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Oxygen isotopic fractionation during UV and visible light photodissociation of ozone

机译:UV和可见光臭氧分解过程中的氧同位素分馏

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Stratospheric ozone is essentially in a steady due to the simultaneous formation and dissociation and found to be enriched (mass-independently) in heavy oxygen isotopes. Though there have been a number of experimental and theoretical studies on the mechanism(s) associated with the formation of isotopically heavy ozone, the decomposition processes were not studied in necessary detail. Here we report a novel feature in the isotopic fractionation of ozone during photodissociation in the UV and visible wavelengths. Photodissociation of ozone produces isotopically light oxygen, enriching the leftover ozone pool. Interestingly, the isotopic fractionation patterns are not similar in the two wavelength regions. Dissociation at visible wavelengths displays a mass-dependent slope (DELTA delta~(17)O/DELTA delta~(18)O=0.54) whereas UV dissociation shows a mass-independent character (DELTA delta~(17)O/DELTA delta~(18)O=0.63). O_3 photodissociation in UV wavelengths is normally associated with another effective channel of dissociation, i.e., O_3+O(~1D). It is demonstrated for the first time that pure UV photodissociation of ozone [i.e., without the O(~1D) channel] gives a slope of unity intriguingly similar to that obtained in the ozone formation process. A combination of the two processes i.e., mass dependent O~(1D)+O_3 reaction and pure UV photodissociation is responsible for the observed slope of 0.63
机译:由于同时形成和分解,平流层中的臭氧基本上处于稳定状态,并发现(独立于质量)富集于重氧同位素中。尽管已经进行了许多与同位素重质臭氧形成有关的机理的实验和理论研究,但未对分解过程进行必要的详细研究。在这里,我们报告了在紫外线和可见光波长下光解离过程中臭氧同位素分馏的新特征。臭氧的光离解产生同位素轻的氧气,丰富了剩余的臭氧池。有趣的是,同位素分馏模式在两个波长区域中并不相似。可见光下的离解显示出质量相关的斜率(Δδ〜(17)O / DELTAδ〜(18)O = 0.54),而UV离解显示出质量无关的特性(DELTAδ〜(17)O / DELTAδ〜 (18)O = 0.63)。紫外线波长下的O_3光解离通常与另一个有效的解离通道相关,即O_3 + O(〜1D)。首次证明臭氧的纯紫外光解离[即没有O(〜1D)通道]产生的单位斜率与在臭氧形成过程中获得的单位斜率非常有趣。取决于质量的O〜(1D)+ O_3反应和纯UV光解离这两个过程的结合导致观察到的斜率为0.63

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