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.     

Assessing the economic feasibility of regional deep saline aquifer CO2 injection and storage: A geomechanics-based workflow applied to the Rose Run sandstone in Eastern Ohio, USA

Typical top-down regional assessments of CO₂ storage feasibility are sufficient for determining the maximum volumetric capacity of deep saline aquifers. However, they do not reflect the regional economic feasibility of storage. This is controlled, in part, by the number and type of injection wells that are necessary to achieve regional CO₂ storage goals. In contrast, the geomechanics-based assessment workflow that we present in this paper follows a bottom-up approach for evaluating regional deep saline aquifer CO₂ storage feasibility. The CO₂ storage capacity of an aquifer is a function of its porous volume as well as its CO₂ injectivity. For a saline aquifer to be considered feasible in this assessment it must be able to store a specified amount of CO₂ at a reasonable cost per ton of CO₂. The proposed assessment workflow has seven steps that include (1) defining the storage project and goals, (2) characterizing the geology and developing a geomechanical model of the aquifer, (3) constructing 3D aquifer models, (4) simulating CO₂ injection, (5,6) evaluating CO₂ injection and storage feasibility (with and without injection well stimulation), and (7) determining whether it is economically feasible to proceed with the storage project. The workflow was applied to a case study of the Rose Run sandstone aquifer in the Eastern Ohio River Valley, USA. We found that it is feasible in this region to inject 113 Mt CO₂/year for 30 years at an associated well cost of less than US $1.31/t CO₂, but only if injectivity enhancement techniques such as hydraulic fracturing and injection induced micro-seismicity are implemented.     

Long-term geochemical evolution of the near field repository: insights from reactive transport modelling and experimental evidences

The KBS-3 underground nuclear waste repository concept designed by the Swedish Nuclear Fuel and Waste Management Co. (SKB) includes a bentonite buffer barrier surrounding the copper canisters and the iron insert where spent nuclear fuel will be placed. Bentonite is also part of the backfill material used to seal the access and deposition tunnels of the repository. The bentonite barrier has three main safety functions: to ensure the physical stability of the canister, to retard the intrusion of groundwater to the canisters, and in case of canister failure, to retard the migration of radionuclides to the geosphere. Laboratory experiments (< 10 years long) have provided evidence of the control exerted by accessory minerals and clay surfaces on the pore water chemistry. The evolution of the pore water chemistry will be a primordial factor on the long-term stability of the bentonite barrier, which is a key issue in the safety assessments of the KBS-3 concept.In this work we aim to study the long-term geochemical evolution of bentonite and its pore water in the evolving geochemical environment due to climate change. In order to do this, reactive transport simulations are used to predict the interaction between groundwater and bentonite which is simulated following two different pathways: (1) groundwater flow through the backfill in the deposition tunnels, eventually reaching the top of the deposition hole, and (2) direct connection between groundwater and bentonite rings through fractures in the granite crosscutting the deposition hole. The influence of changes in climate has been tested using three different waters interacting with the bentonite: present-day groundwater, water derived from ice melting, and deep-seated brine. Two commercial bentonites have been considered as buffer material, MX-80 and Deponit CA-N, and one natural clay (Friedland type) for the backfill. They show differences in the composition of the exchangeable cations and in the accessory mineral content. Results from the simulations indicate that pore water chemistry is controlled by the equilibrium with the accessory minerals, especially carbonates. pH is buffered by precipitation/dissolution of calcite and dolomite, when present. The equilibrium of these minerals is deeply influenced by gypsum dissolution and cation exchange reactions in the smectite interlayer. If carbonate minerals are initially absent in bentonite, pH is then controlled by surface acidity reactions in the hydroxyl groups at the edge sites of the clay fraction, although its buffering capacity is not as strong as the equilibrium with carbonate minerals. The redox capacity of the bentonite pore water system is mainly controlled by Fe(II)-bearing minerals (pyrite and siderite). Changes in the groundwater composition lead to variations in the cation exchange occupancy, and dissolution–precipitation of carbonate minerals and gypsum. The most significant changes in the evolution of the system are predicted when ice-melting water, which is highly diluted and alkaline, enters into the system. In this case, the dissolution of carbonate minerals is enhanced, increasing pH in the bentonite pore water. Moreover, a rapid change in the population of exchange sites in the smectite is expected due to the replacement of Na for Ca.     

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.     

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.