Chemical ageing and transformation of diffusivity in semi-solid multi-component organic aerosol particles

Recent experimental evidence underlines the importance of reduced diffusivity in amorphous semi-solid or glassy atmospheric aerosols. This paper investigates the impact of diffusivity on the ageing of multi-component reactive organic particles representative of atmospheric cooking aerosols. We apply and extend the recently developed KM-SUB model in a study of a 12-component mixture containing oleic and palmitoleic acids. We demonstrate that changes in the diffusivity may explain the evolution of chemical loss rates in ageing semi-solid particles, and we resolve surface and bulk processes under transient reaction conditions considering diffusivities altered by oligomerisation. This new model treatment allows prediction of the ageing of mixed organic multi-component aerosols over atmospherically relevant time scales and conditions. We illustrate the impact of changing diffusivity on the chemical half-life of reactive components in semisolid particles, and we demonstrate how solidification and crust formation at the particle surface can affect the chemical transformation of organic aerosols

Coupling aerosol surface and bulk chemistry with a kinetic double layer model (K2-SUB): oxidation of oleic acid by ozone

We present a kinetic double layer model coupling aerosol surface and bulk chemistry (K2-SUB) based on the PRA framework of gas-particle interactions (Poschl-Rudich-Ammann, 2007). K2-SUB is applied to a popular model system of atmospheric heterogeneous chemistry: the interaction of ozone with oleic acid. We show that our modelling approach allows de-convoluting surface and bulk processes, which has been a controversial topic and remains an important challenge for the understanding and description of atmospheric aerosol transformation. In particular, we demonstrate how a detailed treatment of adsorption and reaction at the surface can be coupled to a description of bulk reaction and transport that is consistent with traditional resistor model formulations. From literature data we have derived a consistent set of kinetic parameters that characterise mass transport and chemical reaction of ozone at the surface and in the bulk of oleic acid droplets. Due to the wide range of rate coefficients reported from different experimental studies, the exact proportions between surface and bulk reaction rates remain uncertain. Nevertheless, the model results suggest an important role of chemical reaction in the bulk and an approximate upper limit of similar to 10(-11) cm(2) s(-1) for the surface reaction rate coefficient. Sensitivity studies show that the surface accommodation coefficient of the gas-phase reactant has a strong non-linear influence on both surface and bulk chemical reactions. We suggest that K2-SUB may be used to design, interpret and analyse future experiments for better discrimination between surface and bulk processes in the oleic acid-ozone system as well as in other heterogeneous reaction systems of atmospheric relevance

Contribution of fungi to primary biogenic aerosols in the atmosphere: wet and dry discharged spores, carbohydrates, and inorganic ions

Biogenic aerosols play important roles in atmospheric chemistry physics, the biosphere, climate, and public health. Here, we show that fungi which actively discharge their spores with liquids into the air, in particular actively wet spore discharging Ascomycota (AAM) and actively wet spore discharging Basidiomycota (ABM), are a major source of primary biogenic aerosol particles and components. We present the first estimates for the global average emission rates of fungal spores. Measurement results and budget calculations based on investigations in Amazonia (Balbina, Brazil, July 2001) indicate that the spores of AAM and ABM may account for a large proportion of coarse particulate matter in tropical rainforest regions during the wet season (0.7–2.3 μg m^−3). For the particle diameter range of 1–10 μm, the estimated proportions are ~25% during day-time, ~45% at night, and ~35% on average. For the sugar alcohol mannitol, the budget calculations indicate that it is suitable for use as a molecular tracer for actively wet discharged basidiospores (ABS). ABM emissions seem to account for most of the atmospheric abundance of mannitol (10–68 ng m^−3), and can explain the observed diurnal cycle (higher abundance at night). ABM emissions of hexose carbohydrates might also account for a significant proportion of glucose and fructose in air particulate matter (7–49 ng m^−3), but the literature-derived ratios are not consistent with the observed diurnal cycle (lower abundance at night). AAM emissions appear to account for a large proportion of potassium in air particulate matter over tropical rainforest regions during the wet season (17–43 ng m^−3), and they can also explain the observed diurnal cycle (higher abundance at night). The results of our investigations and budget calculations for tropical rainforest aerosols are consistent with measurements performed at other locations. Based on the average abundance of mannitol reported for extratropical continental boundary layer air (~25 ng m^−3), we have also calculated a value of ~17 Tg yr^−1 as a first estimate for the global average emission rate of ABS over land surfaces, which is consistent with the typically observed concentrations of ABS (~10³–10^4 m^−3; ~0.1–1 μg m^−3). The global average atmospheric abundance and emission rate of total fungal spores, including wet and dry discharged species, are estimated to be higher by a factor of about three, i.e. 1 μg m^−3 and ~50 Tg yr^−1. Comparisons with estimated rates of emission and formation of other major types of organic aerosol (~47 Tg yr^−1 of anthropogenic primary organic aerosol; 12–70 Tg yr^−1 of secondary organic aerosol) indicate that emissions from fungi should be taken into account as a significant global source of organic aerosol. The effects of fungal spores and related chemical components might be particularly important in tropical regions, where both physicochemical processes in the atmosphere and biological activity at the Earth's surface are particularly intense, and where the abundance of fungal spores and related chemical compounds are typically higher than in extratropical regions

