Search This Blog

Friday, August 15, 2025

Ozone depletion

From Wikipedia, the free encyclopedia
Global monthly average total ozone amount

Ozone depletion consists of two related events observed since the late 1970s: a lowered total amount of ozone in Earth's upper atmosphere, and a much larger springtime decrease in stratospheric ozone (the ozone layer) around Earth's polar regions. The latter phenomenon is referred to as the ozone hole. There are also springtime polar tropospheric ozone depletion events in addition to these stratospheric events.

The main causes of ozone depletion and the ozone hole are manufactured chemicals, especially manufactured halocarbon refrigerants, solvents, propellants, and foam-blowing agents (chlorofluorocarbons (CFCs), HCFCs, halons), referred to as ozone-depleting substances (ODS). These compounds are transported into the stratosphere by turbulent mixing after being emitted from the surface, mixing much faster than the molecules can settle. Once in the stratosphere, they release atoms from the halogen group through photodissociation, which catalyze the breakdown of ozone (O3) into oxygen (O2). Both types of ozone depletion were observed to increase as emissions of halocarbons increased.

Ozone depletion and the ozone hole have generated worldwide concern over increased cancer risks and other negative effects. The ozone layer prevents harmful wavelengths of ultraviolet (UVB) light from passing through the Earth's atmosphere. These wavelengths cause skin cancer, sunburn, permanent blindness, and cataracts, which were projected to increase dramatically as a result of thinning ozone, as well as harming plants and animals. These concerns led to the adoption of the Montreal Protocol in 1987, which bans the production of CFCs, halons, and other ozone-depleting chemicals. Over time, scientists have developed new refrigerants with lower global warming potential (GWP) to replace older ones. For example, in new automobiles, R-1234yf systems are now common, being chosen over refrigerants with much higher GWP such as R-134a and R-12.

The ban came into effect in 1989. Ozone levels stabilized by the mid-1990s and began to recover in the 2000s, as the shifting of the jet stream in the southern hemisphere towards the south pole has stopped and might even be reversing. Recovery was projected to continue over the next century, with the ozone hole expected to reach pre-1980 levels by around 2075. In 2019, NASA reported that the ozone hole was the smallest ever since it was first discovered in 1982. The UN now projects that under the current regulations the ozone layer will completely regenerate by 2045. The Montreal Protocol is considered the most successful international environmental agreement to date.

Ozone cycle overview

The ozone cycle

Three forms (or allotropes) of oxygen are involved in the ozone-oxygen cycle: oxygen atoms (O or atomic oxygen), oxygen gas (O
2
or diatomic oxygen), and ozone gas (O
3
or triatomic oxygen). Ozone is formed in the stratosphere when oxygen gas molecules photodissociate after absorbing UVC photons. This converts a single O
2
into two atomic oxygen radicals. The atomic oxygen radicals then combine with separate O
2
molecules to create two O
3
molecules. These ozone molecules absorb UVB light, following which ozone splits into a molecule of O
2
and an oxygen atom. The oxygen atom then joins up with an oxygen molecule to regenerate ozone. This is a continuing process that terminates when an oxygen atom recombines with an ozone molecule to make two O
2
molecules. It is worth noting that ozone is the only atmospheric gas that absorbs UVB light.

O + O
3
→ 2 O
2
The distribution of atmospheric ozone in partial pressure as a function of altitude
Levels of ozone at various altitudes (DU/km) and absorption of different bands of ultraviolet radiation: In essence, all UVC is absorbed by diatomic oxygen (100–200 nm) or by ozone (triatomic oxygen) (200–280 nm) in the atmosphere. The ozone layer also absorbs most UVB. In contrast, UVA is hardly absorbed and most of it reaches the ground. Consequently UVA makes up almost all the UV light that penetrates the Earth's atmosphere.

The total 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 are the hydroxyl radical (OH·), nitric oxide radical (NO·), chlorine radical (Cl·) and bromine radical (Br·). The dot is a notation to indicate that each species has an unpaired electron and is thus extremely reactive. The effectiveness of different halogens and pseudohalogens as catalysts for ozone destruction varies, in part due to differing routes to regenerate the original radical after reacting with ozone or dioxygen.

While all of the relevant radicals have both natural and man-made sources, human activity has impacted some more than others. As of 2020, most of the OH· and NO· in the stratosphere is naturally occurring, but human activity has drastically increased the levels of chlorine and bromine. These elements are found in stable organic compounds, especially chlorofluorocarbons, which can travel to the stratosphere without being destroyed in the troposphere due to their low reactivity. Once in the stratosphere, the Cl and Br atoms are released from the parent compounds by the action of ultraviolet light, e.g.

