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The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical
Cycloheptatrienyl (tropyl) radical, C{sub 7}H{sub 7}, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C{sub 7}H{sub 7} were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C{sub 7}H{sub 7} are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize to benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C{sub 7}H{sub 7}) radicals but rather only benzyl (C{sub 6}H{sub 5}CH{sub 2}). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C{sub 6}H{sub 5}CH{sub 2}, C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2}. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2}) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).
Computations of permeability of large rock images by dual grid domain decomposition
Not Available
Traits drive global wood decomposition rates more than climate
Wood decomposition is a major component of the global carbon cycle. Decomposition rates vary across climate gradients, which is thought to reflect the effects of temperature and moisture on the metabolic kinetics of decomposers. However, decomposition rates also vary with wood traits, which may reflect the influence of stoichiometry on decomposer metabolism as well as geometry relating the surface areas that decomposers colonize with the volumes they consume. In this paper, we combined metabolic and geometric scaling theories to formalize hypotheses regarding the drivers of wood decomposition rates, and assessed these hypotheses using a global compilation of data on climate, wood traits, and wood decomposition rates. Our results are consistent with predictions from both metabolic and geometric scaling theories. Approximately half of the global variation in decomposition rates was explained by wood traits (nitrogen content and diameter), whereas only a fifth was explained by climate variables (air temperature, precipitation, and relative humidity). These results indicate that global variation in wood decomposition rates is best explained by stoichiometric and geometric wood traits. Our findings suggest that inclusion of wood traits in global carbon cycle models can improve predictions of carbon fluxes from wood decomposition.
Microbe-iron interactions control lignin decomposition in soil
Lignin decomposition is critically linked to terrestrial carbon (C) cycle due to the enormous C mass of lignin and its importance in controlling overall rates of litter decomposition. Interactions between lignin and iron (Fe) minerals have been increasingly recognized as key mediators of lignin decomposition in experimental studies. However, we still lack a quantitative understanding of how Fe minerals interact with microbes to control lignin decomposition. Here, we leveraged experimental results from an incubation of Fe-rich soil, in which lignin decomposition rates were measured at aerobic conditions after four levels of pre-treated O2 availability, to examine microbe-Fe (MiFe) interactions in lignin decomposition with a MiFe model. We quantified how Fe redox cycling interacted with microbial activities to control lignin decomposition via data-model integration. Our results showed that the MiFe model with time-dependent growth and mortality functions better represented CO2 release from lignin decomposition (R2 ranging from 0.96 to 0.97) than models assuming either first-order or Michaelis-Menten kinetics. Reduction of Fe(III) to Fe(II) after pre-treatments with lower O2 availability stimu-lated the Fenton reaction to break down macro-molecular lignin into small molecules available to microbes. The small molecules of lignin and necromass bounded with oxidized Fe and were protected from decomposition. After 1-year incubation, the model implied that most of C stabilized with Fe minerals was derived from small molecular lignin C. Our quantitative analysis of microbe-Fe interactions sheds new light on lignin decomposition and preservation and helps improve model prediction of soil C persistence under global change.
