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Transformation of isoprene coupled with auto-oxidation of SIV inaqueous solutions was studied experimentally and by chemical-kineticmodelling over a broad range of solution acidities (pH=3–9) to complementthe research on aqueous-phase and heterogeneous transformation of isoprenereported recently by many laboratories. Isoprene significantly slowed downthe auto-oxidation in acidic and basic solutions, and accelerated it slightlyin neutral solutions. Simultaneously, production of sulphate ions andformation of solution acidity were significantly reduced. Formation ofsulphite and sulphate derivatives of isoprene - sulphurous acidmono-(2-methyl-4-oxo-but-2-enyl) ester (m/z=163), sulphurous acidmono-(4-hydroxy-2-methyl-but-2-enyl) ester (m/z=165), sulphuricacid mono-(2-methyl-4-oxo-but-2-enyl) ester (m/z=179), sulphuricacid mono-(4-hydroxy-2-methyl-but-2-enyl) ester (m/z=181), andpossible structural isomers of these species – was indicated by electrosprayionisation mass spectrometric analysis of post-reaction mixtures. Theexperimental results were explained by changes in a subtle quantitativebalance of three superimposed processes whose rates depended in differentmanner on the acidity of reacting solutions – the scavenging of sulphoxyradical-anions by isoprene, the formation of sulphoxy radical-anions duringfurther reactions of isoprene radicals, and the auto-oxidation ofSIV itself. A chemical mechanism based on this idea was explorednumerically to show good agreement with experimental data. In basic andneutral solutions, the model overestimated the consumption of isoprene,probably because reactions of primary sulphite and sulphate derivatives ofisoprene with sulphoxy radical-anions were not included. Interaction ofisoprene with sulphur(IV) species and oxygen can possibly result in formationof new organosulphate and organosulphite components of atmospheric aerosolsand waters, and influence the distribution of reactive sulphur and oxygenspecies in isoprene-emitting organisms exposed to SIV pollutants

Reactions of isoprene and sulphoxy radical-anions – a possible source of atmospheric organosulphites and organosulphates