Ozone Depletion - Ozone Cycle Overview

Ozone Cycle Overview

Three forms (or allotropes) of oxygen are involved in the ozone-oxygen cycle: oxygen atoms (O or atomic oxygen), oxygen gas (O₂ or diatomic oxygen), and ozone gas (O₃ or triatomic oxygen). Ozone is formed in the stratosphere when oxygen molecules photodissociate after absorbing an ultraviolet photon whose wavelength is shorter than 240 nm. This converts a single O₂ into two atomic oxygen radicals. The atomic oxygen radicals then combine with separate O₂ molecules to create two O₃ molecules. These ozone molecules absorb UV light between 310 and 200 nm, following which ozone splits into a molecule of O₂ and an oxygen atom. The oxygen atom then joins up with an oxygen molecule to regenerate ozone. This is a continuing process which terminates when an oxygen atom "recombines" with an ozone molecule to make two O₂ molecules.

O + O₃ → 2 O₂ chemical equation

The overall amount of ozone in the stratosphere is determined by a balance between photochemical production and recombination.

Ozone can be destroyed by a number of free radical catalysts, the most important of which are the hydroxyl radical (OH·), the nitric oxide radical (NO·), atomic chlorine ion (Cl·) and atomic bromine ion (Br·). The dot is a common notation to indicate that all of these species have an unpaired electron and are thus extremely reactive. All of these have both natural and man-made sources; at the present time, most of the OH· and NO· in the stratosphere is of natural origin, but human activity has dramatically increased the levels of chlorine and bromine. These elements are found in certain stable organic compounds, especially chlorofluorocarbons (CFCs), which may find their way to the stratosphere without being destroyed in the troposphere due to their low reactivity. Once in the stratosphere, the Cl and Br atoms are liberated from the parent compounds by the action of ultraviolet light, e.g.

CFCl₃ + electromagnetic radiation → CFCl₂ + Cl

The Cl and Br atoms can then destroy ozone molecules through a variety of catalytic cycles. In the simplest example of such a cycle, a chlorine atom reacts with an ozone molecule, taking an oxygen atom with it (forming ClO) and leaving a normal oxygen molecule. The chlorine monoxide (i.e., the ClO) can react with a second molecule of ozone (i.e., O₃) to yield another chlorine atom and two molecules of oxygen. The chemical shorthand for these gas-phase reactions is:

• Cl + O₃ → ClO + O₂ – The chlorine atom changes an ozone molecule to ordinary oxygen

• ClO + O₃ → Cl + 2 O₂ – The ClO from the previous reaction destroys a second ozone molecule and recreates the original chlorine atom, which can repeat the first reaction and continue to destroy ozone.

The overall effect is a decrease in the amount of ozone, though the rate of these processes can be decreased by the effects of null cycles. More complicated mechanisms have been discovered that lead to ozone destruction in the lower stratosphere as well.

A single chlorine atom would keep on destroying ozone (thus a catalyst) for up to two years (the time scale for transport back down to the troposphere) were it not for reactions that remove them from this cycle by forming reservoir species such as hydrogen chloride (HCl) and chlorine nitrate (ClONO₂). On a per atom basis, bromine is even more efficient than chlorine at destroying ozone, but there is much less bromine in the atmosphere at present. As a result, both chlorine and bromine contribute significantly to the overall ozone depletion. Laboratory studies have shown that fluorine and iodine atoms participate in analogous catalytic cycles. However, in the Earth's stratosphere, fluorine atoms react rapidly with water and methane to form strongly bound HF, while organic molecules which contain iodine react so rapidly in the lower atmosphere that they do not reach the stratosphere in significant quantities. Furthermore, a single chlorine atom is able to react with 100,000 ozone molecules. This fact plus the amount of chlorine released into the atmosphere by chlorofluorocarbons (CFCs) yearly demonstrates how dangerous CFCs are to the environment.