The ozone layer prevents most ultraviolet (UV) and other high-energy radiation from penetrating to the earth's surface but does allow through sufficient ultraviolet rays to support the activation of vitamin D in humans. The full radiation, if unhindered by this filtering effect, would destroy animal tissue. Higher levels of radiation resulting from the depletion of the ozone layer have been linked with increases in skin cancers and cataracts and have been implicated in the decline of certain amphibian species.
In 1974 scientists warned that certain industrial chemicals, e.g., chlorofluorocarbons (CFCs) and to a lesser extent, halons and carbon tetrachloride, could migrate to the stratosphere. There, sunlight could free the chlorine or bromine atoms to form chlorine monoxide or other chemicals, which would deplete upper-atmospheric ozone. A seasonal decrease, or "hole," discovered in 1985 in the ozone layer above Antarctica was the first confirmation of a thinning of the layer. The hole occurs over Antarctica because the extreme cold helps the very high clouds characteristic of that area form tiny ice particles of water and nitric acid, which facilitate the chemical reactions involved. In addition, the polar winds, which follow a swirling pattern, create a confined vortex, trapping the chemicals. When the Antarctic spring sun rises in August or September and hits the trapped chemicals, a chain reaction begins in which chlorine, bromine (from the halons), and ice crystals react with the ozone and destroy it very quickly. The effect usually lasts through November. There is a corresponding hole over the Arctic that similarly appears in the spring, although in some years warmer winters there do not result in a major depletion of the ozone layer. A global thinning of the ozone layer results as ozone-rich air from the remaining ozone layer flows into the ozone-poor areas.
Minimum ozone levels in the Antarctic decreased steadily throughout the 1990s, and less dramatic decreases have been found above other areas of the world. In 2000 (and again in 2003 and 2006) the hole reached a record size, extending over more than 10.5 million sq mi (27 million sq km), an area greater than that of North America. In 1987 an international agreement, the Montreal Protocol, was reached on reducing the production of ozone-depleting compounds. Revisions in 1992 called for an end to the production of the worst of such compounds by 1996, and CFC emissions dropped dramatically by 1993. Recovery of the ozone layer, however, is expected to take 50 to 100 years. Damage to the ozone layer can also be caused by sulfuric acid droplets produced by volcanic eruptions.
Although the concentration of the ozone in the ozone layer is very small, it is vitally important to life because it absorbs biologically harmful ultraviolet (UV) radiation emitted from the Sun. UV radiation is divided into three categories, based on its wavelength; these are referred to as UV-A (400-315 nm), UV-B (315-280 nm), and UV-C (280-100 nm). UV-C, which would be very harmful to humans, is entirely screened out by ozone at around 35 km altitude. UV-B radiation can be harmful to the skin and is the main cause of sunburn; excessive exposure can also cause genetic damage, as a result problems such as skin cancer. The ozone layer is very effective at screening out UV-B; for radiation with a wavelength of 290 nm, the intensity at Earth's surface is 350 billion times weaker than at the top of the atmosphere. Nevertheless, some UV-B reaches the surface. Most UV-A reaches the surface; this radiation is significantly less harmful, although it can potentially cause genetic damage.
To appreciate the importance of this ultraviolet radiation screening, we can consider a characteristic of radiation damage called an action spectrum. An action spectrum gives us a measure of the relative effectiveness of radiation in generating a certain biological response over a range of wavelengths. This response might be erythema (sunburn), changes in plant growth, or changes in molecular DNA. Certain wavelengths of UV radiation have a much greater probability of DNA damage than others. Fortunately, where DNA is easily damaged, such as by wavelengths shorter than 290 nm, ozone strongly absorbs UV. At the longer wavelengths where ozone absorbs weakly, DNA damage is less likely.
The thickness of the ozone layer—that is, the total amount of ozone in a column overhead—varies by a large factor worldwide, being in general smaller near the equator and larger as one moves towards the poles. It also varies with season, being in general thicker during the spring and thinner during the autumn in the northern hemisphere. The reasons for this latitude and seasonal dependence are complicated, involving atmospheric circulation patterns as well as solar intensity.