Kinetic model framework for aerosol and cloud surface chemistry and gas-particle interactions ? Part 2: Exemplary practical applications and numerical simulations

International audienceA kinetic model framework with consistent and unambiguous terminology and universally applicable rate equations and parameters for aerosol and cloud surface chemistry and gas-particle interactions has been presented in the preceding companion paper by Pöschl, Rudich and Ammann (Pöschl et al., 2007), abbreviated PRA. It allows to describe mass transport and chemical reaction at the gas-particle interface and to link aerosol and cloud surface processes with gas phase and particle bulk processes. Here we present multiple exemplary model systems and calculations illustrating how the general mass balance and rate equations of the PRA framework can be easily reduced to compact sets of equations which enable a mechanistic description of time and concentration dependencies of trace gas uptake and particle composition in systems with one or more chemical components and physicochemical processes. Time-dependent model scenarios show the effects of reversible adsorption, surface-bulk transport, and chemical aging on the temporal evolution of trace gas uptake by solid particles and solubility saturation of liquid particles. They demonstrate how the transformation of particles and the variation of trace gas accommodation and uptake coefficients by orders of magnitude over time scales of microseconds to days can be explained and predicted from the initial composition and basic kinetic parameters of model systems by iterative calculations using standard spreadsheet programs. Moreover, they show how apparently inconsistent experimental data sets obtained with different techniques and on different time scales can be efficiently linked and mechanistically explained by application of consistent model formalisms and terminologies within the PRA framework. Steady-state model scenarios illustrate characteristic effects of gas phase composition and basic kinetic parameters on the rates of mass transport and chemical reactions. They demonstrate how adsorption and surface saturation effects can explain non-linear gas phase concentration dependencies of surface and bulk accommodation coefficients, uptake coefficients, and bulk solubilities (deviations from Henry's law). Such effects are expected to play an important role in many real atmospheric aerosol and cloud systems involving a wide range of organic and inorganic components of concentrated aqueous and organic solution droplets, ice crystals, and other crystalline or amorphous solid particles

Kinetic model framework for aerosol and cloud surface chemistry and gas-particle interactions: Part 2 ? exemplary practical applications and numerical simulations

International audienceA kinetic model framework with consistent and unambiguous terminology and universally applicable rate equations and parameters for aerosol and cloud surface chemistry and gas-particle interactions has been presented in the preceding companion paper by Pöschl, Rudich and Ammann (Pöschl et al., 2005), abbreviated PRA. It allows to describe mass transport and chemical reaction at the gas-particle interface and to link aerosol and cloud surface processes with gas phase and particle bulk processes. Here we present multiple exemplary model systems and calculations illustrating how the general mass balance and rate equations of the PRA framework can be easily reduced to compact sets of equations which enable a mechanistic description of time and concentration dependencies of trace gas uptake and particle composition in systems with one or more chemical components and physicochemical processes. Time-dependent model scenarios show the effects of reversible adsorption, surface-bulk transport, and chemical aging on the temporal evolution of trace gas uptake by solid particles and solubility saturation of liquid particles. They demonstrate, how the transformation of particles and the variation of trace gas accommodation and uptake coefficients by orders of magnitude over time scales of microseconds to days can be explained and predicted from the initial composition and basic kinetic parameters of model systems by iterative calculations using standard spreadsheet programs. Moreover, they show how apparently inconsistent experimental data sets obtained with different techniques and on different time scales can be efficiently linked and mechanistically explained by application of consistent model formalisms and terminologies within the PRA framework. Steady-state model scenarios illustrate characteristic effects of gas phase composition and basic kinetic parameters on the rates of mass transport and chemical reactions. They demonstrate how adsorption and surface saturation effects can explain non-linear gas phase concentration dependencies of surface and bulk accommodation coefficients, uptake coefficients, and bulk solubilities (deviations from Henry's law). Such effects are expected to play an important role in many real atmospheric aerosol and cloud systems involving a wide range of organic and inorganic components of concentrated aqueous and organic solution droplets, ice crystals, and other crystalline or amorphous solid particles. We hope that the presented model systems and simulations clearly demonstrate the universal applicability and consistency of the PRA framework as a tool and common basis for experimental and theoretical studies investigating and describing atmospheric aerosol and cloud surface chemistry and gas-particle interactions

