposits are related to alkaline igneous activity – either carbonatites or agpaitic nepheline syenites. The total resource in these deposits must relate to the scale of the primary igneous source, but the grade is a complex function of igneous source, magmatic crystallisation, hydrothermal modification and supergene enrichment during weathering. Isotopic data suggest that the sources conducive to the formation of large REE deposits are developed in subcontinental lithospheric mantle, enriched in trace elements either by plume activity, or by previous subduction. The reactivation of such enriched mantle domains in relatively restricted geographical areas may have played a role in the formation of some of the largest deposits (e.g. Bayan Obo). Hydrothermal activity involving fluids from magmatic to meteoric sources may result in the redistribution of the REE and increases in grade, depending on primary mineralogy and the availability of ligands. Weathering and supergene enrichment of carbonatite has played a role in the formation of the highest grade deposits at Mount Weld (Australia) and Tomtor (Russia). For the individual REE with the current highest economic value (Nd and the HREE), the boundaries for the large and giant size classes are 2 orders of magnitude lower, and deposits enriched in these metals (agpaitic systems, ion absorption deposits) may have significant economic impact in the near future. Publisher PDF

This work was completed as part of Magee’s Junior Research Fellowship funded by Imperial College London. Muirhead acknowledges support from Fulbright New Zealand and the Ministry of Science and Innovation. The structure of upper crustal magma plumbing systems controls the distribution of volcanism and influences tectonic processes. However, delineating the structure and volume of plumbing systems is difficult because (1) active intrusion networks cannot be directly accessed; (2) field outcrops are commonly limited; and (3) geophysical data imaging the subsurface are restricted in areal extent and resolution. This has led to models involving the vertical transfer of magma via dikes, extending from a melt source to overlying reservoirs and eruption sites, being favored in the volcanic literature. However, while there is a wealth of evidence to support the occurrence of dike-dominated systems, we synthesize field- and seismic reflection-based observations and highlight that extensive lateral magma transport (as much as 4100 km) may occur within mafic sill complexes. Most of these mafic sill complexes occur in sedimentary basins (e.g., the Karoo Basin, South Africa), although some intrude crystalline continental crust (e.g., the Yilgarn craton, Australia), and consist of interconnected sills and inclined sheets. Sill complex emplacement is largely controlled by host-rock lithology and structure and the state of stress. We argue that plumbing systems need not be dominated by dikes and that magma can be transported within widespread sill complexes, promoting the development of volcanoes that do not overlie the melt source. However, the extent to which active volcanic systems and rifted margins are underlain by sill complexes remains poorly constrained, despite important implications for elucidating magmatic processes, melt volumes, and melt sources. Publisher PDF

This research is funded by the Canadian Mining Research Organization (CAMIRO) and an NSERC CRD grant. Research is also funded by the NSERC-Altius Industrial Research Chair in Mineral Deposits, funded by NSERC, Altius Resources Inc. and the Development Corporation of Newfoundland and Labrador. Metalliferous sedimentary rocks (mudstones, exhalites) associated with the Cambrian precious metal-bearing Lemarchant Zn-Pb-Cu-Au-Ag-Ba volcanogenic massive sulphide (VMS) deposit, Tally Pond volcanic belt, precipitated both before and after VMS mineralization. Sulphur and Pb isotopic studies of sulphides within the Lemarchant exhalites provide insight into the sources of S and Pb in the exhalites as a function of paragenesis and evolution of the deposit and subsequent post-depositional modification. In situ S isotope microanalyses of polymetallic sulphides (euhedral and framboidal pyrite, anhedral chalcopyrite, pyrrhotite, galena and euhedral arsenopyrite) by secondary ion mass spectrometry (SIMS) yielded δ34S values ranging from −38.8 to +14.4 ‰, with an average of ∼ −12.8 ‰. The δ34S systematics indicate sulphur was predominantly biogenically derived via microbial/biogenic sulphate reduction of seawater sulphate, microbial sulphide oxidation and microbial disproportionation of intermediate S compounds. These biogenic processes are coupled and occur within layers of microbial mats consisting of different bacterial/archaeal species, i.e., sulphate reducers, sulphide oxidizers and those that disproportionate sulphur compounds. Inorganic processes or sources (i.e., thermochemical sulphate reduction of seawater sulphate, leached or direct igneous sulphur) also contributed to the S budget in the hydrothermal exhalites and are more pronounced in exhalites that are immediately associated with massive sulphides. Galena Pb isotopic compositions by SIMS microanalysis suggest derivation of Pb from underlying crustal basement (felsic volcanic rocks of Sandy Brook Group), whereas less radiogenic Pb derived from juvenile sources leached from mafic volcanic rocks of the Sandy Brook Group and/or Tally Pond group. This requires that the hydrothermal fluids interacted with juvenile and evolved crust during hydrothermal circulation, which is consistent with the existing tectonic model that suggests a formation of the Tally Pond belt volcanic rocks and associated VMS deposits in a rifted arc environment upon crustal basement of the Ediacaran age Sandy Brook Group and Crippleback Intrusive Suite. Combined S and Pb isotope data illustrate that sulphides within the deposit that are proximal to the vent contain a higher proportion of sulphur derived from thermochemical sulphate reduction (TSR), because hydrothermal fluids are enriched in H2S derived from TSR. They also have lower radiogenic Pb contributions, than sulphides occurring distal from mineralization. Hence, the TSR S and non-radiogenic Pb composition may provide an exploration vector in exhalites associated with similar VMS environments. Postprint

