Abstract
Detailed mechanisms are outlined for the chemical reactions involved In the atmospheric removal of four unsaturated chlorinated aliphatic contaminants, allyl chloride, chloroprene, hexachlorocyclopentadiene and vlnylldene chloride. Rate constants estimated from structure-reactivity relationships Indicate rapid removal for all four compounds by reactions with OH (major), ozone, and NO3, with half-lives of 2-16 hrs for removal by reaction with OH. Reaction products of allyl chloride (formaldehyde, chloroacetaldehyde, peroxychloroacetyl nitrate) and vinylidene chloride (formaldehyde, phosgene, chloroacetyl chloride) are consistent with OH addition-Initiated pathways that include Cl atom elimination. The chlorine atoms produced In the OH reaction sequence react rapidly with all four unsaturated compounds, but these reactions are of negligible Importance for atmospheric removal of the four toxic contaminants studied. Analogous mechanisms are discussed for chloroprene (leading to formaldehyde, CH2 = CCICHO, and CICOCHO) and for hexachlorocyclopentadlene (leading to oxalyl chloride and CICOCCI2COCI).