Arctic shrub expansion generates regional variation in litter decomposition by altering litter quality and the decomposition environment
Abstract The expansion of deciduous shrubs into the graminoid‐dominated arctic tundra is expected to alter litter decomposition by changing litter quality and local abiotic and biotic conditions. However, it remains unclear how shrub expansion will affect litter decomposition at regional scales, where macroclimate is expected to be the dominant regulator of decomposition. To determine the relative influence of macroclimate and local controls on regional patterns of litter mass loss and nitrogen release, we conducted two hierarchical litter decomposition experiments across spatial scales. We decomposed leaf and root litter from a prominent graminoid ( Eriophorum vaginatum ) and three genera of deciduous shrubs ( Betula , Alnus and Salix ) for 1 year within replicated plots at five sites spanning a 160 km latitudinal gradient in northern Alaska. Using Eriophorum litter as a substrate, we found that macroclimate was the primary regulator of mass loss but had opposing effects on leaf and root litter. As summer temperature increased along the latitudinal gradient (11.9 to 13.9°C), leaf litter mass loss increased by 20% whereas root litter mass loss decreased by 33%. Leaf nitrogen release also increased with summer temperature. Conversely, root nitrogen release was controlled by the vegetation type of the decomposition environment. Using different shrub litters as substrates, we found that litter quality and its interaction with soil microclimate and macroclimate controlled decomposition. Overall, shrub root litters decomposed faster than Eriophorum root litter, losing 53% more mass and 190% more nitrogen across all sites and decomposition environments. For leaf litter, however, patterns varied by litter genus, with Salix losing more mass and Betula and Alnus losing less mass than Eriophorum . Our findings demonstrate that shrub expansion in the Arctic can regulate leaf and root litter decomposition at the regional scale through its effects on local controls, primarily litter quality. Ongoing increases in shrub cover are likely to accelerate the turnover of root litter carbon and nitrogen pools in tundra ecosystems. Therefore, including shrub‐related processes in Earth system models will improve our ability to predict regional‐scale litter decomposition and its effects on carbon and nutrient cycling in a warming Arctic. Read the free Plain Language Summary for this article on the Journal blog.
Temperature sensitivity of soil organic carbon decomposition increased with mean carbon residence time: Field incubation and data assimilation
Abstract Temperature sensitivity of soil organic carbon ( SOC ) decomposition is one of the major uncertainties in predicting climate‐carbon (C) cycle feedback. Results from previous studies are highly contradictory with old soil C decomposition being more, similarly, or less sensitive to temperature than decomposition of young fractions. The contradictory results are partly from difficulties in distinguishing old from young SOC and their changes over time in the experiments with or without isotopic techniques. In this study, we have conducted a long‐term field incubation experiment with deep soil collars (0–70 cm in depth, 10 cm in diameter of PVC tubes) for excluding root C input to examine apparent temperature sensitivity of SOC decomposition under ambient and warming treatments from 2002 to 2008. The data from the experiment were infused into a multi‐pool soil C model to estimate intrinsic temperature sensitivity of SOC decomposition and C residence times of three SOC fractions (i.e., active, slow, and passive) using a data assimilation ( DA ) technique. As active SOC with the short C residence time was progressively depleted in the deep soil collars under both ambient and warming treatments, the residences times of the whole SOC became longer over time. Concomitantly, the estimated apparent and intrinsic temperature sensitivity of SOC decomposition also became gradually higher over time as more than 50% of active SOC was depleted. Thus, the temperature sensitivity of soil C decomposition in deep soil collars was positively correlated with the mean C residence times. However, the regression slope of the temperature sensitivity against the residence time was lower under the warming treatment than under ambient temperature, indicating that other processes also regulated temperature sensitivity of SOC decomposition. These results indicate that old SOC decomposition is more sensitive to temperature than young components, making the old C more vulnerable to future warmer climate.
Effect of aging temperature on phase decomposition and mechanical properties in cast duplex stainless steels
The microstructure and mechanical properties in unaged and thermally aged (at 280 oC, 320 oC, 360 oC, and 400 oC to 4300 h) CF–3 and CF–8 cast duplex stainless steels (CDSS) are investigated. The unaged CF–8 steel has Cr-rich M23C6 carbides located at the δ–ferrite/γ– austenite heterophase interfaces that were not observed in the CF–3 steel and this corresponds to a difference in mechanical properties. Both unaged steels exhibit incipient spinodal decomposition into Fe-rich α–domains and Cr-rich α’–domains. During aging, spinodal decomposition progresses and the mean wavelength (MW) and mean amplitude (MA) of the compositional fluctuations increase as a function of aging temperature. Additionally, G–phase precipitates form between the spinodal decomposition domains in CF–3 at 360 oC and 400 oC and in CF–8 at 400 oC. The microstructural evolution is correlated to changes in mechanical properties.
