Carbonaceous Wall Research Articles

Cobalt-catalyzed carbonization from polyacrylonitrile for preparing nitrogen-containing ordered mesoporous carbon CMK-1 electrode with high electric double-layer capacitance

Ordered mesoporous carbon CMK-1 was prepared via carbonization at a relatively low temperature (the first step) followed by partial graphitization (the second step of carbonization at higher temperature) inside the ordered mesopores of cobalt-loaded mesoporous silica MCM-48 using polyacrylonitrile (PAN) as a carbon/nitrogen source. This first step of the carbonization is called “infusibilization”, and the resultant material is denoted as PANinf. In an advanced temperature-programmed desorption analysis of the PANinf/MCM-48 composite, the temperature of the observed HCN signal indicated that carbonization was reduced from 550 to 450 °C by a Co catalyst. The amount of typical N2 formation associated with the selective removal of pyridinic N species, resulting in the graphitic surface formation, also increased at a relatively high temperature (approximately 1000 °C) with the aid of the Co catalyst. The CMK-1 prepared through cobalt-catalyzed carbonization exhibited a higher electric double-layer capacitance with an Et4N+BF4–/propylene carbonate electrolyte, and higher electrical conductivity than CMK-1 prepared without a catalyst. This also implied the progress of graphitization within the carbonaceous wall. These results suggest that the edge planes of the graphitic domains in CMK-1 are predominantly exposed on the surfaces of the carbonaceous walls, resulting in an increase in the number of adsorptive sites for the electrolyte during capacitance measurements.

Ultrasmall Pt NPs-modified flasklike colloidal motors with high mobility and enhanced ion tolerance.

Chemically powered colloidal motors propelled by the self-phoretic effect have attracted widespread attention. However, the low motion efficiency and ion tolerance hinder their application in complex media. Herein, we report a scalable and simple method to synthesize 2.6 nm Platinum nanoparticles (Pt NPs) in the nanoporous wall of carbonaceous flasklike colloidal motors in a ligand-free manner. The obtained Pt NPs-modified flasklike colloidal motors (Pt-FCMs) are propelled by the catalytic decomposition of H2O2 fuels. They exhibit ultrafast mobility with an instantaneous velocity of 134 μm s-1 at 5% H2O2, which is equivalent to 180 bodylengths per second. Particularly, these Pt-FCMs have an enhanced ion tolerance, due to the higher catalytic activity of small-sized Pt NPs in the carbonaceous wall. Furthermore, the direction of motion could be reversed by adding cationic surfactant cetyltrimethylammonium bromide. Such ultrasmall Pt NPs funtionalized flasklike colloidal motors exhibit a great potential utilization in the field of biomedicines and environmental technology.

The Sukari Gold Deposit, Egypt: Geochemical and Geochronological Constraints on the Ore Genesis and Implications for Regional Exploration

