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

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

Proterozoic ocean redox and biogeochemical stasis

The partial pressure of oxygen in Earth’s atmosphere has increased dramatically through time, and this increase is thought to have occurred in two rapid steps at both ends of the Proterozoic Eon (∼2.5–0.543 Ga). However, the trajectory and mechanisms of Earth’s oxygenation are still poorly constrained, and little is known regarding attendant changes in ocean ventilation and seafloor redox. We have a particularly poor understanding of ocean chemistry during the mid-Proterozoic (∼1.8–0.8 Ga). Given the coupling between redox-sensitive trace element cycles and planktonic productivity, various models for mid-Proterozoic ocean chemistry imply different effects on the biogeochemical cycling of major and trace nutrients, with potential ecological constraints on emerging eukaryotic life. Here, we exploit the differing redox behavior of molybdenum and chromium to provide constraints on seafloor redox evolution by coupling a large database of sedimentary metal enrichments to a mass balance model that includes spatially variant metal burial rates. We find that the metal enrichment record implies a Proterozoic deep ocean characterized by pervasive anoxia relative to the Phanerozoic (at least ∼30–40% of modern seafloor area) but a relatively small extent of euxinic (anoxic and sulfidic) seafloor (less than ∼1–10% of modern seafloor area). Our model suggests that the oceanic Mo reservoir is extremely sensitive to perturbations in the extent of sulfidic seafloor and that the record of Mo and chromium enrichments through time is consistent with the possibility of a Mo–N colimited marine biosphere during many periods of Earth’s history

Onset of the aerobic nitrogen cycle during the Great Oxidation Event

The rise of oxygen on the early Earth (about 2.4 billion years ago)1 caused a reorganization of marine nutrient cycles2, 3, including that of nitrogen, which is important for controlling global primary productivity. However, current geochemical records4 lack the temporal resolution to address the nature and timing of the biogeochemical response to oxygenation directly. Here we couple records of ocean redox chemistry with nitrogen isotope (15N/14N) values from approximately 2.31-billion-year-old shales5 of the Rooihoogte and Timeball Hill formations in South Africa, deposited during the early stages of the first rise in atmospheric oxygen on the Earth (the Great Oxidation Event)6. Our data fill a gap of about 400 million years in the temporal 15N/14N record4 and provide evidence for the emergence of a pervasive aerobic marine nitrogen cycle. The interpretation of our nitrogen isotope data in the context of iron speciation and carbon isotope data suggests biogeochemical cycling across a dynamic redox boundary, with primary productivity fuelled by chemoautotrophic production and a nitrogen cycle dominated by nitrogen loss processes using newly available marine oxidants. This chemostratigraphic trend constrains the onset of widespread nitrate availability associated with ocean oxygenation. The rise of marine nitrate could have allowed for the rapid diversification and proliferation of nitrate-using cyanobacteria and, potentially, eukaryotic phytoplankton

Neural Synchrony during Response Production and Inhibition

Inhibition of irrelevant information (conflict monitoring) and/or of prepotent actions is an essential component of adaptive self-organized behavior. Neural dynamics underlying these functions has been studied in humans using event-related brain potentials (ERPs) elicited in Go/NoGo tasks that require a speeded motor response to the Go stimuli and withholding a prepotent response when a NoGo stimulus is presented. However, averaged ERP waveforms provide only limited information about the neuronal mechanisms underlying stimulus processing, motor preparation, and response production or inhibition. In this study, we examine the cortical representation of conflict monitoring and response inhibition using time-frequency analysis of electroencephalographic (EEG) recordings during continuous performance Go/NoGo task in 50 young adult females. We hypothesized that response inhibition would be associated with a transient boost in both temporal and spatial synchronization of prefrontal cortical activity, consistent with the role of the anterior cingulate and lateral prefrontal cortices in cognitive control. Overall, phase synchronization across trials measured by Phase Locking Index and phase synchronization between electrode sites measured by Phase Coherence were the highest in the Go and NoGo conditions, intermediate in the Warning condition, and the lowest under Neutral condition. The NoGo condition was characterized by significantly higher fronto-central synchronization in the 300–600 ms window, whereas in the Go condition, delta- and theta-band synchronization was higher in centro-parietal regions in the first 300 ms after the stimulus onset. The present findings suggest that response production and inhibition is supported by dynamic functional networks characterized by distinct patterns of temporal and spatial synchronization of brain oscillations

Evidence for oxygenic photosynthesis half a billion years before the Great Oxidation Event