Elevated temperature alters microbial communities, but not decomposition rates, during 3 years of in situ peat decomposition
ABSTRACT Peatlands are large carbon sinks with primary production outpacing decomposition of organic matter. Results from the S pruce and P eatland R esponses U nder C hanging E nvironments (SPRUCE) study show net losses of organic matter and increased greenhouse gas production from peatlands in response to whole-ecosystem warming. Here, we investigated how warming and elevated CO 2 impact peat microbial communities and peat soil decomposition rates and characterized microbial communities through amplicon sequencing and compositional changes across four depth increments. Microbial diversity and community composition were significantly impacted by soil depth, temperature, and CO 2 treatment. Bacterial/archaeal α-diversity increased significantly with increasing temperature, and fungal α-diversity was lower under elevated CO 2 treatments. Trans domain microbial networks showed higher complexity of microbial communities in decomposition ladder depths from the warmed enclosures, and the number of highly connected hub taxa within the networks was positively correlated with temperature. Methanogenic hubs were identified in the networks constructed from the warmest enclosures, indicating increased importance of methanogenesis in response to warming. Microbial community responses were not however reflected in measures of peat soil decomposition, as warming and elevated CO 2 had no significant short-term effects on soil mass loss or composition. Regardless of treatment, on average only 4.5% of the original soil mass was lost after 3 years and variation between replicates was high, potentially masking treatment effects. Previous results at the SPRUCE experiment have shown warming is accelerating organic-matter decomposition and CO 2 and CH 4 production, and our results suggest these changes may be driven by warming-induced shifts in microbial communities. IMPORTANCE Microbial community changes in response to climate change drivers have the potential to alter the trajectory of important ecosystem functions. In this paper, we show that while microbial communities in peatland systems responded to manipulations of temperature and CO 2 concentrations, these changes were not associated with similar responses in peat decomposition rates over 3 years. It is unclear however from our current studies whether this functional resiliency over 3 years will continue over the longer time scales relevant to peatland ecosystem functions.
IS Process Hydrogen Production Test for Components and System Made of Industrial Structural Material (II) - H{sub 2}SO{sub 4} decomposition, HI Distillation, and HI Decomposition Section - 18629
Japan Atomic Energy Agency (JAEA) has been conducting research and development on the thermochemical iodine sulfur (IS) process for nuclear-powered hydrogen production. The IS process is one of the promising candidates of heat application of High-Temperature Gas-Cooled Reactors. The IS process consists of three chemical reactions: Bunsen reaction, hydriodic acid (HI) decomposition and sulfuric acid (H{sub 2}SO{sub 4}) decomposition. It is necessary for component materials to have high corrosion resistance because high-temperature strong acids such as HI and H{sub 2}SO{sub 4} are used in the IS process. JAEA, so far, achieved to produce hydrogen for one week continuously with a hydrogen production rate of approximately 30 NL/h by a test apparatus made of glass and fluoro-resin material. As a next step toward practical application, we test-fabricated main components, that is, Bunsen reactor, sulfuric acid decomposer, and HI decomposer, made of industrial materials and investigated their integrity in the practical corrosive environments of the IS process. Based on their results, we have constructed a 100 NL/h-H{sub 2}-scale test apparatus made of industrial materials. This test apparatus is divided by chemical reaction and unit operation into five sections: Bunsen section, H{sub 2}SO{sub 4} decomposition section, HI concentration section, HI distillation section, and HI decomposition section. First, we investigated performance of components in each section. This report discusses test results of the H{sub 2}SO{sub 4} decomposition section, HI distillation section, and HI decomposition section. (authors)
A Conformal Decomposition Finite Element Method for Dynamic Wetting Applications.
Abstract not provided.
