Hydrothermal regeneration of ammonium as a basin-scale driver of primary productivity

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

Oxygenated conditions in the aftermath of the Lomagundi-Jatuli Event : the carbon isotope and rare earth element signatures of the Paleoproterozoic Zaonega Formation, Russia

This study was supported by Estonian Research Council project PRG447, and the Estonian Centre of Analytical Chemistry. K.P. and A.L. were supported by the Research Council of Norway through its Centres of Excellence funding scheme grant No. 223259. K.P. acknowledges the Estonian Research Council grant MOBJD542 and T.M. PUT611.The c. 2.0 Ga Zaonega Formation of the Onega Basin (NW Russia) has been central in efforts to understand what led to the initial rise (Great Oxidation Event, GOE) and postulated fall in free atmospheric oxygen and associated high-amplitude carbon cycle excursions, the Lomagundi-Jatuli Event (LJE) and subsequent Shunga Event during Paleoproterozoic time. The Formation accumulated shortly after the LJE and encompasses both the recovery in the carbon cycle and hypothesised contraction of the oceanic oxidant pool. However, interpreting the correct environmental context recorded by geochemical signatures in the Zaonega rocks is difficult due to a complex depositional and diagenetic history. In order to robustly constrain that history, we undertook a multiproxy study (mineralogy, petrography, carbon isotope and rare earth element composition) of carbonate beds in the upper part of the Zaonega Formation recovered in the 102-m composite section of the OnZap drill-cores. Our findings differentiate primary environmental signatures from secondary overprinting and show that: (i) the best-preserved carbonate beds define an upwards increasing δ13Ccarb trend from c. -5.4‰ to near 0‰; and that (ii) large intra-bed δ13Ccarb variations reflect varying contributions of methanotrophic dissolved inorganic carbon (DIC) to the basinal DIC pool. Rare earth element and yttrium (REYSN) patterns confirm a marine origin of the carbonate beds whereas a consistent positive EuSN anomaly suggests a strong high temperature hydrothermal input during accumulation of the Zaonega Formation. Importantly, the presence of a negative CeSN anomaly in the REYSN pattern indicates an oxygenated atmosphere-ocean system shortly after the LJE and indicates that models invoking a fall in oxygen at that time require reassessment.PostprintPeer reviewe

Hydrothermal dedolomitisation of carbonate rocks of the Paleoproterozoic Zaonega Formation, NW Russia — Implications for the preservation of primary C isotope signals

This study was supported by Estonian Science Agency project PUT696 and PRG447, and Estonian Centre of Analytical Chemistry. K.P. and A.L. were supported by the Research Council of Norway through its Centres of Excellence funding scheme grant No. 223259.The Paleoproterozoic Zaonega Formation in Karelia, NW Russia, has played a key role in understanding the environmental conditions postdating the Great Oxidation and Lomagundi-Jatuli Events. Its carbonate- and organic-rich rocks (shungite) define the postulated Shunga Event representing an accumulation of very organic-rich sediments at c. 2 Ga and are central in ideas about changing ocean-atmosphere composition in the wake of those worldwide biogeochemical phenomena. Our work focussed on a key interval of carbonate rocks in the upper part of the Formation to: (i) obtain new high-resolution carbon, oxygen and strontium isotope data complemented by detailed petrography and mineralogical characterisation and (ii) expand upon previous studies by using our data to constrain geochemical modelling and show in greater detail how magmatic hydrothermal fluids induced dedolomitisation and altered geochemical signals. Our findings show that the δ13Ccarb of calcite-rich intervals are the most altered, with values between −16.9 to 0.6‰, whereas the dolomite-dominated parts retain the best-preserved (i.e. most original) values. Those define a trend of steadily increasing δ13Ccarb, from −6 to +0.5‰, which we interpret as a return to normal marine conditions and carbonate‑carbon values following the Lomagundi-Jatuli Event.PostprintPeer reviewe

The grandest of them all : the Lomagundi-Jatuli Event and Earth's oxygenation

Funding: K.K., A.L. and T.K. received funding from Estonian Science Agency Project PRG447 and Yu.D., A.R., D.R. and P.M. were supported by the state assignment of the Institute of Geology, Karelian Research Centre of the Russian Academy of Sciences.The Paleoproterozoic Lomagundi–Jatuli Event (LJE) is generally considered the largest, in both amplitude and duration, positive carbonate C-isotope (δ13Ccarb) excursion in Earth history. Conventional thinking is that it represents a global perturbation of the carbon cycle between 2.3–2.1 Ga linked directly with, and in part causing, the postulated rise in atmospheric oxygen during the Great Oxidation Event. In addition to new high-resolution δ13Ccarb measurements from LJE-bearing successions of NW Russia, we compiled 14 943 δ13Ccarb values obtained from marine carbonate rocks 3.0–1.0 Ga in age and from selected Phanerozoic time intervals as a comparator of the LJE. Those data integrated with sedimentology show that, contra to consensus, the δ13Ccarb trend of the LJE is facies (i.e. palaeoenvironment) dependent. Throughout the LJE interval, the C-isotope composition of open and deeper marine settings maintained a mean δ13Ccarb value of +1.5 ± 2.4‰, comparable to those settings for most of Earth history. In contrast, the 13C-rich values that are the hallmark of the LJE are limited largely to nearshore-marine and coastal-evaporitic settings with mean δ13Ccarb values of +6.2 ± 2.0‰ and +8.1 ± 3.8‰, respectively. Our findings confirm that changes in δ13Ccarb are linked directly to facies changes and archive contemporaneous dissolved inorganic carbon pools having variable C-isotopic compositions in laterally adjacent depositional settings. The implications are that the LJE cannot be construed a priori as representative of the global carbon cycle or a planetary-scale disturbance to that cycle, nor as direct evidence for oxygenation of the ocean–atmosphere system. This requires rethinking models relying on those concepts and framing new ideas in the search for understanding the genesis of the grandest of all positive C-isotope excursions, its timing and its hypothesized linkage to oxygenation of the atmosphere.Publisher PDFPeer reviewe

On the Preparation of Some Tertiary Amines Containing the 2-Furfuryl Group. Isomerization of Allyl-aryl( 2-furfuryl)-amines to N-Aryl-4H-5, 7 a-epoxyisoindolines

Six new tertiary 2-furfurylamines of the general formula 2-C 4H 30 · CH2 NRAr, w h ere R represents methyl, ethyl or ally!, and Ar phenyl, p-tolyl or p-methoxyphenyl groups, have been prepared by alkylation of the appropriate secondary aryl-(2-furfuryl)- amines with alkyl or ally! halides. It was found that the oily allyl-aryl-(2-furfuryl)-amines, on standing at room temperature, spontaneously isomerized to crystalline N-aryl-4H-5,7a-epoxyisoindolines, formed by a reversible intramolecular Diels-Alder reaction

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