Ocean acidification in the aftermath of the Marinoan glaciation

Boron isotope patterns preserved in cap carbonates deposited in the aftermath of the younger Cryogenian (Marinoan, ca. 635 Ma) glaciation confirm a temporary ocean acidification event on the continental margin of the southern Congo craton, Namibia. To test the significance of this acidification event and reconstruct Earth’s global seawater pH states at the Cryogenian-Ediacaran transition, we present a new boron isotope data set recorded in cap carbonates deposited on the Yangtze Platform in south China and on the Karatau microcontinent in Kazakhstan. Our compiled δ11B data reveal similar ocean pH patterns for all investigated cratons and confirm the presence of a global and synchronous ocean acidification event during the Marinoan deglacial period, compatible with elevated postglacial pCO2 concentrations. Differences in the details of the ocean acidification event point to regional distinctions in the buffering capacity of Ediacaran seawater

Duration and nature of the end-Cryogenian (Marinoan) glaciation

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

Using zircon in mafic migmatites to disentangle complex high-grade gneiss terrains – Terrane spotting in the Lewisian complex, NW Scotland

This research was part of SF’s PhD studies, and he acknowledges a 600 Year Anniversary Scholarship from the University of St Andrews. Analyses were funded through grants with EIMF (IMF545/1114) and NIGL (IP-1473-1114). Fieldwork was funded by NERC grant NE/J021822/1 to PAC. TEJ acknowledges funding from Australian Research Council Discovery Project DP200101104 and support from the State Key Laboratory for Geological Processes and Mineral Resources, China University of Geosciences, Wuhan (Open Fund GPMR201903). PAC acknowledges support from Australian Research Council grant FL160100168. CJH acknowledges support from Leverhulme Trust grants RPG-2015-422 and EM-2017-047\4.The zircon record of complex high-grade gneiss terrains is key to interpreting their tectonothermal evolution. Typically, such studies focus on zircon-rich, felsic rocks, which commonly have a complicated (partial melting, inheritance, partial dissolution, and reprecipitation) zircon record. Here we show that metamorphosed mafic rocks and their retained partial melts (i.e. in situ leucosomes) provide a record of the evolution of crustal blocks that is simpler and easier to interpret. We apply our method to the Archaean high-grade gneisses of the iconic Lewisian complex of NW Scotland and use it to test the proposed terrane model that is based largely on zircon geochronology. Our work focusses on the mafic migmatites of the central region, where we identified the long-established metamorphic age clusters of ca. 2.75 Ga and 2.5 Ga, as well as ca. 2.85 Ga protolith ages. A key finding is that these ages are recognised across both putative terrane blocks of the central region previously proposed to record different tectonothermal histories. Our oldest (inherited) ages are similar to those within other blocks outside the central region. Thus, all these blocks likely share a common pre-metamorphic history, questioning the validity of the terrane model for the Lewisian complex. We demonstrate that mafic lithologies provide a powerful tool for identifying key stages in the polyphase evolution of metamorphic complexes that typify Earth’s earliest rock records and offer additional context for assessing Earth’s geodynamic evolution.PostprintPeer reviewe

The Palaeoproterozoic Francevillian succession of Gabon and the Lomagundi-Jatuli event

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

Not so non-marine? Revisiting the Stoer Group and the Mesoproterozoic biosphere

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 PDFPeer reviewe

The Palaeoproterozoic global carbon cycle : insights from the Loch Maree Group, NW Scotland

Fieldwork was supported by the Edinburgh Geological Society Clough & Mykura Fund, the Carnegie Undergraduate Scholarship and a stipend provided by the Irvine Bequest through the University of St Andrews to G.B.K. Laboratory work, and isotope and geochronology analyses were financed by NERC grant NE/G00398X/1 to A.R.P., A.E.F., D.J.Condon and A.P.M. Thanks go to T. Donnelly, J. Dougans, A. Calder, D. Herd, B. Pooley and A. Mackie for laboratory assistance.Peer reviewedPostprin