AbstractThe Sukari gold deposit (>15 Moz Au) in the Eastern Desert of Egypt is hosted by a deformed granitoid stock (Sukari tonalite-trondhjemite intrusion) and mainly occurs as a network of crosscutting sulfide-bearing quartz (± carbonate) veins and intensely sulfidized-silicified-sericitized wall rock. Emplacement of the Sukari intrusion into a tectonized Neoproterozoic accretionary complex was controlled by a system of NE- to NNE-trending oblique faults that are related to a deep-seated positive flower structure. A robust genetic model has been hampered by the poorly understood relationships between gold mineralization and host rocks. In this study, zircon U-Pb ages of three samples from the Sukari intrusion define a crystallization age of ~695 ± 2 Ma. In contrast, hydrothermal sericite from the ore zone yields an 40Ar/39Ar age of ~625 ± 3 Ma, which coincides with the onset of major sinistral transpression in the region.Features including sigmoidal morphology of gold quartz veins and abundant subhorizontal tension gashes alongside widespread brecciation and recrystallization suggest that quartz veining occurred during renewed shortening and exhumation through the brittle-ductile transition. Petrographic and micro-X-ray fluorescence (µXRF) studies indicate that disseminated gold and sulfides, commonly associated with sericite and carbonate alteration, are mostly confined to stylolitic bands in the quartz veins. Oscillatory and sector zoning patterns, irregular As-rich bands, and truncations between early- and late-genetic pyrites reflect variations in temperature and mechanism of ore deposition, demonstrated by variable As/S and Co/Ni ratios in the different pyrite generations. Laser ablation-inductively coupled plasma-mass spectrometry analysis pinpoints the covariance of gold and arsenic contents in pyrite, but free milling gold inclusions in microfractures consistently have a mercury-bearing electrum composition, depicting different ore formation stages.Ore fluids with δ34SH2s values of –1.9 to –3.0‰, modeled from gold-associated pyrite and arsenopyrite assemblages with nearly identical δ34S values, suggest a likely single source of sulfur. Alternatively, multisourced sulfur could have extensively mixed and equilibrated by fluid reaction with carbonaceous wall rock. Gold deposition was triggered by abrupt changes in fluid pH and fO2. As an implication for future exploration, sites of maximized strain gradients adjacent to granitoid bodies along extensive transpression zones in the district could be highly prospective targets, particularly where imprinted by sericite-carbonate ± graphite alteration.

Distinguishing cellular from abiotic spheroidal microstructures in the ca. 3.4 Ga Strelley Pool Formation.

The morphogenesis of most carbonaceous microstructures that resemble microfossils in Archean (4-2.5Ga old) rocks remains debated. The associated carbonaceous matter may even-in some cases-derive from abiotic organic molecules. Mineral growths associated with organic matter migration may mimic microbial cells, some anatomical features, and known microfossils-in particular those with simple spheroid shapes. Here, spheroid microstructures from a chert of the ca. 3.4 Ga Strelley Pool Formation (SPF) of the Pilbara Craton (Western Australia) were imaged and analyzed with a combination of high-resolution in situ techniques. This provides new insights into carbonaceous matter distributions and their relationships with the crystallographic textures of associated quartz. Thus, we describe five new types of spheroids and discuss their morphogenesis. In at least three types of microstructures, wall coalescence argues for migration of carbonaceous matter onto abiotic siliceous spherulites or diffusion in poorly crystalline silica. The nanoparticulate walls of these coalescent structures often cut across multiple quartz crystals, consistent with migration in/on silica prior to quartz recrystallization. Sub-continuous walls lying at quartz boundaries occur in some coalescent vesicles. This weakens the "continuous carbonaceous wall" criterion proposed to support cellular inferences. In contrast, some clustered spheroids display wrinkled sub-continuous double walls, and a large sphere shows a thick sub-continuous wall with pustules and depressions. These features appear consistent with post-mortem cell alteration, although abiotic morphogenesis remains difficult to rule out. We compared these siliceous and carbonaceous microstructures to coalescent pyritic spheroids from the same sample, which likely formed as "colloidal" structures in hydrothermal context. The pyrites display a smaller size and only limited carbonaceous coatings, arguing that they could not have acted as precursors to siliceous spheroids. This study revealed new textural features arguing for abiotic morphogenesis of some Archean spheroids. The absence of these features in distinct types of spheroids leaves open the microfossil hypothesis in the same rock. Distinction of such characteristics could help addressing further the origin of other candidate microfossils. This study calls for similar investigations of metamorphosed microfossiliferous rocks and of the products of in vitro growth of cell-mimicking structures in presence of organics and silica.

Authigenic anatase within 1 billion-year-old cells.