Top quark precision physics at the International Linear Collider

Top quark production in the process $e^+e^- \rightarrow t\bar{t}$ at a future linear electron positron collider with polarized beams is a powerful tool to determine the scale of new physics. Studies at the \ttbar threshold will allow for precise determination of the top quark mass in a well defined theoretical framework. At higher energies vector, axial vector and tensorial CP conserving couplings can be separately determined for the photon and the $Z^0$ component in the electro-weak production process. The sensitivity to new physics would be dramatically improved w.r.t. to what expected from LHC for electroweak couplings.Comment: White paper for Snowmass CSS 201

The leader operators of the (d+1)(d+1)-dimensional relativistic rotating oscillators

The main pairs of leader operators of the quantum models of relativistic rotating oscillators in arbitrary dimensions are derived. To this end one exploits the fact that these models generate P\"{o}schl-Teller radial problems with remarkable properties of supersymmetry and shape invariance.Comment: 11 page

Decentralizing for a deeper, more supple democracy

Well-designed decentralization can deepen democracy and strengthen the state in five key ways. Decentralizing below the level of social cleavages should undermine secessionism by peeling away moderates from radical leaders. The “fragmentation of authority” critique is mistaken; decentralization transforms the state from a simpler, brittler command structure to one of multilevel complementarity more robust to local failure. Decentralizing services with low economies of scale, with devolved taxation and bail-outs prohibited, should increase accountability. Lastly, the small scale of local politics allows citizens to become political actors, promoting social learning-by-doing, strengthening political legitimacy and ‘democratic suppleness’ from the grass-roots upwards

Interactions of hadrons in the CALICE SiW ECAL prototype

This article presents results of test beams obtained for pions with energies between 2 and 10 GeV which interact in the volume of the highly granular CALICE Silicon-Tungsten electromagnetic calorimeter prototype (SiW ECAL). An algorithm optimised to find interactions in the SiW ECAL at small hadron energies is developed. This allows identifying the interaction point in the calorimeter at an efficiency between 62% and 83% depending on the energy of the primary particle. The unprecedented granularity of the SiW ECAL allows for the distinction between different interaction types. This in turn permits more detailed examinations of hadronic models than was possible with traditional calorimeters. So far, it is possible to disentangle minimum ionising particle (MIP) events, elastic π-nucleus scattering and spallation reactions which lead to the start of a internuclear cascade or which result in a small number of highly ionising particles. Various observables are compared with predictions from hadronic physics lists as contained in the simulation toolkit geant4

A precise characterisation of the top quark electro-weak vertices at the ILC

Top quark production in the process $e^+e^- \to t\bar{t}$ at a future linear electron positron collider with polarised beams is a powerful tool to determine indirectly the scale of new physics. The presented study, based on a detailed simulation of the ILD detector concept, assumes a centre-of-mass energy of $\sqrt{s}=500\,$GeV and a luminosity of $\mathcal{L}=500\,{\rm fb}^{-1}$ equally shared between the incoming beam polarisations of $\mathcal{P}_{e^-}, \mathcal{P}_{e^+} =\pm0.8,\mp0.3$. Events are selected in which the top pair decays semi-leptonically and the cross sections and the forward-backward asymmetries are determined. Based on these results, the vector, axial vector and tensorial $CP$ conserving couplings are extracted separately for the photon and the $Z^0$ component. With the expected precision, a large number of models in which the top quark acts as a messenger to new physics can be distinguished with many standard deviations. This will dramatically improve expectations from e.g. the LHC for electro-weak couplings of the top quark.Comment: This work is an update of arXiv:1307.8102, minor changes w.r.t. v1 (typos, wrong grammar, incomplete sentences etc.