This work was supported by the National Natural Science Foundation of China (Grant No. 41472086, 41272120), the fundamental Research Funds for the Central Universities, China University of Geosciences (Wuhan). The first author also acknowledges China Scholarship Council (Grant No. 201208420001) for supporting his research in the University of St Andrews. PAC acknowledges support from NERC grant NE/J021822/1. In intraplate orogens tectonothermal activity occurs at a site removed from a plate margin and is considered to result from localization of far-field plate-boundary stresses through a combination of pre-existing structural features and modification of lithospheric properties through fluid alteration, enhanced heat flow and potential thermal blanketing effects. The mid-Paleozoic Kwangsian Orogeny (460–400 Ma) in the South China Craton is geodynamically associated with the far-field response to convergence along the northern margin of east Gondwana. Deformation is focused adjacent to the site of both early Neoproterozoic suturing of the Yangtze and Cathaysia blocks and mid-Neoproterozoic rifting within the craton. Furthermore, this region is one of high crustal heat flow and of widespread fluid release and localized crustal melting during orogenesis. In the late Neoproterozoic-Cambrian, the South China Craton constituted part of the lithosphere of greater India and was separated from Australia by the Kuunga Ocean. The closure of the Kuunga Ocean during Cambrian-Ordovician time, resulting in final assembly of Gondwana, permitted the stresses sourced from the Terra Australis accretionary orogen in East Gondwana to propagate inboard across the supercontinent. These stresses localized along the site of the Neoproterozoic Nanhua Rift Basin of South China resulting in basin inversion and development of the intraplate Kwangsian Orogeny. Publisher PDF

The authors thank The Carnegie Trust for the Universities of Scotland for providing funding for Miloš Rydval’s Ph.D. The Scottish pine network expansion has been an ongoing task since 2006, and funding must be acknowledged to the following projects: EU project “Millennium” (017008-2), Leverhulme Trust project “RELiC: Reconstructing 8000 years of Environmental and Landscape change in the Cairngorms (F/00 268/BG)”, and the NERC project “SCOT2K: Reconstructing 2000 years of Scottish climate from tree rings (NE/K003097/1)”. Kevin J. Anchukaitis was also supported by a grant for the US National Science Foundation (ARC-0902051). Nonclimatic disturbance events are an integral element in the history of forests. Although the identification of the occurrence and duration of such events may help to understand environmental history and landscape change, from a dendroclimatic perspective, disturbance can obscure the climate signal in tree rings. However, existing detrending methods are unable to remove disturbance trends without affecting the retention of long-term climate trends. Here, we address this issue by using a novel method for the detection and removal of disturbance events in tree-ring width data to assess their spatiotemporal occurrence in a network of Scots pine (Pinus sylvestris L.) trees from Scotland. Disturbance trends “superimposed” on the tree-ring record are removed before detrending and the climate signals in the precorrection and postcorrection chronologies are evaluated using regional climate data, proxy system model simulations, and maximum latewood density (MXD) data. Analysis of subregional chronologies from the West Highlands and the Cairngorms in the east reveals a higher intensity and more systematic disturbance history in the western subregion, likely a result of extensive timber exploitation. The method improves the climate signal in the two subregional chronologies, particularly in the more disturbed western sites. Our application of this method demonstrates that it is possible to minimise the effects of disturbance in tree-ring width chronologies to enhance the climate signal. Postprint

The authors acknowledge financial support from the National Science Foundation: EAR-1225630 (to J.D.B.) and EAR-1226741 (to M.B.S.). We measured total mercury (THg) and monomethyl mercury (MMHg) concentrations and mercury (Hg) isotopic compositions in sediment and aquatic organisms from the Yuba River (California, USA) to identify Hg sources and biogeochemical transformations downstream of a historical gold mining region. Sediment THg concentrations and δ202Hg decreased from the upper Yuba Fan to the lower Yuba Fan and the Feather River. These results are consistent with the release of Hg during gold mining followed by downstream mixing and dilution. The Hg isotopic composition of Yuba Fan sediment (δ202Hg = −0.38 ± 0.17‰ and Δ199Hg = 0.04 ± 0.03‰; mean ± 1 SD, n = 7) provides a fingerprint of inorganic Hg (IHg) that could be methylated locally or after transport downstream. The isotopic composition of MMHg in the Yuba River food web was estimated using biota with a range of %MMHg (the percent of THg present as MMHg) and compared to IHg in sediment, algae, and the food web. The estimated δ202Hg of MMHg prior to photodegradation (−1.29 to −1.07‰) was lower than that of IHg and we suggest this is due to mass-dependent fractionation (MDF) of up to −0.9‰ between IHg and MMHg. This result is in contrast to net positive MDF (+0.4 to +0.8‰) previously observed in lakes, estuaries, coastal oceans, and forests. We hypothesize that this unique relationship could be due to differences in the extent or pathway of biotic MMHg degradation in stream environments. Postprint