The siliciclastic ~1Ga-old strata of the Torridon Group, Scotland, contain some of the most exquisitely preserved three-dimensional organic-walled microfossils (OWMs) of the Precambrian. A very diverse microfossil assemblage is hosted in a dominantly phosphatic and clay mineral matrix, within the Diabaig and the Cailleach Head (CH) Formations. In this study, we report on several microfossil taxa within the CH Formation (Leiosphaeridia minutissima, Leiosphaeridia crassa, Synsphaeridium spp. and Myxococcoides spp.) that include populations of cells containing an optically transparent and highly refringent mineral, here identified using electron microscopy as anatase (TiO2 ). Most anatase crystals occur entirely within individual cells, surrounded by unbroken carbonaceous walls. Rarely, an anatase crystal may protrude outside a cell, interpreted to correspond to zones where the cell wall had broken down prior to anatase precipitation. Where an anatase crystal entombs an organic intracellular inclusion (ICI), the ICI is large and well preserved. These combined observations indicate that the intracellular anatase is an authigenic sedimentary phase, making this the first report of in situ precipitated anatase intimately associated with microfossils. The ability of anatase to preserve relatively large volumes of intracellular and cell wall organic material in these cells suggests that the crystallisation of anatase entombed cellular contents particularly quickly, soon after the death of the cell. This is consistent with the strong affinity of Ti for organic material, the low solubility of TiO2 , and reports of Ti occurring in living organisms. With the data currently available, we propose a mineralisation pathway for anatase involving Ti complexation with organic ligands within specific cells, leading to localised post-mortem anatase nucleation inside these cells as the complexes broke down. Further overgrowth of the anatase crystals was likely fuelled by very early diagenetic mobilisation of Ti that had been bound to more labile organic material nearby in the sediments.

Mineralized Granitic Porphyry of the Yangla Copper Deposit, Western Yunnan, China: Geochemistry of Fluid Inclusions and H-O, S, and Pb Isotopes

The Yangla copper deposit (YCD) is located in the central part of the Jinshajiang tectonic belt (Jinshajiang metallogenic belt) and is one of the most important copper deposits which has the large-scale copper reserves of the northwestern Yunnan, China. The ore bodies are strictly controlled by the stratum, pluton, and structure, which are layered, lens, and vein-like within the contact or fracture zone of the pluton and surrounding rock. At Yangla, two styles of mineralization occur at the brecciated contact zone between the pluton (granodiorite and granitic porphyry) and carbonaceous wall rock and include strata bound/lens-shaped replacement of carbonate rocks (skarn style) and porphyry-style sulfide-quart-calcite veins. But, the granitic porphyry mineralization have received less attention; the isotope and fluid inclusion studies are relatively scarce for limited porphyry ore bodies that have been discovered at the YCD. Quartz-hosted fluid inclusions from the recently discovered granitic porphyry have homogenization temperature averaging around 180±20°C and 300±20°C with salinities ranging from 4 to 22 wt.% NaCleq, pointing toward the contribution of medium temperature-medium salinity and low temperature-low salinity fluids during the metallogenesis. These fluid inclusions have δ18OH2O values ranging between -1.91‰ and -1.02‰ and δD values ranging between -143.10‰ and -110‰, suggesting that the ore-forming fluid was a mix of magmatic and meteoric water. Ore-related pyrite/chalcopyrite have δ34SV-CDT values ranging from -1.0‰ to 1.0‰ and whole rocks have δ34SΣS = 0.34, suggesting that sulfur mainly derived from magmatic rocks of the Yangla mining area. The sulfides 208Pb/204Pb ranged from 38.8208-38.9969, 207Pb/204Pb from 15.7079-15.7357, and 206Pb/204Pb from 18.5363-18.7045, indicating that the lead mainly originated from the upper crust. It is demonstrated that the evolution of ore-forming fluid is continuous from the skarn ore body (SOB) stage to the porphyritic ore body stage and belong to the products of the same ore-forming fluid system, and the unisothermal mixing and cooling actions were maybe the main mechanism at the metallic minerals precipitation in mineralized granitic porphyry (MGP). A model is proposed according to the early stage, a magmatic fluid reacted and replaced with the surrounding carbonate rocks and then formed skarn-type ore bodies. The magmatic-hydrothermal fluid subsequently deposited porphyry-type quartz-calcite veins, veinlets, and stockwork mineralization.