Anaerobic nitrogen cycling on a Neoarchean ocean margin

This study was supported financially by NERC Fellowship NE/H016805/2 (to AZ), NERC Standard Grant NE/J023485/2 (to AZ and MC), NSF EAR-1455258 (to CKJ).A persistently aerobic marine nitrogen cycle featuring the biologically mediated oxidation of ammonium to nitrate has likely been in place since the Great Oxidation Event (GOE) some 2.3 billion years ago. Although nitrogen isotope data from some Neoarchaean sediments suggests transient nitrate availability prior to the GOE, these data are open to other interpretations. This is especially so as these data come from relatively deep-water environments that were spatially divorced from shallow-water settings that were the most likely sites for the accumulation of oxygen and the generation of nitrate. Here we present the first nitrogen isotope data from contemporaneous shallow-water sediments to constrain the nitrogen cycle in shallow Late Archaean settings. The BH-1 Sacha core through the Campbellrand-Malmani carbonate platform records a transition from a shallow siliciclastic/carbonate ramp to a rimmed carbonate shelf with the potential for reduced communication with the open ocean. In these settings nitrogen isotope δ15N data from sub- to peri-tidal and lagoonal settings are close to 0‰, indicating diazotrophy or the complete utilization of remineralised ammonium with an isotopic composition of near 0‰. Our dataset also includes negative δ15N values that suggest the presence of an ammonium pool of concentrations sufficient to have allowed for non-quantitative assimilation. We suggest that this condition may have been the result of upwelling of phosphorus-rich deep waters into the photic zone, stimulating primary productivity and creating an enhanced flux of organic matter that was subsequently remineralised and persisted in the dominantly anoxic Neoarchaean marine environment. Notably, we find only limited evidence of coupled nitrification/denitrification, even in these shallow water environments, calling into question previous suggestions that the Late Archaean nitrogen cycle was characterized by widespread aerobic nitrogen cycling. Rather, aerobic nitrogen cycling was likely spatially heterogeneous and tied to loci of high oxygen production while zones of shallow water anoxia persisted.PostprintPeer reviewe

Effects of early marine diagenesis and site-specific depositional controls on carbonate-associated sulfate : insights from paired S and O isotopic analyses

Acknowledgment is made to the donors of the American Chemical Society Petroleum Research Fund (#57548-ND2) to D.F. for partial support of this research and from the Estonian Research Council (#PUT611, #PRG836) to O.H and A.L.Carbon, sulfur and oxygen isotope profiles in Silurian strata of the Baltoscandian Basin (Estonia), coincident with the Ireviken Bioevent, provide insights into basin-scale and platform-specific depositional processes. Paired carbon isotope records preserve a positive isotope excursion during the early Wenlock, coincident with faunal turnover, yet δ13C variability of this excursion compared to other locations within the paleobasin reflects local depositional influences superimposed on a global signal. In comparison, sulfur isotope records do not preserve a systematic isotopic excursion over the same interval. Instead, sulfur isotope records have high sample-to-sample stratigraphic variability, particularly in shallow-water carbonate rocks (scatter up to ~10‰ for δ34SCAS and ~ 25‰ for δ34Spyr). This pattern of isotopic variability is also found between sites from the same carbonate platform, where the magnitude and isotopic variability in δ34SCAS and δ34Spyr differ depending on relative local sea level (and therefore facies). Such facies-dependent variability reflects more closed- versus more open-system diagenetic conditions where pulses of increased sedimentation rate in the shallow water environments generates greater isotopic variability in both δ34SCAS and δ34Spyr. Increased reworking and proximity to the shoreline results in local sulfide oxidation, seen as a decrease in δ34SCAS in the most proximal settings. Platform-scale evolution of isotopically distilled pore-fluids associated with dolomitization results in increased δ34SCAS in deep water settings. Correlations in paired δ34SCAS-δ18OCAS data support these conclusions, demonstrating the local alteration of CAS during deposition and early marine diagenesis. We present a framework to assess the sequence of diagenetic and depositional environmental processes that have altered δ34SCAS and find that δ34S of ~27–28‰ approximates Silurian seawater sulfate. Our findings provide a mechanism to understand the elevated variability in many deep-time δ34SCAS records that cannot otherwise be reconciled with behavior of the marine sulfate reservoir.PostprintPeer reviewe

Two-billion-year-old evaporites capture Earth's great oxidation

Funding sources: Simons Foundation (SCOL 339006 to C.L.B.), European Research Council (ERC Horizon 2020 grant 678812 to M.C.), Research Council of Norway (RCN Centres of Excellence funding scheme project 223259 to K.P. and A.L.), Estonian Science Agency (PUT696 to K.K., A.L., K.P., T.K.).Major changes in atmospheric and ocean chemistry occurred in the Paleoproterozoic Era (2.5–1.6 billion years ago). Increasing oxidation dramatically changed Earth’s surface, but few quantitative constraints exist on this important transition. This study describes the sedimentology, mineralogy, and geochemistry of a remarkably preserved two-billion-year-old and ~800 meter-thick evaporite succession from the Onega Basin in Russian Karelia. The deposit consists of a basal unit dominated by halite (~100 m) followed by anhydrite-magnesite (~500 m) and dolomite-magnesite (~200 m) dominated units. The evaporite minerals robustly constraint marine sulfate concentrations to at least 10 millimoles per kilogram of water, representing an oxidant reservoir equivalent to over 20% of the modern ocean-atmosphere oxidizing capacity. These results show that substantial amounts of surface oxidant accumulated during this critical transition in Earth’s oxygenation.PostprintPeer reviewe