The effects of morphology, mobility size, and secondary organic aerosol (SOA) material coating on the ice nucleation activity of black carbon in the cirrus regime

• Main Authors: C. Zhang, Y. Zhang, M. J. Wolf, L. Nichman, C. Shen, T. B. Onasch, L. Chen, D. J. Cziczo
• Format: Article
• Language: English
• Published: Copernicus Publications 2020-11-01
• Series: Atmospheric Chemistry and Physics
• Online Access: https://acp.copernicus.org/articles/20/13957/2020/acp-20-13957-2020.pdf

<p>There is evidence that black carbon (BC) particles may affect cirrus formation and, hence, global climate by acting as potential ice nucleating particles (INPs) in the troposphere. Nevertheless, the ice nucleation (IN) ability of bare BC and BC coated with secondary organic aerosol (SOA) material remains uncertain. We have systematically examined the IN ability of 100–400&thinsp;nm size-selected BC particles with different morphologies and different SOA coatings representative of anthropogenic (toluene and <span class="inline-formula"><i>n</i></span>-dodecane) and biogenic (<span class="inline-formula"><i>β</i></span>-caryophyllene) sources in the cirrus regime (<span class="inline-formula">−46</span> to <span class="inline-formula">−38</span>&thinsp;<span class="inline-formula">^∘</span>C). Several BC proxies were selected to represent different particle morphologies and oxidation levels. Atmospheric aging was further replicated with the exposure of SOA-coated BC to OH. The results demonstrate that the 400&thinsp;nm hydrophobic BC types nucleate ice only at or near the homogeneous freezing threshold. Ice formation at cirrus temperatures below homogeneous freezing thresholds, as opposed to purely homogeneous freezing, was observed to occur for some BC types between 100 and 200&thinsp;nm within the investigated temperature range. More fractal BC particles did not consistently act as superior INPs over more spherical ones. SOA coating generated by oxidizing <span class="inline-formula"><i>β</i></span>-caryophyllene with O<span class="inline-formula">₃</span> did not seem to affect BC IN ability, probably due to an SOA-phase state transition. However, SOA coatings generated from OH oxidation of various organic species did exhibit higher IN-onset supersaturation ratio with respect to ice (SS<span class="inline-formula">_<i>i</i></span>), compared with bare BC particles, with the toluene-SOA coating showing an increase in SS<span class="inline-formula">_<i>i</i></span> of 0.1–0.15 while still below the homogeneous freezing threshold. Slightly oxidized toluene SOA coating seemed to have a stronger deactivation effect on BC IN ability than highly oxidized toluene SOA, which might be caused by oligomer formation and the<span id="page13958"/> phase state transition of toluene SOA under different oxidation levels. <span class="inline-formula"><i>n</i></span>-dodecane and <span class="inline-formula"><i>β</i></span>-caryophyllene-derived SOA-coated BC only froze in the homogeneous regime. We attribute the inhibition of IN ability to the filling of the pores on the BC surface by the SOA material coating. OH exposure levels of <span class="inline-formula"><i>n</i></span>-dodecane and <span class="inline-formula"><i>β</i></span>-caryophyllene SOA coating experiments, from an equivalent atmospheric exposure time from 10 to 90&thinsp;d, did not render significant differences in the IN potential. Our study of selected BC types and sizes suggests that increases in diameter, compactness, and/or surface oxidation of BC particles lead to more efficient IN via the pore condensation freezing (PCF) pathway, and that coatings of common SOA materials can inhibit the formation of ice.</p>