Stable and Clumped Isotope Characterization of Authigenic Carbonates in Methane Cold Seep Environments

Cold seep environments are characterized by methane-rich fluid migration and discharge at the seafloor. These environments are also intimately linked to microbial communities, which oxidize methane anaerobically, increase alkalinity and promote authigenic carbonate precipitation. We have analyzed a suite of methane-derived authigenic carbonate (MDAC) crusts from the North and Barents Sea using stable and clumped isotopes (δ¹³C, δ¹⁸O, δ⁴⁴Ca, and Δ₄₇) to characterize the sources of fluids as well as the environment of carbonate authigenesis. We additionally assess the potential of MDACs as a Δ₄₇-based paleotemperature archive. The MDACs occur as three main textural-mineralogic types: micritic Mg-calcite cements, micritic aragonite cements and cavity filling aragonite cements. We find that micritic Mg-calcite cements have low δ¹³C_(VPDB) values (−30 to −47‰), high δ⁴⁴Ca_(SW) values (−0.4 to −0.8‰), and Δ₄₇-temperatures (0–6 °C) consistent with shallow sub-seafloor precipitation in isotopic equilibrium. Micritic aragonite cements and cavity filling aragonite cements both have a wider range in δ¹³C_(VPDB) values (−18 to −58‰), lower δ⁴⁴Ca_(SW) values (−0.8 to −1.6‰) and a larger range in Δ₄₇-based apparent temperatures (–2 – 25 °C) with samples displaying equilibrium and disequilibrium clumped isotope values. The range in apparent temperatures as well as δ⁴⁴Ca_(SW) values seen in the aragonite MDACs suggest two kinetic processes: a kinetic isotope effect (KIE) due to the incomplete equilibration of carbon and oxygen isotopes among DIC species from the different sources of DIC (i.e., seawater, methane-sourced DIC and DIC residual to CO₂ degassing or diffusion) and a KIE due to a fast, irreversible precipitation affecting the cations, particularly Ca, bound to carbonate mineral. Our results improve the understanding of kinetic effects on clumped isotope temperatures in MDACs and demonstrate how the multi-isotopic approach combined with textural-mineralogic criteria can be used to identify MDACs for accurate paleotemperature reconstructions

Boron concentrations and isotopic compositions in methane-derived authigenic carbonates : constraints and limitations in reconstructing formation conditions

The work is supported by Norwegian Research Council through the schemes PETROMAKS2-NORCRUST (grant number 255150 ) and Centre for Arctic Gas Hydrate, Environment and Climate (CAGE grant number 223259 ) as well as Lundin Norway AS. Cruise MSM57-1/-2 was funded by the German Research Foundation (DFG), the Research Center/Excellence Cluster “The Ocean in the Earth System” at MARUM–Center for Marine and Environmental Sciences, University of Bremen and funds from CAGE.The boron content and isotopic composition (δ11B), of marine carbonates have the potential to constrain CO2 chemistry during carbonate growth conditions. However, obtaining and interpreting boron compositions from authigenic carbonates in geological archives present several challenges that may substantially limit their application. In particular, contamination from non-carbonate phases during sample preparation must be carefully avoided, and a variety of controls on boron composition during authigenic growth conditions must be evaluated. To advance understanding of the use and limitations of boron in authigenic carbonates, we present data and modelling results on methane-derived authigenic carbonate (MDAC), a by-product of microbially mediated anaerobic oxidation of methane, taken from three cold seep sites along the Norwegian margin. We present a novel sequential leaching method to isolate the boron signals from the micritic (Mg-calcite) and cavity-filling (aragonitic) MDAC cements in these complex multi-phase samples. This method successfully minimizes contamination from non-carbonate phases. To investigate the factors that could potentially contribute to the observed boron signals, we construct a numerical model to simulate the evolution of MDAC δ11B and B/Ca ratios over its growth history. We show that diagenetic fluid composition, depths of precipitation, the physical properties of sediments (such as porosity), and mineral surface kinetics all contribute to the observed boron compositions in the different carbonate cements. While broad constraints may be placed on fluid composition, the multiple competing controls on boron in these diagenetic settings limit the ability to place unique solutions on fluid CO2 chemistry using boron in these authigenic carbonates.Publisher PDFPeer 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

Isotope and microbiome analysis indicates variety of N-cycle processes controlling N2O fluxes in a drained peatland forest soil : EGU21-10809