Nanospherical mesoporous carbon-supported gold as an efficient heterogeneous catalyst in the elimination of mass transport limitations

This study proposes ordered mesoporous carbon nanosphere-supported gold catalysts to eliminate the diffusion limitation inside the long channels of bulk mesoporous materials. The nanospherical catalysts have a spherical morphology with a diameter of approximately 90 nm, uniform pore sizes of 2.5 nm, and high surface areas of approximately 600 m2/g; and the bulk catalysts have similar mesoporous textural properties with nanospherical catalysts but an irregular bulk shape. Metallic gold particles are both intercalated inside carbonaceous walls. The Madon-Boudart (MB) test shows that nanospherical catalysts exhibit no diffusion limitations in the reduction of nitroarenes, even for a large 2,6-dimethylnitrobenzene (2,6-DMNB) molecule. By comparison, the bulk-ordered mesoporous carbon-supported gold catalysts display distinct mass transfer inhibition. The nanospherical mesoporous carbon-supported gold catalysts are highly active and selective for the reduction of nitroarenes to corresponding amines, reaching turnover frequency (TOF) values of 13.7, 16.1, 7.6 and 26.8 min−1 for converting 4-nitrophenol (4-NP), 2-nitrophenol (2-NP), 4-(tert-butyl)-2-nitrophenol (4-TB-2-NP), and 2,6-DMNB, respectively. The catalysts are stable and can be re-used more than 15 times.

Combined Experimental, Theoretical, and Molecular Simulation Approach for the Description of the Fluid-Phase Behavior of Hydrocarbon Mixtures within Shale Rocks

An experimental, theoretical, and molecular simulation consolidated framework for the efficient characterization of the adsorption and fluid-phase behavior of multi-component hydrocarbon mixtures within tight shale rocks is presented. Fluid molecules are described by means of a top-down coarse-grained model where simple Mie intermolecular potentials are parametrized by means of the statistical associating fluid theory. A four-component (methane, pentane, decane, naphthalene) mixture is used as a surrogate model with a composition representative of commonly encountered shale oils. Shales are modeled as a hierarchical network of nanoporous slits in contact with a mesoporous region. The rock model is informed by the characterization of four distinct and representative shale core samples through nitrogen adsorption, thermogravimetric analysis, and contact angle measurements. Experimental results suggest the consideration of two types of pore surfaces: a carbonaceous wall representing the kerogen regions of a ...

Ni-catalyzed carbonization of furfuryl alcohol polymer in ordered mesoporous silica MCM-48 giving ordered mesoporous carbon CMK-1 with high electric double-layer capacitance

Ordered mesoporous carbon CMK-1 was partially graphitized during carbonization treatment of furfuryl alcohol (FA) polymer inside the ordered mesopores of Ni-loaded MCM-48. FA polymer was successfully produced within the mesopores of MCM-48 by thermal treatment at 90 °C. A typical weight decrease of the FA-polymer/MCM-48 composite occurred from 300 to 400 °C by carbonization treatment. Ni(II) species acts as a catalyst for dehydrogenation from 500 to 640 °C, and then CH4 fragments formed in situ can reduce Ni(II) to Ni(0) at 640 °C. The metallic Ni thus formed can then act as a catalyst for the formation of the graphitic structure within the mesopores of MCM-48 at 1000 °C. The CMK-1 obtained with the aid of the Ni catalyst exhibited a higher electric double-layer capacitance with a tetraethylammonium tetrafluoroborate/propylene carbonate electrolyte, compared to normal CMK-1. The results suggest that the edge planes of the graphitic domains in CMK-1 are predominantly exposed on the surface of carbonaceous walls, which leads to an increase in the number of adsorptive sites for the electrolyte during the capacitance measurements.

