Ozone depletion describes two distinct, but related observations: a slow, steady decline of about 4% per decade in the total volume of ozone in Earth's stratosphere (ozone layer) since the late 1970s, and a much larger, but seasonal, decrease in stratospheric ozone over Earth's polar regions during the same period. The latter phenomenon is commonly referred to as the ozone hole. In addition to this well-known stratospheric ozone depletion, there are also tropospheric ozone depletion events, which occur near the surface in polar regions during spring.
The detailed mechanism by which the polar ozone holes form is different from that for the mid-latitude thinning, but the most important process in both trends is catalytic destruction of ozone by atomic chlorine and bromine.The main source of these halogen atoms in the stratosphere is photodissociation of chlorofluorocarbon (CFC) compounds, commonly called freons, and of bromofluorocarbon compounds known as halons. These compounds are transported into the stratosphere after being emitted at the surface.Both ozone depletion mechanisms strengthened as emissions of CFCs and halons increased.
CFCs and other contributory substances are commonly referred to as ozone-depleting substances (ODS). Since the ozone layer prevents most harmful UVB wavelengths (270–315 nm) of ultraviolet light (UV light) from passing through the Earth's atmosphere, observed and projected decreases in ozone have generated worldwide concern leading to adoption of the Montreal Protocol that bans the production of CFCs and halons as well as related ozone depleting chemicals such as carbon tetrachloride and trichloroethane. It is suspected that a variety of biological consequences such as increases in skin cancer, cataracts, damage to plants, and reduction of plankton populations in the ocean's photic zone may result from the increased UV exposure due to ozone depletion.
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 produces two oxygen atoms. The atomic oxygen then combines with O2 to create O3. 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
Layers of the atmosphere (not to scale)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 (Cl·) and bromine (Br·). All of these have both natural and manmade 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. ('h' is Planck's constant, 'ν' is frequency of electromagnetic radiation)
CFCl3 + hν → 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,[4] 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
ClO + O3 → Cl + 2 O2
The overall effect is a decrease in the amount of ozone. 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.
Quantitative understanding of the chemical ozone loss process
New research on the breakdown of a key molecule in these ozone-depleting chemicals, dichlorine peroxide (Cl2O2), calls into question the completeness of present atmospheric models of polar ozone depletion. Specifically, chemists at NASA's Jet Propulsion Laboratory in Pasadena, California, found in 2007 that the temperatures, and the spectrum and intensity of radiation present in the stratosphere created conditions insufficient to allow the rate of chemical-breakdown required to release chlorine radicals in the volume necessary to explain observed rates of ozone depletion. Instead, laboratory tests, designed to be the most accurate reflection of stratospheric conditions to date, showed the decay of the crucial molecule almost a magnitude lower than previously thought.
That result motivated further measurements by different methods, resulting in cross-sections that agree with the older, higher ones. If the new results hold up, the purported discrepancy will be resolved.
Observations on ozone layer depletion
The most pronounced decrease in ozone has been in the lower stratosphere. However, the ozone hole is most usually measured not in terms of ozone concentrations at these levels (which are typically of a few parts per million) but by reduction in the total column ozone, above a point on the Earth's surface, which is normally expressed in Dobson units, abbreviated as "DU". Marked decreases in column ozone in the Antarctic spring and early summer compared to the early 1970s and before have been observed using instruments such as the Total Ozone Mapping Spectrometer (TOMS).
Chemicals in the atmosphere
CFCs in the atmosphere
Chlorofluorocarbons (CFCs) were invented by Thomas Midgley in the 1920s. They were used in air conditioning/cooling units, as aerosol spray propellants prior to the 1980s, and in the cleaning processes of delicate electronic equipment. They also occur as by-products of some chemical processes. No significant natural sources have ever been identified for these compounds — their presence in the atmosphere is due almost entirely to human manufacture. As mentioned in the ozone cycle overview above, when such ozone-depleting chemicals reach the stratosphere, they are dissociated by ultraviolet light to release chlorine atoms. The chlorine atoms act as a catalyst, and each can break down tens of thousands of ozone molecules before being removed from the stratosphere. Given the longevity of CFC molecules, recovery times are measured in decades. It is calculated that a CFC molecule takes an average of 15 years to go from the ground level up to the upper atmosphere, and it can stay there for about a century, destroying up to one hundred thousand ozone molecules during that time.
Verification of observations
Scientists have been increasingly able to attribute the observed ozone depletion to the increase of man-made (anthropogenic) halogen compounds from CFCs by the use of complex chemistry transport models and their validation against observational data (e.g. SLIMCAT, CLaMS). These models work by combining satellite measurements of chemical concentrations and meteorological fields with chemical reaction rate constants obtained in lab experiments. They are able to identify not only the key chemical reactions but also the transport processes which bring CFC photolysis products into contact with ozone.
Interest in ozone layer depletion
While the effect of the Antarctic ozone hole in decreasing the global ozone is relatively small, estimated at about 4% per decade, the hole has generated a great deal of interest because:
The decrease in the ozone layer was predicted in the early 1980s to be roughly 7% over a 60 year period.[citation needed]
The sudden recognition in 1985 that there was a substantial "hole" was widely reported in the press. The especially rapid ozone depletion in Antarctica had previously been dismissed as a measurement error.[citation needed]
Many[citation needed] were worried that ozone holes might start to appear over other areas of the globe but to date the only other large-scale depletion is a smaller ozone "dimple" observed during the Arctic spring over the North Pole. Ozone at middle latitudes has declined, but by a much smaller extent (about 4–5% decrease).
If the conditions became more severe (cooler stratospheric temperatures, more stratospheric clouds, more active chlorine), then global ozone may decrease at a much greater pace. Standard global warming theory predicts that the stratosphere will cool.