This research was financially co-supported by the Strategic Priority Research Program (B) of the Chinese Academy of Sciences (XDB03010301), the National Key Project for Basic Research of China (2011CB403102 and 2015CB452604), the Chinese National Natural Science Foundation (41225006, 41472061, and 40973026), and the Specialized Research Fund for the Doctoral Program of Higher Education (20120022110001) Integration of lithostratigraphic, magmatic, and metamorphic data from the Lhasa-Qiangtang collision zone in central Tibet (including the Bangong suture zone and adjacent regions of the Lhasa and Qiangtang terranes) indicates assembly through divergent double sided subduction. This collision zone is characterized by the absence of Early Cretaceous high-grade metamorphic rocks and the presence of extensive magmatism with enhanced mantle contributions at ca. 120–110 Ma. Two Jurassic−Cretaceous magmatic arcs are identified from the Caima−Duobuza−Rongma−Kangqiong−Amdo magmatic belt in the western Qiangtang Terrane and from the Along Tso−Yanhu−Daguo−Baingoin−Daru Tso magmatic belt in the northern Lhasa Terrane. These two magmatic arcs reflect northward and southward subduction of the Bangong Ocean lithosphere, respectively. Available multidisciplinary data reconcile that the Bangong Ocean may have closed during the Late Jurassic−Early Cretaceous (most likely ca. 140–130 Ma) through arc-arc “soft” collision rather than continent-continent “hard” collision. Subduction zone retreat associated with convergence beneath the Lhasa Terrane may have driven its rifting and separation from the northern margin of Gondwana leading to its accretion within Asia. Postprint

This project was funded by a Swiss National Science Foundation fellowship for prospective researchers PBEZP2-137335 and a Marie Curie Intra-European Fellowship (PIEF-GA-2012-331501) to RSH. Fieldwork was supported by an Arctic Field Grant 219165/E10 (The Research Council of Norway) to RSH. ESB acknowledges support for this work from NASA (NNA15BB02A and NNA13AA94A). Abstract In order to investigate the effect of glaciation on mineral weathering, the stream water chemistry and the bacterial community composition were analysed in two catchments containing nominally identical sedimentary formations but which differed in the extent of glaciation. The stream waters were analysed for major ions, δ34S, δ18OSO4 and δ18OH2O and associated stream sediments were analysed by 16S rRNA gene tagged sequencing. Sulphate comprised 72–86% and 35–45% of the summer anion budget (in meq) in the unglaciated and glaciated catchments respectively. This indicates that sulfuric acid generated from pyrite weathering is a significant weathering agent in both catchments. Based on the relative proportions of cations, sulphate and bicarbonate, the stream water chemistry of the unglaciated catchment was found to be consistent with a sulphide oxidation coupled to silicate dissolution weathering process whereas in the glaciated catchment both carbonates and silicates weathered via both sulfuric and carbonic acids. Stable isotope measurements of sulphate, together with inferences of metabolic processes catalysed by resident microbial communities, revealed that the pyrite oxidation reaction differed between the two catchments. No δ34S fractionation relative to pyrite was observed in the unglaciated catchment and this was interpreted to reflect pyrite oxidation under oxic conditions. In contrast, δ34S and δ18OSO4 values were positively correlated in the glaciated catchment and were positively offset from pyrite. This was interpreted to reflect pyrite oxidation under anoxic conditions with loss of S intermediates. This study suggests that glaciation may alter stream water chemistry and the mechanism of pyrite oxidation through an interplay of biological, physical and chemical factors. Postprint

This work was supported by NASA Exobiology (NNX07AV54G) (A.Z. and J.F.), a Natural Environment Research Council Fellowship (NE/H016805) (A.Z.), the National Science Foundation (NSF EAR-0525503 and EAR-1124411) (J.M.), and the NASA Astrobiology Institute (PSARC, NNA04CC06A) (J.M.). Sulfide oxidation forms a critical step in the global sulfur cycle, although this process is notoriously difficult to constrain due to the multiple pathways and highly reactive intermediates involved. Multiple sulfur isotopes (δ34S and Δ33S) can provide a powerful tool for unravelling sulfur cycling processes in modern (and ancient) environments, although they have had limited application to systems with well-resolved oxidative S cycling. In this study, we report the major (δ34S) and minor (Δ33S) isotope values of sulfur compounds in streams and sediments from the sulfidic Frasassi cave system, Marche Region, Italy. These microaerophilic cave streams host prominent white biofilms dominated by chemolithotrophic organisms that oxidize sulfide to S0, allowing us to estimate S isotope fractionations associated with in situ sulfide oxidation and to evaluate any resulting isotope biosignatures. Our results demonstrate that chemolithotrophic sulfide oxidation produces 34S enrichments in the S0 products that are larger than those previously measured in laboratory experiments, with 34ɛS0-H2S of up to 8‰ calculated. These small reverse isotope effects are similar to those produced during phototrophic sulfide oxidation (≤ 7‰), but distinct from the small normal isotope effects previously calculated for abiotic oxidation of sulfide with O2 (~-5‰). An inverse correlation between the magnitude of 34ɛS0-H2S effects and sulfide availability, along with substantial differences in Δ33S, both support complex sulfide oxidation pathways and intracellular recycling of S intermediates by organisms inhabiting the biofilms. At the ecosystem level, we calculate fractionations of less than 40‰ between sulfide and sulfate in the water column and in the sediments. These fractionations are smaller than those typically calculated for systems dominated by sulfate reduction (> 50‰), and contrast with the commonly held assumption that oxidative recycling of sulfide generally increases overall fractionations. The relatively small fractionations appear to be related to the sequestration of S0 in the biofilms (either intra- or extra-cellularly), which removes this intermediate substrate from fractionation by further disproportionation or oxidation reactions. In addition, the net 33λH2S-SO4 values calculated in this system are larger than data published for systems dominated by reductive sulfur cycling, partially due to the isotopic imprint of chemolithotrophic sulfide oxidation on the aqueous sulfide pool. These distinct isotopic relationships are retained in the sedimentary sulfur pool, suggesting that trends in 34S and 33S isotope values could provide an isotopic fingerprint of such chemolithotrophic ecosystems in modern and ancient environments. Postprint