Mineralization mechanisms in the Shangfanggou giant porphyry-skarn Mo–Fe deposit of the east Qinling, China: Constraints from H–O–C–S–Pb isotopes

The giant Shangfanggou skarn-porphyry Mo–Fe deposit, one of the largest Mo deposits in the East Qinling Orogen, is hosted by the Neoproterozoic Luanchuan Group on the southern margin of the North China Craton. The mineralization occurs mainly as veinlets and in veinlet-disseminated form within altered schists, skarns, hornfelses, and/or marbles. The hydrothermal alteration and mineralization at Shangfanggou took place over four stages. Stage 1 involved potassic alteration and silicification in the porphyry, skarnization and magnetization in carbonate strata, and hornfelsization in schists. Quartz–molybdenite veins associated with phyllic alteration were produced in the porphyry during stage 2, along with sericitization, chloritization, serpentinization, and silicification in the skarns, hornfelses and/or marbles. Quartz–polymetallic sulfide veins related to phyllic alteration were produced during stage 3, and ore-barren quartz±calcite±pyrite veins associated with weak carbonatation were produced during stage 4. C, O, and D isotope compositions of hydrothermal calcite, dolomite, magnetite, phlogopite, and quartz from different stages of mineralization during the formation of the Shangfanggou deposit range from −12.9‰ to +8.8‰, −3.2‰ to +22.7‰, and −100‰ to −80‰, respectively. Sulfur isotope compositions of sulfides from the ores of the Shanfanggou deposit range from 3.6‰ to 4.4‰. 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios of 17.648 to 18.742 (apart from one magnetite with a value of 20.78), 15.526 to 15.690, and 38.197 to 39.823 in the Shanfanggou deposit. The evolution of the ore-forming fluids in the Shangfanggou deposit, as revealed by δ18O, δD, and δ13C isotope studies, was one of progressive modification of the magmatic fluids through fluid–wall rock interactions along conduits during fluid ascent, and this signifies the involvement of formation/strata water during the earlier stages of mineralization, and the predominance of meteoric waters over magmatic fluids in the later stages. The carbon, sulfur, and lead isotope compositions suggest mixing took place between the magmas and the host rocks within the region. Integrating the data obtained from studies of the regional geology, ore geology, fluid inclusions, and C–H–O–S–Pb isotope geochemistry, we conclude that the Shangfanggou Mo–Fe deposit is a porphyry-skarn type system that formed during a transition from compressional to extensional tectonics during the Jurassic–Early Cretaceous continental collision between the North China Craton and Yangtze Craton. The ore materials were sourced from magmatic ore-forming fluids that mixed with components derived from carbonaceous wall rocks during their ascent, and which were gradually mixed with meteoric waters, especially in the later stages.

A qualitative approach to adsorption mechanism identification on microporous carbonaceous surfaces

The paper presents results of research on identification of localized and other adsorption mechanisms, on geometrically heterogeneous graphite-like carbonaceous surfaces. It attempts to get an insight into properties of individual adsorptive molecule movement near attractive adsorption sites, arising from adsorbent surface geometrical heterogeneities. In particular, a shape and volume of space occupied by the continuously moving molecule mass center are investigated. To this aim, kinematic equilibrium of the particle moving near a hypothetical microporous carbonaceous adsorbent wall is considered, and then compared with thermodynamic equilibrium. The proposed approach enables to examine effects of certain surface geometry on the shape and volume of space occupied by adsorbed particles, and so to outline temperature conditions for the localized adsorption mechanism predomination. Thus, it provides a cognitive basis to answer the question, what particular mechanism (localized or other—e.g. mobile) should be assumed for a class of adsorption systems in order to select the most appropriate mathematical adsorption model. Hence, it makes it possible for more reliable examination of real porous structures, based on adsorption measurements.

To what extent can mutual shifting of folded carbonaceous walls in slit-like pores affect their adsorption properties?

We have performed systematic Monte Carlo studies on the influence of shifting the walls in slit-like systems constructed from folded graphene sheets on their adsorption properties. Specifically, we have analysed the effect on the mechanism of argon adsorption (T = 87 K) and on adsorption and separation of three binary gas mixtures: CO2/N2, CO2/CH4 and CH4/N2 (T = 298 K). The effects of the changes in interlayer distance were also determined. We show that folding of the walls significantly improves the adsorption and separation properties in comparison to ideal slit-like systems. Moreover, we demonstrate that mutual shift of sheets (for small interlayer distances) causes the appearance of small pores between opposite bulges. This causes an increase in vapour adsorption at low pressures. Due to overlapping of interactions with opposite walls causing an increase in adsorption energy, the mutual shift of sheets is also connected with the rise in efficiency of mixture separation. The effects connected with sheet orientation vanish as the interlayer distance increases.

