Sulfur transport modeling

The advent of fast computers and the availability of detailed data on the occurrence of certain chemical species have made it possible to construct meaningful cycle models with a much smaller and faster spatial and temporal resolution. These spatial and time scales correspond to those in weather forecast models, i.e. down to 100 km and 1 h. Transport processes (e.g., for CO2 and sulfur compounds) in the oceans and atmosphere can be explicitly described in such models. These are often referred to as "tracer transport models." This type of model will also be discussed briefly in this chapter. 

Aquifers with double porosity (e.g. sandstones with fractures and pore volume) require special considerations with regard to transport modeling even if no reactive mass transport in its proper sense is taken into account. This problem is demonstrated with the following example of an aquifer regeneration in an uranium mine. The ore was leached in this mine by in-situ leaching (ISL) using sulfuric acid. The hydrochemical composition of the water that is in the aquifer after this in-situ leaching process is shown as ISL in Table 40 ... 

Understanding the processes that control atmospheric aerosol concentrations and representing these processes in chemical transport models rests in large part on the accuracy of emissions inventories of aerosols and gaseous precursors. The most widely applied approach to developing such inventories is characterization of emissions per unit of activity (called emission factors ) combined with characterization of the intensity and geographic distribution of these activities. This approach is well developed for some gas-phase species. Emission of SO2 from fossil fuel combustion provides an example. Most sulfur in... 

Rodhe H. and Isaksen I. (1980) Global distribution of sulfur compounds in treh troposphere estimated in a height/latitude transport model. J. Geopkys. Res. 85, 7401 -7409. 

More complicated models of sulfur transport and deposition differ in details but typically use the same chemical reactions and mechanisms as shown above. 

Noppel et al. (2002) have continued the development of the hydrate model using ab initio calculations of the structures of small water-sulfuric acid clusters. The predicted nucleation rates by the Noppel et al. (2002) model are generally higher than those predicted by previous models. The nucleation rates have been parameterized for use in chemical transport models by Vehkamaki et al. (2002). 

Rodhe, H. and I. Isaken. 1980. Global distribntion of sulfur compounds in the troposphere estimated in a height-latitnde transport model. J. Geophys. Res. Oceans Atmos. 85 7401-7409. 

The parameterization of impedance-based models is difficult for operating profiles that have high ampere-hour throughput in short times. Such conditions result in non-steady-state conditions and do not allow precise measurements of impedance parameters. Therefore, Thele et al. extended the ECM presented in Figure 9.19 by means of an electrolyte transport model, which describes the generation and transport of sulfuric acid inside the porous electrodes [47]. They removed the Warburg impedance and expressed the OCV as the difference between the positive and negative standard potentials [18] ... 

Selection of pollution control methods is generally based on the need to control ambient air quaUty in order to achieve compliance with standards for critetia pollutants, or, in the case of nonregulated contaminants, to protect human health and vegetation. There are three elements to a pollution problem a source, a receptor affected by the pollutants, and the transport of pollutants from source to receptor. Modification or elimination of any one of these elements can change the nature of a pollution problem. For instance, tall stacks which disperse effluent modify the transport of pollutants and can thus reduce nearby SO2 deposition from sulfur-containing fossil fuel combustion. Although better dispersion aloft can solve a local problem, if done from numerous sources it can unfortunately cause a regional one, such as the acid rain now evident in the northeastern United States and Canada (see Atmospheric models). References 3—15 discuss atmospheric dilution as a control measure. The better approach, however, is to control emissions at the source. 

A variety of models have been developed to study acid deposition. Sulfuric acid is formed relatively slowly in the atmosphere, so its concentrations are beUeved to be more uniform than o2one, especially in and around cities. Also, the impacts are viewed as more regional in nature. This allows an even coarser hori2ontal resolution, on the order of 80 to 100 km, to be used in acid deposition models. Atmospheric models of acid deposition have been used to determine where reductions in sulfur dioxide emissions would be most effective. Many of the ecosystems that are most sensitive to damage from acid deposition are located in the northeastern United States and southeastern Canada. Early acid deposition models helped to estabUsh that sulfuric acid and its precursors are transported over long distances, eg, from the Ohio River Valley to New England (86—88). Models have also been used to show that sulfuric acid deposition is nearly linear in response to changing levels of emissions of sulfur dioxide (89). 