The stable carbon isotopic composition of dissolved organic matter (δ13C-DOC) reveals information about its source and extent of biological processing. Here we report the lowest δ13C-DOC values (−43.8‰) measured to date in surface waters. The streams were located in the High Arctic, a region currently experiencing rapid changes in climate and carbon cycling. Based on the widespread occurrence of methane cycling in permafrost regions and the detection of the pmoA gene, a proxy for aerobic methanotrophs we conclude that the low δ13C-DOC values are due to organic matter partially derived from methanotrophs consuming biologically produced, 13C-depleted methane. These findings demonstrate the significant impact that biological activity has on the stream water chemistry exported from permafrost and glaciated environments in the Arctic. Given that the catchments studied here are representative of larger areas of the Arctic, occurrences of low δ13C-DOC values may be more widespread than previously recognized, with implications for understanding C cycling in these environments. Publisher PDF

This study was supported financially by NERC Fellowship NE/H016805/2 (to AZ) and a NERC Standard Grant NE/J023485/2 (to AZ, MC and SP). The Great Oxidation Event (GOE) represents a crucial juncture in Earth history, signifying the rise in atmospheric oxygen from parts per million to per cent levels at ~2.45-2.32 billion-years-ago (Ga). Although planetary oxygenation undoubtedly led to the inception of the contemporary Earth system, the trigger(s) and mechanism(s) controlling this chemical reorganisation remain elusive. Quantitative estimates of the atmosphere's composition in the prelude to the GOE are central to understanding this oxygenation event. Previous analyses of 2.65-2.5 Ga sediments from the Griqualand Basin (South Africa) invoke a tantalising picture of an unusual Earth environment, alluding to an atmosphere periodically dominated by a layer of organic particles ("haze") formed from methane photolysis. However, as yet this hypothesis has remained untested. Here we present four new coupled carbon and quadruple sulphur isotope records from distal, time equivalent (2.7-2.5 Ga), sedimentary successions from South Africa and Western Australia. These extended records reveal similar chemostratigraphic trends, supporting a dynamic terminal-Neoarchaean atmosphere, oscillating between a hazy state at elevated methane concentrations, and a haze-free anoxic background state. We suggest these atmospheric aberrations were related to heightened biogenic methane fluxes fuelled by enhanced nutrient delivery from climatically or weathering induced feedbacks. These data question the canonical view of a simple, unidirectional planetary oxygenation and signify that the overture to the GOE was governed by complex feedbacks within the Earth-biosphere system. Publisher PDF

This work was supported by the NASA Astrobiology Institute under Cooperative Agreement No. NNA15BB03A issued through the Science Mission Directorate (TWL), a Natural Environment Research Council Fellowship (NE/H016805/2) (AZ), and National Science Foundation grants (EAR-0951509, OCE-1061476, EAR-1124389, and OCE-1155346) and a Packard Fellowship (DAF). Microbial processes dominate geochemical cycles at and near the Earth’s surface today. Their role was even greater in the past, with microbes being the dominant life form for the first 90% of Earth’s history. Most of their metabolic pathways originated billions of years ago as both causes and effects of environmental changes of the highest order, such as the first accumulation of oxygen in the oceans and atmosphere. Microbial processes leave behind diverse geochemical fingerprints that can remain intact for billions of years. These rock-bound signatures are now steering our understanding of how life coevolved with the environments on early Earth and are guiding our search for life elsewhere in the universe. Postprint