In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks
Zr-based metal organic frameworks (MOFs) have been recently shown to be among the fastest catalysts of nerve-agent hydrolysis in solution. We report a detailed study of the adsorption and decomposition of a nerve-agent simulant, dimethyl methylphosphonate (DMMP), on UiO-66, UiO-67, MOF-808, and NU-1000 using synchrotron-based X-ray powder diffraction, X-ray absorption, and infrared spectroscopy, which reveals key aspects of the reaction mechanism. The diffraction measurements indicate that all four MOFs adsorb DMMP (introduced at atmospheric pressures through a flow of helium or air) within the pore space. In addition, the combination of X-ray absorption and infrared spectra suggests direct coordination of DMMP to the Zr6 cores of all MOFs, which ultimately leads to decomposition to phosphonate products. These experimental probes into the mechanism of adsorption and decomposition of chemical warfare agent simulants on Zr-based MOFs open new opportunities in rational design of new and superior decontamination materials.
Embedding spatial decomposition in parareal in time power system simulation
We propose an approach for combining two decompositions in power system simulation, temporal and spatial, with a goal to achieve faster simulation time than utilizing either one of them alone. The proposed approach builds upon the structure of the Parareal algorithm for temporal decomposition and explores an efficient way of embedding the spatial decomposition into its coarse and fine solutions. This introduces two types of simultaneous parallelism in power system simulations - parallelism between system areas and between coarse integration intervals for time integration. The results from the application of the proposed approach are shown on a two-area system comprised of the IEEE 16-machine, 68-bus, and the IEEE 50-machine, 145-bus system.
CP decomposition for tensors via alternating least squares with QR decomposition
The CP tensor decomposition is used in applications such as machine learning and signal processing to discover latent low-rank structure in multidimensional data. Computing a CP decomposition via an alternating least squares (ALS) method reduces the problem to several linear least squares problems. The standard way to solve these linear least squares subproblems is to use the normal equations, which inherit special tensor structure that can be exploited for computational efficiency. However, the normal equations are sensitive to numerical ill-conditioning, which can compromise the results of the decomposition. In this paper, we develop versions of the CP-ALS algorithm using the QR decomposition and the singular value decomposition, which are more numerically stable than the normal equations, to solve the linear least squares problems. Our algorithms utilize the tensor structure of the CP-ALS subproblems efficiently, have the same complexity as the standard CP-ALS algorithm when the input is dense and the rank is small, and are shown via examples to produce more stable results when ill-conditioning is present. Our MATLAB implementation achieves the same running time as the standard algorithm for small ranks, and we show that the new methods can obtain lower approximation error.
Design and characterization of a solar-enhanced microwave plasma reactor for atmospheric pressure carbon dioxide decomposition
The decomposition of carbon dioxide (CO 2 ) is a main step in carbon re-utilization approaches aimed to fulfill fuels and chemicals demands and mitigate environmental emissions. Plasmachemical CO 2 decomposition processes can be highly efficient; however, their reliance on electrical energy can limit their economic viability and sustainability advantage. In contrast, solar thermochemical CO 2 decomposition approaches can have limited efficiency, but their direct use of the most abundant form of renewable energy affords them the greatest sustainability potential. Solar-Enhanced Microwave Plasma (SEMP) chemical synthesis, based on the direct interaction between microwave plasma and concentrated solar radiation, is investigated as a novel approach to combine the advantages of plasmachemical and solar thermochemical processes. SEMP is motivated by the potential for synergistic effects between solar photons and plasma species, implied by the markedly greater spectral absorption of nonequilibrium CO 2 plasma compared to that of equilibrium CO 2 , to lead to enhanced chemical decomposition. The design, development, and characterization of a SEMP reactor for atmospheric pressure CO 2 decomposition is presented. The reactor is powered by a 1.25 kW magnetron and by up to 525 W of incident radiative power from a high-flux solar simulator. Experimental results reveal that the microwave plasma absorbs up to 20% of concentrated solar radiation at a solar-to-electrical power ratio of 0.5, and that relative absorption decreases with increasing solar input power. Yet, conversion efficiency and plasma energy efficiency increase with increasing solar power, up to 9% and 25% respectively, for a solar-to-electrical power ratio of 0.75. The enhanced process performance appears to be a consequence of the greater power density in the plasma caused by the direct absorption of solar radiation.