Archean turbidite hosted orogenic gold mineralization in the Gadag greenstone belt, Western Dharwar Craton, Peninsular India

Turbidite hosted orogenic gold mineralization in the Archean Gadag greenstone belt of the Western Dharwar Craton, forms a major auriferous zone (Central Auriferous Zone) extending over a strike length of about 12km in the Gadag duplex. The turbidite sequence comprises thick inter-bedded, medium to coarse grained lithic graywacke and thin laminated layers of fine grained carbonaceous phyllite. Gold bearing quartz veins impregnate preferentially along the en-echelon shear planes, fractures and schistosity planes. Auriferous quartz veins are enveloped by the altered wall rocks.Mineralogy of the auriferous zone is dominated by gangue minerals like quartz, ankerite, chlorite, sericite and carbonaceous matter, with subordinate plagioclase. Monazite and xenotime are the important accessory minerals. Arsenopyrite and pyrite are the major sulfide minerals, but pyrrhotite, chalcopyrite, sphalerite, galena and scheelite are also present. Gold in native state occurs within quartz, silicates and arsenopyrite.Notable distinctions in mineral assemblage, texture and in chemical compositions of altered wall rocks compared to the precursor host rock in the study area implies that the metasomatism and wall rock alterations are the results of pervasive infiltration and intense interaction between hydrothermal fluids and the surrounding host rocks over a prolonged period.Sulfides, carbonates, carbonaceous matter, K2O, MgO, CaO, Cr, Ni, Cu, Pb, Zn, As and higher values of gold (0.98–4.72ppm) are added into the altered wall rocks, immediately enveloping the auriferous quartz vein bodies. The chondrite normalized REE pattern of altered wall rocks exhibits enriched LREE (LaN/YbN=av. 9.54), with prominent negative Eu anomaly. The observed variation in geochemical characteristics and mineral assemblages in the alteration zones indicates differential response of the host rock and intensity of alteration depending on the composition of host rocks and hydrothermal fluids.The auriferous hydrothermal fluids were of low salinity (2.0 to 6.6wt.% NaCl), dominated by CO2–H2O (about 30mol% CO2) with moderate densities (0.7 to 1.04g/cm3), and gold deposition occurred over a wide temperature range between 175°C and 325°C. Gold deposition was influenced by fluid mixing, phase separation and redox reactions. Mixing between CO2–H2O fluids and more reduced fluids, which evolved during fluid reaction with adjacent carbonaceous wall rocks, was the key factor causing gold deposition.The formation of the Gadag duplex, deformation, folds and reverse strike slip faults (discontinuities) was caused by the compression associated with subduction related tectonic processes. During the initial period of intrusive magmatism (2,555±6Ma), regional metamorphism occurred in the entire greenstone belt, while during later period, hydrothermal fluids responsible for gold mineralization probably were derived from metamorphic processes as well as from intrusive granites. Such fluids channeled through the thrust in host turbidite sequence carrying dissolved gold, associated metals and sulfur, ultimately were precipitated in a reducing environment in the splays to the thrust in the Gadag duplex at about 2,522±6Ma, resulting in retrograde alteration assemblages.

A novel carbon foam: making carbonaceous “lather” from biomass

Carbon foams have attracted much attention since they were first developed in 1960s. Most of the reported carbon foams are of thick cell walls, which do not make effective use of the carbon skeleton in application. Herein, we present a biomass-derived carbon foam with nano-thickness carbonaceous walls. Different from the conventional oven heating process, the carbon foam was prepared with the assistance of microwave irradiation within only a few minutes. The prepared carbon foam has reticular morphology. The meshes of the network are in the dimensions ranging from about 10–50 μm and connected by thin carbonaceous walls with thickness of about 25 nm. The carbon foam has narrowly distributed slit mesopores around 2–4 nm. Active groups like hydroxyl, carbonyl, and epoxy groups are detected in its structure. It has potential to be applied as electrochemical material or catalyst support.

