Evaluation of isoprene nitrate chemistry in detailed chemical mechanisms
Evaluation of isoprene nitrate chemistry in detailed chemical mechanisms
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评估硝酸异戊二烯化学的详细化学机制
DOI：
10.5194/acp-22-14783-2022
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发表时间：
2022-11
影响因子：
6.3
通讯作者：
Alfred W. Mayhew;B. H. Lee;J. Thornton;T. Bannan;J. Brean;J. Hopkins;James D. Lee;Beth S. Nelson;C. Percival;A. Rickard;M. Shaw;P. Edwards;J. F. Hamilton
中科院分区：
文献类型：
--
作者：
Alfred W. Mayhew;B. H. Lee;J. Thornton;T. Bannan;J. Brean;J. Hopkins;James D. Lee;Beth S. Nelson;C. Percival;A. Rickard;M. Shaw;P. Edwards;J. F. Hamilton
抽象的。异戊二烯硝酸盐是大气中重要的化学物质，有助于形成臭氧和二次有机气溶胶（SOA）的化学循环，对气候和空气质量产生影响。准确的化学机制对于化学模式中异戊二烯硝酸盐等物种的大气化学预测非常重要。近年来，对异戊二烯硝酸盐化学的研究导致了一系列可用于模拟大气异戊二烯氧化的机制的发展。本工作使用0-D化学箱模型来评估三种化学详细机制的能力，以预测在中国大城市北京的夏季观察到的四组异戊二烯衍生的硝酸盐的昼夜分布。模型C5 H9 NO 5异构体，包括异戊二烯过氧化氢硝酸盐（IPN）物种的分析，突出了显着的贡献，非IPN物种的C5 H9 NO 5测量，包括潜在的大贡献的硝基氧羟基环氧（INHE）。异戊二烯羟基硝酸酯（IHNs）来自OH引发和NO3引发的化学的异构体分布的变化进行了讨论，是最新的烷氧基自由基化学的重要性，准确预测异戊二烯羰基硝酸酯（ICN）的形成。所有的机制低于预测的C4 H7 NO 5主要形成的主要异戊二烯氧化产物，甲基乙烯基酮（MVK）和甲基丙烯醛（MACR）。这项工作探讨了现有的化学机制，以准确地代表异戊二烯硝酸盐化学在城市地区显着影响的人为和生物化学相互作用的能力。它提出了在环境情景下调查异戊二烯硝酸盐时应考虑的因素，调查了不同异构体分布对碘化物化学电离质谱（I--CIMS）校准的潜在影响，并为异戊二烯机制的未来发展提出了一些建议。
Abstract. 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.