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Night-time radical chemistry during the NAMBLEX campaign

机译：NAMBLEX活动期间的夜间自由基化学

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Night-time chemistry in the Marine Boundary Layer has been modelledusing a number of observationally constrained zero-dimensionalbox-models. The models were based upon the Master Chemical Mechanism(MCM) and the measurements were taken during the North AtlanticMarine Boundary Layer Experiment (NAMBLEX) campaign at Mace Head,Ireland in July–September 2002.The model could reproduce, within the combined uncertainties, themeasured concentration of HO2 (within 30–40%) during thenight 31 August–1 September and of HO2+RO2 (within15–30%) during several nights of the campaign. The model alwaysoverestimated the NO3 measurements made by DifferentialOptical Absorption Spectroscopy (DOAS) by up to an order ofmagnitude or more, but agreed with the NO3 Cavity Ring-DownSpectroscopy (CRDS) measurements to within 30–50%. The mostlikely explanation of the discrepancy between the two instrumentsand the model is the reaction of the nitrate radical withinhomogeneously distributed NO, which was measured atconcentrations of up to 10 ppt, even though this is notenough to fully explain the difference between the DOAS measurementsand the model.A rate of production and destruction analysis showed that radicalswere generated during the night mainly by the reaction of ozonewith light alkenes. The cycling between HO2/RO2and OH was maintained during the night by the lowconcentrations of NO and the overall radical concentrationwas limited by slow loss of peroxy radicals to form peroxides. Astrong peak in [NO2] during the night 31 August–1September allowed an insight into the radical fluxes and theconnections between the HOx and the NO3 cycles.
机译：海洋边界层的夜间化学反应已使用许多受观测约束的零维箱模型进行了建模。这些模型基于主化学机理（MCM），并且在2002年7月至9月于爱尔兰梅斯黑德的北大西洋海洋边界层实验（NAMBLEX）活动中进行了测量。 该模型可以复制，在组合不确定性范围内，在8月31日至9月1日夜间测得的HO 2 （在30-40％之内）和HO 2 + RO 2 （在15％到30％之间）在广告系列的几个晚上。该模型始终高估了差分光学吸收光谱法（DOAS）对NO 3 的测量，幅度高达一个数量级或更高，但与NO 3 腔衰荡光谱法（CRDS）一致）测量值在30％到50％之间。两种仪器和模型之间差异的最可能解释是硝酸根自由基在均匀分布的NO中的反应，该硝酸根的测量浓度最高为10 ppt，尽管这不足以完全解释DOAS测量与模型之间的差异。 产生和破坏的速率分析表明，自由基是在夜间产生的，主要是由臭氧与轻质烯烃的反应引起的。 NO的低浓度使HO 2 / RO 2 与OH之间的循环在夜间得以维持，总自由基浓度受到过氧自由基缓慢损失而形成过氧化物的限制。在8月31日至9月1日的夜晚，[NO 2 ]出现了强烈的峰值，这使得人们可以洞悉自由基通量以及HO x 与NO 3 周期。

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