Peroxy radical chemistry and the control of ozone photochemistry at Mace Head, Ireland during the summer of 2002
Peroxy radical chemistry and the control of ozone photochemistry at Mace Head, Ireland during the summer of 2002
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2002 年夏天，爱尔兰 Mace Head 的过氧自由基化学和臭氧光化学控制
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发表时间：
2005
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通讯作者：
J. Plane
中科院分区：
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作者：
Z. Fleming;P. Monks;A. Rickard;D. Heard;W. Bloss;P. Seakins;T. Still;R. Sommariva;M. Pilling;R. Morgan;T. J. Green;N. Brough;G. Mills;S. Penkett;A. Lewis;James D. Lee;A. Saiz‐Lopez;J. Plane
本文介绍了2002年夏季在北大西洋海洋边界层实验（NAMBLEX）中使用PEroxy Radical Chemical Amplification（PERCA）技术进行的过氧自由基（HO 2 + H2O RO 2）测量，并将其纳入海洋边界层化学的研究范围。一套其他的化学参数（NO，NO2，NO3，CO，CH 4，O3，VOCs，过氧化物），光解频率和气象测量，被用来详细分析过氧自由基在对流层氧化循环和臭氧形成中的作用。在所遇到的条件下，过氧自由基每日最大值从10到40 pptv不等。日周期呈不对称形状，通常转移到下午。使用基于主化学机制的箱模型，整个活动的平均模型测量一致性为2.5。卤素氧化物添加到模型中增加了模型/测量一致性的水平，显然是通过HOx的重新形成。j（HCHO）之间存在良好的相关性。[甲醛]和过氧自由基的重要性，甲醛在遥远的大气中作为HO x源，特别是在下午的指示。过氧自由基显示出对[NO 2 ]的强烈依赖性，临界点为0.1 ppbv，其中自由基随着反应性VOC负荷的增加而增加，这是一个低于代表性城市运动的值。HO 2 /（HO 2 + PORO 2）比值随[NOx]的变化而变化，在0.2 ~ 0.6范围内，随NOx的增加而线性增加。重要的过氧自由基的夜间水平进行了测量高达25 pptv。臭氧-烯烃和NO3-烯烃化学对夜间过氧自由基产生的贡献平均为59%和41%。活动期间平均净臭氧产生率为0.11± 0.3ppbvh-1。臭氧产生速率与[NO]呈线性关系（dln（P（O3））/dln（NO）=1.0）。结果表明，N（O 3）（臭氧的产生/破坏的原位净光化学速率）将是强烈敏感的海洋边界层中的小变化[NO]，这对改变欧洲大陆边界层中的NOx负荷有影响。
Peroxy radical (HO 2 +ΣRO 2 ) measurements, using the PEroxy Radical Chemical Amplification (PERCA) technique at the North Atlantic Marine Boundary Layer EXperiment (NAMBLEX) at Mace Head in summer 2002, are presented and put into the context of marine, boundary-layer chemistry. A suite of other chemical parameters (NO, NO 2 , NO 3 , CO, CH 4 , O 3 , VOCs, peroxides), photolysis frequencies and meteorological measurements, are used to present a detailed analysis of the role of peroxy radicals in tropospheric oxidation cycles and ozone formation. Under the range of conditions encountered the peroxy radical daily maxima varied from 10 to 40 pptv. The diurnal cycles showed an asymmetric shape typically shifted to the afternoon. Using a box model based on the master chemical mechanism the average model measurement agreement was 2.5 across the campaign. The addition of halogen oxides to the model increases the level of model/measurement agreement, apparently by respeciation of HO x . A good correlation exists between j (HCHO).[HCHO] and the peroxy radicals indicative of the importance of HCHO in the remote atmosphere as a HO x source, particularly in the afternoon. The peroxy radicals showed a strong dependence on [NO 2 ] with a break point at 0.1 ppbv, where the radicals increased concomitantly with the reactive VOC loading, this is a lower value than seen at representative urban campaigns. The HO 2 /(HO 2 +ΣRO 2 ) ratios are dependent on [NO x ] ranging between 0.2 and 0.6, with the ratio increasing linearly with NO x . Significant night-time levels of peroxy radicals were measured up to 25 pptv. The contribution of ozone-alkenes and NO 3 -alkene chemistry to night-time peroxy radical production was shown to be on average 59 and 41%. The campaign mean net ozone production rate was 0.11±0.3 ppbv h -1 . The ozone production rate was strongly dependent on [NO] having linear sensitivity (dln(P(O 3 ))/dln(NO)=1.0). The results imply that the N(O 3 ) (the in-situ net photochemical rate of ozone production/destruction) will be strongly sensitive in the marine boundary layer to small changes in [NO] which has ramifications for changing NO x loadings in the European continental boundary layer.