Gas Phase and Gas-Solid Interface Ozonolysis of Nitrogen Containing Alkenes: Nitroalkenes, Enamines, and Nitroenamines

Emerging contaminants are of concern due to their rapidly increasing numbers and potential ecological and human health effects. In this study, the synergistic effects of the presence of multifunctional nitro, amino and carbon-carbon double bond (C= C) groups on the gas phase ozonolysis in O2 or at the air/solid interface were investigated using five simple model compounds. The gas phase ozonolysis rate constants at 296 K were (3.5 +/- 0.9) x 10-20 cm3 molecule-1 s-1 for 2-methyl-1-nitroprop-1-ene and (6.8 +/- 0.8) x 10-19 cm3 molecule-1 s-1 for 4-methyl-4-nitro-1-pentene, with lifetimes of 134 and 7 days in the presence of 100 ppb ozone in the atmosphere, respectively. The rate constants for gas phase E-N,N-dimethyl-1-propenylamine and N,N-dimethylallylamine reactions with ozone were too fast (> 10-18 cm3 molecule-1 s-1) to be measured, implying lifetimes of less than 5 days. A multiphase kinetics model (KM-GAP) was used to probe the gas-solid kinetics of 1-dimethylamino-2-nitroethylene, yielding a rate constant for the surface reaction of 1.8 x 10-9 cm2 molecule-1 s-1 and in the bulk 1x 10-16 cm3 molecule-1 s-1. These results show that a nitro group attached to the C=C lowers the gas phase rate constant by 2-3 orders of magnitude compared to the simple alkenes, while amino groups have the opposite effect. The presence of both groups provides counterbalancing effects. Products with deleterious health effects including dimethylformamide and formaldehyde were identified by FTIR. The identified products differentiate whether the initial site of ozone attack is C=C and/or the amino group. This study provides a basis for predicting the environmental fates of emerging contaminants and shows that both the toxicity of both the parent compounds and the products should be taken into account in assessing their environmental impacts.