Atmospheric chemistry, sources and sinks of carbon suboxide, C<sub>3</sub>O<sub>2</sub>

oleh: S. Keßel, D. Cabrera-Perez, A. Horowitz, P. R. Veres, P. R. Veres, P. R. Veres, R. Sander, D. Taraborrelli, D. Taraborrelli, M. Tucceri, J. N. Crowley, A. Pozzer, C. Stönner, L. Vereecken, L. Vereecken, J. Lelieveld, J. Williams

Format: Article
Diterbitkan: Copernicus Publications 2017-07-01

Deskripsi

Carbon suboxide, O  =  C  =  C  =  C  =  O, has been detected in ambient air samples and has the potential to be a noxious pollutant and oxidant precursor; however, its lifetime and fate in the atmosphere are largely unknown. In this work, we collect an extensive set of studies on the atmospheric chemistry of C<sub>3</sub>O<sub>2</sub>. Rate coefficients for the reactions of C<sub>3</sub>O<sub>2</sub> with OH radicals and ozone were determined as <i>k</i><sub>OH</sub> =  (2.6 ± 0.5)  ×  10<sup>−12</sup> cm<sup>3</sup> molecule<sup>−1</sup> s<sup>−1</sup> at 295 K (independent of pressure between  ∼  25 and 1000 mbar) and <i>k</i><sub>O<sub>3</sub></sub>  &lt;  1.5  ×  10<sup>−21</sup> cm<sup>3</sup> molecule<sup>−1</sup> s<sup>−1</sup> at 295 K. A theoretical study on the mechanisms of these reactions indicates that the sole products are CO and CO<sub>2</sub>, as observed experimentally. The UV absorption spectrum and the interaction of C<sub>3</sub>O<sub>2</sub> with water (Henry's law solubility and hydrolysis rate constant) were also investigated, enabling its photodissociation lifetime and hydrolysis rates, respectively, to be assessed. <br><br> The role of C<sub>3</sub>O<sub>2</sub> in the atmosphere was examined using in situ measurements, an analysis of the atmospheric sources and sinks and simulation with the EMAC atmospheric chemistry–general circulation model. The results indicate sub-pptv levels at the Earth's surface, up to about 10 pptv in regions with relatively strong sources, e.g. influenced by biomass burning, and a mean lifetime of  ∼  3.2 days. These predictions carry considerable uncertainty, as more measurement data are needed to determine ambient concentrations and constrain the source strengths.