The early Earth was characterized by the absence of oxygen in the ocean–atmosphere system, in contrast to the well-oxygenated conditions that prevail today. Atmospheric concentrations first rose to appreciable levels during the Great Oxidation Event, roughly 2.5–2.3 Gyr ago. The evolution of oxygenic photosynthesis is generally accepted to have been the ultimate cause of this rise, but it has proved difficult to constrain the timing of this evolutionary innovation. The oxidation of manganese in the water column requires substantial free oxygen concentrations, and thus any indication that Mn oxides were present in ancient environments would imply that oxygenic photosynthesis was ongoing. Mn oxides are not commonly preserved in ancient rocks, but there is a large fractionation of molybdenum isotopes associated with the sorption of Mo onto the Mn oxides that would be retained. Here we report Mo isotopes from rocks of the Sinqeni Formation, Pongola Supergroup, South Africa. These rocks formed no less than 2.95 Gyr ago in a nearshore setting. The Mo isotopic signature is consistent with interaction with Mn oxides. We therefore infer that oxygen produced through oxygenic photosynthesis began to accumulate in shallow marine settings at least half a billion years before the accumulation of significant levels of atmospheric oxygen

Trace elements at the intersection of marine biological and geochemical evolution

Life requires a wide variety of bioessential trace elements to act as structural components and reactive centers in metalloenzymes. These requirements differ between organisms and have evolved over geological time, likely guided in some part by environmental conditions. Until recently, most of what was understood regarding trace element concentrations in the Precambrian oceans was inferred by extrapolation, geochemical modeling, and/or genomic studies. However, in the past decade, the increasing availability of trace element and isotopic data for sedimentary rocks of all ages has yielded new, and potentially more direct, insights into secular changes in seawater composition – and ultimately the evolution of the marine biosphere. Compiled records of many bioessential trace elements (including Ni, Mo, P, Zn, Co, Cr, Se, and I) provide new insight into how trace element abundance in Earth's ancient oceans may have been linked to biological evolution. Several of these trace elements display redox-sensitive behavior, while others are redox-sensitive but not bioessential (e.g., Cr, U). Their temporal trends in sedimentary archives provide useful constraints on changes in atmosphere-ocean redox conditions that are linked to biological evolution, for example, the activity of oxygen-producing, photosynthetic cyanobacteria. In this review, we summarize available Precambrian trace element proxy data, and discuss how temporal trends in the seawater concentrations of specific trace elements may be linked to the evolution of both simple and complex life. We also examine several biologically relevant and/or redox-sensitive trace elements that have yet to be fully examined in the sedimentary rock record (e.g., Cu, Cd, W) and suggest several directions for future studies

The bromine and chlorine isotope composition of primary halite deposits and their significance for the secular isotope composition of seawater

We determined the chlorine and bromine isotope compositions of 83 halite samples from nine different geological periods between the Orosirian and the present in order to study the secular Cl and Br isotope variations in the ocean during the last 2 billion years. Relatively large Cl (-0.24 to +0.51‰ vs. SMOC) and Br (-0.24 to +1.08‰ vs. SMOB) isotope variations are found in these halite samples. Two different methods, one in which the isotope fractionation between the brine and the salt is used, and a second in which the relationship between the isotope compositions and the Br/Cl ratios in the halite samples is used were applied to establish the original Cl and Br isotope compositions of the ocean. Both approaches showed that the Cl and Br isotope compositions of the ocean have always been close to the modern value (which is by definition 0‰ for both isotope systems) and that at most very small variations in Br and Cl isotope composition of seawater have occurred during the last 2 billion years. This indicates that, unlike in other isotope systems that often show significant isotope variations over geologic time, Cl and Br isotope compositions can be used directly to determine processes that occurred in the deposits of interest without need for correction for secular variations.This research is part of the project ‘‘BRISOACTIONS” that has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 702001. We are grateful to Gilian Schout (Utrecht University), Alex Klomp and JanWillem Weegink (both TNO Geological Survey) for their help in sample selection from the Triassic and Upper Permian. We thank Pierre Burckel (IPGP) for Cl and Br analyses by ICP-MS and Laure Cordier (IPGP) for the analyses by ICP-OES. Parts of this work were supported by the IPGP multidisciplinary program PARI, by Paris–IdF region SESAME Grant no. 12015908, NSERC Discovery and Accelerator Grant to AB, and by Australian Research Council Grant DP160100607 to JJB

Current Design of Mixed-Ligand Complexes of Magnesium(II): Synthesis, Crystal Structure, Thermal Properties and Biological Activity against <i>Mycolicibacterium Smegmatis</i> and <i>Bacillus Kochii</i>

The interaction of Mg2+ with 2-furoic acid (HFur) and oligopyridines, depending on the synthesis conditions, leads to the formation of mixed-ligand complexes [Mg(H2O)4(phen)]·2HFur·phen·H2O (1), [Mg(NO3)2(phen)2] (2) and [Mg3(Fur)6(bpy)2]·3CH3CN (3); these structures were determined with an SC X-ray analysis. According to the X-ray diffraction data, in complex 1, obtained in ambient conditions, the magnesium cation coordinated four water molecules and one phenanthroline fragment, while in complexes 2 and 3 (synthesized in an inert atmosphere), the ligand environment of the complexing agent was represented by neutral oligopyridine molecules and acid anions. The thermal behavior of 1 and 2 was studied using a simultaneous thermal analysis (STA). The in vitro biological activity of complexes 1–3 was studied in relation to the non-pathogenic Mycolicibacterium smegmatis and the virulent strain Mycobacterium tuberculosis H37Rv