Kinetic modeling of Secondary Organic Aerosol formation: effects of particle- and gas-phase reactions of semivolatile products

The distinguishing mechanism of formation of secondary organic aerosol (SOA) is the partitioning of semivolatile hydrocarbon oxidation products between the gas and aerosol phases. While SOA formation is typically described in terms of partitioning only, the rate of formation and ultimate yield of SOA can also depend on the kinetics of both gas- and aerosol-phase processes. We present a general equilibrium/kinetic model of SOA formation that provides a framework for evaluating the extent to which the controlling mechanisms of SOA formation can be inferred from laboratory chamber data. With this model we examine the effect on SOA formation of gas-phase oxidation of first-generation products to either more or less volatile species, of particle-phase reaction (both first- and second-order kinetics), of the rate of parent hydrocarbon oxidation, and of the extent of reaction of the parent hydrocarbon. The effect of pre-existing organic aerosol mass on SOA yield, an issue of direct relevance to the translation of laboratory data to atmospheric applications, is examined. The importance of direct chemical measurements of gas- and particle-phase species is underscored in identifying SOA formation mechanisms

Global modeling of secondary organic aerosol formation from aromatic hydrocarbons: high- vs low-yield pathways

Formation of SOA from the aromatic species toluene, xylene, and, for the first time, benzene, is added to a global chemical transport model. A simple mechanism is presented that accounts for competition between low and high-yield pathways of SOA formation, wherein secondary gas-phase products react further with either nitrogen oxide (NO) or hydroperoxy radical (HO2) to yield semi- or non-volatile products, respectively. Aromatic species yield more SOA when they react with OH in regions where the [NO]/[HO2] ratios are lower. The SOA yield thus depends upon the distribution of aromatic emissions, with biomass burning emissions being in areas with lower [NO]/[HO2] ratios, and the reactivity of the aromatic with respect to OH, as a lower initial reactivity allows transport away from industrial source regions, where [NO]/[HO2] ratios are higher, to more remote regions, where this ratio is lower and, hence, the ultimate yield of SOA is higher. As a result, benzene is estimated to be the most important aromatic species with regards to formation of SOA, with a total production nearly equal that of toluene and xylene combined. In total, while only 39% percent of the aromatic species react via the low-NOx pathway, 72% of the aromatic SOA is formed via this mechanism. Predicted SOA concentrations from aromatics in the Eastern United States and Eastern Europe are actually largest during the summer, when the [NO]/[HO2] ratio is lower. Global production of SOA from aromatic sources is estimated at 3.5 Tg/yr, resulting in a global burden of 0.08 Tg, twice as large as previous estimates. The contribution of these largely anthropogenic sources to global SOA is still small relative to biogenic sources, which are estimated to comprise 90% of the global SOA burden, about half of which comes from isoprene. Compared to recent observations, it would appear there are additional pathways beyond those accounted for here for production of anthropogenic SOA. However, owing to differences in spatial distributions of sources and seasons of peak production, there are still regions in which aromatic SOA produced via the mechanisms identified here are predicted to contribute substantially to, and even dominate, the local SOA concentrations, such as outflow regions from North America and South East Asia during the wintertime, though total SOA concentrations there are small (~0.1 μg/m^³)

Application-specific design of sports equipment from anisotropic fiber-reinforced plastics with stiffness related coupling effect

AbstractFloating sports equipment such as snowboards experience extreme loads during riding it. A common style in riding a freestyle snowboard is to use a handrail to slide sideways on it. During this maneuver the steel edge of a snowboard could easily hook into the handrail, researches worked out. This will lead to an abrupt interruption in the athletes motion. This problematic aspect is eliminated by using an all new anisotropic layer design (ALD)snowboard which was developed and tested by the Professorship of Lightweight Structures and Polymer Technology (SLK) in cooperation with the Competence Center for Structural Lightweight (SLB e. V.)