CFCl
3
+ electromagnetic radiation → Cl· + ·CFCl
2

Ozone is a highly reactive molecule that easily reduces to the more stable oxygen form with the assistance of a catalyst. Cl and Br atoms 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 (O
3
), taking an oxygen atom to form chlorine monoxide (ClO) and leaving an oxygen molecule (O
2
). The ClO can react with a second molecule of ozone, releasing the chlorine atom and yielding two molecules of oxygen. The chemical shorthand for these gas-phase reactions is:

  • Cl· + O
    3
    → ClO + O
    2

    A chlorine atom removes an oxygen atom from an ozone molecule to make a ClO molecule
  • ClO + O
    3
    → Cl· + 2 O
    2

    This ClO can also remove an oxygen atom from another ozone molecule; the chlorine is free to repeat this two-step cycle

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 also been discovered that lead to ozone destruction in the lower stratosphere.

A single chlorine atom would continuously destroy ozone (thus a catalyst) for up to two years (the time scale for transport back down to the troposphere) except for reactions that remove it from this cycle by forming reservoir species such as hydrogen chloride (HCl) and chlorine nitrate (ClONO
2
). Bromine is even more efficient than chlorine at destroying ozone on a per-atom basis, but there is much less bromine in the atmosphere at present. Both chlorine and bromine contribute significantly to overall ozone depletion. Laboratory studies have also shown that fluorine and iodine atoms participate in analogous catalytic cycles. However, fluorine atoms react rapidly with water vapour, methane and hydrogen to form strongly bound hydrogen fluoride (HF) in the Earth's stratosphere, while organic molecules containing iodine react so rapidly in the lower atmosphere that they do not reach the stratosphere in significant quantities.

A single chlorine atom is able to react with an average of 100,000 ozone molecules before it is removed from the catalytic cycle. This fact plus the amount of chlorine released into the atmosphere yearly by chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) demonstrates the danger of CFCs and HCFCs to the environment.

Observations on ozone layer depletion

Lowest value of ozone measured by TOMS each year in the ozone hole

The ozone hole is usually measured by reduction in the total column ozone above a point on the Earth's surface. This is normally expressed in Dobson units; abbreviated as "DU". The most prominent decrease in ozone has been in the lower stratosphere. 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).

Reductions of up to 70 percent in the ozone column observed in the austral (southern hemispheric) spring over Antarctica and first reported in 1985 (Farman et al.) are continuing. Antarctic total column ozone in September and October have continued to be 40–50 percent lower than pre-ozone-hole values since the 1990s. A gradual trend toward "healing" was reported in 2016. In 2017, NASA announced that the ozone hole was the weakest since 1988 because of warm stratospheric conditions. It is expected to recover around 2070.

The amount lost is more variable year-to-year in the Arctic than in the Antarctic. The greatest Arctic declines are in the winter and spring, reaching up to 30 percent when the stratosphere is coldest.

Reactions that take place on polar stratospheric clouds (PSCs) play an important role in enhancing ozone depletion. PSCs form more readily in the extreme cold of the Arctic and Antarctic stratosphere. This is why ozone holes first formed, and are deeper, over Antarctica. Early models failed to take PSCs into account and predicted a gradual global depletion, which is why the sudden Antarctic ozone hole was such a surprise to many scientists.

It is more accurate to speak of ozone depletion in middle latitudes rather than holes. Total column ozone declined below pre-1980 values between 1980 and 1996 for mid-latitudes. In the northern mid-latitudes, it then increased from the minimum value by about two percent from 1996 to 2009 as regulations took effect and the amount of chlorine in the stratosphere decreased. In the Southern Hemisphere's mid-latitudes, total ozone remained constant over that time period. There are no significant trends in the tropics, largely because halogen-containing compounds have not had time to break down and release chlorine and bromine atoms at tropical latitudes.

Large volcanic eruptions have been shown to have substantial albeit uneven ozone-depleting effects, as observed with the 1991 eruption of Mt. Pinatubo in the Philippines.

Ozone depletion also explains much of the observed reduction in stratospheric and upper tropospheric temperatures. The source of the warmth of the stratosphere is the absorption of UV radiation by ozone, hence reduced ozone leads to cooling. Some stratospheric cooling is also predicted from increases in greenhouse gases such as CO
2
and CFCs themselves; however, the ozone-induced cooling appears to be dominant.

