Abstract. Most laboratory atmospheric chamber studies probing the chemical and physical properties of secondary organic aerosol (SOA) perform such experiments with mixing ratios of volatile organic compounds (VOCs) well-above atmospheric relevance (≳50 ppbv). When performing ozonolysis of biogenic VOCs at mixing ratios of atmospheric relevance (≲10 ppbv), repeatability of replicate experiments is hindered by the limitations of conventional VOC injection techniques. To overcome these limitations, two novel components (stop/flow and split valves) were embedded in a conventional VOC injection setup, thereby permitting the use of higher VOC volumes of injection to attain low VOC mixing ratios, and the delivery of the VOC to the environmental chamber as a short, discrete pulse for subsequent reaction. Implementation of these novel VOC injection components has resulted in improvements in variability between replicate chamber experiments of up to a factor of 7 with respect to particle number, mass, and size distributions at both high and low VOC mixing ratios (50 and 10 ppbv, respectively). These improvements permit extension of quantitative measurements of SOA formation to VOC mixing ratios at or near atmospheric levels, where new particle formation (NPF) and SOA mass loading are typically within experimental variability.

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The impact of relative humidity (RH) on organic new particle formation (NPF) from ozonolysis of monoterpenes remains an area of active debate. Previous reports provide contradictory results indicating both depression and enhancement of NPF under conditions of moderate RH, while others do not indicate a potential impact. Only several reports have suggested that the effect may depend on absolute mixing ratio of the precursor volatile organic compound (VOC, ppbv). Herein we report on the impact of RH on NPF from dark ozonolysis of α- and β-pinene at mixing ratios ranging from 0.2 to 80 ppbv. We show that RH enhances NPF (by a factor of eight) at the lowest α-pinene mixing ratio, with a very strong dependence on α-pinene mixing ratio from 4 to 22 ppbv. At higher mixing ratios, the effect of RH plateaus, with resulting modest decreases in NPF. In the case of α- and β-pinene, NPF is enhanced at low mixing ratios due to a combination of chemistry, accelerated kinetics, and reduced partitioning of semi-volatile oxidation products to the particulate phase. Reduced partitioning would limit particle growth, permitting increased gas-phase concentrations of semi- and low-volatility products, which could favor NPF.

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.