Changes in Stratospheric Ozone

Whereas greenhouse gases warm the troposphere, they cool the stratosphere
.The reason is that greenhouse gases in the troposphere prevent significant
thermal-IR radiation emitted by the Earths surface from reaching the
stratosphere, where such radiation would otherwise be absorbed by ozone
and background carbon dioxide, warming the stratosphere. Black carbon and
brown carbon particles also warm the troposphere by absorbing solar
radiation, but tropospheric BC and BrC have relatively little temperature effect
in the strato-sphere because of their relatively modest absorption of the
Earths thermal-IR radiation (Jacobson, 2002a, 2010b). However, aircraft
emissions of black carbon go directly into the stratosphere at high latitudes,
par-ticularly over the Arctic. Such emissions affect Arctic stratospheric and
tropospheric temperatures. Tropospheric warming due to greenhouse gases
and absorbing aerosol particles increases the evaporation of water from the
oceans and soils, and some of this water vapor reaches the stratosphere.
Between 1954 and 2000, for example, stratospheric water vapour increased 1
percent per year (0.45 ppmv per decade; Rosenlof et al., 2001). This trend
reversed itself slightly in the lower stratosphere from 2001 to 2005, possi-bly
due to changes in atmospheric circulation (Ran-del et al., 2006). However,
stratospheric water vapour appears to have increased again from 2006 to 2010
(Hurst et al., 2011). Stratospheric cooling and water vapor increase affect the
ozone layer in at least four ways. First, in the stratosphere (at 25 km), a
decrease in tem-perature due to tropospheric global warming increases ozone
when only the temperature dependence of gas chemistry is considered (Figure
12.30b). As strato-spheric temperature decreases, ozone increases, due
primarily to the slower loss rate of ozone at higher temperature by the
reaction O(g)+ O3 (g) (Evans et al., 1998). In addition, although most reactions
proceed more slowly when temperature decreases, the reaction

O(g) + O 2 (g) + M O 3(g) + M occurs more rapidly

when temperature decreases. Thus,when only temper-ature effects on

chemistry are considered, a cooling of the stratosphere slightly increases
global stratospheric ozone. Second, as water vapor increases in the
stratosphere due to global warming, OH(g) increases by Reaction 12.9,
accelerating the HOx (g) catalytic ozone destruc-tion cycle and decreasing
ozone (e.g., Dvortsov and Solomon, 2001). Thus, when only the effect of the
increase in stratospheric water vapor on chemistry is considered, global
warming slightly destroys stratospheric ozone . This loss mechanism of ozone
with increasing water vapor is important in the stratosphere, but not at the
surface. Third, stratospheric cooling decreases the saturation vapor pressure of
water, allowing more water vapor to condense onto stratospheric sulfuric acid-
water aerosol particles, causing them to grow larger. The increase in the size of
these aerosol particles increases the rates of chemical reaction on their
surfaces. Because such reactions convert CFC and HCFC by-products to more
active chlorine gases that photolyze to prod-ucts that destroy ozone,a
decrease in stratospheric temperature reduces global stratospheric ozone
when only the effect of cooling on aerosol particle size is considered. Fourth,
stratospheric cooling increases the occur-rence, size, and lifetime of PSCs
(polar stratospheric clouds). Type I PSCs form below 195 K, and Type II PSCs
form below 187 K. Stratospheric cooling increases the frequency of
temperatures below these critical levels during winter, increasing Types I and II
PSC lifetime and size, enhanc-ing polar ozone loss. Some polar ozone loss to
date is due to increased PSC formation caused by strato-spheric cooling that
accompanies near-surface global warming