A DFT study of the reactions of O3 with Hg° or Br

In the mid 1980s the study of ozone reactivity gained a significant interest with the discoveries of the stratospheric ozone hole (Farman et al., 1985) and of the ozone depletion events in the polar boundary layer (Oltmans et al., 1989). In the stratosphere, the mechanism involves heterogeneous reactions on polar stratospheric clouds that lead to chlorine activation (Solomon et al., 1986). In contrast, tropospheric ozone depletion occurring during polar springtime rather involves reactive bromine species. They are released during a series of photochemical and heterogeneous reactions often called the bromine explosion (see the review of Simpson et al., 2007). In this reaction sequence, an essential step is the generation of photolyzable Br₂, the precursor of two Br atoms, via the multiphasic reaction (1):

(1)

HOBr + Br⁻ + H⁺ → H₂O + Br₂

The production of reactive HOBr could occur with the oxidation of BrO by HO₂.     

The role of remote sensing in hydrological modelling of the Okavango Delta, Botswana

A coupled surface water-groundwater model of the Okavango Delta has been built based on the United States Geological Survey software MODFLOW 2000 including the SFR2 package for stream-flow routing. It will provide a new tool for evaluating water management and climate change scenarios. The delta's size and limited accessibility make direct, on the ground data acquisition difficult. Remote sensing methods are the most promising source of acquiring spatially distributed data for both model input parameters and calibration. Topography, aquifer thickness, channel positions, evapotranspiration and precipitation data are all based on remote sensing. Simulated flooding patterns are compared to patterns derived from visible to thermal NOAA-AVHRR data and microwave radar ENVISAT-ASAR data.     

Health benefits valuation of regulatory intervention for air pollution control in thermal power plants in Delhi,India

This study estimates minimum marginal health benefits (morbidity reduction only) of air pollution control and total health benefits arising from regulatory intervention regarding the adoption of the World Bank emission guidelines (WBEG) for thermal power plants (TPPs) in Delhi. The Industrial Source Complex-Short-Term Version–3 (ISCST3) model has been used to estimate the contribution to air pollution from TPPs. The household health production function (avertive behaviour) has been used to value health benefits of air pollution control. The study revealed that the ambient air pollution due to TPPs is reduced by between 62.17% to 83.45% by adopting the WBEG. Annual marginal benefit due to reduction in exposure to air pollution by 1 μg m^?3 is estimated to be US$0.353 per person. Total annual health benefits for adopting the WBEG for TPPs are estimated at US$235.19 million. This study provides a novel methodology to evaluate health benefits of regulatory intervention.     

Quantifying local traffic contributions to NO2 and NH3 concentrations in natural habitats

NO₂ and NH₃ concentrations were measured across a Special Area for Conservation in southern England, at varying distances from the local road network. Exceedances of the critical levels for these pollutants were recorded at nearly all roadside locations, extending up to 20 m away from roads at some sites. Further, paired measurements of NH₃ and NO₂ concentrations revealed differences between ground and tree canopy levels. At “background” sites, away from the direct influence of roads, concentrations were higher within tree canopies than at ground level; the reverse pattern was, however, seen at roadside locations. Calculations of pollutant deposition rates showed that nitrogen inputs are dominated by NH₃ at roadside sites. This study demonstrates that local traffic emissions contribute substantially to the exceedance of critical levels and critical loads, and suggests that on-site monitoring is needed for sites of nature conservation value which are in close proximity to local transport routes.     

Influence of Building Density and Roof Shape on the Wind and Dispersion Characteristics in an Urban Area: A Numerical Study

The Computational Fluid Dynamics code CFX-TASCflow is used for simulating the wind flow and pollutant concentration patterns in two-dimensional wind-tunnel models of an urban area. Several two-dimensional multiple street canyon configurations are studied corresponding to different areal densities and roof shapes. A line source of a tracer gas is placed at the bottom of one street canyon for modelling street-level traffic emissions. The flow fields resulting from the simulations correspond to the patterns observed in street canyons. In particular and in good agreement with observations, a dual vortex system is predicted for a deep flat-roof street canyon configuration, while an even more complex vortex system is evidenced in the case of slanted-roof square street canyons. In agreement with measurement data, high pollutant concentration levels are predicted either on the leeward or the windward side of the street canyon, depending on the geometrical details of the surrounding buildings.     

