NO at low concentration can enhance the formation of highly oxygenated biogenic molecules in the atmosphere.

The interaction between nitrogen monoxide (NO) and organic peroxy radicals (RO2) greatly impacts the formation of highly oxygenated organic molecules (HOM), the key precursors of secondary organic aerosols. It has been thought that HOM production can be significantly suppressed by NO even at low concentrations. Here, we perform dedicated experiments focusing on HOM formation from monoterpenes at low NO concentrations (0 - 82 pptv). We demonstrate that such low NO can enhance HOM production by modulating the RO2 loss and favoring the formation of alkoxy radicals that can continue to autoxidize through isomerization. These insights suggest that HOM yields from typical boreal forest emissions can vary between 2.5%-6.5%, and HOM formation will not be completely inhibited even at high NO concentrations. Our findings challenge the notion that NO monotonically reduces HOM yields by extending the knowledge of RO2-NO interactions to the low-NO regime. This represents a major advance towards an accurate assessment of HOM budgets, especially in low-NO environments, which prevails in the pre-industrial atmosphere, pristine areas, and the upper boundary layer.

The Cooling Rate- and Volatility-Dependent Glass-Forming Properties of Organic Aerosols Measured by Broadband Dielectric Spectroscopy.

Glass transitions of secondary organic aerosols (SOA) from liquid/semisolid to solid phase states have important implications for aerosol reactivity, growth, and cloud formation properties. In the present study, glass transition temperatures (Tg) of isoprene SOA components, including isoprene hydroxy hydroperoxide (ISOPOOH), isoprene-derived epoxydiols (IEPOX), 2-methyltetrols, and 2-methyltetrol sulfates, were measured at atmospherically relevant cooling rates (2-10 K/min) by thin film broadband dielectric spectroscopy. The results indicate that 2-methyltetrol sulfates have the highest glass transition temperature, while ISOPOOH has the lowest glass transition temperature. By varying the cooling rate of the same compound from 2 to 10 K/min, the Tg of these compounds increased by 4-5 K. This temperature difference leads to a height difference of 400-800 m in the atmosphere for the corresponding updraft induced cooling rates, assuming a hygroscopicity value (κ) of 0.1 and relative humidity less than 95%. The Tg of the organic compounds was found to be strongly correlated with volatility, and a semiempirical formula between glass transition temperatures and volatility was derived. The Gordon-Taylor equation was applied to calculate the effect of relative humidity (RH) and water content at five mixing ratios on the Tg of organic aerosols. The model shows that Tg could drop by 15-40 K as the RH changes from <5 to 90%, whereas the mixing ratio of water in the particle increases from 0 to 0.5. These results underscore the importance of chemical composition, updraft rates, and water content (RH) in determining the phase states and hygroscopic properties of organic particles.