Direct Numerical Simulation of combustion near a carbonaceous surface in a quiescent flow

In this work, unsteady gasification and oxidation of carbonaceous materials with gas-phase combustion under oxy-combustion conditions is studied. An original analytical solution is derived to validate the numerical species boundary condition for the heterogeneous surface reactions with frozen gas-phase. Direct Numerical Simulations accounting for multi-species diffusion and detailed chemistry with both species and energy boundary conditions taking into account the Stefan flux were subsequently performed to study combustion near a carbonaceous wall. Transition from gasification to solid carbon oxidation and gas-phase ignition is evidenced. The competition between homogeneous and heterogeneous reactions is discussed based on the analysis of the time-dependent surface and gas-phase species consumption and production rates. Transient histories of surface species as well as spatial profiles of gas-phase species, heat release and temperature are presented for two identified structures of gas-phase CO/O2 reaction zone. In order to quantify the error induced by the Hirschfelder &Curtiss approximation for the multi-species diffusion and to evaluate the importance of the Dufour and Soret terms, a library dedicated to the computation of complex diffusion phenomena has been used to rebuild a priori, species and Soret fluxes for mass diffusion as well as Fourier, species and Dufour diffusion heat fluxes. Eventually, characteristic times of gas and surface reactions and those corresponding to the switch between the two structures of the gas-phase reaction zone are obtained over a wide range of initial O2/CO2 concentrations.

Cyclo-meta-phenylene revisited: nickel-mediated synthesis, molecular structures, and device applications.

From a one-pot nickel-mediated Yamamoto-type coupling reaction of m-dibromobenzene, five congeners of [n]cyclo-meta-phenylenes were synthesized and fully characterized. The [n]cyclo-meta-phenylenes possessed a commonly shared arylene unit and intermolecular contacts but varied in packing structures in the crystalline solid state. Columnar assembly of larger congeners yielded nanoporous crystals with carbonaceous walls to capture minor protic or aliphatic solvent molecules. The concise and scalable synthesis allowed exploration of the macrocyclic hydrocarbons as bipolar charge carrier transport materials in organic light-emitting diode devices.

Two taxonomic novelties in the Sordariomycetidae: Ceratolenta caudata gen. et sp. nov. and Platytrachelon abietis gen. et comb. nov. for Ceratosphaeria abietis

Wood-inhabiting taxa of the Sordariomycetidae comprise several distantly related monotypic or small genera, which lack familial or ordinal affiliation and share a simple and inconspicuous morphology of dark ascomata with carbonaceous walls and long necks, stipitate asci and hyaline ellipsoidal, fusiform to cylindrical ascospores. Recent collections of an undescribed fungus and of Ceratosphaeria abietis reveal two additional evolutionary lineages characterized by this simple and indistinct teleomorph morphology. Phylogenetic analysis of three genes, small and large subunit nuclear ribosomal DNA (nc28S and nc18S rDNA) combined with the second largest subunit of RNA polymerase II (rpb2), supports the recognition of two new genera, Ceratolenta and Platytrachelon for C. abietis. Platytrachelon abietis is redescribed and illustrated based on additional collections. In culture it produced a dematiaceous hyphomycetous anamorph with blastic conidiogenesis and ellipsoidal, septate, pale brown conidia. It was associated with a synanamorph producing cylindrical, strongly curved hyaline conidia. Molecular data suggest a relationship of Platytrachelon with the Papulosaceae, while Ceratolenta forms a monophylum on a separate branch. Both taxonomic novelties possess striking morphological similarities with Ceratosphaeria, Lentomitella and Rhodoveronaea, which recently were reinstated based on DNA sequence data. A key to morphologically similar wood-inhabiting fungi classified in the Sordariomycetidae is provided.

