Evaluation of isoprene nitrate chemistry in detailed chemical mechanisms

Alfred W. Mayhew, Ben H. Lee, Joel A. Thornton, Thomas J. Bannan, James Brean, James R. Hopkins, James D. Lee, Beth S. Nelson, Carl Percival, Andrew R. Rickard, Marvin D. Shaw, Peter M. Edwards, Jaqueline F. Hamilton*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


Isoprene nitrates are important chemical species in the atmosphere which contribute to the chemical cycles that form ozone and secondary organic aerosol (SOA) with implications for climate and air quality. Accurate chemical mechanisms are important for the prediction of the atmospheric chemistry of species such as isoprene nitrates in chemical models. In recent years, studies into the chemistry of isoprene nitrates have resulted in the development of a range of mechanisms available for use in the simulation of atmospheric isoprene oxidation. This work uses a 0-D chemical box model to assess the ability of three chemically detailed mechanisms to predict the observed diurnal profiles of four groups of isoprene-derived nitrates in the summertime in the Chinese megacity of Beijing. An analysis of modelled C5H9NO5 isomers, including isoprene hydroperoxy nitrate (IPN) species, highlights the significant contribution of non-IPN species to the C5H9NO5 measurement, including the potentially large contribution of nitrooxy hydroxyepoxide (INHE). The changing isomer distribution of isoprene hydroxy nitrates (IHNs) derived from OH-initiated and NO3-initiated chemistry is discussed, as is the importance of up-To-date alkoxy radical chemistry for the accurate prediction of isoprene carbonyl nitrate (ICN) formation. All mechanisms under-predicted C4H7NO5 as predominately formed from the major isoprene oxidation products, methyl vinyl ketone (MVK) and methacrolein (MACR). This work explores the current capability of existing chemical mechanisms to accurately represent isoprene nitrate chemistry in urban areas significantly impacted by anthropogenic and biogenic chemical interactions. It suggests considerations to be taken when investigating isoprene nitrates in ambient scenarios, investigates the potential impact of varying isomer distributions on iodide chemical ionisation mass spectrometry (I-CIMS) calibrations, and makes some proposals for the future development of isoprene mechanisms.

Original languageEnglish
Pages (from-to)14783-14798
JournalAtmospheric Chemistry and Physics
Issue number22
Publication statusPublished - 21 Nov 2022

Bibliographical note

Funding Information:
The authors acknowledge the support from Pingqing Fu, Zifa Wang, Jie Li, and Yele Sun from IAP for hosting the APHH-Beijing campaign at IAP. They also thank Tuan Vu, Roy Harrison, Di Liu, and Bill Bloss from the University of Birmingham; Alastair Lewis, William Dixon, Marvin Shaw, and Stefan Swift from the University of York; Siyao Yue, Liangfang Wei, Hong Ren, Qiaorong Xie, Wanyu Zhao, Linjie Li, Ping Li, Shengjie Hou, and Qingqing Wang from IAP; Kebin He and Xiaoting Chen from Tsinghua University; and James Allan from the University of Manchester for providing logistic and scientific support for the field campaigns.

© Author(s) 2022.

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