Ozone estimation

To estimate the effect of automobile traffic and motor fuels on ozone formation, it is necessary to know the composition of exhaust gas in detail. Figure 5.26 gives an example of a gas phase chromatographic analysis of a conventional unleaded motor fuel. 

In this sequence the Cl also acts as a catalyst and two molecules are destroyed. It is estimated that before the Cl is finally removed from the atmosphere in 1—2 yr by precipitation, each Cl atom will have destroyed approximately 100,000 molecules (60). The estimated O -depletion potential of some common CFCs, hydrofluorocarbons, HFCs, and hydrochlorofluorocarbons, HCFCs, are presented in Table 10. The O -depletion potential is defined as the ratio of the emission rate of a compound required to produce a steady-state depletion of 1% to the amount of CFC-11 required to produce the 1% depletion. The halons, bromochlorofluorocarbons or bromofluorocarbons that are widely used in fire extinguishers, are also ozone-depleting compounds. Although halon emissions, and thus the atmospheric concentrations, are much lower than the most common CFCs, halons are of concern because they are from three to ten times more destmctive to O, than the CFCs. 

Each refiner has the flexibiUty to choose the specific formulation to produce based on the economics of the individual refineries. REG meeting the statutory requirements must be sold in the nine areas of the country which have the worst ozone (qv) problem. In addition, all other areas of the country which exceed the ozone NAAQS may elect the REG regulations, and EPA has estimated that 40% of the nation s gasoline should be subject to REG rules (66). 

O ne. Air pollution (qv) levels are commonly estimated by determining ozone through its chemiluminescent reaction with ethylene. A relatively simple photoelectric device is used for rapid routine measurements. The device is caHbrated with ozone from an ozone generator, which in turn is caHbrated by the reaction of ozone with potassium iodide (308). Detection limits are 6—9 ppb with commercially available instmmentation (309). 

Ha.logen Compounds. Fluorine is unreactive toward ozone at ordinary temperatures. Chlorine is oxidized to Cl20 and Cl20y, bromine to Br Og, and iodine to I2O2 and I4O2. Oxidation of haUde ions by ozone increases with the atomic number of haUde. Fluoride is unreactive chloride reacts slowly, ultimately forming chlorate and bromide is readily oxidized to hypobromite (38). Oxidation of iodide is extremely rapid, initially yielding hypoiodite the estimated rate constant is 2 x 10 (39). HypohaUte ions are oxidized to haUtes hypobromite reacts faster than hypochlorite (40). 

The EPA is reviewing and revising the Air QuaUty and Other Photochemical Oxidants (Criteria Document) and reevaluating the national ambient air quahty standards (158). The EPA is also proposing that manufacturers (>10,000 lb 03/yr) and users (>25,000 lb 03/yr) submit data annually to the EPA on estimated ozone releases (159). 

Trichloroethylene is being evaluated by the industry as a precursor in the production of hydrochlorofluorocarbons (HCEC), the replacement products for the chlorofluorocarbons impHcated in the depletion of the stratospheric ozone. At this time it is too early to project any estimates or probabihties for potential volume changes as a result of this opportunity (23). 

Seinfeld (33) indicates that photochemical models estimating peak ozone concentrations in urban areas are generally within 30% of measured peaks. 

Burning fossil fuels can release air pollutants such as carbon dioxide, sulfur oxides, nitrogen oxides, ozone, and particulate matter. Sulfur and nitrogen oxides contribute to acid rain ozone is a component of urban smog, and particulate matter affects respiratory health. In fact, several studies have documented a disturbing correlation between suspended particulate levels and human mortality. It is estimated that air pollution may help cause 500,000 premature deaths and millions of new respiratory illnesses each year. 

In order to estimate the extent of ozone depletion caused by a given release of CFCs, computer models of the atmosphere are employed. These models incorporate information on atmospheric motions and on the rates of over a hundred chemical and photochemical reactions. The results of measurements of the various trace species in the atmosphere are then used to test the models. Because of the complexity of atmospheric transport, the calculations were carried out initially with one-dimensional models, averaging the motions and the concentrations of chemical species over latitude and longitude, leaving only their dependency on altitude and time. More recently, two-dimensional models have been developed, in which the averaging is over longitude only. 

The net reaction for this two-step mechanism is the conversion of an O3 molecule and an oxygen atom into two O2 molecules. In this mechanism, chlorine atoms catalyze ozone decomposition. They participate in the mechanism, but they do not appear in the overall stoichiometry. Although chlorine atoms are consumed in the first step, they are regenerated in the second. The cyclical nature of this process means that each chlorine atom can catalyze the destruction of many O3 molecules. It has been estimated that each chlorine atom produced by a CFC molecule in the upper stratosphere destroys about 100,000 molecules of ozone before it is removed by other reactions such as recombination CF2 Cl -b Cl CF2 CI2... 

C16-0012. Estimate the equilibrium constant for the ozone formation reaction at 825 °C. 

The revealed preference method is an indirect approach that is used in order to monetize use values. This method observes the real choice between money and the environmental goods. Methods often include observations of consumers or producers behaviour or actions, such as the hedonic price method and the production function method. The hedonic price method determines values from actual market transactions. These transactions are used to see how the price of a market commodity varies when a related environmental good changes, such as the effects of noise or air pollution on house prices. The production function method is used to estimate the value of the environmental effects on production. This method is suitable when consumption or production of a private good is affected by the environmental good. An example is the valuation of ground-level ozone levels by valuing the impact on the production of wheat or timber, which has market prices. The problem with the revealed preference method is that it does not contain all the individuals values that affect the WTP. 

Recent estimates indicate that the level of carbon dioxide in the atmosphere has increased by a third since the beginning of the industrial age, and that it contributes significantly to global warming. Other major contributors include methane, tropospheric ozone, and nitrous oxide. Methane is the principal component of natural gas, but it is also produced by other sources such as rice paddies and farm animals. Tropospheric ozone is generated naturally and by the sunlight-... 

Extensive research has been conducted into the atmospheric chemistry of organic chemicals because of air quality concerns. Recently, Atkinson and coworkers (1984, 1985, 1987, 1988, 1989, 1990, 1991), Altshuller (1980, 1991) and Sabljic and Glisten (1990) have reviewed the photochemistry of many organic chemicals of environmental interest for their gas phase reactions with hydroxyl radicals (OH), ozone (03) and nitrate radicals (N03) and have provided detailed information on reaction rate constants and experimental conditions, which allowed the estimation of atmospheric lifetimes. Klopffer (1991) has estimated the atmospheric lifetimes for the reaction with OH radicals to range from 1 hour to 130 years, based on these reaction rate constants and an assumed constant concentration of OH... 

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