Paradoxical ozone associations could be due to methyl nitrite from combustion of methyl ethers or esters in engine fuels

We review studies of the effects of low ambient ozone concentrations on morbidity that found a negative coefficient for ozone concentration. We call this a Paradoxical Ozone Association (POA). All studies were in regions with methyl ether in gasoline. All but one study carefully controlled for the effects of other criterion pollutants, so the phenomenon cannot be attributed to them. One was in southern California in mid-summer when ozone levels are highest. Because ozone is created by sunlight, the most plausible explanation for a POA would be an ambient pollutant that is rapidly destroyed by sunlight, such as methyl nitrite (MN). A previously published model of engine exhaust chemistry suggested methyl ether in the fuel will create MN in the exhaust. MN is known to be highly toxic, and closely related alkyl nitrites are known to induce respiratory sensitivity in humans. Support for the interpretation comes from many studies, including three linking asthma symptoms to methyl tertiary butyl ether (MTBE) and the observation that a POA has not been seen in regions without ether in gasoline. We also note that studies in southern California show a historical trend from more significant to less significant ozone-health associations. The timing of those changes is consistent with the known timing of the introduction of gasoline oxygenated with MTBE in that region.