FormationThe majority of tropospheric ozone formation occurs when nitrogen oxides (NOx), carbon monoxide (CO) and volatile organic compounds (VOCs), such as xylene, react in the atmosphere in the presence of sunlight. NOx and VOCs are called ozone precursors. Motor vehicle exhaust, industrial emissions, and chemical solvents are the major anthropogenic sources of these chemicals. Another source is windshield washer fluid. Although these precursors often originate in urban areas, winds can carry NOx hundreds of kilometers, causing ozone formation to occur in less populated regions as well. Methane, a VOC whose atmospheric concentration has increased tremendously during the last century, contributes to ozone formation but on a global scale rather than in local or regional photochemical smog episodes. In situations where this exclusion of methane from the VOC group of substances is not obvious, the term Non-Methane VOC (NMVOC) is often used. The chemical reactions involved in tropospheric ozone formation are a series of complex cycles in which carbon monoxide and VOCs are oxidised to water vapour and carbon dioxide. The reactions involved in this process are illustrated here with CO but similar reactions occur for VOC as well. Oxidation begins with the reaction of CO with the hydroxyl radical. The hydrogen atom formed by this reacts rapidly with oxygen to give a peroxy radical HO2
Peroxy radicals then go on to react with NO to give NO2 which is photolysed to give atomic oxygen and through reaction with oxygen a molecule of ozone:
The net effect of these reactions is:
This cycle involving HOx and NOx is terminated by the reaction of OH with NO2 to form nitric acid or by the reaction of peroxy radicals with each other to form peroxides. The chemistry involving VOCs is much more complex but the same reaction of peroxy radicals oxidizing NO to NO2 is the critical step leading to ozone formation. Health effects
Ozone is known to have the following health effects at concentrations common in urban air:
A statistical study of 95 large urban communities in the United States found significant association between ozone levels and premature death. The study estimated that a one-third reduction in urban ozone concentrations would save roughly 4000 lives per year (Bell et. al, 2004). Problem areas
The United States Environmental Protection Agency has developed an Air Quality index to help explain air pollution levels to the general public. 8-hour average ozone concentrations of 85 to 104 ppbv are described as "Unhealthy for Sensitive Groups", 105 ppbv to 124 ppbv as "unhealthy" and 125 ppb to 404 ppb as "very unhealthy" [3]. The EPA has designated over 300 counties of the United States, clustered around the most heavily populated areas (especially in California and the Northeast), as failing to comply with the National Ambient Air Quality Standards. See also
ReferencesMichelle L. Bell; Aidan McDermott; Scott L. Zeger; Jonathan M. Samet; Francesca Dominici (2004). "Ozone and Short-term Mortality in 95 US Urban Communities, 1987-2000". Journal of the American Medical Association. 292, 2372-2378. Seinfeld, John H.; Pandis, Spyros N (1998). Atmospheric Chemistry and Physics - From Air Pollution to Climate Change. John Wiley and Sons, Inc. ISBN 0-471-17816-0 Wayne, Richard P (2000). Chemistry of Atmospheres (3rd Ed.). Oxford University Press. ISBN 0-19-850375-X External links
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