Kinetic regimes and limiting cases of gas uptake and heterogeneous reactions in atmospheric aerosols and clouds: a general classification scheme

Heterogeneous reactions are important to atmospheric chemistry and are therefore an area of intense research. In multiphase systems such as aerosols and clouds, chemical reactions are usually strongly coupled to a complex sequence of mass transport processes and results are often not easy to interpret. Here we present a systematic classification scheme for gas uptake by aerosol or cloud particles which distinguishes two major regimes: a reaction-diffusion regime and a mass transfer regime. Each of these regimes includes four distinct limiting cases, characterised by a dominant reaction location (surface or bulk) and a single rate-limiting process: chemical reaction, bulk diffusion, gas-phase diffusion or mass accommodation. The conceptual framework enables efficient comparison of different studies and reaction systems, going beyond the scope of previous classification schemes by explicitly resolving interfacial transport processes and surface reactions limited by mass transfer from the gas phase. The use of kinetic multi-layer models instead of resistor model approaches increases the flexibility and enables a broader treatment of the subject, including cases which do not fit into the strict limiting cases typical of most resistor model formulations. The relative importance of different kinetic parameters such as diffusion, reaction rate and accommodation coefficients in this system is evaluated by a quantitative global sensitivity analysis. We outline the characteristic features of each limiting case and discuss the potential relevance of different regimes and limiting cases for various reaction systems. In particular, the classification scheme is applied to three different datasets for the benchmark system of oleic acid reacting with ozone in order to demonstrate utility and highlight potential issues. In light of these results, future directions of research needed to elucidate the multiphase chemical kinetics in this and other reaction systems are discussed

Molecular corridors and kinetic regimes in the multiphase chemical evolution of secondary organic aerosol

The dominant component of atmospheric, organic aerosol is that derived from the oxidation of volatile organic compounds (VOCs), so-called secondary organic aerosol (SOA). SOA consists of a multitude of organic compounds, only a small fraction of which has historically been identified. Formation and evolution of SOA is a complex process involving coupled chemical reaction and mass transport in the gas and particle phases. Current SOA models do not embody the full spectrum of reaction and transport processes, nor do they identify the dominant rate-limiting steps in SOA formation. Based on molecular identification of SOA oxidation products, we show here that the chemical evolution of SOA from a variety of VOC precursors adheres to characteristic "molecular corridors" with a tight inverse correlation between volatility and molar mass. The slope of these corridors corresponds to the increase in molar mass required to decrease volatility by one order of magnitude (-dM / dlogC_0). It varies in the range of 10–30 g mol^(−1), depending on the molecular size of the SOA precursor and the O : C ratio of the reaction products. Sequential and parallel reaction pathways of oxidation and dimerization or oligomerization progressing along these corridors pass through characteristic regimes of reaction-, diffusion-, or accommodation-limited multiphase chemical kinetics that can be classified according to reaction location, degree of saturation, and extent of heterogeneity of gas and particle phases. The molecular corridors and kinetic regimes help to constrain and describe the properties of the products, pathways, and rates of SOA evolution, thereby facilitating the further development of aerosol models for air quality and climate

The effect of viscosity and diffusion on the HO₂ uptake by sucrose and secondary organic aerosol particles

We report the first measurements of HO2 uptake coefficients, γ, for secondary organic aerosol (SOA) particles and for the well-studied model compound sucrose which we doped with copper(II). Above 65% relative humidity (RH), γ for copper(II)-doped sucrose aerosol particles equalled the surface mass accommodation coefficient α=0.22±0.06, but it decreased to γ=0.012±0.007 upon decreasing the RH to 17 %. The trend of γ with RH can be explained by an increase in aerosol viscosity and the contribution of a surface reaction, as demonstrated using the kinetic multilayer model of aerosol surface and bulk chemistry (KM-SUB). At high RH the total uptake was driven by reaction in the near-surface bulk and limited by mass accommodation, whilst at low RH it was limited by surface reaction. SOA from two different pre-cursors, α-pinene and 1,3,5-trimethylbenzene (TMB), was investigated, yielding low uptake coefficients of γ<0.001 and γ=0.004±0.002, respectively. It is postulated that the larger values measured for TMB-derived SOA compared to α-pinene-derived SOA are either due to differing viscosity, a different liquid water content of the aerosol particles, or an HO2 + RO2 reaction occurring within the aerosol particles

Investigation of lower hybrid physics through power modulation experiments on Alcator C-Mod

Lower hybrid current drive (LHCD) is an attractive tool for off-axis current profile control in magnetically confined tokamak plasmas and burning plasmas (ITER), because of its high current drive efficiency. The LHCD system on Alcator C-Mod operates at 4.6 GHz, with ~ 1 MW of coupled power, and can produce a wide range of launched parallel refractive index (n[subscript ∣∣]) spectra. A 32 chord, perpendicularly viewing hard x-ray camera has been used to measure the spatial and energy distribution of fast electrons generated by lower hybrid (LH) waves. Square-wave modulation of LH power on a time scale much faster than the current relaxation time does not significantly alter the poloidal magnetic field inside the plasma and thus allows for realistic modeling and consistent plasma conditions for different n[subscript ∣∣] spectra. Inverted hard x-ray profiles show clear changes in LH-driven fast electron location with differing n[subscript ∣∣]. Boxcar binning of hard x-rays during LH power modulation allows for ~ 1 ms time resolution which is sufficient to resolve the build-up, steady-state, and slowing-down phases of fast electrons. Ray-tracing/Fokker-Planck modeling in combination with a synthetic hard x-raydiagnostic shows quantitative agreement with the x-ray data for high n[subscript ∣∣] cases. The time histories of hollow x-ray profiles have been used to measure off-axis fast electron transport in the outer half of the plasma, which is found to be small on a slowing down time scale.United States. Dept. of Energy (Award DE-FC02-99ER54512)United States. Dept. of Energy (Award DE-AC02-76CH03073

Control orchestration protocol:unified transport API for distributed cloud and network orchestration

In the context of the fifth generation of mobile technology (5G), multiple technologies will converge into a unified end-to-end system. For this purpose, software defined networking (SDN) is proposed, as the control paradigm will integrate all network segments and heterogeneous optical and wireless network technologies together with massive storage and computing infrastructures. The control orchestration protocol is presented as a unified transport application programming interface solution for joint cloud/network orchestration, allowing interworking of heterogeneous control planes to provide provisioning and recovery of quality of service (QoS)-aware end-to-end services. End-to-end QoS is guaranteed by provisioning and restoration schemes, which are proposed for optical circuit/packet switching restoration by means of signal monitoring and adaptive modulation and adaptive route control, respectively. The proposed solution is experimentally demonstrated in an international multi-partner test bed, which consists of a multi-domain transport network comprising optical circuit switching and optical packet switching domains controlled by SDN/OpenFlow and Generalized Multiprotocol Label Switching (GMPLS) control planes and a distributed cloud infrastructure. The results show the dynamic provisioning of IT and network resources and recovery capabilities of the architecture.Grant numbers : This work was partially supported by the Spanish MINECO project DESTELLO (TEC2015-69256-R)