Taphonomy of very ancient microfossils from the ∼3400 Ma Strelley Pool Formation and ∼1900 Ma Gunflint Formation: New insights using a focused ion beam

Focused ion beam (FIB) milling permits the accurate extraction of ultrathin (c. 100nm) cross sectional lamellae from microfossils found in geological thin sections. Subsequent TEM analysis of these lamellae can provide unique insights into the ultrastructure, chemistry and taphonomy of Precambrian microfossils at the micrometer to nanometer scale. Combining serial FIB milling with SEM imaging extends this capability to three dimensional (3D) tomographic reconstruction and visualization of Precambrian microfossils, revealing information not available in light microscopy.Here we apply these techniques to two iconic silicified microfossil assemblages, from the ∼3400Ma Strelley Pool Formation of Western Australia and the ∼1900Ma Gunflint Formation of Canada. All the examined microfossils have carbonaceous walls surrounded by pure silica. Impregnation of microfossil walls by nano-grains of silica is common, together with variable degrees of wall displacement and replacement by silica. All microfossils are rigidly preserved in 3D and show little or no folding or compression. However, there are also notable differences in taphonomic preservation. Our examples of the spheroidal Gunflint microfossil Huroniospora showed the highest fidelity of preservation with a continuous carbonaceous wall fossilized by spheroidal nano-silica grains that resemble those found on bacterial surfaces in modern silicifying hot-spring environments. The nucleation of these silica nano-spheres on the microfossil walls has induced an artificial ‘saw-tooth-like’ ridged wall texture that may subsequently hinder species-level identification. The Strelley Pool microfossils in comparison show a lower fidelity of preservation with small parts of the microfossil walls completely replaced by silica, plus extensive recrystallization of spheroidal silica nano-grains to angular micro-quartz. Our examples of the sheath-like filamentous Gunflint microfossil Siphonophycus showed the lowest fidelity of preservation with many gaps in the carbonaceous walls and significant redistribution of carbon by recrystallizing silica grains. A model is presented to explain these observations.Criteria for distinguishing highly probable microfossils from non-cellular carbonaceous microstructures (e.g., botryoids and grain coatings) using FIB-based imaging are put forward for the first time here, using examples drawn from the Strelley Pool Formation and comparisons with younger Gunflint material.The combined in situ techniques of FIB–TEM and FIB–SEM nano-tomography potentially provide a wealth of new nano-scale information regarding the biogenicity, antiquity and taphonomy of Precambrian microfossils. However, the destructive nature of both techniques makes their application to unique palaeontological specimens problematical.

Dust in fusion devices—a multi-faceted problem connecting high- and low-temperature plasma physics

Small particles with sizes between a few nanometers and a few 10 µm (dust) are formed in fusion devices by plasma–surface interaction processes. Though it is not a major problem today, dust is considered a problem that could arise in future long pulse fusion devices. This is primarily due to its radioactivity and due to its very high chemical reactivity. Dust formation is particularly pronounced when carbonaceous wall materials are used. Dust particles can be transported in the tokamak over significant distances. Radioactivity leads to electrical charging of dust and to its interaction with plasmas and electric fields. This may cause interference with the discharge but may also result in options for particle removal. This paper discusses some of the multi-faceted problems using information both from fusion research and from low-temperature dusty plasma work.

Contents of fixed-ammonium (NH4 +) in lamprophyres in the Zhenyuan gold orefield, Yunnan Province, China: Implications for its characteristics of the source region

This paper determined the fixed-ammonium (NH4 +) contents of lamprophyres in the Zhenyuan gold orefield, Yunnan Province, China. The results show that the NH4 + contents of minettes in the orefield range from 120 × 10−6 to 469 × 10−6 and those of kersantites from 74.3 × 10−6 to 136 × 10−6. These values are higher than those of other mantle-derived rocks (less than 50 × 10−6), but lower than those of carbonaceous wall rocks in the orefield (from 1200 × 10−6 to 1343 × 10−6). Combining with the Sr isotopic composition, this paper suggested that lamprophyres in the orefield with high NH4 + contents relative to other mantle-derived rocks would not have resulted from the primary magma contaminated by crustal materials in the process of rising or in the magma chamber, but from mantel metasomatism.