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Interactions of bromine, chlorine, and iodine photochemistry during ozone depletions in Barrow, Alaska

机译:溴,氯和碘的相互作用在臭椿耗尽过程中,阿拉斯加

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The springtime depletion of tropospheric ozone in the Arctic is known to be caused by active halogen photochemistry resulting from halogen atom precursors emitted from snow, ice, or aerosol surfaces. The role of bromine in driving ozone depletion events (ODEs) has been generally accepted, but much less is known about the role of chlorine radicals in ozone depletion chemistry. While the potential impact of iodine in the High Arctic is more uncertain, there have been indications of active iodine chemistry through observed enhancements in filterable iodide, probable detection of tropospheric IO, and recently, observation of snowpack photochemical production of I2. Despite decades of research, significant uncertainty remains regarding the chemical mechanisms associated with the bromine-catalyzed depletion of ozone, as well as the complex interactions that occur in the polar boundary layer due to halogen chemistry. To investigate this, we developed a zero-dimensional photochemical model, constrained with measurements from the 2009 OASIS field campaign in Barrow, Alaska. We simulated a 7-day period during late March that included a full ozone depletion event lasting 3 days and subsequent ozone recovery to study the interactions of halogen radicals under these different conditions. In addition, the effects of iodine added to our Base Model were investigated. While bromine atoms were primarily responsible for ODEs, chlorine and iodine were found to enhance the depletion rates and iodine was found to be more efficient per atom at depleting ozone than Br. The interaction between chlorine and bromine is complex, as the presence of chlorine can increase the recycling and production of Br atoms, while also increasing reactive bromine sinks under certain conditions. Chlorine chemistry was also found to have significant impacts on both HO2 and RO2, with organic compounds serving as the primary reaction partner for Cl atoms. The results of this work highlight the need for future studies on the production mechanisms of Br2 and Cl2, as well as on the potential impact of iodine in the High Arctic.
机译:众所周知,北极臭氧的春天耗竭是由雪,冰或气溶胶表面排出的卤素原子前体产生的活性卤素光化学引起的。溴在驾驶臭氧耗尽事件(ODES)在驱动臭氧耗尽事件(ODES)中的作用,但是关于氯自由基在臭氧耗尽化学中的作用而闻名。虽然碘在高北极中的潜在影响更不确定,但通过观察到的可过滤碘化物,对流层IO的可能检测,最近,有可能的活性碘化学的指示,并且最近观察了I2的积雪光化学生产。尽管有数十年的研究,但是关于与溴催化耗竭相关的化学机制,以及由于卤素化学而在极性边界层中发生的复杂相互作用,仍然存在显着的不确定性。为了调查这一点,我们开发了一种零维光化学模型,限制了2009年禁止禁区的2009年绿洲场地运动的测量。我们在3月底模拟了7天的时间,其中包括持续3天和后续臭氧恢复的全臭氧耗尽事件,以研究在这些不同条件下卤素自由基的相互作用。此外,研究了加入到我们基础模型中的碘的影响。虽然溴原子主要负责ODES,但发现氯和碘被发现增强耗尽率,并且发现碘在耗尽臭氧的每种原子比BR更有效。氯和溴之间的相互作用是复杂的,因为氯可以增加Br原子的再循环和产生,同时还在某些条件下增加反应性溴水池。还发现氯化学对HO2和RO2产生显着的影响,有机化合物用作CL原子的主要反应合作伙伴。这项工作的结果突出了对BR2和Cl2的生产机制的未来研究,以及碘在高北极的潜在影响。
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