Nickel Isotope Variations in Terrestrial Silicate Rocks and Geological Reference Materials Measured by MC-ICP-MS

International audienceAlthough initial studies have demonstrated the applicability of Ni isotopes for cosmochemistry and as a potential biosignature, the Ni isotope composition of terrestrial igneous and sedimentary rocks, and ore deposits remains poorly known. Our contribution is fourfold: (a) to detail an analytical procedure for Ni isotope determination, (b) to determine the Ni isotope composition of various geological reference materials, (c) to assess the isotope composition of the Bulk Silicate Earth relative to the Ni isotope reference material NIST SRM 986 and (d) to report the range of mass-dependent Ni isotope fractionations in magmatic rocks and ore deposits. After purification through a two-stage chromatography procedure, Ni isotope ratios were measured by MC-ICP-MS and were corrected for instrumental mass bias using a double-spike correction method. Measurement precision (two standard error of the mean) was between 0.02 and 0.04‰, and intermediate measurement precision for NIST SRM 986 was 0.05‰ (2s). Igneous- and mantle-derived rocks displayed a restricted range of δ60/58Ni values between −0.13 and +0.16‰, suggesting an average BSE composition of +0.05‰. Manganese nodules (Nod A1; P1), shale (SDO-1), coal (CLB-1) and a metal-contaminated soil (NIST SRM 2711) showed positive values ranging between +0.14 and +1.06‰, whereas komatiite-hosted Ni-rich sulfides varied from −0.10 to −1.03‰

Ediacara biota flourished in oligotrophic and bacterially dominated marine environments across Baltica.

Middle-to-late Ediacaran (575-541 Ma) marine sedimentary rocks record the first appearance of macroscopic, multicellular body fossils, yet little is known about the environments and food sources that sustained this enigmatic fauna. Here, we perform a lipid biomarker and stable isotope (δ15Ntotal and δ13CTOC) investigation of exceptionally immature late Ediacaran strata (<560 Ma) from multiple locations across Baltica. Our results show that the biomarker assemblages encompass an exceptionally wide range of hopane/sterane ratios (1.6-119), which is a broad measure of bacterial/eukaryotic source organism inputs. These include some unusually high hopane/sterane ratios (22-119), particularly during the peak in diversity and abundance of the Ediacara biota. A high contribution of bacteria to the overall low productivity may have bolstered a microbial loop, locally sustaining dissolved organic matter as an important organic nutrient. These oligotrophic, shallow-marine conditions extended over hundreds of kilometers across Baltica and persisted for more than 10 million years

Multiple sulphur and iron isotope composition of detrital pyrite in Archaean sedimentary rocks : a new tool for provenance analysis

Author Posting. © The Author(s), 2009. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Earth and Planetary Science Letters 286 (2009): 436-445, doi:10.1016/j.epsl.2009.07.008.Multiple S (δ34S and δ33S) and Fe (δ56Fe) isotope analyses of rounded pyrite grains from 3.1 to 2.6 Ga conglomerates of southern Africa indicate their detrital origin, which supports anoxic surface conditions in the Archaean. Rounded pyrites from Meso- to Neoarchaean gold and uranium-bearing strata of South Africa are derived from both crustal and sedimentary sources, the latter being characterised by non-mass dependent fractionation of S isotopes (Δ33S as negative as -1.35‰) and large range of Fe isotope values (δ56Fe between -1.1 and 1.2‰). Most sediment-sourced pyrite grains are likely derived from sulphide nodules in marine organic matter-rich shales, sedimentary exhalites and volcanogenic massive sulphide deposits. Some sedimentary pyrite grains may have been derived from in situ sulphidised Fe-oxides, prior to their incorporation into the conglomerates, as indicated by unusually high positive δ56Fe values. Sedimentary sulphides without significant non-mass dependent fractionation of S isotopes were also present in the source of some conglomerates. The abundance in these rocks of detrital pyrite unstable in the oxygenated atmosphere may suggest factors other than high pO2 as the cause for the absence of significant non-mass dependent fractionation processes in the 3.2 – 2.7 Ga atmosphere. Rounded pyrites from the ca. 2.6 Ga conglomerates of the Belingwe greenstone belt in Zimbabwe have strongly fractionated δ34S, Δ33S and δ56Fe values, the source of which can be traced back to black shale-hosted massive sulphides in the underlying strata. The study demonstrates the utility of combined multiple S and Fe isotope analysis for provenance reconstruction of Archaean sedimentary successions.AH acknowledges support by NAI International Collaboration Grant and NRF grant FA2005040400027. AB participation was supported by NSF grant EAR-937 05-45484, NAI award No. NNA04CC09A, and NSERC 938 Discovery grant. Rouxel's contribution was supported by NSF OCE-0622982

