Interpretations of stratospheric photochemistry
Interpretations of stratospheric photochemistry
复制标题
平流层光化学的解释
DOI：
10.1029/rg016i004p00491
复制
发表时间：
1978
影响因子：
25.2
通讯作者：
J. Podolske
中科院分区：
文献类型：
--
作者：
H. Johnston;J. Podolske
平流层痕量物质（十亿分之一或更少）对臭氧（百万分之一）的影响可以忽略不计，除非它们在催化循环中相互作用以再生痕量物质。将催化循环、零循环和消耗序列而不是基本化学反应视为臭氧光化学的组成部分是适当的。臭氧的一般微分方程被转换为直接识别催化循环和序列的等效方程。本文的新颖之处在于这种转换的执行和使用的完整性。这种处理平流层光化学的方法在 O/sub x/、NO/sub x/、H2O/sub x/ 和 CIX 反应族之间正确分配臭氧破坏率。甲烷-烟雾的化学特征被清晰地展现出来。从已发表的 NO/sub 2/ 和 CIO 测量值的中值来看，NO/sub 2/、CIO 和 O/sub 3/ 足以破坏 23-35 km 范围内臭氧形成的速度，并且 NO/sub x/ 反应和 CIX 反应的重要性似乎大致相等。如果测得的 NO/sub 2/ 和 CIO 的中值代表全球平均值，则无需调用该地区任何新的或未知的臭氧汇。 NO/sub 2/ 或 CIO 观察到的高值不太可能代表全球平均值。由于缺乏对平流层中 HOO 的观测，该方法无法确定 H2O/sub x/ 反应对臭氧光化学的贡献大小。这些结论取决于平流层观测的准确性和某些速率常数。需要额外的测量，特别是 HOO、NO/sub 2/、CIO 和 H2O。« less
Trace stratospheric species (parts per billion or less) have negligible effects on ozone (parts per million) unless they interact in catalytic cycles that regenerate the trace species. It is appropriate to regard catalytic cycles, null cycles, and consumptive sequences, rather than the elementary chemical reactions, as the components of ozone photochemistry. A general differential equation for ozone is transformed to an equivalent equation that directly identifies the catalytic cycles and sequences. The novel aspect of this article is the completeness with which this transformation is carried out and used. This method of treating stratospheric photochemistry properly partitions ozone destruction rates among O/sub x/, NO/sub x/, HO/sub x/, and CIX families of reactions. The features of the methane-smog chemistry are clearly brought out. From the midvalues of published measurements of NO/sub 2/ and CIO, it appears that NO/sub 2/, CIO, and O/sub 3/, are sufficient to destroy ozone as fast as it is formed in the range 23-35 km, and NO/sub x/ reactions and CIX reactions appear to be roughly equal in importance. There is no need to invoke any new or unknown sink for ozone in this region if the midvalues of measured NO/sub 2/ and CIO are representative ofmore » the global average. It is improbable that the high values observed for NO/sub 2/ or for CIO are representative of the global average values. The magnitude of the contribution of HO/sub x/ reactions to ozone photochemistry cannot be found by this method because of lack of observations of HOO in the stratosphere. These conclusions depend on the accuracy of the stratospheric observations and certain rate constants. Additional measurements are needed, especially for HOO, NO/sub 2/, CIO, and HO.« less