This work was funded in part by the Natural Environment Research Council in the form of a PhD studentship to Higson and by a U.S. National Science Foundation grant to Singer (EAR-1226741). Sediment supply from banks and terraces has important implications for grain-size distributions in alluvial rivers (and by extension for aquatic habitat), as well as for the delivery of floodplain-stored nutrients and contaminants to the aquatic environment. The interactions between streamflow hydrographs and lateral channel boundary failure control the sediment supply from banks and terraces. However, the relationships between variable flow and discrete sediment supply from catastrophic erosion of lateral boundaries and subsequent mass sediment flux in rivers are not well characterised by existing methods and models that focus only on one of several relevant interrelated processes. In order to improve predictive capability of catastrophic sediment supply from lateral boundaries, we adopt a new approach to modelling the process interactions between stream hydrology, erosion of banks/terraces, and the corresponding discrete supply of sediment to channels. We develop a modelling framework for terrace –-channel coupling that combines existing theories of flow through porous media, bank stability, and fractional sediment flux. We demonstrate the utility of this modelling approach by assessing hydrologically driven erosion, evolution of grain size in the channel, and fine sediment flux from a study site along the Yuba River in California over individual flood hydrographs and over decadal historical flow series. We quantify the supply of sediment eroded from a contaminated nineteenth century fan terrace of hydraulic gold mining tailingsintersecting the Yuba and find that a threshold for erosion exists at a stage in the channel in excess of 8 m and that threshold can produce episodic sediment concentrations in excess of ~ 300 mg L− 1. The modelling produced erosion and fine sediment pulses from each of three major floods in the past several decades until the flow velocity drops below 500 m s− 1 when a bed armor layer forms, while no sediment was generated from the terrace during smaller floods. We further assess the impact on terrace erosion of various river management scenarios with distinct hydrograph shapes and find increased erosion potential when the terrace contains antecedent moisture or the flood time series is run over an extended duration. Sensitivity analysis demonstrated that elevated antecedent moisture within the lateral boundary and increased hydrograph rising time each reduce bank stability and thus increase volumes of failed material. We also find that fluctuations in the hydrograph typically associated with hydroelectricity generation result in a more stable terrace than those of a longer duration because there is less time for hyporheic stream water to infiltrate the lateral boundary. This study demonstrates that changes in hydrograph shape as a consequence of climatic forcing or anthropogenic dam releases may have considerable impacts upon sediment delivery and associated contaminants from banks and terraces to the downstream environment. Publisher PDF

The authors acknowledge financial support from Rhodes University and the National Research Foundation of South Africa (Grant UID 87358). Abstract This report is concerned with the influence of measurement temperature on luminescence lifetime and on the spectral emission features of luminescence from α-Al2O3:C. The lifetimes were determined from time-resolved luminescence spectra. Spectral measurements were done using thermoluminescence and X-ray excited optical luminescence. The emission spectra of α-Al2O3:C studied in this work shows prominent bands at 330, 380 and 420 nm associated with vacancies in the oxygen sub-lattice in α-Al2O3:C and an additional band at 695 nm due to Cr substitution for Al. Emission bands below 500 nm are independent of temperature below 125 °C but widen with temperature. Direct evidence of thermal quenching of the 420 nm emission band is provided. Beyond 200 °C, the 380 and 420 nm bands merge and widen, with the 420 nm emission dominant. Before the onset of thermal quenching, luminescence lifetimes are affected by retrapping both in the shallow- and in the main electron trap. This was deduced from features of time-resolved luminescence spectra measured from samples with and without the shallow trap. Additional measurements with temperature decreasing from 160 to 20 °C, after phototransfer as well as after a considerable delay between irradiation and measurement, suggest that the change in lifetimes could also be related to other factors including slight shifts in emission wavelength for the 380 and 420 nm emissions. Postprint

Natural Environment Research Council (NERC grant NE/J021822/1) provided financial support for this study. The Natal Metamorphic Province consists of, from north to south, the Tugela, Mzumbe, and Margate terranes. These were accreted to the southeastern margin of the Kaapvaal Craton in the late Mesoproterozoic, and followed by intrusion of a large suite of A-type granitoid bodies. New U-Pb data from zircon, titanite, and monazite further constrains the temporal framework of these geological events. The Tugela and Mzumbe terranes record protracted magmatism in an island arc complex from ∼1200 Ma to 1160 Ma, followed by the accretion of these terranes onto the southern margin of the Kaapvaal Craton at ∼1150 Ma. Arc magmatism in the Margate Terrane continued until ∼1120 Ma and was followed by extension and bimodal volcanism immediately prior to accretion to the Kaapvaal/Mzumbe continental margin at ∼1090 Ma. This accretion was accompanied by high-pressure and high-temperature metamorphism, juxtaposition of the Mzumbe and Margate terranes along the Melville Thrust, and the formation of a number of syntectonic intrusive units derived from melting of the pre-existing arc crust. After accretion, extensional collapse is evidenced by the intrusion of mafic/ultramafic and alkaline intermediate magmatic suites at ∼1085 Ma, resulting from mafic underplating and/or lower crustal delamination. Nd and Hf isotopic data imply the magmatic rocks of the Natal Metamorphic Province were derived from relatively juvenile continental crust, initially generated by island arc magmatism and subsequently reworked during the accretion event(s). The combined Kaapvaal-NMP region (the southern margin of the enlarged Kalahari Craton) then experienced extensive sinistral transcurrent deformation centered along a series of discrete steep shear zones that are found from the Kaapvaal cratonic margin to the southernmost portion of the Natal Metamorphic Province. This deformation is accompanied by low-pressure, (ultra)high-temperature metamorphism, isobaric cooling, and intrusion of the voluminous A-type Oribi Gorge Suite porphyritic granites and charnockites throughout the Mzumbe and Margate Terranes. Postprint