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Petrography and the REE-composition of apatite in the Paleoproterozoic Pilgujärvi Sedimentary Formation, Pechenga Greenstone Belt, Russia

The first globally significant phosphorous-rich deposits appear in the Paleoproterozoic at around 2 Ga, however, the specific triggers leading to apatite precipitation are debated. We examine phosphorous-rich rocks (up to 8 wt% P2O5) in 1.98–1.92 Ga old Pilgujärvi Sedimentary Formation, Pechenga Greenstone Belt, Russia. Phosphates in these rocks occur as locally derived and resedimented sand-to-gravel/pebble sized grains consisting of apatite-cemented muddy sediments. Phosphatic grains can be subdivided into four petrographic types (A–D), each has a distinct REE signature reflecting different early-to-late diagenetic conditions and/or metamorphic overprint. Pyrite containing petrographic type D, which typically has a flat REE pattern, negative Ce anomaly and positive Eu anomaly, is the best preserved of the four types and best records conditions present during apatite precipitation. Type D phosphatic grains precipitated under (sub)oxic basinal conditions with a significant hydrothermal influence. These characteristics are similar to Zaonega Formation phosphates of NW Russia’s Onega Basin, and consistent with phosphogenesis triggered by the development of anoxic(sulfidic)–(sub)oxic redoxclines at shallow sediment depth during the Paleoproterozoic

Constraining the conditions of phosphogenesis : stable isotope and trace element systematics of Recent Namibian phosphatic sediments

This study was supported by the Estonian Science Agency project PRG447 and the Estonian Centre of Analytical Chemistry. K. Paiste was supported by the European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement No 894831. We would also like to thank the organizers and participants of the Regional Graduate Network in Oceanography Discovery Camp 2015, funded by the Agouron Institute and the Scientific Committee for Oceanographic Research (SCOR), as well as the Namibian Ministry of Fisheries and Marine Resources and the captain and crew of R/V Mirabilis for access to the coring site.Modern phosphogenesis occurs on continental margins influenced by upwelling and high primary productivity. The formation of phosphatic sediments is coupled to global climate fluctuations, biological cycling of phosphorus and local redox conditions. Although the processes involved in phosphogenesis are well described, high-resolution data on the redox and stable isotope systematics in Recent in-situ phosphorites are scarce. In this contribution, we investigate the trace element and sulfur, nitrogen and organic carbon stable isotope composition of Recent in-situ phosphatic sediments off the coast of Namibia. Also, we examine the reliability of different widely used geochemical proxies in phosphatic sediments. Our results suggest a shift from sulfidic to suboxic conditions, coinciding with the maximum in solid calcium phosphate mineral concentration. This shift is accompanied by unidirectional changes in Mo and Re enrichments and TOC abundance. Relatively low pyrite δ34S values (ca -20‰) of phosphatic sediments indicate open system fractionation during phosphogenesis. The initiation of phosphogenesis is also accompanied by negative shifts in sedimentary δ13Corg and δ15N values. Phosphate associated sulfate (PAS) δ34S values are lower than modern seawater sulfate values, suggesting the involvement of chemolithotrophic sulfur oxidation. Our results show a shift in redox conditions from sulfidic to (sub)oxic, coupled with active sulfur cycling are prerequisites for phosphogenesis. Phosphatic sediments show substantial enrichments in U and V highlighting the complexity of using these elements, as well as V/(V+Ni) and V/Cr, as redox proxies particularly in phosphorites and phosphatic sediments.PostprintPostprintPeer reviewe

ORR activity and stability of Co-N/C catalysts based on silicon carbide derived carbon and the impact of loading in acidic media

This work was supported by the EU through the European Regional Development Fund under projects TK141 “Advanced materials and high-technology devices for energy recuperation systems” (2014-2020.4.01.15-0011), NAMUR ”Nanomaterials - research and applications” (3.2.0304.12-0397) and by the Estonian institutional research grant No. IUT20-13.A simple and facile synthesis method was used to produce two Co-N/C type oxygen reduction reaction (ORR) catalysts. The materials were initially characterized by utilizing a variety of physical methods. Most importantly, the XPS analysis revealed high amounts of pyridinic nitrogen and Co-Nx species in the case of both studied Co-N/C catalysts. The electrochemical characterization showed that both of the synthesized Co-N/C catalysts have a high ORR activity in acidic media, displaying a half-wave potential of 0.70 V vs RHE. Additionally, the effect of varying the catalyst loading was studied and it was found that increasing the catalyst loading from 0.1 to 1.8 mg cm−2 significantly improved the ORR activity and the electron transfer number. Finally, several catalysts were subjected to a week-long stability test in order to establish their activity degradation rates. It was found that increased degradation rates of the Co-N/C catalysts were established at decreased catalyst loadings.European Commission; ERDF 2014-2020.4.01.15-0011,TK141, NAMUR 3.2.0304.12-0397; Estonian institutional research grant No. IUT20-13; Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART

