Hydroxyl radical atmospheric lifetimes, 252, Table

Hydroxyl radical, OH, is the principal atmospheric oxidant for a vast array of organic and inorganic compounds in the atmosphere. In addition to being the primary oxidant of non-methane hydrocarbons (representative examples of these secondary reactions are given in Table 6), OH radical controls the rate of CO and CH4 oxidation. Furthermore, the OH reaction with ozone also limits the destruction of O3 in the troposphere, it also determines the lifetime of CH3CI, CHsBr, and a wide range of HCFC s, and it controls the rate of NO to HNO3 conversion. Concentration profiles for hydroxyl radical in the atmosphere are shown in Fig. 2. 

Pedersen and Sehested (2002) showed that the aqueous-phase reaction of isoprene with ozone was insignificant for the processing of isoprene in the atmosphere. They estimated the overall and individual lifetimes of isoprene due to reactions with ozone and the hydroxyl radical, at 25 "C and typical in-cloud conditions. The results (Table 3) indicate that clouds generally should not contribute much to the processing of isoprene in the atmosphere. Only in the aqueous phase, were the lifetimes of isoprene due to reactions with ozone and with OH radicals comparable. Similar conclusions were drawn for methyl vinyl ketone, while for methacrolein the clouds could reduce the overall atmospheric lifetime by 50 %. 

Table 2.1 lists atmospheric sulfur compounds. The principal sulfur compounds in the atmosphere are H2S, CH3SCH3, CS2, OCS, and SO2. Sulfur occurs in five oxidation states in the atmosphere. (See Box) Chemical reactivity of atmospheric sulfur compounds is inversely related to their sulfur oxidation state. Reduced sulfur compounds, those with oxidation state -2 or —1, are rapidly oxidized by the hydroxyl radical and, to a lesser extent, by other species, with resulting atmospheric lifetimes of a few days. The water solubility of sulfur species increases with oxidation state reduced sulfur species occur preferentially in the gas phase, whereas the (+6) compounds often tend to be found in particles or droplets. Once converted to compounds in the S(+6) state, sulfur species residence times are determined by removal by wet and dry deposition. 

Compounds released to the environment distribute among the major environmental compartments, air, water, soil, and biota as a function of their physical chemical properties and models can provide a basis to predict how different compounds behave. Adverse effects will depend on persistence in a compartment. In this context, it is readily apparent that the hydroxyl radical serves as a very efficient atmospheric scavenger. Other oxidants may show activity with a limited series of compounds, but the hydroxyl radical is unique in the broad range of organic compounds with which it reacts and the rates at which these reactions proceed. Lifetimes for selected compounds based on reactions with the hydroxyl radical are compiled in Table 6.28. 

TABLE 6.28 Atmospheric Lifetimes Based on Reaction with Hydroxyl Radical... 

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