Predictions of ozone levels remain difficult, but the precision of models' predictions of observed values and the agreement among different modeling techniques have increased steadily. The World Meteorological Organization Global Ozone Research and Monitoring Project—Report No. 44 is strongly in favor of the Montreal Protocol, but notes that a UNEP 1994 Assessment overestimated ozone loss for the 1994–1997 period.

Compounds in the atmosphere

Chlorofluorocarbons (CFCs) and other halogenated ozone-depleting substances (ODS) are mainly responsible for man-made chemical ozone depletion. The total amount of effective halogens (chlorine and bromine) in the stratosphere can be calculated and are known as the equivalent effective stratospheric chlorine (EESC).

CFCs as refrigerants were invented by Thomas Midgley Jr. in the 1930s. They were used in air conditioning and cooling units, as aerosol spray propellants prior to the 1970s, 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 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 about five to seven 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.

1,1,1-Trichloro-2,2,2-trifluoroethane, also known as CFC-113a, is one of four man-made chemicals newly discovered in the atmosphere by a team at the University of East Anglia. CFC-113a is the only known CFC whose abundance in the atmosphere is still growing. Its source remains a mystery, but illegal manufacturing is suspected by some. CFC-113a seems to have been accumulating unabated since 1960. Between 2012 and 2017, concentrations of the gas jumped by 40 percent.

A study by an international team of researchers published in Nature found that since 2013 emissions that are predominately from north-eastern China have released large quantities of the banned chemical Chlorofluorocarbon-11 (CFC-11) into the atmosphere. Scientists estimate that without action, these CFC-11 emissions will delay the recovery of the planet's ozone hole by a decade.

Aluminum oxide

Satellites burning up upon re-entry into Earth's atmosphere produce aluminum oxide (Al2O3) nanoparticles that endure in the atmosphere for decades. Estimates for 2022 alone were ~17 metric tons (~30 kg of nanoparticles per ~250 kg satellite). Increasing populations of satellite constellations can eventually lead to significant ozone depletion.

Very short-lived substances (VSLS)

"Very short-lived substances" are a class of ozone-depleting chemicals, allowed by the Montreal Protocol, that degrade in under 6 months. 90% are naturally produced, for example bromine-based chemicals generated by seaweed and phytoplankton, but 10% are manmade, for example dichloromethane.

Computer modeling

Scientists have attributed ozone depletion to the increase of man-made (anthropogenic) halogen compounds from CFCs by combining observational data with computer models. These complex chemistry transport models (e.g. SLIMCAT, CLaMS—Chemical Lagrangian Model of the Stratosphere) work by combining measurements of chemicals and meteorological fields with chemical reaction rate constants. They identify key chemical reactions and transport processes that bring CFC photolysis products into contact with ozone.

Ozone hole and its causes

Ozone hole in North America during 1984 (abnormally warm, reducing ozone depletion) and 1997 (abnormally cold, resulting in increased seasonal depletion). Source: NASA

The Antarctic ozone hole is an area of the Antarctic stratosphere in which the recent ozone levels have dropped to as low as 33 percent of their pre-1975 values. The ozone hole occurs during the Antarctic spring, from September to early December, as strong westerly winds start to circulate around the continent and create an atmospheric container. Within this polar vortex, over 50 percent of the lower stratospheric ozone is destroyed during the Antarctic spring.

As explained above, the primary cause of ozone depletion is the presence of chlorine-containing source gases (primarily CFCs and related halocarbons). In the presence of UV light, these gases dissociate, releasing chlorine atoms, which then go on to catalyze ozone destruction. The Cl-catalyzed ozone depletion can take place in the gas phase, but it is substantially enhanced in the presence of polar stratospheric clouds (PSCs).

These polar stratospheric clouds form during winter, in the extreme cold. Polar winters are dark, consisting of three months without solar radiation (sunlight). The lack of sunlight contributes to a decrease in temperature and the polar vortex traps and chills the air. Temperatures are around or below −80 °C. These low temperatures form cloud particles. There are three types of PSC clouds—nitric acid trihydrate clouds, slowly cooling water-ice clouds, and rapid cooling water-ice (nacreous) clouds—provide surfaces for chemical reactions whose products will, in the spring lead to ozone destruction.

The photochemical processes involved are complex but well understood. The key observation is that, ordinarily, most of the chlorine in the stratosphere resides in "reservoir" compounds, primarily chlorine nitrate (ClONO
2
) as well as stable end products such as HCl. The formation of end products essentially removes Cl from the ozone depletion process. Reservoir compounds sequester Cl, which can later be made available via absorption of light at wavelengths shorter than 400 nm. During the Antarctic winter and spring, reactions on the surface of the polar stratospheric cloud particles convert these "reservoir" compounds into reactive free radicals (Cl and ClO). Denitrification is the process by which the clouds remove NO
2
from the stratosphere by converting it to nitric acid in PSC particles, which then are lost by sedimentation. This prevents newly formed ClO from being converted back into ClONO
2
.

