TS.2.1.3 Changes in Atmospheric Halocarbons, Stratospheric Ozone, Tropospheric Ozone and Other Gases

CFCs and hydrochlorofluorocarbons (HCFCs) are greenhouse gases that are purely anthropogenic in origin and used in a wide variety of applications. Emissions of these gases have decreased due to their phase-out under the Montreal Protocol, and the atmospheric concentrations of CFC-11 and CFC-113 are now decreasing due to natural removal processes. Observations in polar firn cores since the TAR have now extended the available time series information for some of these greenhouse gases. Ice core and in situ data confirm that industrial sources are the cause of observed atmospheric increases in CFCs and HCFCs. {2.3}

The Montreal Protocol gases contributed +0.32 ± 0.03 W m^–2 to direct radiative forcing in 2005, with CFC-12 continuing to be the third most important long-lived radiative forcing agent. These gases as a group contribute about 12% of the total forcing due to LLGHGs. {2.3}

The concentrations of industrial fluorinated gases covered by the Kyoto Protocol (hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), sulphur hexafluoride (SF₆)) are relatively small but are increasing rapidly. Their total radiative forcing in 2005 was +0.017 W m^–2. {2.3}

Tropospheric ozone is a short-lived greenhouse gas produced by chemical reactions of precursor species in the atmosphere and with large spatial and temporal variability. Improved measurements and modelling have advanced the understanding of chemical precursors that lead to the formation of tropospheric ozone, mainly carbon monoxide, nitrogen oxides (including sources and possible long-term trends in lightning) and formaldehyde. Overall, current models are successful in describing the principal features of the present global tropospheric ozone distribution on the basis of underlying processes. New satellite and in situ measurements provide important global constraints for these models; however, there is less confidence in their ability to reproduce the changes in ozone associated with large changes in emissions or climate, and in the simulation of observed long-term trends in ozone concentrations over the 20th century. {7.4}

Tropospheric ozone radiative forcing is estimated to be +0.35 [+0.25 to +0.65] W m^–2 with a medium level of scientific understanding. The best estimate of this radiative forcing has not changed since the TAR. Observations show that trends in tropospheric ozone during the last few decades vary in sign and magnitude at many locations, but there are indications of significant upward trends at low latitudes. Model studies of the radiative forcing due to the increase in tropospheric ozone since pre-industrial times have increased in complexity and comprehensiveness compared with models used in the TAR. {2.3, 7.4}

Changes in tropospheric ozone are linked to air quality and climate change. A number of studies have shown that summer daytime ozone concentrations correlate strongly with temperature. This correlation appears to reflect contributions from temperature-dependent biogenic volatile organic carbon emissions, thermal decomposition of peroxyacetylnitrate, which acts as a reservoir for nitrogen oxides (NO_x), and association of high temperatures with regional stagnation. Anomalously hot and stagnant conditions during the summer of 1988 were responsible for the highest surface-level ozone year on record in the north-eastern USA. The summer heat wave in Europe in 2003 was also associated with exceptionally high local ozone at the surface. {Box 7.4}

The radiative forcing due to the destruction of stratospheric ozone is caused by the Montreal Protocol gases and is re-evaluated to be –0.05 ± 0.10 W m^–2, weaker than in the TAR, with a medium level of scientific understanding. The trend of greater and greater depletion of global stratospheric ozone observed during the 1980s and 1990s is no longer occurring; however, global stratospheric ozone is still about 4% below pre-1980 values and it is not yet clear whether ozone recovery has begun. In addition to the chemical destruction of ozone, dynamical changes may have contributed to NH mid-latitude ozone reduction. {2.3}

Direct emission of water vapour by human activities makes a negligible contribution to radiative forcing. However, as global mean temperatures increase, tropospheric water vapour concentrations increase and this represents a key feedback but not a forcing of climate change. Direct emission of water to the atmosphere by anthropogenic activities, mainly irrigation, is a possible forcing factor but corresponds to less than 1% of the natural sources of atmospheric water vapour. The direct injection of water vapour into the atmosphere from fossil fuel combustion is significantly lower than that from agricultural activity. {2.5}

Based on chemical transport model studies, the radiative forcing from increases in stratospheric water vapour due to oxidation of CH₄ is estimated to be +0.07 ± 0.05 W m^–2. The level of scientific understanding is low because the contribution of CH₄ to the corresponding vertical structure of the water vapour change near the tropopause is uncertain. Other potential human causes of stratospheric water vapour increases that could contribute to radiative forcing are poorly understood. {2.3}