Effects of NOx and SO2 on the secondary organic aerosol formation from photooxidation of α-pinene and limonene

Defeng Zhao, Sebastian H. Schmitt, Mingjin Wang, Ismail-Hakki Acir, Ralf Tillmann, Zhaofeng Tan, Anna Novelli, Hendrik Fuchs, Iida Pullinen, Robert Wegener, Franz Rohrer, Jürgen Wildt (+3 others)
2018 Atmospheric Chemistry and Physics  
<p><strong>Abstract.</strong> Anthropogenic emissions such as NO<sub><i>x</i></sub> and SO<sub>2</sub> influence the biogenic secondary organic aerosol (SOA) formation, but detailed mechanisms and effects are still elusive. We studied the effects of NO<sub><i>x</i></sub> and SO<sub>2</sub> on the SOA formation from the photooxidation of <i>α</i>-pinene and limonene at ambient relevant NO<sub><i>x</i></sub> and SO<sub>2</sub> concentrations (NO<sub><i>x</i></sub>: &amp;lt;<span
more » ... </span>1to 20<span class="thinspace"></span>ppb, SO<sub>2</sub>: &amp;lt;<span class="thinspace"></span>0.05 to 15<span class="thinspace"></span>ppb). In these experiments, monoterpene oxidation was dominated by OH oxidation. We found that SO<sub>2</sub> induced nucleation and enhanced SOA mass formation. NO<sub><i>x</i></sub> strongly suppressed not only new particle formation but also SOA mass yield. However, in the presence of SO<sub>2</sub> which induced a high number concentration of particles after oxidation to H<sub>2</sub>SO<sub>4</sub>, the suppression of the mass yield of SOA by NO<sub><i>x</i></sub> was completely or partly compensated for. This indicates that the suppression of SOA yield by NO<sub><i>x</i></sub> was largely due to the suppressed new particle formation, leading to a lack of particle surface for the organics to condense on and thus a significant influence of vapor wall loss on SOA mass yield. By compensating for the suppressing effect on nucleation of NO<sub><i>x</i></sub>, SO<sub>2</sub> also compensated for the suppressing effect on SOA yield. Aerosol mass spectrometer data show that increasing NO<sub><i>x</i></sub> enhanced nitrate formation. The majority of the nitrate was organic nitrate (57–77<span class="thinspace"></span>%), even in low-NO<sub><i>x</i></sub> conditions (&amp;lt;<span class="thinspace"></span> ∼ <span class="thinspace"></span>1<span class="thinspace"></span>ppb). Organic nitrate contributed 7–26<span class="thinspace"></span>% of total organics assuming a molecular weight of 200<span class="thinspace"></span>g<span class="thinspace"></span>mol<sup>−1</sup>. SOA from <i>α</i>-pinene photooxidation at high NO<sub><i>x</i></sub> had a generally lower hydrogen to carbon ratio (H<span class="thinspace"></span>∕<span class="thinspace"></span>C), compared to low NO<sub><i>x</i></sub>. The NO<sub><i>x</i></sub> dependence of the chemical composition can be attributed to the NO<sub><i>x</i></sub> dependence of the branching ratio of the RO<sub>2</sub> loss reactions, leading to a lower fraction of organic hydroperoxides and higher fractions of organic nitrates at high NO<sub><i>x</i></sub>. While NO<sub><i>x</i></sub> suppressed new particle formation and SOA mass formation, SO<sub>2</sub> can compensate for such effects, and the combining effect of SO<sub>2</sub> and NO<sub><i>x</i></sub> may have an important influence on SOA formation affected by interactions of biogenic volatile organic compounds (VOCs) with anthropogenic emissions.</p>
doi:10.5194/acp-18-1611-2018 fatcat:t4sk7ml2hjgedbbyzm2lb3nvpi