Atmospheric removal mechanisms

Lindberg SE (1980) Mercury partitioning in apower plant plume and its influence on atmospheric removal mechanisms. Atmos Environ 14 227— 231. 

Ammonia is the primary basic gas in the atmosphere and, after N2 and N20, is the most abundant nitrogen-containing compound in the atmosphere. The significant sources of NH3 are animal waste, ammonification of humus followed by emission from soils, losses of NH3-based fertilizers from soils, and industrial emissions (Table 2.8). The ammonium (NH ) ion is an important component of the continental tropospheric aerosol. Because NH3 is readily absorbed by surfaces such as water and soil, its residence time in the lower atmosphere is estimated to be quite short, about 10 days. Wet and dry deposition of NH3 are the main atmospheric removal mechanisms for NH3. In fact, deposition of atmospheric NH3 and NH4" may represent an important nutrient to the biosphere in some areas. Atmospheric concentrations of NH3 are quite variable, depending on proximity to a source-rich region. NH3 mixing ratios over continents range typically between 0.1 and lOppb. 

A solution of sodium methoxide, prepared from sodium (23 g) and dry methanol (500 mL), was added drop-wise at 0 °C to a stirred suspension of aminoacetonitrile hydrochloride (18, 100 g, 1.08 mol) in dry methanol (100 rnL). After stirring for 2 h at rt the precipitated sodium chloride was filtered off and the filtrate concentrated in vacuo. EtOAc (20 mL) was added and evaporated under reduced pressure to remove all traces of methanol. The oily residue was dissolved in dry EtOAc (100 mL) and anhydrous sodium sulfate added. After cooling, the precipitate was filtered off. The solution of crude aminoacetonitrile was used without further purification. This solution was added drop-wise during a period of 1 h to a vigorously stirred, ice-cooled solution of carbon disulphide (100 mL, 1.66 mol) in dry EtOAc (100 mL) under an N2 atmosphere. Continued mechanical stirring and water-free conditions were essential. The mixture was stirred at 0 °C for 1 h. The resultant precipitate was filtered off, washed with EtaO and dried, giving the product 50 as yellow crystals (99 g, 75 % on amount of sodium), m.p. 131 °C dec. IR (KBr) v max 1630, 1500 cm. ... 

Environmental Fate. Sensitized photolysis studies in water and oxidation/reduction studies in both air and water are lacking, as are biodegradation studies in surface and groundwaters. These kinds of studies are important, since they represent the fundamental removal mechanisms available to isophorone in the environment. In addition, the kinetic studies for the atmospheric reactions are important for understanding the significance of a removal mechanism and predicting the reactions that may control the fate of a chemical in the environment. 

Once PAHs enter the atmosphere, they are distributed between gas and particle phases and subject to removal mechanisms, such as oxidative and... 

Figure 7.1 Major sources and modes of atmospheric aerosol particles and principal removal mechanisms (Whitby and Cantrell, 1976 Seinfeld and Pandis, 1998).

In ambient air, the primary removal mechanism for acrolein is predicted to be reaction with photochemically generated hydroxyl radicals (half-life 15-20 hours). Products of this reaction include carbon monoxide, formaldehyde, and glycolaldehyde. In the presence of nitrogen oxides, peroxynitrate and nitric acid are also formed. Small amounts of acrolein may also be removed from the atmosphere in precipitation. Insufficient data are available to predict the fate of acrolein in indoor air. In water, small amounts of acrolein may be removed by volatilization (half-life 23 hours from a model river 1 m deep), aerobic biodegradation, or reversible hydration to 0-hydroxypropionaldehyde, which subsequently biodegrades. Half-lives less than 1-3 days for small amounts of acrolein in surface water have been observed. When highly concentrated amounts of acrolein are released or spilled into water, this compound may polymerize by oxidation or hydration processes. In soil, acrolein is expected to be subject to the same removal processes as in water. 

Although only 10% of atmospheric ozone resides in the troposphere (0-15 km altitude) it has a profound impact on tropospheric chemistry. Ozone concentrations in the troposphere vary from typically 20-40 ppb for a remote pristine site to 100-200 ppb in a highly polluted urban environment. Ozone is a reactive molecule, which readily adds to carbon-carbon double bonds [8]. Reaction with ozone provides an important removal mechanism for many unsaturated reactive organic compounds. 

Thus the lifetime of a constituent with a first order removal process is equal to the inverse of the first order rate constant for its removal. Taking an example from atmospheric chemistry, the major removal mechanism for many trace gases is reaction with hydroxyl radical, OH. Considering two substances with very different rate constants for this reaction, methane and nitrogen dioxide... 

In summary, it appears [cf. Robinson and Robbins (214)] that photochemical reactions involving N02 and hydrocarbons and absorption by alkaline water drops with or without metal catalysts are the major mechanisms for oxidizing SC. The complex nature of these removal mechanisms will, however, make their inclusion in any atmospheric photochemical model difficult. This will be discussed in Section V. 

---