Chemical reducing pedoenvironment in a peatland influenced by hematitic phyllite lithology in the southern Espinhaço chain,Brazil

A peatland in Pinheiro, Diamantina City, Minas Gerais State - Brazil, was sampled at different depths of two profiles with diverse vegetation coverings (grassland field and bush) in order to collect materials that might reflect changes in the chemical states of iron over the peat formation coming from original minerals such as hematitic phyllite surrounding the boggy pedon. Samples collected were chemically, structurally and magnetically characterized. The results show that both series of peats are composed of organic matter and minerals such as quartz, kaolinite, gibbsite, rutile and muscovite. Deeper layers present only quartz. Mössbauer spectroscopy shows that iron is present in both electron states, Fe²⁺ and Fe³⁺, under both vegetations, each valence appearing in the spectra in the form of a discrete doublet. No hyperfine magnetic splitting was observed in any spectrum at room temperature. The Mössbauer subspectral area of Fe²⁺ tended to increase from the upper to deeper layers. Magnetic measurements reveal that the magnetic response of the surface samples is the highest, displaying a sharp decrease below 15 cm and that the magnetic signal is a superposition of (super)paramagnetic and ferrimagnetic contributions. Samples from the grassland field also show a diamagnetic component for the deeper layers.     

Bio‐Inspired Formal Synthesis of Hirsutellones A–C Featuring an Electrophilic Cyclization Triggered by Remote Lewis Acid‐Activation

A bio‐inspired strategy was used to complete the formal synthesis of the antitubercular hirsutellone B and congeners A and C, through construction of its decahydrofluorene core from a linear polyene strand activated at both ends by a silyl enol ether and an allyl acetate. Our synthesis features a key electrophilic cyclization, starting with the remote activation (by [Yb(OTf)₃] or BF₃ ? OEt₂) of the allyl acetate and stereoselectively affording the C ring. This was followed by an intramolecular Diels–Alder reaction to get the tricyclic core of the natural product. The stereoselective reduction of the resulting ketone towards the formal intermediate was critical to the success of this strategy.     

Simulation of a mixed-conducting membrane-based gas turbine power plant for CO<Subscript>2</Subscript> capture: system level analysis of operation stability and individual process unit degradation

A gas turbine power plant for CO₂ capture, based on oxygen-permeable membranes with mixed ionic-electronic conductivity, was analysed with respect to long-term stability by means of numerical simulation. Due to the attractive transport and physicochemical properties of mixed-conducting La₂NiO_4+δ, this nickelate was selected as a prototype membrane material for this application. Experiments showed very slow degradation of La₂NiO_4+δ membranes at oxygen chemical potentials close to atmospheric conditions, which are associated with kinetic demixing and other microstructure-related factors. Interaction with CO₂ in the intermediate temperature range also leads to lower oxygen permeation, whilst increasing oxygen pressure may cause partial phase decomposition and microstructural changes, thus again limiting the range of possible operation conditions. The relevant operational constraints were included in a detailed membrane-based gas turbine power plant model. The membrane performance degradation with time was approximated by a linear function with average rate of 3.3% per 1,000 operation hours. Furthermore, performance deterioration of the gas turbine compressor and turbine were also considered. Simulations revealed that the power plant is substantially affected by degradation of the ceramic membranes and turbomachinery components. The already rather small operating window was further narrowed when compared with a conventional gas turbine power plant. Two different designs of the membrane-based power plant were analysed: (1) with and (2) without additional combustors (afterburners) between the membrane reactor and the gas turbine. Afterburners increase thermal efficiency as well as power output, but also lead to non-negligible CO₂ emissions. In order to have a frame of comparison, results for a conventional gas turbine power plant with degradation of turbomachinery components are also presented. Simulations representing changes in ambient temperature and fuel composition as well as failure incidents were executed to analyse the susceptibility of the gas turbine power plant to external and internal changes.