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A comprehensive organic nitrate chemistry: insights into the lifetime of atmospheric organic nitrates

机译:综合有机硝酸盐化学:洞察大气有机硝酸盐的寿命

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Organic nitrate chemistry is the primary control over the lifetime of nitrogen oxides (NOx) in rural and remote continental locations. As NOx emissions decrease, organic nitrate chemistry becomes increasingly important to urban air quality. However, the lifetime of individual organic nitrates and the reactions that lead to their production and removal remain relatively poorly constrained, causing organic nitrates to be poorly represented by models. Guided by recent laboratory and field studies, we developed a detailed gas-phase chemical mechanism representing most of the important individual organic nitrates. We use this mechanism within the Weather Research and Forecasting (WRF) model coupled with Chemistry (WRF-Chem) to describe the role of organic nitrates in nitrogen oxide chemistry and in comparisons to observations. We find the daytime lifetime of total organic nitrates with respect to all loss mechanisms to be 2.6h in the model. This is consistent with analyses of observations at a rural site in central Alabama during the Southern Oxidant and Aerosol Study (SOAS) in summer 2013. The lifetime of the first-generation organic nitrates is ~2h versus the 3.2h lifetime of secondary nitrates produced by oxidation of the first-generation nitrates. The different generations are subject to different losses, with dry deposition to the surface being the dominant loss process for the second-generation organic nitrates and chemical loss being dominant for the first-generation organic nitrates. Removal by hydrolysis is found to be responsible for the loss of ~30% of the total organic nitrate pool.
机译:有机硝酸盐化学是对农村和远程大陆地点的氮氧化物(NOx)寿命的主要控制。由于NOX排放减少,有机硝酸盐化学对城市空气质量越来越重要。然而,各种有机硝酸盐的寿命和导致其生产和去除的反应仍然存在相对较差的受损,导致有机硝酸盐由模型表示不佳。以最近的实验室和田间研究为指导,我们开发了一种具有代表大多数重要个体有机硝酸盐的气相化学机制。我们在天气研究和预测(WRF)模型中使用这种机制,与化学(WRF-CHEM)相结合,描述有机硝酸盐在氮氧化物化学中的作用及其观察结果。我们在模型中找到所有损失机制的全部有机硝酸盐的白天寿命。这与2013年夏季氧化剂和气溶胶研究(SOAS)在阿拉巴马州的农村遗址的观察分析一致。第一代有机硝酸盐的寿命为〜2h,与仲硝酸盐的3.2h寿命相比第一代硝酸盐的氧化。不同一代受不同的损失,对表面干燥沉积是第二代有机硝酸盐的主要损失过程和用于第一代有机硝酸盐的化学损失。发现水解除去负责损失总有机硝酸盐池的〜30%。

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