Ethanol Decomposition on Pd–Au Alloy Catalysts
The mechanisms of ethanol (EtOH) decomposition via C–C or C–O bond cleavage on alloy surfaces are currently not well understood. Here, we model EtOH decomposition on close-packed Pd–Au catalytic surfaces using density functional theory (DFT) calculations and derived Brønsted–Evans–Polanyi (BEP) relationships. Three characteristic Pd–Au surfaces are considered, Pd 1 Au 2 (111), Pd 2 Au 1 (111), and a Pd monolayer (ML), Pd ML (111), on a Au substrate. We show that, on close-packed Pd–Au surfaces, the C–C bond is easier to cleave than C–O, indicating that the formation of CH 4 and CO is favored as the products of EtOH decomposition. Interestingly, we find that, though the C–C and C–O activation barriers on Pd ML (111) are generally lower than those on the other two surfaces, it is less active for EtOH decomposition due to a slow release of H 2 and possible carbon coking. Pd 2 Au 1 (111), on the other hand, has a higher theoretical reaction rate due to facile H 2 evolution from the surface and less carbon coking. A comparison of the surface d-band with the activation energy barriers shows that there is a trade-off between the barriers for C–C bond cleavage and H 2 association, with Pd 2 Au 1 (111) having the best performance. Temperature-programmed desorption experiments of EtOH on Pd/Au surfaces show significant C–C bond cleavage and both CH 4 and CO production on surfaces with Pd–Au interface sites. Furthermore, neither Auger electron spectroscopy nor EtOH reflection–adsorption infrared spectroscopy provide evidence of C–O bond cleavage. Finally, the experimental reaction rate for methane production from C–C bond cleavage was higher on surfaces with more Au present due to minimal carbon contamination and the promotion of product desorption. This combined theoretical and experimental study shows that, though Au is catalytically inactive for EtOH decomposition, it can dramatically promote the surface activity for EtOH steam reforming due to the existence of active Pd–Au surface ensemble sites.
Precipitation-site competition in duplex stainless steels: Cu clusters vs spinodal decomposition interfaces as nucleation sites during thermal aging
Competing microstructural evolution mechanisms can exist simultaneously when duplex stainless steels are operating for several decades in a high temperature service environment. Such competition between different microstructural evolution pathways can be difficult to ascertain using simple model alloy systems necessitating detailed structural and compositional analysis of phase transformation mechanisms in complex alloys Thus, in this study duplex stainless steels with complex but well understood chemistries were used to investigate the relative importance of different heterogeneous nucleation sites – specifically spinodal decomposition and Cu clustering – on precipitation of Ni-Si-Mn particles during long term thermal aging. Precipitation of Ni-Si-Mn particles in duplex stainless steels and ferritic steels during thermal aging and irradiation is known to have profound effect on mechanical properties. Using duplex stainless steels with custom modified compositions along with atom probe tomography characterization and first-passage kinetic Monte Carlo (FPKMC) simulations it is revealed that while the interface between Cr and Fe formed during spinodal decomposition can be a pathway for diffusion of Ni, Si, Mn, and Cu, it is not a site that encourages precipitation of Ni-Si-Mn rich particles. Instead, the presence of a higher concentration of Cu in these steels leads to formation of small Cu clusters with high energy interfaces that act as nucleation sites for Ni-Si-Mn particles because of its strong interaction particularly with Ni increasing the chemical driving force for precipitation. These results will help inform predictive models for the use of duplex stainless steels and other precipitation-hardened alloys for extended operation at high temperatures.