The Whalesback Cu-rich volcanogenic massive sulfide deposit in the Newfoundland Appalachians is a highly deformed deposit found on a steep limb of a closed and boudinaged overturned fold. The deposit was intensely deformed at low temperature but medium pressure (>175 MPa) during the accretion of the composite Lushs Bight oceanic tract-Dashwoods terrane onto the Humber margin at ca. 480 Ma. The ore mineralogy consists of chalcopyrite, pyrrhotite, and pyrite with lesser sphalerite and trace Ag, Bi, and Hg tellurides. Four styles of sulfide mineralization are present: (1) disseminated (5%); (2) vein (50%); (3) breccia (25%); and (4) semimassive to massive (20%). Independent of mineralization style, massive pyrite and pyrrhotite (and some chalcopyrite) are commonly parallel to main S2 schistosity in the deposit, whereas late chalcopyrite piercement veins occur at a high angle to S2. The progressive increase in pressure and temperature produced a remobilization sequence wherein sphalerite was the first sulfide phase to cross the brittle-ductile boundary, followed by pyrrhotite and, finally, chalcopyrite. Maximum temperature was not high enough for the pyrite to cross the brittle-ductile boundary. Instead, pyrite grains were incorporated and transported by pyrrhotite and chalcopyrite during the ductile remobilization events, rounding and fracturing them. Remobilization of the sulfides occurred mainly by plastic flow, but some solution transport and reprecipitation is locally observed. In situ secondary ion mass spectrometry sulfur isotope geochemistry of sulfides yielded values of δ34S ranging from 2.7‰ to 4.7‰ for pyrite, 2.1‰ to 4.0‰ for pyrrhotite, and 1.3‰ to 4.7‰ for chalcopyrite. Sulfur isotope modeling suggests that at least 60% of the sulfur was derived from leaching of igneous rocks (i.e., basalts), with the remainder derived from thermochemical sulfate reduction of seawater sulfate during alteration of the basalts by seawater. At the deposit scale, sulfur isotopes retained their original signature and did not reequilibrate during the secondary deformation and remobilization events. Postprint

Detrital zircons from modern sediments display an episodic temporal distribution of U-Pb crystallization ages forming a series of 'peaks' and 'troughs'. The peaks are interpreted to represent either periods of enhanced generation of granitic magma perhaps associated with mantle overturn and superplume events, or preferential preservation of continental crust during global collisional orogenesis. The close association of those peaks with the assembly of supercontinents implies a causal relationship between collisional orogenesis and the presence of zircon age peaks. Here these two end-member models (episodic periodicity of increased magmatism versus selective preservation during collisional orogenesis) are assessed using U-Pb, Hf, and O analysis of detrital zircons from sedimentary successions deposited during the ∼1.3-1.1 Ga accretionary, ∼1.1-0.9 Ga collisional, and

Zircon U–Pb and Lu–Hf isotopic data along with whole-rock elemental and Sr–Nd isotopic analytical results for the Xin'anzhai and Tongtiange granitic plutons in the Ailaoshan suture zone record the transition from subduction to collision associated with the accretion of Indochina to Yangtze Blocks. The Xin'anzhai monzogranite yields zircon U–Pb age of 251.6 ± 2.0 Ma and εHf(t) values of − 6.2– − 9.8. The Tongtiange leucogranite gives zircon U–Pb age of 247.5 ± 2.2 Ma and εHf(t) values ranging from − 3.1 to − 11.1. The Tongtiange leucogranites have lower MgO, Na2O, CaO, FeOt and TiO2 contents but higher A/CNK values than those of the Xin'anzhai monzogranites. The εNd(t) values for Xin'anzhai and Tongtiange plutons are in the range of − 8.5 to − 8.8 and − 10.6 to − 11.4, respectively, similar to those of the Ailaoshan metamorphic basement. The Tongtiange leucogranites are the product of dehydration melting of mica-rich metasedimentary rocks whereas the primary source of the Xin'anzhai monzogranites is probably Proterozoic gneiss with an addition of 35–45% Proterozoic amphibolite. Our geochronological results, together with other published data, indicate the presence of Permo-Triassic magmatism associated with the Indosinian Orogeny along the Ailaoshan suture zone. This zone links with the Jinshajiang suture toward the northwest and the Song Ma–Hainan suture to the southeast. It is herein proposed that latest Permian convergent margin magmatism represented by the Xin'anzhai granitoid pluton (~ 252 Ma) terminated through the accretion of the Simao-Indochina to the South China Blocks, which marks the commencement of the Indosinian Orogeny resulting in the generation of the ~ 247 Ma Tongtiange S-type leucogranite. Postprint