When the Antarctic ozone hole breaks up, the ozone-depleted air drifts out into nearby areas. Decreases in the ozone level of up to 10% have been reported in New Zealand in the month following the break-up of the Antarctic ozone hole.
Consequences of ozone layer depletion
Since the ozone layer absorbs UVB ultraviolet light from the Sun, ozone layer depletion is expected to increase surface UVB levels, which could lead to damage, including increases in skin cancer. This was the reason for the Montreal Protocol. Although decreases in stratospheric ozone are well-tied to CFCs and there are good theoretical reasons to believe that decreases in ozone will lead to increases in surface UVB, there is no direct observational evidence linking ozone depletion to higher incidence of skin cancer in human beings. This is partly due to the fact that UVA, which has also been implicated in some forms of skin cancer, is not absorbed by ozone, and it is nearly impossible to control statistics for lifestyle changes in the populace.
Increased UV
Ozone, while a minority constituent in the Earth's atmosphere, is responsible for most of the absorption of UVB radiation. The amount of UVB radiation that penetrates through the ozone layer decreases exponentially with the slant-path thickness/density of the layer. Correspondingly, a decrease in atmospheric ozone is expected to give rise to significantly increased levels of UVB near the surface.
Increases in surface UVB due to the ozone hole can be partially inferred by radiative transfer model calculations, but cannot be calculated from direct measurements because of the lack of reliable historical (pre-ozone-hole) surface UV data, although more recent surface UV observation measurement programmes exist (e.g. at Lauder, New Zealand).
Because it is this same UV radiation that creates ozone in the ozone layer from O2 (regular oxygen) in the first place, a reduction in stratospheric ozone would actually tend to increase photochemical production of ozone at lower levels (in the troposphere), although the overall observed trends in total column ozone still show a decrease, largely because ozone produced lower down has a naturally shorter photochemical lifetime, so it is destroyed before the concentrations could reach a level which would compensate for the ozone reduction higher up.[citation needed]
Biological effects
The main public concern regarding the ozone hole has been the effects of increased surface UV and microwave radiation on human health. So far, ozone depletion in most locations has been typically a few percent and, as noted above, no direct evidence of health damage is available in most latitudes. Were the high levels of depletion seen in the ozone hole ever to be common across the globe, the effects could be substantially more dramatic. As the ozone hole over Antarctica has in some instances grown so large as to reach southern parts of Australia and New Zealand, environmentalists have been concerned that the increase in surface UV could be significant.[citation needed]
Effects on humans
UVB (the higher energy UV radiation absorbed by ozone) is generally accepted to be a contributory factor to skin cancer. In addition, increased surface UV leads to increased tropospheric ozone, which is a health risk to humans.[citation needed] The increased surface UV also represents an increase in the vitamin D synthetic capacity of the sunlight.
The cancer preventive effects of vitamin D represent a possible beneficial effect of ozone depletion.In terms of health costs, the possible benefits of increased UV irradiance may outweigh the burden.
1. Basal and Squamous Cell Carcinomas -- The most common forms of skin cancer in humans, basal and squamous cell carcinomas, have been strongly linked to UVB exposure. The mechanism by which UVB induces these cancers is well understood — absorption of UVB radiation causes the pyrimidine bases in the DNA molecule to form dimers, resulting in transcription errors when the DNA replicates. These cancers are relatively mild and rarely fatal, although the treatment of squamous cell carcinoma sometimes requires extensive reconstructive surgery. By combining epidemiological data with results of animal studies, scientists have estimated that a one percent decrease in stratospheric ozone would increase the incidence of these cancers by 2%.
2. Malignant Melanoma — Another form of skin cancer, malignant melanoma, is much less common but far more dangerous, being lethal in about 15–20% of the cases diagnosed. The relationship between malignant melanoma and ultraviolet exposure is not yet well understood, but it appears that both UVB and UVA are involved. Experiments on fish suggest that 90 to 95% of malignant melanomas may be due to UVA and visible radiation[26] whereas experiments on opossums suggest a larger role for UVB.[25] Because of this uncertainty, it is difficult to estimate the impact of ozone depletion on melanoma incidence. One study showed that a 10% increase in UVB radiation was associated with a 19% increase in melanomas for men and 16% for women.[27] A study of people in Punta Arenas, at the southern tip of Chile, showed a 56% increase in melanoma and a 46% increase in nonmelanoma skin cancer over a period of seven years, along with decreased ozone and increased UVB levels.
3. Cortical Cataracts -- Studies are suggestive of an association between ocular cortical cataracts and UV-B exposure, using crude approximations of exposure and various cataract assessment techniques. A detailed assessment of ocular exposure to UV-B was carried out in a study on Chesapeake Bay Watermen, where increases in average annual ocular exposure were associated with increasing risk of cortical opacity [29]. In this highly exposed group of predominantly white males, the evidence linking cortical opacities to sunlight exposure was the strongest to date. However, subsequent data from a population-based study in Beaver Dam, WI suggested the risk may be confined to men. In the Beaver Dam study, the exposures among women were lower than exposures among men, and no association was seen.[30] Moreover, there were no data linking sunlight exposure to risk of cataract in African Americans, although other eye diseases have different prevalences among the different racial groups, and cortical opacity appears to be higher in African Americans compared with whites.
4. Increased Tropospheric Ozone -- Increased surface UV leads to increased tropospheric ozone. Ground-level ozone is generally recognized to be a health risk, as ozone is toxic due to its strong oxidant properties. At this time, ozone at ground level is produced mainly by the action of UV radiation on combustion gases from vehicle exhausts.[citation needed]