Modelling of gibbsite calcination in a fluidized bed reactor

A steady state, non‐isothermal fluidized bed reactor model for co‐current flow of gas and solids has been developed as a series of Continuous Stirred Tank Reactor (CSTR) compartments. For each CSTR compartment, mass and energy balances were coupled with a particle‐scale gibbsite calcination kinetic model previously developed by the authors. The overall solids residence time distribution is captured by the compartment calcination model. The multi‐scale model was solved numerically through an iterative procedure that alternated between solving particle‐scale and reactor‐scale parts of the model. Gas, water vapour and solids concentrations, as well as particle and gas temperatures and gibbsite conversion profiles, are predicted inside the calcination reactor. The developed model can be used to facilitate improvements in the operation and design of industrial‐scale reactors

A 200-million year delay in permanent atmospheric oxygenation

S.W.P. acknowledges support from a Leverhulme Research Fellowship and a Royal Society Wolfson Research Merit Award. A.B. acknowledges support from the University of Johannesburg in the form of a Distinguished Visiting Professorship. D.T.J. acknowledges support from a NASA Exobiology award (NNX15AP58G).The rise of atmospheric oxygen fundamentally changed the chemistry of surficial environments and the nature of Earth’s habitability1. Early atmospheric oxygenation occurred over a protracted period of extreme climatic instability marked by multiple global glaciations2,3, with the initial rise of oxygen concentration to above 10−5 of the present atmospheric level constrained to about 2.43 billion years ago4,5. Subsequent fluctuations in atmospheric oxygen levels have, however, been reported to have occurred until about 2.32 billion years ago4, which represents the estimated timing of irreversible oxygenation of the atmosphere6,7. Here we report a high-resolution reconstruction of atmospheric and local oceanic redox conditions across the final two glaciations of the early Palaeoproterozoic era, as documented by marine sediments from the Transvaal Supergroup, South Africa. Using multiple sulfur isotope and iron–sulfur–carbon systematics, we demonstrate continued oscillations in atmospheric oxygen levels after about 2.32 billion years ago that are linked to major perturbations in ocean redox chemistry and climate. Oxygen levels thus fluctuated across the threshold of 10−5 of the present atmospheric level for about 200 million years, with permanent atmospheric oxygenation finally arriving with the Lomagundi carbon isotope excursion at about 2.22 billion years ago, some 100 million years later than currently estimated.PostprintPeer reviewe

Multi-stage shrinking core model for thermal decomposition reactions with a self-inhibiting nature

Among the variety of thermal decomposition reactions, some display self-inhibiting behaviour, where the produced gas negatively influences the reaction progress. Further, a build-up of internal pressure caused by the product gas may alter the reaction pathway over the reaction duration in a way that favours a particular pathway over others. Two well-known cases of this kind of reaction are the thermal decomposition of limestone and gibbsite, in which carbon dioxide and water vapour are the produced gases, respectively. A multi-stage, multi-reaction, shrinking core model is proposed for this type of reaction. The model emphasises the role of the produced gas, not only in the mass transfer rate, but also in the reaction kinetics. It also includes parallel and series reaction pathways, which allows for the presence of an intermediate species. The model has been applied to the conversion of gibbsite to alumina, and it includes the formation of boehmite as an intermediate product. The model results are in good agreement with experimental data for gibbsite calcination reported in the literature. Gibbsite conversion, boehmite formation and subsequent consumption, as well as alumina formation, are successfully simulated. Further, the corresponding kinetic parameters are estimated for all reactions of interest