Since stratospheric ozone is produced by solar UV radiation, one might expect to find the highest ozone levels over the tropics and the lowest over polar regions. The same argument would lead one to expect the highest ozone levels in the summer and the lowest in the winter. The observed behavior is very different: most of the ozone is found in the mid-to-high latitudes of the northern and southern hemispheres, and the highest levels are found in the spring, not summer, and the lowest in the autumn, not winter in the northern hemisphere. During winter, the ozone layer actually increases in depth. This puzzle is explained by the prevailing stratospheric wind patterns, known as the Brewer-Dobson circulation. While most of the ozone is indeed created over the tropics, the stratospheric circulation then transports it poleward and downward to the lower stratosphere of the high latitudes. However in the southern hemisphere, owing to the ozone hole phenomenon, the lowest amounts of column ozone found anywhere in the world are over the Antarctic in the southern spring period of September and October.
The ozone layer is higher in altitude in the tropics, and lower in altitude in the extratropics, especially in the polar regions. This altitude variation of ozone results from the slow circulation that lifts the ozone-poor air out of the troposphere into the stratosphere. As this air slowly rises in the tropics, ozone is produced by the overhead sun which photolyzes oxygen molecules. As this slow circulation bends towards the mid-latitudes, it carries the ozone-rich air from the tropical middle stratosphere to the mid-and-high latitudes lower stratosphere. The high ozone concentrations at high latitudes are due to the accumulation of ozone at lower altitudes.
The Brewer-Dobson circulation moves very slowly. The time needed to lift an air parcel from the tropical tropopause near 16 km (50,000 ft) to 20 km is about 4-5 months (about per day). Even though ozone in the lower tropical stratosphere is produced at a very slow rate, the lifting circulation is so slow that ozone can build up to relatively high levels by the time it reaches 26 km.
Ozone amounts over the continental United States (25°N to 49°N) are highest in the northern spring (April and May). These ozone amounts fall over the course of the summer to their lowest amounts in October, and then rise again over the course of the winter. Again, wind transport of ozone is principally responsible for the seasonal evolution of these higher latitude ozone patterns.
The total column amount of ozone generally increases as we move from the tropics to higher latitudes in both hemispheres. However, the overall column amounts are greater in the northern hemisphere high latitudes than in the southern hemisphere high latitudes. In addition, while the highest amounts of column ozone over the Arctic occur in the northern spring (March-April), the opposite is true over the Antarctic, where the lowest amounts of column ozone occur in the southern spring (September-October). Indeed, the highest amounts of column ozone anywhere in the world are found over the Arctic region during the northern spring period of March and April. The amounts then decrease over the course of the northern summer. Meanwhile, the lowest amounts of column ozone anywhere in the world are found over the Antarctic in the southern spring period of September and October, owing to the ozone hole phenomenon.
The ozone layer can be depleted by free radical catalysts, including nitric oxide (NO), hydroxyl (OH), atomic chlorine (Cl), and atomic bromine (Br). While there are natural sources for all of these species, the concentrations of chlorine and bromine have increased markedly in recent years due to the release of large quantities of manmade organohalogen compounds, especially chlorofluorocarbons (CFCs) and bromofluorocarbons. These highly stable compounds are capable of surviving the rise to the stratosphere, where Cl and Br radicals are liberated by the action of ultraviolet light. Each radical is then free to initiate and catalyze a chain reaction capable of breaking down over 100,000 ozone molecules. Ozone levels, over the northern hemisphere, have been dropping by 4% per decade. Over approximately 5% of the Earth's surface, around the north and south poles, much larger (but seasonal) declines have been seen; these are the ozone holes.
On August 2, 2003, scientists announced that the depletion of the ozone layer may be slowing down due to the international ban on CFCs. Three satellites and three ground stations confirmed that the upper atmosphere ozone depletion rate has slowed down significantly during the past decade. The study was organized by the American Geophysical Union. Some breakdown can be expected to continue due to CFCs used by nations which have not banned them, and due to gases which are already in the stratosphere. CFCs have very long atmospheric lifetimes, ranging from 50 to over 100 years, so the final recovery of the ozone layer is expected to require several lifetimes.
Compounds containing C–H bonds have been designed to replace the function of CFC's (such as HCFC), since these compounds are more reactive and less likely to survive long enough in the atmosphere to reach the stratosphere where they could affect the ozone layer. However, while being less damaging than CFC's, HCFC's have an ozone depleting potential of between 0.01 and 0.1, meaning that HCFC's also have a significant negative impact on the ozone layer. HCFC's are therefore also being phased out.