Secondary organic aerosol formation from m-xylene, toluene, and benzene

Secondary organic aerosol (SOA) formation from the photooxidation of m-xylene, toluene, and benzene is investigated in the Caltech environmental chambers. Experiments are performed under two limiting NOx conditions; under high-NOx conditions the peroxy radicals (RO2) react only with NO, while under low-NOx conditions they react only with HO2. For all three aromatics studied (m-xylene, toluene, and benzene), the SOA yields (defined as the ratio of the mass of organic aerosol formed to the mass of parent hydrocarbon reacted) under low-NOx conditions substantially exceed those under high-NOx conditions, suggesting the importance of peroxy radical chemistry in SOA formation. Under low-NOx conditions, the SOA yields for m-xylene, toluene, and benzene are constant (36%, 30%, and 37%, respectively), indicating that the SOA formed is effectively nonvolatile under the range of Mo(>10 μg m−3) studied. Under high-NOx conditions, aerosol growth occurs essentially immediately, even when NO concentration is high. The SOA yield curves exhibit behavior similar to that observed by Odum et al. (1996, 1997a, b), although the values are somewhat higher than in the earlier study. The yields measured under high-NOx conditions are higher than previous measurements, suggesting a "rate effect" in SOA formation, in which SOA yields are higher when the oxidation rate is faster. Experiments carried out in the presence of acidic seed aerosol reveal no change of SOA yields from the aromatics as compared with those using neutral seed aerosol

Genome wide expression profiling reveals suppression of host defence responses during colonisation by Neisseria meningitides but not N. lactamica.

Both Neisseria meningitidis and the closely related bacterium Neisseria lactamica colonise human nasopharyngeal mucosal surface, but only N. meningitidis invades the bloodstream to cause potentially life-threatening meningitis and septicaemia. We have hypothesised that the two neisserial species differentially modulate host respiratory epithelial cell gene expression reflecting their disease potential. Confluent monolayers of 16HBE14 human bronchial epithelial cells were exposed to live and/or dead N. meningitidis (including capsule and pili mutants) and N. lactamica, and their transcriptomes were compared using whole genome microarrays. Changes in expression of selected genes were subsequently validated using Q-RT-PCR and ELISAs. Live N. meningitidis and N. lactamica induced genes involved in host energy production processes suggesting that both bacterial species utilise host resources. N. meningitidis infection was associated with down-regulation of host defence genes. N. lactamica, relative to N. meningitidis, initiates up-regulation of proinflammatory genes. Bacterial secreted proteins alone induced some of the changes observed. The results suggest N. meningitidis and N. lactamica differentially regulate host respiratory epithelial cell gene expression through colonisation and/or protein secretion, and that this may contribute to subsequent clinical outcomes associated with these bacteria

Slope Control in Western Boundary Currents

An analytic solution is presented for the steady-state depth-averaged western boundary current flowing over the continental slope by combining three highly idealized models: the Stommel model, the Munk model, and the arrested topographic wave model. The main vorticity balance over the slope is between planetary vorticity advection and the slope-induced bottom stress torque, which is proportional to rv(h-1)x where r is the Rayleigh friction coefficient, h is the water depth, and v is the meridional velocity. This slope-induced torque provides the necessary source of vorticity for poleward flow over the slope, its simple interpretation being that vorticity is produced because the bottom stress has to act over the seaward-deepening water column. The character of the solution depends on the slope α as well as on the assumed bottom drag coefficient, and the length scale of the boundary current is ∼√2r/(βα). It is further shown that, if the depth-averaged velocity flows along isobaths, then the stretching of water columns associated with cross-isobath geostrophic flow, which compensates bottom Ekman transport, is identical to the slope-induced torque by the geostrophic velocities

