Rowland F Sherwood
Department of Chemistry, University of California Irvine, Irvine, CA 92697, USA.
Philos Trans R Soc Lond B Biol Sci. 2006 May 29;361(1469):769-90. doi: 10.1098/rstb.2005.1783.
Solar ultraviolet radiation creates an ozone layer in the atmosphere which in turn completely absorbs the most energetic fraction of this radiation. This process both warms the air, creating the stratosphere between 15 and 50 km altitude, and protects the biological activities at the Earth's surface from this damaging radiation. In the last half-century, the chemical mechanisms operating within the ozone layer have been shown to include very efficient catalytic chain reactions involving the chemical species HO, HO2, NO, NO2, Cl and ClO. The NOX and ClOX chains involve the emission at Earth's surface of stable molecules in very low concentration (N2O, CCl2F2, CCl3F, etc.) which wander in the atmosphere for as long as a century before absorbing ultraviolet radiation and decomposing to create NO and Cl in the middle of the stratospheric ozone layer. The growing emissions of synthetic chlorofluorocarbon molecules cause a significant diminution in the ozone content of the stratosphere, with the result that more solar ultraviolet-B radiation (290-320 nm wavelength) reaches the surface. This ozone loss occurs in the temperate zone latitudes in all seasons, and especially drastically since the early 1980s in the south polar springtime-the 'Antarctic ozone hole'. The chemical reactions causing this ozone depletion are primarily based on atomic Cl and ClO, the product of its reaction with ozone. The further manufacture of chlorofluorocarbons has been banned by the 1992 revisions of the 1987 Montreal Protocol of the United Nations. Atmospheric measurements have confirmed that the Protocol has been very successful in reducing further emissions of these molecules. Recovery of the stratosphere to the ozone conditions of the 1950s will occur slowly over the rest of the twenty-first century because of the long lifetime of the precursor molecules.
太阳紫外线辐射在大气中形成臭氧层,而臭氧层又会完全吸收这种辐射中能量最高的部分。这一过程既使空气变暖,在15至50千米的高度形成平流层,又保护地球表面的生物活动免受这种有害辐射的影响。在过去的半个世纪里,已证明在臭氧层内发生作用的化学机制包括涉及化学物质HO、HO₂、NO、NO₂、Cl和ClO的非常有效的催化链式反应。NOₓ和ClOₓ链涉及在地球表面排放浓度极低的稳定分子(N₂O、CCl₂F₂、CCl₃F等),这些分子在大气中飘荡长达一个世纪,然后才吸收紫外线辐射并分解,在平流层臭氧层中部产生NO和Cl。合成氯氟烃分子排放量的不断增加导致平流层臭氧含量大幅减少,结果是更多的太阳紫外线B辐射(波长290 - 320纳米)到达地球表面。这种臭氧损耗在温带地区全年都会发生,自20世纪80年代初以来,在南极春季尤其严重——即“南极臭氧空洞”。导致这种臭氧消耗的化学反应主要基于原子Cl和ClO,即其与臭氧反应的产物。1992年对1987年联合国《蒙特利尔议定书》的修订案禁止了氯氟烃的进一步生产。大气测量证实,该议定书在减少这些分子的进一步排放方面非常成功。由于前体分子的寿命很长,平流层要恢复到20世纪50年代的臭氧状况将在21世纪余下的时间里缓慢实现。