Large eddy simulation of thermally induced oscillations in the convective boundary layer

Mesoscale circulations induced by differential boundary layer heating due to surface inhomogeneities on scales of 5 km and more can significantly change the average properties and the structure of the convective boundary layer (CBL) as well as trigger off temporal oscillations. The results of one of the first numerical case studies using large eddy simulation (LES) on the mesoscale suggest that mesoscale circulations exhibit a considerably larger average kinetic energy than convection under homogeneous conditions. This affects turbulent transport processes and should be accounted for in larger-scale models even if their turbulence parameterizations rely on homogeneous control runs of high-resolution models. This case study uses the Hannover parallelized large eddy simulation model (PALM) with prescribed 1D sinusoidal surface heat flux variations on wavelengths from 2.5 to 40 km. The resulting mesoscale circulations are analyzed by means of domain-averaged cross sections, time averaged and normalized with the boundary layer height, as well as power spectra and domain-averaged time series. The simulated mesoscale circulations were periodic. Vertical profiles and time series demonstrate that the onset of the mesoscale circulation triggers off a temporal boundary layer oscillation, whose period and amplitude depend on the surface heat flux perturbation wavelength and amplitude and on the background wind component perpendicular to the surface inhomogeneity orientation. Spectral analysis shows that the mesoscale circulations damp convection equally in all directions. A hypothesis of the oscillation mechanism is briefly discussed. Copyright 2003 American Meteorological Societ

Ultra-high–strength Bainitic Steels

Novel bainitic microstructures, consisting of slender ferrite plates (tens of nm) in a matrix of retained austenite, have reported maximum yield strength of 1.4 GPa, ultimate tensile strength of 2.2 GPa, 30% ductility and respectable levels of fracture toughness (∼51 MPa m0.5). The unusual combination of properties is attributed to the fine bainitic plates and the presence of retained austenite in the microstructure.The authors acknowledge financial support from the Spanish Ministerio de Educación y Ciencia for the financial support in the form of Ramón y Cajal contracts (RyC 2002 and 2004 respectively). Some of this work was carried out under the auspices of an EPSRC/MOD sponsored project on bainitic steels at the University of Cambridge; we are extremely grateful for this support over a period of three years. The authors are extremely grateful to Prof. H. K. D.Peer reviewe

Function-related replacement of bacterial siderophore pathways

© The Author(s) 2018. Bacterial genomes are rife with orphan biosynthetic gene clusters (BGCs) associated with secondary metabolism of unrealized natural product molecules. Often up to a tenth of the genome is predicted to code for the biosynthesis of diverse metabolites with mostly unknown structures and functions. This phenomenal diversity of BGCs coupled with their high rates of horizontal transfer raise questions about whether they are really active and beneficial, whether they are neutral and confer no advantage, or whether they are carried in genomes because they are parasitic or addictive. We previously reported that Salinispora bacteria broadly use the desferrioxamine family of siderophores for iron acquisition. Herein we describe a new and unrelated group of peptidic siderophores called salinichelins from a restricted number of Salinispora strains in which the desferrioxamine biosynthesis genes have been lost. We have reconstructed the evolutionary history of these two different siderophore families and show that the acquisition and retention of the new salinichelin siderophores co-occurs with the loss of the more ancient desferrioxamine pathway. This identical event occurred at least three times independently during the evolution of the genus. We surmise that certain BGCs may be extraneous because of their functional redundancy and demonstrate that the relative evolutionary pace of natural pathway replacement shows high selective pressure against retention of functionally superfluous gene clusters

What is the Role of Acid-Acid Interactions in Asymmetric Phosphoric Acid Organocatalysis? A Detailed Mechanistic Study using Interlocked and Non-Interlocked Catalysts

Organocatalysis has revolutionized asymmetric synthesis. However, the supramolecular interactions of organocatalysts in solution are often neglected, although the formation of catalyst aggregates can have a strong impact on the catalytic reaction. For phosphoric acid based organocatalysts, we have now established that catalyst-catalyst interactions can be suppressed by using macrocyclic catalysts, which react predominantly in a monomeric fashion, while they can be favored by integration into a bifunctional catenane, which react mainly as phosphoric acid dimers. For acyclic phosphoric acids, we found a strongly concentration dependent behavior, involving both monomeric and dimeric catalytic pathways. Based on a detailed experimental analysis, DFT-calculations and a direct NMR-based observation of the catalyst aggregates, we could demonstrate that intermolecular acid-acid interactions have a drastic influence on the reaction rate and stereoselectivity of the asymmetric transfer-hydrogenation catalyzed by chiral phosphoric acids

Analysis of large oxygenated and nitrated polycyclic aromatic hydrocarbons formed under simulated diesel engine exhaust conditions (by compound fingerprints with SPE/LC-API-MS)

