Ozone (O3) is a constituent of the troposphere (it is also an important constituent of certain regions of the stratosphere commonly known as the Ozone layer). Photochemical and chemical reactions involving it drive many of the chemical processes that occur in the atmosphere by day and by night. At abnormally high concentrations brought about by human activities (largely incomplete combustion of fossil fuels, such as gasoline, diesel, etc.), it is a pollutant, and a constituent of smog. Many highly energetic reactions produce it, ranging from combustion to photocopying. Often laser printers will have a smell of ozone, which in high concentrations is toxic. Ozone is a powerful oxidizing agent readily reacting with other chemical compounds to make many possibly toxic oxides.
The troposphere extends from the surface of the Earth to between 12 and 20 kilometers above the surface of the Earth and consists of many layers. Ozone is more concentrated above the mixing layer, or ground layer. Ground-level ozone, though less concentrated than ozone aloft, is more of a problem because of its health effects.
Tropospheric ozone is a greenhouse gas and initiates the chemical removal of methane and other hydrocarbons from the atmosphere. Thus, its concentration affects how long these compounds remain in the air.
Satellites can measure tropospheric ozone.[1][2] Measurements specifically of ground-level ozone require in situ monitoring technology.
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The 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, CO, 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.
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).
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 mole fractions of 85 to 104 nmol/mol are described as "Unhealthy for Sensitive Groups", 105 nmol/mol to 124 nmol/mol as "unhealthy" and 125 nmol/mol to 404 nmol/mol 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.
Michelle 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