Excerpt from Thinning of the ozone layer: Facts and consequences

Author/s: Brett M. Coldiron, MD Cincinnati, Ohio

NATURAL HISTORY OF OZONE

Ozone is naturally created by the absorption of high-energy solar Ultra-Violet Radiation
(UVR) by doublet oxygen molecules. This energy splits oxygen molecules. The majority of these
single oxygen atoms recombine with doublet oxygen forming the triplet oxygen, ozone molecule.
Ozone is unstable and reacts quickly with anything nearby, including other singlet oxygens, to
revert back to doublet oxygen. It may also react with free hydrogen to form hydroxyl groups or
water. A small steady-state amount of ozone is maintained in the stratosphere. If all the ozone in
the stratosphere was brought down to sea level it would only be about 3 mm thick (the ozone
column). The ozone layer is thin, widely scattered, and vulnerable. The ozone layer has a natural
cycle that increases with increased UVR from the sun and changes with the season.

WHAT IS CAUSING OZONE DEPLETION?

The largest ozone-depleting reactions involve nitrous oxide and nitrogen dioxide. These
chemically catalyze the conversion of ozone to doublet oxygen in a number of chemical reactions.
Nitrogen gases are derived from supersonic aircraft, microorganisms, fertilizers, and human air
pollution. Microbially produced nitrous oxide is probably the most important source. Nitrous oxide
can undergo repeated photolysis to generate radicals capable of thinning the ozone. Most of the
bromine in the stratosphere is believed to come from methyl bromine, the origin of which is
uncertain but possibly from seawater. Certainly, these are not new sources and we must look
further for the cause of the current ozone decline. Ozone depletion is at least partly due to
halocarbons such as Freon (CFCs) and bromide compounds. CFCs have many uses, including
air conditioning, foam extrusion, and industrial solvents. Halons, such as certain bromide
compounds, are uniquely effective in lightweight fire extinguishers. Halocarbons are
disassociated by UVC in the 200 to 227 nm range. As already explained, UVC does not, and is
unlikely to, reach down to the troposphere, even under conditions of severe ozone depletion. The
UVR that penetrates the stratosphere is UVB. Unfortunately, the wavelength of UVB is not short
enough to disassociate halocarbons in the troposphere in which the reactive intermediates would
be quickly inactivated. Photo disassociated chlorine quickly joins with a free oxygen to form
chlorine monoxide, which is the form in which it is usually found in the stratosphere. The chlorine
monoxide acts as a catalyst to destroy ozone, creating an ordinary oxygen molecule and free
chlorine, which repeats the cycle. The chlorine is not consumed in the reaction. Bromine radicals
act in a similar fashion. Bromine is believed to be 10 to 100 times more destructive than chlorine.
Bromine is a more effective catalyst and less is kept in nonparticipating "reservoir species"
because of chemical instability. Other sources of halocarbons include carbon tetrachloride, which
is used as dry cleaning fluid, and methylchloroform, which is used to clean computer boards and
jet engine parts. All these halocarbons are photedisassociated in the stratosphere. The radicals
produced then react with ozone and break it down to oxygen much faster than normal. This results
in a lower steady-state ozone level.
Note: UVA, UVB and UVC are types of UV radiation and are classified based on their
wavelength.

Reference:
Brett M. Coldiron, M. (1992). Thinning of the ozone layer: Facts and consequences . Cincinnati,
Ohio: Journal of the American Academy of Dermatology.