Novel nighttime free radical chemistry in severe nitrogen dioxide pollution episodes

During winter air pollution episodes, nitrogen dioxide concentrations can far exceed health based guidelines, but to date, there has been no wholly adequate explanation of the atmospheric chemical production of very high concentrations of nitrogen dioxide during such episodes, despite inclusion of the thermal oxidation of nitric oxide with dioxygen, as well as the well known reaction with ozone. In laboratory studies we have shown that both petrol engine exhaust and petrol vapour catalyse the thermal oxidation of nitric oxide to nitrogen dioxide and have identified certain dialkenes as the chemical agent responsible (Shi and Harrison, 1997). It is postulated that addition of nitrogen dioxide to the dialkene forms a reactive free radical species which initiates a chain reaction during which peroxy species are formed which convert NO to NO2. A numerical box model including explicit hydrocarbon chemistry and incorporating this mechanism, shows that rates of nitrogen dioxide production observed in London in December 1991 and hitherto unexplained, are explicable by the presence of conjugate dialkenes at concentrations comparable with those which have been observed in polluted urban atmospheres.