Atmospheric Chemical Transport Models 1 Model Types

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. 

Chemical vapor deposition (CVD) of thin solid films from gaseous reactants is reviewed. General process considerations such as film thickness, uniformity, and structure are discussed, along with chemical vapor deposition reactor systems. Fundamental issues related to nucleation, thermodynamics, gas-phase chemistry, and surface chemistry are reviewed. Transport phenomena in low-pressure and atmospheric-pressure chemical vapor deposition systems are described and compared with those in other chemically reacting systems. Finally, modeling approaches to the different types of chemical vapor deposition reactors are outlined and illustrated with examples. 

We can attempt to apply the same type of model to the H2S data, however there are two additional unknown factors involved. First, we do not have a measurement of the sea surface concentrations of H2S. Second, the piston velocity of H2S is enhanced by a chemical enrichment factor which, in laboratory studies, increases the transfer rate over that expected for the unionized species alone. Balls and Liss (5Q) demonstrated that at seawater pH the HS- present in solution contributes significantly to the total transport of H S across the interface. Since the degree of enrichment is not known under field conditions, we have assumed (as an upper limit) that the transfer occurs as if all of the labile sulfide (including HS ana weakly complexed sulfide) was present as H2S. In this case, the piston velocity of H2S would be the same as that of Radon for a given wind velocity, with a small correction (a factor of 1.14) for the estimated diffusivity difference. If we then specify the piston velocity and OH concentration we could calculate the concentration of H2S in the surface waters. Using the input conditions from model run B from Figure 4a (OH = 5 x 106 molecules/cm3, Vd = 3.1 m/day) yields a sea surface sulfide concentration of approximately 0.1 nM. Figure S illustrates the diurnal profile of atmospheric H2S which results from these calculations. 

Several types of models are commonly used to describe the dispersion of atmospheric contaminants. Among these are the box, plume, and puff models. None are suitable, however, for describing the coupled transport and reaction phenomena that characterize atmospheres in which chemical reaction processes are important. Simulation models that have been proposed for the prediction of concentrations of photochemically formed pollutants in an urban airshed are reviewed here. The development of a generalized kinetic mechanism for photochemical smog suitable for inclusion in an urban airshed model, the treatment of emissions from automobiles, aircraft, power plants, and distributed sources, and the treatment of temporal and spatial variations of primary meteorological parameters are also discussed. 

Bullock (1997) used the Regional Lagrangian Model of Air Pollution (RELMAP) to simulate the emission, transport, chemical transformation, and wet and dry deposition of elemental mercury gas, divalent mercury gas, and particulate mercury from various point and area source types to develop an atmospheric mercury emissions inventory by anthropogenic source type. The results of the RELMAP model are shown in Table 5-3. On a percentage basis, various combustion processes (medical waste incinerators, municipal waste incinerators, electric utility power production [fossil fuel burning] and nonutility power and heat generation) account for 83% of all anthropogenic emissions in the United States. Overall, of the emissions produced, 41% were associated with elemental mercury vapor (Hg°), 41% with the mercuric form (Hg2+), and 18% was mercury associated with particulates. 

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