Physical Modeling of Emissions from Naturally Ventilated Underground Parking Garages

The dispersion of pollutants from naturally ventilated underground parking garages has been studied in a boundary layer wind tunnel. Two idealized model setups have been analysed, one was simulating pollutant dispersion around an isolated rectangular building and one was representing dispersion in a finite array of idealized building blocks. Flow and dispersion close to modelled ground level emission sources was measured. The results illustrate the complexity of the flow around buildings and provide insight in pollutant transport from ground level sources located directly on building surfaces. As a result, areas critical with respect to high pollutant concentrations could be visualized. Particularly, the results show high concentration gradients on the surface of the buildings equipped with modelled emission sources. Inside the boundary layers on the building walls, a significant amount of pollutants is transported to upwind locations on the surface of the building. The paper documents the potential of physical modelling to be used for the simulation and measurement of dispersion close to emission sources and within complex building arrangements.     

Modelling Tracer Dispersion from Landfills

Several wind tunnel experiments of tracer dispersion from reduced-scale landfill models are presented in this paper. Different experimental set-ups, hot-wire anemometry, particle image velocimetry and tracer concentration measurements were used for the characterisation of flow and dispersion phenomena nearby the models. The main aim of these experiments is to build an extensive experimental data set useful for model validation purposes. To demonstrate the potentiality of the experimental data set, a validation exercise on several mathematical models was performed by means of a statistical technique. The experiments highlighted an increase in pollutant ground level concentrations immediately downwind from the landfill because of induced turbulence and mean flow deflection. This phenomenon turns out to be predominant for the dispersion process. Tests with a different set-up showed an important dependence of the dispersion phenomena from the landfill height and highlighted how complex orographic conditions downwind of the landfill do not affect significantly the dispersion behaviour. Validation exercises were useful for model calibration, improving code reliability, as well as evaluating performances. The Van Ulden model proved to give the most encouraging results.     

Extension of the EUROS Integrated Air Quality Model to Fine Particulate Matter by Coupling to CACM/MADRID 2

The European Operational Smog (EUROS) integrated air quality modelling system has been extended to model fine particulate matter (PM). From an extended literature study, the Caltech Atmospheric Chemistry Mechanism and the Model of Aerosol Dynamics, Reaction, Ionisation and Dissolution were selected and recently coupled to EUROS. Currently, modelling of mass and chemical composition of aerosols in two size fractions (PM_2.5 and PM_10–2.5) is possible. The chemical composition is expressed in terms of seven components: ammonium, nitrate, sulphate, elementary carbon, primary inorganic compounds, primary organic compounds and secondary organic compounds. Calculated PM₁₀ concentrations and chemical composition are presented for two summer months of the year 2003 (1 July to 31 August).     

Oil spill cleanup cost estimation—Developing a mathematical model for marine environment

The field of oil spill cost modelling is not as well explored as desirable. Generally speaking, the existing models have either low accuracy, in that their predictions are far from the real cost, or low applicability, in that they are only valid under very specific conditions; such as in one particular country. This work strives to construct a model that is functional in a global scope and still possess a high level of accuracy. The resulting attempt is in many ways superior to the publicly available competitors, not only because of its predictive capacity but also because the model is quick to use, and its input variables should be readily available to any informed user. The model is more accurate comparing with similar available models. However, further study is needed to modify it to obtain more realistic results.     

Three-Dimensional Modelling of Concentration Fluctuations in Complicated Geometry

The strong fluctuating component in the measured concentration time series of a dispersing gaseous pollutant in the atmospheric boundary layer, and the hazard level associated to short-term concentration levels, demonstrate the necessity of calculating the magnitude of turbulent fluctuations of concentration using computational simulation models. Moreover the computation of concentration fluctuations in cases of dispersion in realistic situations, such as built-up areas or street canyons, is of special practical interest for hazard assessment purposes. In this paper, the formulation and evaluation of a model for concentration fluctuations, based on a transport equation, are presented. The model is applicable in cases of complex geometry. It is included in the framework of a computational code, developed for simulating the dispersion of buoyant pollutants over complex geometries. The experimental data used for the model evaluation concerned the dispersion of a passive gas in a street canyon between 4 identical rectangular buildings performed in a wind tunnel. The experimental concentration fluctuations data have been derived from measured high frequency concentrations. The concentration fluctuations model is evaluated by comparing the model's predictions with the observations in the form of scatter plots, quantile-quantile plots, contour plots and statistical indices as the fractional bias, the geometrical mean variance and the factor-of-two percentage. From the above comparisons it is concluded that the overall model performance in the present complex geometry case is satisfactory. The discrepancies between model predictions and observations are attributed to inaccuracies in prescribing the actual wind tunnel boundary conditions to the computational code.