Hvitved-Jacobsen, T., J. Vollertsen, andN. Tanaka (1999), Wastewater quality changes during transport in sewers — An integrated aerobic and anaerobic model concept for carbon and sulfur microbial transformations, Water Sci. Tech., 39(2), 242-249. 

However, it is well known that various pollutants including sulfur compounds can be transported by air from country to country in the whole Asian domain and especially in North East Asia. Thus, model calculations have shown that in 1991— 1994 about 35% of oxidized sulfur species deposited in South Korea was transported from other locations, mainly from China (Sofiev, 1999). Accordingly, in spite of a national reduction in SO2 emission, the sulfur depositions are still very significant. 

Figure 8.7 Simplified model of nicotiniamine (NA) function in plant cells. Iron is transported across the plasma membrane by the Strategy I or Strategy II uptake systems. Once inside the cell, NA is the default chelator of iron to avoid precipitation and catalysis of radical oxygen species. The iron is then donated to proteins, iron-sulfur clusters and haem, while ferritin and iron precipitation are only present during iron excess. (From Hell and Stephan, 2003. With kind permission of Springer Science and Business Media.)...

To model sulfur dioxide absorption by the blood through the walls of the upper airways, as demonstrated by Frank et one must include the transport rates of sulfur dioxide across a mucus-tissue interface, a tissue layer, and a tissue-blood interface (Figure 7-2). For the case of release of dissolved gas back into the exhaled air, which is depleted of gas in the lower lung, the mucus layer would still represent the greatest resistance to transfer. Consequently, the overall transfer coefficient, kg, would still be given by ki/H. 

Iron-sulfur proteins belong to the class of electron-transport proteins [29]. They contain an iron sulfur cluster, e.g. [4Fe-4S], which shuttles between different oxidation states. The structure of the cluster is quite consistent among a series of these proteins, but their redox potentials vary widely. Synthetic models of iron-sulfur proteins have been designed [30] to investigate the factors that determine the reduction potential of the core and to mimic other biologically... 

Based on the studies on the KD306-type sulfur-resisting methanation catalyst, the non-isothermal one-dimensional and two-dimensional reaction-diffusion models for the key-components have been established, which were solved using an orthogonal collocation method. The simulation values of the effectiveness factors for the methanation reaction ch4 and the shift reaction fco2are in fair agreement with the experimental values, which indicates that both models are able to predict intraparticle transport and reaction processes within catalyst pellets. 

Based on the use of the NARCM regional model of climate and formation of the field of concentration and size distribution of aerosol, Munoz-Alpizar et al. (2003) calculated the transport, diffusion, and deposition of sulfate aerosol using an approximate model of the processes of sulfur oxidation that does not take the chemical processes in urban air into account. However, the 3-D evolution of microphysical and optical characteristics of aerosol was discussed in detail. The results of numerical modeling were compared with observational data near the surface and in the free troposphere carried out on March 2, 4, and 14, 1997. Analysis of the time series of observations at the airport in Mexico City revealed low values of visibility in the morning due to the small thickness of the ABL, and the subsequent improvement of visibility as ABL thickness increased. Estimates of visibility revealed its strong dependence on wind direction and aerosol size distribution. Calculations have shown that increased detail in size distribution presentation promotes a more reliable simulation of the coagulation processes and a more realistic size distribution characterized by the presence of the accumulation mode of aerosol with the size of particles 0.3 pm. In this case, the results of visibility calculations become more reliable, too. 

Equations (4.1) through (4.18) are supplemented in each cell of the spatial division of the ocean surface with initial conditions (Table 4.3). The boundary conditions for Equations (4.11) through (4.18) are zero. The calculation procedure to estimate sulfur concentration consists of two stages. First, at each time moment th for all cells Qiy, Equations (4.1)-(4.18) are solved by the quasi-linearization method, and all reservoirs of sulfur are estimated for ti+x = tf + At, where time step At is chosen from the convergence state of the calculation procedure. Then, at moment t(+1 using the climate unit of the global model these estimates are specified with account of the atmospheric transport and ocean currents over time At. 

---