Atmospheric pseudohalogen chemistry

D. J. Lary (1, 2, 3)

1 GMAO - Global Modeling and Assimilation Office
2 GEST at the University of Maryland Baltimore County
3 Unilever R&D

There are at least three reasons why hydrogen cyanide is likely to be significant for atmospheric chemistry. The first is well known, HCN is a product and marker of biomass burning. However, if a detailed ion chemistry of lightning is considered then it is almost certain than in addition to lightning producing NO_x, it also produces HO_x and HCN. Unlike NO_x and HO_x, HCN is long-lived and could therefore be a useful marker of lightning activity. Observational evidence is considered to support this view. Thirdly, the chemical decomposition of HCN leads to the production of small amounts of CN and NCO. NCO can be photolyzed in the visible portion of the spectrum yielding N atoms. The production of N atoms is significant as it leads to the titration of nitrogen from the atmosphere via N+N?N₂. Normally the only modelled source of N atoms is NO photolysis which happens largely in the UV Schumann-Runge bands. However, NCO photolysis occurs in the visible and so could be involved in titration of atmospheric nitrogen in the lower stratosphere and troposphere. HCN emission inventories are worthy of attention. The CN and NCO radicals have been termed pseudohalogens since the 1920s. They are strongly bound, univalent, radicals with an extensive and varied chemistry. The products of the atmospheric oxidation of HCN are NO, CO and O₃. N+CH₄ and N+CH₃OH are found to be important sources of HCN. Including the pseudohalogen chemistry gives a small increase in ozone and total reactive nitrogen (NO_y).

Domaines: Océan, Atmosphère

D. J. Lary. Atmospheric pseudohalogen chemistry. Atmospheric Chemistry and Physics Discussions, 2004, 4 (5), pp.5381-5405. ⟨hal-00301426⟩