The analysis of organic compounds in combustion exhaust particles and the chemical transformation of soot by nitrogen oxides are key aspects of assessment and mitigation of the climate and health effects of aerosol emissions from fossil fuel combustion and biomass burning. In this study we present experimental and analytical techniques for efficient investigation of oxygenated and nitrated derivatives of large polycyclic aromatic hydrocarbons (PAHs), which can be regarded as well-defined soot model substances. For coronene and hexabenzocoronene exposed to nitrogen dioxide under simulated diesel exhaust conditions, several reaction products with high molecular mass could be characterized by liquid chromatography-atmospheric pressure chemical (and photo) ionization-mass spectrometry (LC-APCI-MS and LC-APPI-MS). The main products of coronene contained odd numbers of nitrogen atoms (m/z 282, 256, 338), whereas one of the main products of hexabenzocoronene exhibited an even number of nitrogen atoms (m/z 391). Various reaction products containing carbonyl and nitro groups could be tentatively identified by combining chromatographic and mass spectrometric information, and changes of their relative abundance were observed to depend on the reaction conditions. This analytical strategy should highlight a relatively young technique for the characterization of various soot-contained, semi-volatile, and semi-polar reaction products of large PAHs

The Treatment of Uncertainties in Reactive Pollution Dispersion Models at Urban Scales

The ability to predict NO2 concentrations ([NO¬2]) within urban street networks is important for the evaluation of strategies to reduce exposure to NO2. However, models aiming to make such predictions involve the coupling of several complex processes: traffic emissions under different levels of congestion; dispersion via turbulent mixing; chemical processes of relevance at the street-scale. Parameterisations of these processes are challenging to quantify with precision. Predictions are therefore subject to uncertainties which should be taken into account when using models within decision making. This paper presents an analysis of mean [NO¬2] predictions from such a complex modelling system applied to a street canyon within the city of York, UK including the treatment of model uncertainties and their causes. The model system consists of a micro-scale traffic simulation and emissions model, a Reynolds Averaged turbulent flow model coupled to a reactive Lagrangian particle dispersion model. The analysis focuses on the sensitivity of predicted in-street increments of [NO¬2] at different locations in the street to uncertainties in the model inputs. These include physical characteristics such as background wind direction, temperature and background ozone concentrations; traffic parameters such as overall demand and primary NO2 fraction; as well as model parameterisations such as roughness lengths, turbulent time- and length-scales and chemical reaction rate coefficients. Predicted [NO¬2] is shown to be relatively robust with respect to model parameterisations, although there are significant sensitivities to the activation energy for the reaction NO+O3 as well as the canyon wall roughness length. Under off-peak traffic conditions, demand is the key traffic parameter. Under peak conditions where the network saturates, road-side [NO¬2] is relatively insensitive to changes in demand and more sensitive to the primary NO2 fraction. The most important physical parameter was found to be the background wind direction. The study highlights the key parameters required for reliable [NO¬2] estimations suggesting that accurate reference measurements for wind direction should be a critical part of air quality assessments for in-street locations. It also highlights the importance of street scale chemical processes in forming road-side [NO¬2], particularly for regions of high NOx emissions such as close to traffic queues

Factors associated with self-assessed increase in tobacco consumption among over-indebted individuals in Germany: a cross-sectional study

Background Over-indebtedness is an increasing phenomenon in industrialised nations causing individual hardship and societal problems. Nonetheless, few studies have explored smoking among over-indebted individuals. Methods A cross-sectional survey (n=949) on retrospectively assessed changes in tobacco consumption was carried out in 2006 and 2007 among clients of 84 officially approved debt and insolvency counselling centres in Germany (response rate 39.7%). Logistic regressions were performed to explore factors associated with reports of increased smoking after onset of over-indebtedness. Results 63% of all respondents stated daily or occasional tobacco consumption. Almost one fifth reported an increase in smoking after becoming over-indebted. Females were less likely to report increased smoking than men (aOR 0.66, 95% CI 0.44-0.99) whereas respondents who had been over-indebted for more than 10 years were more likely to report increased smoking than those who had been over-indebted for less than five years (aOR 1.66; 95%-CI 1.00-2.76). The odds of increased smoking were also elevated among those who reported that their families and friends had withdrawn from them as a consequence of their over-indebtedness (aOR 1.82; 95%-CI 1.06-3.14). Conclusions The study identifies over-indebted individuals and particularly over-indebted men as a high-risk group of smokers. Low levels of social embeddedness/support were associated with a further increase in smoking after becoming over-indebted. Given recent increases of over-indebtedness, the findings highlight the need to develop appropriate public health policies

Large-Eddy Simulation of Flow and Pollutant Transport in Urban Street Canyons with Ground Heating

Our study employed large-eddy simulation (LES) based on a one-equation subgrid-scale model to investigate the flow field and pollutant dispersion characteristics inside urban street canyons. Unstable thermal stratification was produced by heating the ground of the street canyon. Using the Boussinesq approximation, thermal buoyancy forces were taken into account in both the Navier–Stokes equations and the transport equation for subgrid-scale turbulent kinetic energy (TKE). The LESs were validated against experimental data obtained in wind-tunnel studies before the model was applied to study the detailed turbulence, temperature, and pollutant dispersion characteristics in the street canyon of aspect ratio 1. The effects of different Richardson numbers (Ri) were investigated. The ground heating significantly enhanced mean flow, turbulence, and pollutant flux inside the street canyon, but weakened the shear at the roof level. The mean flow was observed to be no longer isolated from the free stream and fresh air could be entrained into the street canyon at the roof-level leeward corner. Weighed against higher temperature, the ground heating facilitated pollutant removal from the street canyon.Singapore-MIT Alliance for Research and Technology. Center for Environmental Sensing and Monitorin