Gas phase kinetic and quantum chemical studies of the reactions of silylene with the methylsilanes. Absolute rate constants, temperature dependences, RRKM modelling and potential energy surfaces

Time resolved studies of silylene, SiH2, generated by the 193 nm laser. ash photolysis of phenylsilane, have been carried out to obtain rate coefficients for its bimolecular reactions with methyl-, dimethyl- and trimethyl-silanes in the gas phase. The reactions were studied over the pressure range 3 - 100 Torr with SF6 as bath gas and at five temperatures in the range 300 - 625 K. Only slight pressure dependences were found for SiH2 + MeSiH3 ( 485 and 602 K) and for SiH2 + Me2SiH2 ( 600 K). The high pressure rate constants gave the following Arrhenius parameters: [GRAPHICS] These are consistent with fast, near to collision-controlled, association processes. RRKM modelling calculations are consistent with the observed pressure dependences ( and also the lack of them for SiH2 + Me3SiH). Ab initio calculations at both second order perturbation theory (MP2) and coupled cluster (CCSD(T)) levels, showed the presence of weakly-bound complexes along the reaction pathways. In the case of SiH2 + MeSiH3 two complexes, with different geometries, were obtained consistent with earlier studies of SiH2 + SiH4. These complexes were stabilised by methyl substitution in the substrate silane, but all had exceedingly low barriers to rearrangement to product disilanes. Although methyl groups in the substrate silane enhance the intrinsic SiH2 insertion rates, it is doubtful whether the intermediate complexes have a significant effect on the kinetics. A further calculation on the reaction MeSiH + SiH4 shows that the methyl substitution in the silylene should have a much more significant kinetic effect ( as observed in other studies).

Ice formation and development in aged, wintertime cumulus over the UK: observations and modelling

In situ high resolution aircraft measurements of cloud microphysical properties were made in coordination with ground based remote sensing observations of a line of small cumulus clouds, using Radar and Lidar, as part of the Aerosol Properties, PRocesses And InfluenceS on the Earth's climate (APPRAISE) project. A narrow but extensive line (~100 km long) of shallow convective clouds over the southern UK was studied. Cloud top temperatures were observed to be higher than −8 °C, but the clouds were seen to consist of supercooled droplets and varying concentrations of ice particles. No ice particles were observed to be falling into the cloud tops from above. Current parameterisations of ice nuclei (IN) numbers predict too few particles will be active as ice nuclei to account for ice particle concentrations at the observed, near cloud top, temperatures (−7.5 °C). The role of mineral dust particles, consistent with concentrations observed near the surface, acting as high temperature IN is considered important in this case. It was found that very high concentrations of ice particles (up to 100 L−1) could be produced by secondary ice particle production providing the observed small amount of primary ice (about 0.01 L−1) was present to initiate it. This emphasises the need to understand primary ice formation in slightly supercooled clouds. It is shown using simple calculations that the Hallett-Mossop process (HM) is the likely source of the secondary ice. Model simulations of the case study were performed with the Aerosol Cloud and Precipitation Interactions Model (ACPIM). These parcel model investigations confirmed the HM process to be a very important mechanism for producing the observed high ice concentrations. A key step in generating the high concentrations was the process of collision and coalescence of rain drops, which once formed fell rapidly through the cloud, collecting ice particles which caused them to freeze and form instant large riming particles. The broadening of the droplet size-distribution by collision-coalescence was, therefore, a vital step in this process as this was required to generate the large number of ice crystals observed in the time available. Simulations were also performed with the WRF (Weather, Research and Forecasting) model. The results showed that while HM does act to increase the mass and number concentration of ice particles in these model simulations it was not found to be critical for the formation of precipitation. However, the WRF simulations produced a cloud top that was too cold and this, combined with the assumption of continual replenishing of ice nuclei removed by ice crystal formation, resulted in too many ice crystals forming by primary nucleation compared to the observations and parcel modelling.

