The relevance of reactions of the methyl peroxy radical (CH3O2) and methylhypochlorite (CH3OCl) for Antarctic chlorine activation and ozone loss
The relevance of reactions of the methyl peroxy radical (CH3O2) and methylhypochlorite (CH3OCl) for Antarctic chlorine activation and ozone loss
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甲基过氧自由基（CH3O2）和次氯酸甲酯（CH3OCl）的反应与南极氯活化和臭氧损失的相关性
DOI：
10.1080/16000889.2018.1507391
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发表时间：
--
期刊：
影响因子：
--
通讯作者：
Lehmann
中科院分区：
文献类型：
--
作者：
Müller;Grooß;Robrecht;Lehmann
南极春季维持高浓度的活性氯使得强烈的化学臭氧破坏发生。在极地涡旋核心的平流层下层（大约16-18公里，85-55 hPa, 390-430 K），尽管HCl的气相快速生成发生，但仍保持着高水平的活性氯。维持是通过HCl零循环实现的，其中HCl产量通过立即再激活来平衡。甲基过氧自由基（CH3O2）的化学反应对这些HCl零循环至关重要，因此对极地涡旋核心平流层下层的南极氯和臭氧损失化学反应至关重要。关键的反应是这个反应；在模拟极地臭氧损失时不应忽视这一反应。在这里，我们研究了代表平流层低层极地涡旋核心条件的盒模式模拟中ch3o2的全部化学性质。这些模拟包括CH3O2+ Cl反应，CH3O2+ ClO反应的产物次氯酸甲酯（CH3OCl），以及随后CH3OCl的化学分解。我们发现，当考虑CH3OCl的形成时，重要的是要考虑CH3OCl的主要损失通道，即光解和与Cl的反应。在这种情况下，在我们的模拟中，CH3O2+ ClO反应中CH3OCl的形成对极性氯化学只有适度的影响。模拟的CH3OCl （ppb）混合比峰值出现在臭氧混合比最低的时候。此外，我们的模型模拟表明，CH3O2+ Cl反应对极性氯化学没有很强的影响。在9月下旬臭氧浓度最低的时期，模拟了ch3o2的增强值，甲醛（约100 ppt）和甲醇（约5 ppt）的值也随之增强。
The maintenance of large concentrations of active chlorine in Antarctic spring allows strong chemical ozone destruction to occur. In the lower stratosphere (approximately 16–18 km, 85–55 hPa, 390–430 K) in the core of the polar vortex, high levels of active chlorine are maintained, although rapid gas-phase production of HCl occurs. The maintenance is achieved through HCl null cycles in which the HCl production is balanced by immediate reactivation. The chemistry of the methyl peroxy radical (CH3O2) is essential for these HCl null cycles and thus for Antarctic chlorine and ozone loss chemistry in the lower stratosphere in the core of the polar vortex. The key reaction here is the reaction; this reaction should not be neglected in simulations of polar ozone loss. Here we investigate the full chemistry of CH3O2in box-model simulations representative for the conditions in the core of the polar vortex in the lower stratosphere. These simulations include the reaction CH3O2+ Cl, the product methylhypochlorite (CH3OCl) of the reaction CH3O2+ ClO, and the subsequent chemical decomposition of CH3OCl. We find that when the formation of CH3OCl is taken into account, it is important that also the main loss channels for CH3OCl, namely photolysis and reaction with Cl are considered. Provided that this is the case, there is only a moderate impact of the formation of CH3OCl in the reaction CH3O2+ ClO on polar chlorine chemistry in our simulations. Simulated peak mixing ratios of CH3OCl (ppb) occur at the time of the lowest ozone mixing ratios. Further, our model simulations indicate that the reaction CH3O2+ Cl does not have a strong impact on polar chlorine chemistry. During the period of the lowest ozone concentrations in late September, enhanced values of CH3O2are simulated and, as a consequence, also enhanced values of formaldehyde (about 100 ppt) and methanol (about 5 ppt).
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羟基自由基与甲基氢过氧化物反应的动力学及机理
DOI：
10.1021/j100342a050
发表时间：
1989
期刊：
The Journal of Physical Chemistry
影响因子：
--
作者：
Ghanshyam L. Vaghjiani;A. Ravishankara
通讯作者：
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影响因子：
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作者：
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通讯作者：
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DOI：
10.1016/j.jqsrt.2007.01.058
发表时间：
2007
影响因子：
2.3
作者：
P. Ricaud;D. Alexandre;B. Barret;E. L. Flochmoën;E. Motte;G. Berthet;F. Lefévre;D. Murtagh
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D. Murtagh
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影响因子：
6.3
作者：
Wohltmann I
通讯作者：
Wohltmann I
DOI：
10.1039/c2cp22834c
发表时间：
2012-02
期刊：
Physical chemistry chemical physics : PCCP
影响因子：
--
作者：
K. Leather;A. Bacak;R. Wamsley;A. Archibald;Alexander Husk;D. Shallcross;C. Percival
通讯作者：
K. Leather;A. Bacak;R. Wamsley;A. Archibald;Alexander Husk;D. Shallcross;C. Percival