Secondary aerosol formation from atmospheric reactions of aliphatic amines

Although aliphatic amines have been detected in both urban and rural atmospheric aerosols, little is known about the chemistry leading to particle formation or the potential aerosol yields from reactions of gas-phase amines. We present here the first systematic study of aerosol formation from the atmospheric reactions of amines. Based on laboratory chamber experiments and theoretical calculations, we evaluate aerosol formation from reaction of OH, ozone, and nitric acid with trimethylamine, methylamine, triethylamine, diethylamine, ethylamine, and ethanolamine. Entropies of formation for alkylammonium nitrate salts are estimated by molecular dynamics calculations enabling us to estimate equilibrium constants for the reactions of amines with nitric acid. Though subject to significant uncertainty, the calculated dissociation equilibrium constant for diethylammonium nitrate is found to be sufficiently small to allow for its atmospheric formation, even in the presence of ammonia which competes for available nitric acid. Experimental chamber studies indicate that the dissociation equilibrium constant for triethylammonium nitrate is of the same order of magnitude as that for ammonium nitrate. All amines studied form aerosol when photooxidized in the presence of NOx with the majority of the aerosol mass present at the peak of aerosol growth consisting of aminium (R3NH+) nitrate salts, which repartition back to the gas phase as the parent amine is consumed. Only the two tertiary amines studied, trimethylamine and triethylamine, are found to form significant non-salt organic aerosol when oxidized by OH or ozone; calculated organic mass yields for the experiments conducted are similar for ozonolysis (15% and 5% respectively) and photooxidation (23% and 8% respectively). The non-salt organic aerosol formed appears to be more stable than the nitrate salts and does not quickly repartition back to the gas phase

High-pressure phases and transitions of the layered alkaline earth nitridosilicates SrSiN2 and BaSiN2

We investigate the high-pressure phase diagram of SrSiN2 and BaSiN2 with density-functional calculation. Searching a manifold of possible candidate structures, we propose new structural modifications of SrSiN2 and BaSiN2 attainable in high-pressure experiments. The monoclinic ground state of SrSiN2 transforms at 3 GPa into an orthorhombic BaSiN2 type. At 14 GPa a CaSiN2-type structure becomes the most stable configuration of SrSiN2. A hitherto unknown Pbcm modification is adopted at 85 GPa and, finally, at 131 GPa a LiFeO2-type structure. The higher homologue BaSiN2 transforms to a CaSiN2 type at 41 GPa and further to a Pbcm modification at 105 GPa. Both systems follow the pressure-coordination rule: the coordination environment of Si increases from tetrahedral through trigonal bipyramidal to octahedral. Some high-pressure phases are related in structure through simple group–subgroup mechanisms, indicating displacive phase transformations with low activation barriers

Exclusive Photoproduction of Large Momentum-Transfer K and K* Mesons

The reactions gamma p -> K+ Lambda and gamma p -> K* Lambda are analyzed within perturbative QCD, allowing for diquarks as quasi-elementary constituents of baryons. The diquark-model parameters and the quark-diquark distribution amplitudes of proton and Lambda are taken from previous investigations of electromagnetic baryon form factors and Compton-scattering off protons. Unpolarized differential cross sections and polarization observables are computed for different choices of the K and K* distribution amplitudes. The asymptotic form of the K distribution amplitude (proportional to x1 x2) is found to provide a satisfactory description of the K photoproduction data.Comment: 32 pages, 7 figures available as tared, compressed and uuencoded PS-file

A graphene transmon operating at 1 T

A superconducting transmon qubit resilient to strong magnetic fields is an important component for proposed topological and hybrid quantum computing (QC) schemes. Transmon qubits consist of a Josephson junction (JJ) shunted by a large capacitance, coupled to a high quality factor superconducting resonator. In conventional transmon devices, the JJ is made from an Al/AlO$_x$/Al tunnel junction which ceases operation above the critical magnetic field of Al, 10 mT. Alternative junction technologies are therefore required to push the operation of these qubits into strong magnetic fields. Graphene JJs are one such candidate due to their high quality, ballistic transport and electrically tunable critical current densities. Importantly the monolayer structure of graphene protects the JJ from orbital interference effects that would otherwise inhibit operation at high magnetic field. Here we report the integration of ballistic graphene JJs into microwave frequency superconducting circuits to create the first graphene transmons. The electric tunability allows the characteristic band dispersion of graphene to be resolved via dispersive microwave spectroscopy. We demonstrate that the device is insensitive to the applied field and perform energy level spectroscopy of the transmon at 1 T, more than an order of magnitude higher than previous studies.Comment: attached supplementary materia