Use of fused airborne scanning laser altimetry and digital map data for urban flood modelling

Flood modelling of urban areas is still at an early stage, partly because until recently topographic data of sufficiently high resolution and accuracy have been lacking in urban areas. However, Digital Surface Models (DSMs) generated from airborne scanning laser altimetry (LiDAR) having sub-metre spatial resolution have now become available, and these are able to represent the complexities of urban topography. The paper describes the development of a LiDAR post-processor for urban flood modelling based on the fusion of LiDAR and digital map data. The map data are used in conjunction with LiDAR data to identify different object types in urban areas, though pattern recognition techniques are also employed. Post-processing produces a Digital Terrain Model (DTM) for use as model bathymetry, and also a friction parameter map for use in estimating spatially-distributed friction coefficients. In vegetated areas, friction is estimated from LiDAR-derived vegetation height, and (unlike most vegetation removal software) the method copes with short vegetation less than ~1m high, which may occupy a substantial fraction of even an urban floodplain. The DTM and friction parameter map may also be used to help to generate an unstructured mesh of a vegetated urban floodplain for use by a 2D finite element model. The mesh is decomposed to reflect floodplain features having different frictional properties to their surroundings, including urban features such as buildings and roads as well as taller vegetation features such as trees and hedges. This allows a more accurate estimation of local friction. The method produces a substantial node density due to the small dimensions of many urban features.

Stochastic modelling of rainfall from satellite data

Satellite-based rainfall monitoring is widely used for climatological studies because of its full global coverage but it is also of great importance for operational purposes especially in areas such as Africa where there is a lack of ground-based rainfall data. Satellite rainfall estimates have enormous potential benefits as input to hydrological and agricultural models because of their real time availability, low cost and full spatial coverage. One issue that needs to be addressed is the uncertainty on these estimates. This is particularly important in assessing the likely errors on the output from non-linear models (rainfall-runoff or crop yield) which make use of the rainfall estimates, aggregated over an area, as input. Correct assessment of the uncertainty on the rainfall is non-trivial as it must take account of • the difference in spatial support of the satellite information and independent data used for calibration • uncertainties on the independent calibration data • the non-Gaussian distribution of rainfall amount • the spatial intermittency of rainfall • the spatial correlation of the rainfall field This paper describes a method for estimating the uncertainty on satellite-based rainfall values taking account of these factors. The method involves firstly a stochastic calibration which completely describes the probability of rainfall occurrence and the pdf of rainfall amount for a given satellite value, and secondly the generation of ensemble of rainfall fields based on the stochastic calibration but with the correct spatial correlation structure within each ensemble member. This is achieved by the use of geostatistical sequential simulation. The ensemble generated in this way may be used to estimate uncertainty at larger spatial scales. A case study of daily rainfall monitoring in the Gambia, west Africa for the purpose of crop yield forecasting is presented to illustrate the method.

Wind-tunnel modelling of dispersion from a scalar area source in urban-like roughness

A wind-tunnel study was conducted to investigate ventilation of scalars from urban-like geometries at neighbourhood scale by exploring two different geometries a uniform height roughness and a non-uniform height roughness, both with an equal plan and frontal density of λ p = λ f = 25%. In both configurations a sub-unit of the idealized urban surface was coated with a thin layer of naphthalene to represent area sources. The naphthalene sublimation method was used to measure directly total area-averaged transport of scalars out of the complex geometries. At the same time, naphthalene vapour concentrations controlled by the turbulent fluxes were detected using a fast Flame Ionisation Detection (FID) technique. This paper describes the novel use of a naphthalene coated surface as an area source in dispersion studies. Particular emphasis was also given to testing whether the concentration measurements were independent of Reynolds number. For low wind speeds, transfer from the naphthalene surface is determined by a combination of forced and natural convection. Compared with a propane point source release, a 25% higher free stream velocity was needed for the naphthalene area source to yield Reynolds-number-independent concentration fields. Ventilation transfer coefficients w T /U derived from the naphthalene sublimation method showed that, whilst there was enhanced vertical momentum exchange due to obstacle height variability, advection was reduced and dispersion from the source area was not enhanced. Thus, the height variability of a canopy is an important parameter when generalising urban dispersion. Fine resolution concentration measurements in the canopy showed the effect of height variability on dispersion at street scale. Rapid vertical transport in the wake of individual high-rise obstacles was found to generate elevated point-like sources. A Gaussian plume model was used to analyse differences in the downstream plumes. Intensified lateral and vertical plume spread and plume dilution with height was found for the non-uniform height roughness