Long-term mineral transformation of Ca-rich oil shale ash waste

Power generation and other industries using solid fossil fuels like coal, lignite, oil shale and peat are responsible for producing large quantities of solid residues that are often chemically reactive and/or unstable and are disposed in holding ponds and deposition sites. Stability and long-term behaviour of such deposits are typically studied in short-term laboratory experiments that cannot describe nor predict long-term changes taking place in these materials. Here, we study long-term (>40 years) transformations, in highly alkaline conditions, of the Ca-rich ash deposit in Estonia composed of oil shale processing residues from the Eesti power plant. Detailed mineralogical, chemical and micromorphological analyses using X-ray diffraction, X-ray fluorescence, 29Si nuclear magnetic resonance, scanning electron microscopy and other methods were applied in order to identify the composition of the waste with a focus on formation and transformation of semicrystalline phases in the deposit. The results show progressive formation of calcium-silicate-hydrate (C-S-H) type phase at the expense of silicate minerals and amorphous glass phases with increasing depth and age of the sediments, from about 25% in the upper part of the depository to over 60% in the oldest-deepest part. This demonstrates that over time the high alkalinity of the ash is responsible for initiating natural alkali-activation. The formation of C-S-H-type phases increases the mechanical strength of the sediment and ensures long-term stability of waste deposits. These findings may encourage the use of these ashes in binder or other construction material production or as construction aggregates

Geochemistry of the early Cambrian succession in the western Anti-Atlas, Morocco: implications on provenance and paleoredox conditions

The Igoudine and Amouslek formations (TerreneuvianâCambrian Epoch 2 boundary) in the western Anti-Atlas of Morocco record the replacement of stromatolite-dominated microbial consortia by thrombolite-metazoan consortia. Carbonate and calcareous shales of both formations have been analyzed for major, trace, and rare earth elements to study their geochemical characteristics and evaluate the provenance of the terrigenous fraction and paleoredox conditions. Discrimination diagrams for the source rocks based on major elements and selected trace elements indicate that the terrigenous fractions of the sediments were likely derived from predominantly felsic rocks, and the source rocks have been identified to be the PaleoproterozoicâNeoproterozoic granites and metasediments of the Kerdous inlier. Paleoredox proxies such as U/Al, V/Al and Mo/Al suggest that the Igoudine and Amouslek formations were deposited in the oxic environment. Our data show that the local water column was prevailingly oxidized before, during and after the transition from the microbial consortium (stromatolite-dominated biota) to the thrombolite-archaeocyathan consortium and shelly metazoans within the studied interval. This implies that the seawater redox status was not driving this change in these biological communities

Chromium evidence for protracted oxygenation during the Paleoproterozoic

Accepted manuscript version, licensed CC BY-NC-ND 4.0. It has commonly been proposed that the development of complex life is tied to increases in atmospheric oxygenation. However, there is a conspicuous gap in time between the oxygenation of the atmosphere 2.4 billion years ago (Ga) and the first widely-accepted fossil evidence for complex eukaryotic cells . At present the gap could either represent poor sampling, poor preservation, and/or difficulties in recognizing early eukaryote fossils, or it could be real and the evolution of complex cells was delayed due to relatively low and/or variable O2 levels in the Paleoproterozoic. To assess the extent and stability of Paleoproterozoic O2 levels, we measured chromium-based oxygen proxies in a core from the Onega Basin (NW-Russia), deposited billion years ago—a few hundred million years prior to the oldest definitive fossil evidence for eukaryotes. Fractionated chromium isotopes are documented throughout the section (max. ‰ ), suggesting a long interval (possibly >100 million years) during which oxygen levels were higher and more stable than in the billion years before or after. This suggests that, if it is the case that complex cells did not evolve until after 1.7 Ga, then this delay was not due to O2-limitation. Instead, it could reflect other limiting factors—ecological or environmental—or could indicate that it simply takes a long time—more than the tens to >100 million years recorded in Onega Basin sediments—for such biological innovations to evolve