Circuit Theory

Contains reports on three research projects

Stresses in isostatic granular systems and emergence of force chains

Progress is reported on several questions that bedevil understanding of granular systems: (i) are the stress equations elliptic, parabolic or hyperbolic? (ii) how can the often-observed force chains be predicted from a first-principles continuous theory? (iii) How to relate insight from isostatic systems to general packings? Explicit equations are derived for the stress components in two dimensions including the dependence on the local structure. The equations are shown to be hyperbolic and their general solutions, as well as the Green function, are found. It is shown that the solutions give rise to force chains and the explicit dependence of the force chains trajectories and magnitudes on the local geometry is predicted. Direct experimental tests of the predictions are proposed. Finally, a framework is proposed to relate the analysis to non-isostatic and more realistic granular assemblies.Comment: 4 pages, 2 figures, Corrected typos and clkearer text, submitted to Phys. Rev. Let

Duties of the junior accountant

We hope to set forth herein the drudgery, and sometimes the pettiness, that is inseparable from accounting, so that those contemplating taking up the work may do so with open eyes.https://egrove.olemiss.edu/aicpa_guides/1199/thumbnail.jp

Mechanistic Modeling of Microtopographic Impacts on CO2 and CH4 Fluxes in an Alaskan Tundra Ecosystem Using the CLM-Microbe Model

Spatial heterogeneities in soil hydrology have been confirmed as a key control on CO2 and CH4 fluxes in the Arctic tundra ecosystem. In this study, we applied a mechanistic ecosystem model, CLM-Microbe, to examine the microtopographic impacts on CO2 and CH4 fluxes across seven landscape types in Utqiaġvik, Alaska: trough, low-centered polygon (LCP) center, LCP transition, LCP rim, high-centered polygon (HCP) center, HCP transition, and HCP rim. We first validated the CLM-Microbe model against static-chamber measured CO2 and CH4 fluxes in 2013 for three landscape types: trough, LCP center, and LCP rim. Model application showed that low-elevation and thus wetter landscape types (i.e., trough, transitions, and LCP center) had larger CH4 emissions rates with greater seasonal variations than high-elevation and drier landscape types (rims and HCP center). Sensitivity analysis indicated that substrate availability for methanogenesis (acetate, CO2 + H2) is the most important factor determining CH4 emission, and vegetation physiological properties largely affect the net ecosystem carbon exchange and ecosystem respiration in Arctic tundra ecosystems. Modeled CH4 emissions for different microtopographic features were upscaled to the eddy covariance (EC) domain with an area-weighted approach before validation against EC-measured CH4 fluxes. The model underestimated the EC-measured CH4 flux by 20% and 25% at daily and hourly time steps, suggesting the importance of the time step in reporting CH4 flux. The strong microtopographic impacts on CO2 and CH4 fluxes call for a model-data integration framework for better understanding and predicting carbon flux in the highly heterogeneous Arctic landscape

Inelastic neutron scattering studies of methyl chloride synthesis over alumina

Not only is alumina the most widely used catalyst support material in the world, it is also an important catalyst in its own right. One major chemical process that uses alumina in this respect is the industrial production of methyl chloride. This is a large scale process (650 000 metric tons in 2010 in the United States), and a key feedstock in the production of silicones that are widely used as household sealants. In this Account, we show how, in partnership with conventional spectroscopic and reaction testing methods, inelastic neutron scattering (INS) spectroscopy can provide additional insight into the active sites present on the catalyst, as well as the intermediates present on the catalyst surface.<p></p> INS spectroscopy is a form of vibrational spectroscopy, where the spectral features are dominated by modes involving hydrogen. Because of this, most materials including alumina are largely transparent to neutrons. Advantageously, in this technique, the entire “mid-infrared”, 0–4000 cm<sup>–1</sup>, range is accessible; there is no cut-off at 1400 cm<sup>–1</sup> as in infrared spectroscopy. It is also straightforward to distinguish fundamental modes from overtones and combinations. <p></p> A key parameter in the catalyst’s activity is the surface acidity. In infrared spectroscopy of adsorbed pyridine, the shifts in the ring stretching modes are dependent on the strength of the acid site. However, there is a very limited spectral range available. We discuss how we can observe the low energy ring deformation modes of adsorbed pyridine by INS spectroscopy. These modes can undergo shifts that are as large as those seen with infrared inspectroscopy, potentially enabling finer discrimination between acid sites. <p></p> Surface hydroxyls play a key role in alumina catalysis, but in infrared spectroscopy, the presence of electrical anharmonicity complicates the interpretation of the O–H stretch region. In addition, the deformations lie below the infrared cut-off. Both of these limitations are irrelevant to INS spectroscopy, and all the modes are readily observable. When we add HCl to the catalyst surface, the acid causes changes in the spectra. We can then deduce both that the surface chlorination leads to enhanced Lewis acidity and that the hydroxyl group must be threefold coordinated. <p></p> When we react η-alumina with methanol, the catalyst forms a chemisorbed methoxy species. Infrared spectroscopy clearly shows its presence but also indicates the possible coexistence of a second species. Because of INS spectroscopy’s ability to discriminate between fundamental modes and combinations, we were able to unambiguously show that there is a single intermediate present on the surface of the active catalyst. This work represents a clear example where an understanding of the chemistry at the molecular level can help rationalize improvements in a large scale industrial process with both financial and environmental benefits. <p></p&gt

