Molecular Composition of Oxygenated Organic Molecules and Their Contributions to Organic Aerosol in Beijing.

The understanding at a molecular level of ambient secondary organic aerosol (SOA) formation is hampered by poorly constrained formation mechanisms and insufficient analytical methods. Especially in developing countries, SOA related haze is a great concern due to its significant effects on climate and human health. We present simultaneous measurements of gas-phase volatile organic compounds (VOCs), oxygenated organic molecules (OOMs), and particle-phase SOA in Beijing. We show that condensation of the measured OOMs explains 26-39% of the organic aerosol mass growth, with the contribution of OOMs to SOA enhanced during severe haze episodes. Our novel results provide a quantitative molecular connection from anthropogenic emissions to condensable organic oxidation product vapors, their concentration in particle-phase SOA, and ultimately to haze formation.

A modelling study of OH, NO3 and H2SO4 in 2007-2018 at SMEAR II, Finland: analysis of long-term trends.

Major atmospheric oxidants (OH, O3 and NO3) dominate the atmospheric oxidation capacity, while H2SO4 is considered as a main driver for new particle formation. Although numerous studies have investigated the long-term trend of ozone in Europe, the trends of OH, NO3 and H2SO4 at specific sites are to a large extent unknown. The one-dimensional model SOSAA has been applied in several studies at the SMEAR II station and has been validated by measurements in several projects. Here, we applied the SOSAA model for the years 2007-2018 to simulate the atmospheric chemical components, especially the atmospheric oxidants OH and NO3, as well as H2SO4 at SMEAR II. The simulations were evaluated with observations from several shorter and longer campaigns at SMEAR II. Our results show that daily OH increased by 2.39% per year and NO3 decreased by 3.41% per year, with different trends of these oxidants during day and night. On the contrary, daytime sulfuric acid concentrations decreased by 2.78% per year, which correlated with the observed decreasing concentration of newly formed particles in the size range of 3-25 nm with 1.4% per year at SMEAR II during the years 1997-2012. Additionally, we compared our simulated OH, NO3 and H2SO4 concentrations with proxies, which are commonly applied in case a limited number of parameters are measured and no detailed model simulations are available.

The role of highly oxygenated organic molecules in the Boreal aerosol-cloud-climate system.

Over Boreal regions, monoterpenes emitted from the forest are the main precursors for secondary organic aerosol (SOA) formation and the primary driver of the growth of new aerosol particles to climatically important cloud condensation nuclei (CCN). Autoxidation of monoterpenes leads to rapid formation of Highly Oxygenated organic Molecules (HOM). We have developed the first model with near-explicit representation of atmospheric new particle formation (NPF) and HOM formation. The model can reproduce the observed NPF, HOM gas-phase composition and SOA formation over the Boreal forest. During the spring, HOM SOA formation increases the CCN concentration by ~10 % and causes a direct aerosol radiative forcing of -0.10 W/m2. In contrast, NPF reduces the number of CCN at updraft velocities < 0.2 m/s, and causes a direct aerosol radiative forcing of +0.15 W/m2. Hence, while HOM SOA contributes to climate cooling, NPF can result in climate warming over the Boreal forest.

α-Pinene Autoxidation Products May Not Have Extremely Low Saturation Vapor Pressures Despite High O:C Ratios.

COSMO-RS (conductor-like screening model for real solvents) and three different group-contribution methods were used to compute saturation (subcooled) liquid vapor pressures for 16 possible products of ozone-initiated α-pinene autoxidation, with elemental compositions C10H16O4-10 and C20H30O10-12. The saturation vapor pressures predicted by the different methods varied widely. COSMO-RS predicted relatively high saturation vapor pressures values in the range of 10(-6) to 10(-10) bar for the C10H16O4-10 "monomers", and 10(-11) to 10(-16) bar for the C20H30O10-12 "dimers". The group-contribution methods predicted significantly (up to 8 order of magnitude) lower saturation vapor pressures for most of the more highly oxidized monomers. For the dimers, the COSMO-RS predictions were within the (wide) range spanned by the three group-contribution methods. The main reason for the discrepancies between the methods is likely that the group-contribution methods do not contain the necessary parameters to accurately treat autoxidation products containing multiple hydroperoxide, peroxy acid or peroxide functional groups, which form intramolecular hydrogen bonds with each other. While the COSMO-RS saturation vapor pressures for these systems may be overestimated, the results strongly indicate that despite their high O:C ratios, the volatilities of the autoxidation products of α-pinene (and possibly other atmospherically relevant alkenes) are not necessarily extremely low. In other words, while autoxidation products are able to adsorb onto aerosol particles, their evaporation back into the gas phase cannot be assumed to be negligible, especially from the smallest nanometer-scale particles. Their observed effective contribution to aerosol particle growth may therefore involve rapid heterogeneous reactions (reactive uptake) rather than effectively irreversible physical absorption.