An overview of Earth's global electric circuit and atmospheric conductivity

The Earth’s global atmospheric electric circuit depends on the upper and lower atmospheric boundaries formed by the ionosphere and the planetary surface. Thunderstorms and electrified rain clouds drive a DC current (∼1 kA) around the circuit, with the current carried by molecular cluster ions; lightning phenomena drive the AC global circuit. The Earth’s near-surface conductivity ranges from 10−7 S m−1 (for poorly conducting rocks) to 10−2 S m−1 (for clay or wet limestone), with a mean value of 3.2 S m−1 for the ocean. Air conductivity inside a thundercloud, and in fair weather regions, depends on location (especially geomagnetic latitude), aerosol pollution and height, and varies from ∼10−14 S m−1 just above the surface to 10−7 S m−1 in the ionosphere at ∼80 km altitude. Ionospheric conductivity is a tensor quantity due to the geomagnetic field, and is determined by parameters such as electron density and electron–neutral particle collision frequency. In the current source regions, point discharge (coronal) currents play an important role below electrified clouds; the solar wind-magnetosphere dynamo and the unipolar dynamo due to the terrestrial rotating dipole moment also apply atmospheric potential differences. Detailed measurements made near the Earth’s surface show that Ohm’s law relates the vertical electric field and current density to air conductivity. Stratospheric balloon measurements launched from Antarctica confirm that the downward current density is ∼1 pA m−2 under fair weather conditions. Fortuitously, a Solar Energetic Particle (SEP) event arrived at Earth during one such balloon flight, changing the observed atmospheric conductivity and electric fields markedly. Recent modelling considers lightning discharge effects on the ionosphere’s electric potential (∼+250 kV with respect to the Earth’s surface) and hence on the fair weather potential gradient (typically ∼130 V m−1 close to the Earth’s surface. We conclude that cloud-to-ground (CG) lightning discharges make only a small contribution to the ionospheric potential, and that sprites (namely, upward lightning above energetic thunderstorms) only affect the global circuit in a miniscule way. We also investigate the effects of mesoscale convective systems on the global circuit.

Introduction. Stochastic physics and climate modelling

Finite computing resources limit the spatial resolution of state-of-the-art global climate simulations to hundreds of kilometres. In neither the atmosphere nor the ocean are small-scale processes such as convection, clouds and ocean eddies properly represented. Climate simulations are known to depend, sometimes quite strongly, on the resulting bulk-formula representation of unresolved processes. Stochastic physics schemes within weather and climate models have the potential to represent the dynamical effects of unresolved scales in ways which conventional bulk-formula representations are incapable of so doing. The application of stochastic physics to climate modelling is a rapidly advancing, important and innovative topic. The latest research findings are gathered together in the Theme Issue for which this paper serves as the introduction.

Decadal predictability of the Atlantic Ocean in a coupled GCM: forecast skill and optimal perturbations using Linear Inverse Modelling

The decadal predictability of three-dimensional Atlantic Ocean anomalies is examined in a coupled global climate model (HadCM3) using a Linear Inverse Modelling (LIM) approach. It is found that the evolution of temperature and salinity in the Atlantic, and the strength of the meridional overturning circulation (MOC), can be effectively described by a linear dynamical system forced by white noise. The forecasts produced using this linear model are more skillful than other reference forecasts for several decades. Furthermore, significant non-normal amplification is found under several different norms. The regions from which this growth occurs are found to be fairly shallow and located in the far North Atlantic. Initially, anomalies in the Nordic Seas impact the MOC, and the anomalies then grow to fill the entire Atlantic basin, especially at depth, over one to three decades. It is found that the structure of the optimal initial condition for amplification is sensitive to the norm employed, but the initial growth seems to be dominated by MOC-related basin scale changes, irrespective of the choice of norm. The consistent identification of the far North Atlantic as the most sensitive region for small perturbations suggests that additional observations in this region would be optimal for constraining decadal climate predictions.

Modelling the global coastal ocean

Shelf and coastal seas are regions of exceptionally high biological productivity, high rates of biogeochemical cycling and immense socio-economic importance. They are, however, poorly represented by the present generation of Earth system models, both in terms of resolution and process representation. Hence, these models cannot be used to elucidate the role of the coastal ocean in global biogeochemical cycles and the effects global change (both direct anthropogenic and climatic) are having on them. Here, we present a system for simulating all the coastal regions around the world (the Global Coastal Ocean Modelling System) in a systematic and practical fashion. It is based on automatically generating multiple nested model domains, using the Proudman Oceanographic Laboratory Coastal Ocean Modelling System coupled to the European Regional Seas Ecosystem Model. Preliminary results from the system are presented. These demonstrate the viability of the concept, and we discuss the prospects for using the system to explore key areas of global change in shelf seas, such as their role in the carbon cycle and climate change effects on fisheries.