The heterogeneous OH oxidation of palmitic acid in single component and internally mixed aerosol particles: vaporization, secondary chemistry, and the role of particle phase

International audienceWe studied the OH oxidation of submicron aerosol particles consisting of pure palmitic acid (PA) or thin (near monolayer) coatings of PA on aqueous and effloresced inorganic salt particles. Experiments were performed as a function of particle size and OH exposure using a continuous-flow photochemical reaction chamber coupled to a chemical ionization mass spectrometer (CIMS) system, for detection of gas and particle-bound organics, and a DMA/CPC for monitoring particle size distributions. The loss rate of PA observed for pure PA aerosols and PA on crystalline NaCl aerosols indicates that the OH oxidation of PA at the gas-aerosol interface is efficient. The pure PA oxidation data are well represented by a model consisting of four main processes: 1) surface-only reactions between OH and palmitic acid, 2) secondary reactions between palmitic acid and OH oxidation products, 3) volatilization of condensed-phase mass, and 4) a surface renewal process. Using this model we infer a value of ?OH between 0.8 and 1. The oxidation of palmitic acid in thin film coatings of salt particles is also efficient, though the inferred ?OH is lower, ranging from ~0.3 (+0.1/?0.05) for coatings on solid NaCl and ~0.05 (±0.01) on aqueous NaCl particles. These results, together with simultaneous data on particle size change and volatilized oxidation products, provide support for the ideas that oxidative aging of aliphatic organic aerosol is a source of small oxidized volatile organic compounds (OVOCs), and that OH oxidation may initiate secondary condensed-phase reactions

Assessing the impact of interfering organic matter on soil metaproteomic workflow

Funding: Matthias Waibel was funded by the University of Galway College of Science and the Irish Research Council under GOIPG/2016/1215. The James Hutton Institute receives funding support from the Rural and Environment Science and Analytical Services Division of the Scottish Government. Open access funding provided by IReL.Soil organic matter (SOM) is biologically, chemically, and physically complex. As a major store of nutrients within soil, it plays an important role in nutrient provision to plants. An enhanced understanding of SOM utilisation processes could underpin better fertiliser management for plant growth, with reduced environmental losses. Metaproteomics can allow the characterisation of protein profiles and could help gaining insights into SOM microbial decomposition mechanisms. Here, we applied three different extraction methods to two soil types to recover SOM with different characteristics. Specifically, water extractable organic matter, mineral associated organic matter and protein-bound organic matter were targeted with the aim to investigate the metaproteome enriched in those extractions. As a proof-of-concept replicated extracts from one soil were further analysed for peptide identification using liquid chromatography followed by tandem mass spectrometry. We employ a framework for mining mass spectra for both peptide assignment and fragmentation pattern characterisation. Different extracts were found to exhibit contrasting total protein and humic substance content for the two soils investigated. Overall, water extracts displayed the lowest humic substance content (in both soils) and the highest number of peptide identifications (in the soil investigated) with most frequent peptide hits associated with diverse substrate/ligand binding proteins of Proteobacteria and derived taxa. Our framework also highlighted a strong peptidic signal in unassigned and unmatched spectra, information that is currently not captured by the pipelines employed in this study. Taken together, this work points to specific areas for optimisation in chromatography and mass spectrometry to adequately characterise SOM associated metaproteomes.Publisher PDFPeer reviewe