We thank the NASA postdoctoral program (EES) and the NASA Exobiology Program grant number NNX16AI37G (RB) for funding. Multiple lines of evidence have revealed a thriving marine biosphere capable of diverse metabolic strategies back to at least 3.5 billion years ago (Ga). However, little is known about microbial ecosystems in lakes and rivers during the Mesoarchean and their role in the evolution of the biosphere. Here we report new carbon and nitrogen isotopic data from the fluvio-lacustrine Lalla Rookh Sandstone in Western Australia (∼3.0 Ga) – one of the oldest known non-marine sedimentary deposits. Organic δ13C values (-30‰ to -38‰) are best interpreted as recording carbon fixation by methanogens using the acetyl CoA pathway mixed with organisms using the Calvin cycle, while δ15N data (0‰ to -1‰) likely reflect biological N2 fixation using FeMo-nitrogenase. When compared with data from the literature, we show that lacustrine habitats of Mesoarchean age (3.2-2.8 Ga) are systematically depleted in δ13C (-37 ± 5‰) relative to marginal marine (-32 ± 7‰) and open marine settings (-27 ± 3‰), suggesting that methanogenesis was relatively more important in lacustrine communities. Our findings highlight: (a) the widespread use of biological N2 fixation by the Mesoarchean biosphere, (b) the potential importance of continental habitats for methane production and perhaps for the formation of hydrocarbon haze, and (c) the possible role of land masses in driving microbial diversification on the early Earth. Postprint

APM, DJC, ARP and AEF were supported by NERC grant NE/G00398X/1. Organic-rich rocks (averaging 2–5% total organic carbon) and positive carbonate-carbon isotope excursions (δ13C > 5‰ and locally much higher, i.e. the Lomagundi-Jatuli Event) are hallmark features of Palaeoproterozoic successions and are assumed to archive a global event of unique environmental conditions following the c. 2.3 Ga Great Oxidation Event. Here we combine new and published geochronology that shows that the main Palaeoproterozoic carbon burial episodes (CBEs) preserved in Russia, Gabon and Australia were temporally discrete depositional events between c. 2.10 and 1.85 Ga. In northwest Russia we can also show that timing of the termination of the Lomagundi-Jatuli Event may have differed by up to 50 Ma between localities, and that Ni mineralisation occurred at c. 1920 Ma. Further, CBEs have traits in common with Mesozoic Oceanic Anoxic Events (OAEs); both are exceptionally organic-rich relative to encasing strata, associated with contemporaneous igneous activity and marked by organic carbon isotope profiles that exhibit a stepped decrease followed by a stabilisation period and recovery. Although CBE strata are thicker and of greater duration than OAEs (100 s of metres versus metres, ∼106 years versus ∼105 years), their shared characteristics hint at a commonality of cause(s) and feedbacks. This suggests that CBEs represent processes that can be either basin-specific or global in nature and a combination of circumstances that are not unique to the Palaeoproterozoic. Our findings urge circumspection and re-consideration of models that assume CBEs are a Deep Time singularity. Postprint

We thank The Carnegie Trust for the Universities of Scotland for providing funding for Miloš Rydval’s PhD. The Scottish pine network expansion has been an ongoing task since 2007 and funding must be acknowledged to the following projects: EU project ‘Millennium’ (017008-2), Leverhulme Trust project ‘RELiC: Reconstructing 8000 years of Environmental and Landscape change in the Cairngorms (F/00 268/BG)’ and the NERC project ‘SCOT2K: Reconstructing 2000 years of Scottish climate from tree rings (NE/K003097/1)’. This study presents a summer temperature reconstruction using Scots pine tree-ring chronologies for Scotland allowing the placement of current regional temperature changes in a longer-term context. ‘Living-tree’ chronologies were extended using ’subfossil’ samples extracted from nearshore lake sediments resulting in a composite chronology > 800 years in length. The North Cairngorms (NCAIRN) reconstruction was developed from a set of composite blue intensity high-pass and ring-width low-pass chronologies with a range of detrending and disturbance correction procedures. Calibration against July-August mean temperature explains 56.4% of the instrumental data variance over 1866-2009 and is well verified. Spatial correlations reveal strong coherence with temperatures over the British Isles, parts of western Europe, southern Scandinavia and northern parts of the Iberian Peninsula. NCAIRN suggests that the recent summer-time warming in Scotland is likely not unique when compared to multi-decadal warm periods observed in the 1300s, 1500s, and 1730s, although trends before the mid-16th century should be interpreted with some caution due to greater uncertainty. Prominent cold periods were identified from the 16th century until the early 1800s – agreeing with the so-called Little Ice Age observed in other tree-ring reconstructions from Europe - with the 1690s identified as the coldest decade in the record. The reconstruction shows a significant cooling response one year following volcanic eruptions although this result is sensitive to the datasets used to identify such events. In fact, the extreme cold (and warm) years observed in NCAIRN appear more related to internal forcing of the summer North Atlantic Oscillation. Publisher PDF

