Nontrivial Impact of Relative Humidity on Organic New Particle Formation from Ozonolysis of cis-3-Hexenyl Acetate

Abstract

The impact of relative humidity (RH) on organic new particle formation (NPF) from ozonolysis of biogenic volatile organic compounds (BVOCs) remains an area of active debate. Previous reports provide contradictory results indicating both depression and enhancement of NPF under conditions of high RH. Herein we report on the impact of RH on NPF from dark ozonolysis of cis-3-hexenyl acetate (CHA), a green-leaf volatile (GLV) emitted by vegetation. We show that RH inhibits NPF by this BVOC, essentially shutting it down at RH levels > 1 %. While the mechanism for inhibition of NPF remains unclear, we demonstrate that it is likely not due to increased losses of CHA to the humid chamber walls. New oxidation products dominant under humid conditions were identified that, based on estimated vapor pressures (VPs), should enhance NPF; however, it is possible that the vapor phase concentration of these low volatility products is not sufficient to initiate NPF. Furthermore, reaction of C3-excited state Criegee intermediates (CIs) with water may lead to the formation of small carboxylic acids that do not contribute to NPF. This hypothesis is supported by experiments with quaternary O3 + CHA + α-pinene + RH systems, which showed decreases in total α-pinene-derived NPF at ~ 0% RH and subsequent recovery at elevated RH.