TY - JOUR

T1 - Observations of highly oxidized molecules and particle nucleation in the atmosphere of Beijing

AU - Brean, James

AU - Harrison, Roy M.

AU - Shi, Zongbo

AU - Beddows, David C. S.

AU - Acton, W. Joe F.

AU - Hewitt, C. N.

AU - Squires, Freya

AU - Lee, James

PY - 2019/3/27

Y1 - 2019/3/27

N2 - Particle nucleation is one of the main sources of atmospheric particulate matter by number, with new particles having great relevance for human health and climate. Highly oxidised multifunctional organic molecules (HOMs) have been recently identified as key constituents in the growth, and, sometimes, in initial formation of new particles. While there have been many studies of HOMs in atmospheric chambers, flow tubes and clean environments, analyses of data from polluted environments are scarce. Here, measurements of HOMs and particle size distributions down to small molecular clusters are presented alongside VOC and trace gas data from a campaign in Beijing. Many gas phase HOMs have been characterised and their temporal trends and behaviours analysed in the context of new particle formation. The HOMs identified have a comparable degree of oxidation to those seen in other, cleaner, environments, likely due to an interplay between the higher temperatures facilitating rapid hydrogen abstractions and the higher concentrations of NOx and other RO2. terminators ending the autoxidation sequence more rapidly. Our data indicate that alkylbenzenes, monoterpenes, and isoprene are important precursor VOCs for HOMs in Beijing. Many of the C5 and C10 compounds derived from isoprene and monoterpenes have a slightly greater degree of average oxidation state of carbon compared to those from other precursors. Most HOMs except for large dimers have daytime peak concentrations, indicating the importance of OH. chemistry in the formation of HOMs, as O3 is lower on the days with higher HOM concentrations; similarly, VOC concentrations are lower on the days with higher HOM concentrations. The daytime peaks of HOMs coincide with the growth of freshly formed new particles, and their initial formation coincides with the peak in sulphuric acid vapours, suggesting that the nucleation process is sulphuric acid-dependent, with HOMs contributing to subsequent particle growth.

AB - Particle nucleation is one of the main sources of atmospheric particulate matter by number, with new particles having great relevance for human health and climate. Highly oxidised multifunctional organic molecules (HOMs) have been recently identified as key constituents in the growth, and, sometimes, in initial formation of new particles. While there have been many studies of HOMs in atmospheric chambers, flow tubes and clean environments, analyses of data from polluted environments are scarce. Here, measurements of HOMs and particle size distributions down to small molecular clusters are presented alongside VOC and trace gas data from a campaign in Beijing. Many gas phase HOMs have been characterised and their temporal trends and behaviours analysed in the context of new particle formation. The HOMs identified have a comparable degree of oxidation to those seen in other, cleaner, environments, likely due to an interplay between the higher temperatures facilitating rapid hydrogen abstractions and the higher concentrations of NOx and other RO2. terminators ending the autoxidation sequence more rapidly. Our data indicate that alkylbenzenes, monoterpenes, and isoprene are important precursor VOCs for HOMs in Beijing. Many of the C5 and C10 compounds derived from isoprene and monoterpenes have a slightly greater degree of average oxidation state of carbon compared to those from other precursors. Most HOMs except for large dimers have daytime peak concentrations, indicating the importance of OH. chemistry in the formation of HOMs, as O3 is lower on the days with higher HOM concentrations; similarly, VOC concentrations are lower on the days with higher HOM concentrations. The daytime peaks of HOMs coincide with the growth of freshly formed new particles, and their initial formation coincides with the peak in sulphuric acid vapours, suggesting that the nucleation process is sulphuric acid-dependent, with HOMs contributing to subsequent particle growth.

UR - https://doi.org/10.5194/acp-2019-156

U2 - 10.5194/acp-19-14933-2019

DO - 10.5194/acp-19-14933-2019

M3 - Journal article

VL - 19

SP - 14933

EP - 14947

JO - Atmospheric Chemistry and Physics

JF - Atmospheric Chemistry and Physics

SN - 1680-7316

IS - 23

ER -