Neodymium isotope data on exhalites and tuffs from the Cambrian Lemarchant volcanogenic massive sulphide (VMS) deposit provide insights into the tectonic environment of the Tally Pond group, Canada. New data from exhalites from the Lemarchant area show evolved values of εNd513 = 6.0 to 1.8, whereas the associated volcanic rocks have εNd513 of +0.4 to +1.4. The Lemarchant exhalite εNd compositions overlap the underlying Ganderian Neoproterozoic Sandy Brook Group (εNdt = 6.5 to 1.9) and Crippleback Intrusive Suite (εNdt = 5.9 to 5.2). The evolved Nd isotopic signatures suggest that the volcanic rocks of the Tally Pond group were formed upon Ganderian arc basement, which itself was possibly built upon, or proximal to, the Gondwanan Amazonian margin. Erosion of older crustal material and Tally Pond group volcanic rocks, together with coeval eruption of the volcanic rocks, released Nd-rich detritus into the water column. Uptake of eroded detrital and scavenged Nd resulted in mixed Nd sources (juvenile and evolved), which are archived in the exhalites. The results of this study are of significance not only for occurrences of exhalites within the Tally Pond group, but also have exploration implications for VMS districts globally. Postprint

U–Pb SHRIMP zircon crystallization ages and Ar–Ar and K–Ar mica cooling ages for basement rocks of the Yaminué and Nahuel Niyeu areas in northeastern Patagonia are presented. Granitoids that cover the time span from Ordovician to Early Triassic constitute the main outcrops of the western sector of the Yaminué block. The southern Yaminué Metaigneous Complex comprises highly deformed Ordovician and Permian granitoids crosscut by undeformed leucogranite dikes (U–Pb SHRIMP zircon age of 254 ± 2 Ma). Mica separates from highly deformed granitoids from the southern sector yielded an Ar–Ar muscovite age of 182 ± 3 Ma and a K–Ar biotite age of 186 ± 2 Ma. Moderately to highly deformed Permian to Early Triassic granitoids made up the northern Yaminué Complex. The Late Permian to Early Triassic (U–Pb SHRIMP zircon age of 252 ± 6 Ma) Cabeza de Vaca Granite of the Yaminué block yielded Jurassic mica K–Ar cooling ages (198 ± 2, 191 ± 1, and 190 ± 2 Ma). At the boundary between the Yaminué and Nahuel Niyeu blocks, K–Ar muscovite ages of 188 ± 3 and 193 ± 5 Ma were calculated for the Flores Granite, whereas the Early Permian Navarrete granodiorite, located in the Nahuel Niyeu block, yielded a K–Ar biotite age of 274 ± 4 Ma. The Jurassic thermal history is not regionally uniform. In the supracrustal exposures of the Nahuel Niyeu block, the Early Permian granitoids of its western sector as well as other Permian plutons and Ordovician leucogranites located further east show no evidence of cooling age reset since mica ages suggest cooling in the wake of crystallization of these intrusive rocks. In contrast, deeper crustal levels are inferred for Permian–Early Triassic granitoids in the Yaminué block since cooling ages for these rocks are of Jurassic age (198–182 Ma). Jurassic resetting is contemporaneous with the massive Lower Jurassic Flores Granite, and the Marifil and Chon Aike volcanic provinces. This intraplate deformational pulse that affected northeastern Patagonia during the Early Jurassic (Sinemurian–Pliensbachian) was responsible for the partial (re)exhumation of the mid-crustal Paleozoic basement along reactivated discrete NE–SW to ENE–WSW lineaments and the resetting of isotopic systems. These new thermochronological data indicate that Early Permian magmatic rocks of the Nahuel Niyeu block were below 300 °C for ca. 20 Ma prior to the onset of the main magmatic episode of the Late Permian to Triassic igneous and metaigneous rocks of the Yaminué block. Fil: Martínez Dopico, Carmen Irene. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Geocronología y Geología Isotopica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Geocronología y Geología Isotópica; Argentina Fil: Tohver, Eric. University of Western Australia. School of Earth and Geographical Sciences; Australia Fil: Lopez, Monica Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Geocronología y Geología Isotopica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Geocronología y Geología Isotópica; Argentina Fil: Wemmer, Klaus. Universität Göttingen; Alemania Fil: Rapalini, Augusto Ernesto. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Geociencias Básicas, Aplicadas y Ambientales de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Geociencias Básicas, Aplicadas y Ambientales de Buenos Aires; Argentina Fil: Cawood, Peter A.. Monash University; Australia. University of St. Andrews; Reino Unido

Funding for this project was provided by the NASA postdoctoral program (EES), the Lewis and Clark Fund (EES), an NSERC PGS-D grant (EJB), the NSF ELT (TWL, NJP) and FESD (TWL) programs, and the NASA Astrobiology Institute (TWL, NJP). The Poll a’Mhuilt Member of the Stoer Group (Torridonian Supergroup) in Scotland has been heralded as a rare window into the ecology of Mesoproterozoic terrestrial environments. Its unusually high molybdenum concentrations and large sulphur isotope fractionations have been used as evidence to suggest that lakes 1.2 billion years ago were better oxygenated and enriched in key nutrients relative to contemporaneous oceans, making them ideal habitats for the evolution of eukaryotes. Here we show with new Sr and Mo isotope data, supported by sedimentological evidence, that the depositional setting of this unit was likely connected to the ocean and that the elevated Mo and S contents can be explained by evapo-concentration of seawater. Thus, it remains unresolved if Mesoproterozoic lakes were important habitats for early eukaryotic life. Publisher PDF

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