Evaluation of the reaction artifacts in an annular denuder-based sampler resulting from the heterogeneous ozonolysis of naphthalene

Goriaux, Mathieu; Pflieger, Maryline; Monod, Anne; Gligorovski, Sasho; Strekowski, Rafal S.; Wortham, Henri

Evaluation of the reaction artifacts in an annular denuder-based sampler resulting from the heterogeneous ozonolysis of naphthalene

2014

The heterogeneous ozonolysis of naphthalene adsorbed on XAD-4 resin was studied using an annular denuder technique. The experiments involved depositing a known quantity of naphthalene on the XAD-4 resin and then measuring the quantity of the solid naphthalene that reacted away under a constant flow of gaseous ozone (0.064 to 4.9 ppm) for a defined amount of time. All experiments were performed at room temperature (26 to 30 °C) and atmospheric pressure. The kinetic rate coefficient for the ozonolysis reaction of naphthalene adsorbed on XAD-4 resin is reported to be (10.1 ± 0.4) × 10⁻¹⁹ cm³ molecule⁻¹ s⁻¹(error is 2σ, precision only). This value is five times greater than the currently recommended literature value for the homogeneous gas phase reaction of naphthalene with ozone. The obtained rate coefficient is used to evaluate reaction artifacts from field concentration measurements of naphthalene, acenaphthene, and phenanthrene. The observed uncertainties associated with field concentration measurements of naphthalene, acenaphthene, and phenanthrene are reported to be much higher than the uncertainties associated with the artifact reactions. Consequently, ozone reaction artifact appears to be negligible compared to the observed field measurement uncertainty results.

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