Photodissociation of nitrogen dioxide forms an oxygen atom, followed by third-body recombination:
If NO is converted back to nitrogen dioxide only by , this is a null cycle with no net ozone production. Oxidation of a volatile organic compound by OH generates organic peroxy radicals, and often hydroperoxyl radicals, which instead oxidize NO without consuming ozone:
The newly formed nitrogen dioxide can then photolyse, giving net ozone production. These chain reactions require sunlight, radical production and both precursor families.
In an NOx-limited ozone-production regime, NO is too scarce for efficient peroxy-radical conversion; competing peroxide-forming radical termination becomes important. Reducing nitrogen-oxide emissions then reduces ozone production. In a VOC-limited ozone-production regime, plentiful nitrogen oxides remove OH through , so organic oxidation and radical supply are limiting. Reducing volatile-organic emissions is effective there, while a modest nitrogen-oxide reduction can initially increase ozone by reducing radical termination and NO titration. Sufficiently large nitrogen-oxide reductions can move the system into the limited regime and eventually lower ozone. The appropriate control therefore depends on the chemical regime and the regional transport history, not merely the largest local emission. The ozone isopleth diagram below uses an explicitly schematic response function to show derivative signs, not a fitted concentration or emissions-control prediction.[ref]
Figure 1.
Original schematic showing opposite local ozone responses to nitrogen-oxide controls in two chemical regimes
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Sanford Sillman Created 2026-10-20 Updated 2026-11-05
Sanford Sillman coauthored regional photochemical modelling of the sensitivity of ozone to nitrogen oxides and hydrocarbons. The work distinguishes chemical regimes rather than assuming that reducing either precursor has the same effect everywhere.
Competing radical production, propagation, and termination processes can change the response. This is why a regional ozone-control strategy needs information about chemical regime as well as emission totals.[ref]