Micropaleontology and chemostratigraphy of the Neoproterozoic Mbuji-Mayi Supergroup, Democratic Republic of Congo.

peer reviewe

Cochleatina: an enigmatic Ediacaran–Cambrian survivor among small carbonaceous fossils (SCFs)

Conspicuously few body-fossil taxa are known to span the Ediacaran-Cambrian boundary, a pattern usually taken to signal either a terminal Proterozoic mass extinction, or taphonomic failure. We draw attention to the emerging record of small carbonaceous fossils (SCFs), which exhibit continuous preservation spanning this critical interval. Here we focus on the enigmatic SCF Cochleatina, a morphologically complex coil-shaped problematicum that ranges across the Ediacaran-Cambrian divide, and potentially among the oldest fossil occurrences of metazoans. We report new material of Cochleatina canilovica from the Ediacaran of Estonia and Ukraine, which offers new characters for assessing its palaeobiology. Significantly, new specimens include sets of three-alike triplets of Cochleatina adhering to organic sheets, suggesting a clustering habit, or grouping of elements within an individual during life; an important step in constraining the morphology and ecology of this Ediacaran-Cambrian problematicum. We present revised systematic descriptions for Cochleatina and C. canilovica, and critically evaluate previous biological interpretations, drawing comparisons with metazoan, algal and protistan analogues. We reject hypotheses supporting Cochleatina as a metazoan mouthpart, and suggest new grounds for viewing Cochleatina as a potential multicomponent predator that trapped protists among microbial mats. Most occurrences are from Baltica, but we synthesise sporadic reports of Cochleatina from other palaeocontinents, pointing to its global distribution during the latest ~10 Myr of the Ediacaran and majority of the earliest Cambrian Fortunian Stage. As a rare example of an ‘Ediacaran survivor’, Cochleatina highlights the broader significance of SCFs as a novel means of tracking evolutionary patterns through the Proterozoic-Phanerozoic transition

Mathematical Model of the Shell with the Infill for Retaining Structures

A description of finite element model and analysis of a shell with an infill is performed. A large diameter thin cylindrical shell structure with the edge leaning against compressible foundation soil is analyzed. Different materials are considered individually for the models of each structure shell and infill component (metal or reinforced concrete shell, and granular or elastic infill in a shell and foundation soil loaded by the structure). Contact conditions between 1) the infill and the shell’s inner surface and 2) between the foundation material and the shell edge are analyzed. An example of calculating strain conditions in the shell according to the proposed finite element model and tasks of its development process and specification are provided in this paper

Triple iron isotope constraints on the role of ocean iron sinks in early atmospheric oxygenation

International audienceThe role that iron played in the oxygenation of Earth’s surface is equivocal. Iron could have consumed molecular oxygen when Fe3+-oxyhydroxides formed in the oceans, or it could have promoted atmospheric oxidation by means of pyrite burial. Through high-precision iron isotopic measurements of Archean-Paleoproterozoic sediments and laboratory grown pyrites, we show that the triple iron isotopic composition of Neoarchean-Paleoproterozoic pyrites requires both extensive marine iron oxidation and sulfide-limited pyritization. Using an isotopic fractionation model informed by these data, we constrain the relative sizes of sedimentary Fe3+-oxyhydroxide and pyrite sinks for Neoarchean marine iron. We show that pyrite burial could have resulted in molecular oxygen export exceeding local Fe2+ oxidation sinks, thereby contributing to early episodes of transient oxygenation of Archean surface environments