The role of sunlight in ozone depletion is the reason why the Antarctic ozone depletion is greatest during spring. During winter, even though PSCs are at their most abundant, there is no light over the pole to drive chemical reactions. During the spring, however, sunlight returns and provides energy to drive photochemical reactions and melt the polar stratospheric clouds, releasing considerable ClO, which drives the hole mechanism. Further warming temperatures near the end of spring break up the vortex around mid-December. As warm, ozone and NO
2
-rich air flows in from lower latitudes, the PSCs are destroyed, the enhanced ozone depletion process shuts down, and the ozone hole closes.

Most of the ozone that is destroyed is in the lower stratosphere, in contrast to the much smaller ozone depletion through homogeneous gas-phase reactions, which occurs primarily in the upper stratosphere.

Effects

Since the ozone layer absorbs UVB ultraviolet light from the sun, ozone layer depletion increases surface UVB levels (all else equal), which could lead to damage, including an increase in skin cancer. This was the reason for the Montreal Protocol. Although decreases in stratospheric ozone are well-tied to CFCs and increases in surface UVB, there is no direct observational evidence linking ozone depletion to higher incidence of skin cancer and eye damage in human beings. This is partly because UVA, which has also been implicated in some forms of skin cancer, is not absorbed by ozone, and because it is nearly impossible to control statistics for lifestyle changes over time. Ozone depletion may also influence wind patterns.

Increased UV

Ozone, while a minority constituent in 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 and density of the layer. When stratospheric ozone levels decrease, higher levels of UVB reach the Earth's surface. UV-driven phenolic formation in tree rings has dated the start of ozone depletion in northern latitudes to the late 1700s.

In October 2008, the Ecuadorian Space Agency published a report called HIPERION. The study used ground instruments in Ecuador and the last 28 years' data from 12 satellites of several countries, and found that the UV radiation reaching equatorial latitudes was far greater than expected, with the UV Index climbing as high as 24 in Quito; the WHO considers 11 as an extreme index and a great risk to health. The report concluded that depleted ozone levels around the mid-latitudes of the planet are already endangering large populations in these areas. Later, the CONIDA, the Peruvian Space Agency, published its own study, which yielded almost the same findings as the Ecuadorian study.

Biological effects

The main public concern regarding the ozone hole has been the effects of increased surface UV 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. If the high levels of depletion seen in the ozone hole were 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 affect parts of Australia, New Zealand, Chile, Argentina, and South Africa, environmentalists have been concerned that the increase in surface UV could be significant. Excessive ultraviolet radiation (UVR) has reducing effects on the rates of photosynthesis and growth of benthic diatom communities (microalgae species that increase water quality and are pollution resistant) that are present in shallow freshwater. Ozone depletion not only affects human health but also has a profound impact on biodiversity. It damages plants and trees at the cellular level, affecting their growth, vitality, photosynthesis, water balance, and defense mechanisms against pests and diseases. This sets off a cascade of ecological impacts, harming soil microbes, insects, wildlife, and entire ecosystems.

Ozone depletion would magnify all of the effects of UV on human health, both positive (including production of vitamin D) and negative (including sunburn, skin cancer, and cataracts). In addition, increased surface UV leads to increased tropospheric ozone, which is a health risk to humans.

Basal and squamous cell carcinomas

The most common forms of skin cancer in humans, basal and squamous cell carcinomas, have been strongly linked to UV-B exposure. The mechanism by which UVB induces these cancers is well understood—absorption of UV-B 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 every one percent decrease in long-term stratospheric ozone would increase the incidence of these cancers by 2%.

Melanoma

Another form of skin cancer, Melanoma, is much less common but far more dangerous, being lethal in about 15–20 percent of the cases diagnosed. The relationship between melanoma and ultraviolet exposure is not yet fully understood, but it appears that both UV-B and UV-A are involved. Because of this uncertainty, it is difficult to estimate the effect of ozone depletion on melanoma incidence. One study showed that a 10 percent increase in UV-B radiation was associated with a 19 percent increase in melanomas for men and 16 percent for women. A study of people in Punta Arenas, at the southern tip of Chile, showed a 56 percent increase in melanoma and a 46 percent increase in non-melanoma skin cancer over a period of seven years, along with decreased ozone and increased UVB levels.

Cortical cataracts

Epidemiological studies suggest 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. In this highly exposed group of predominantly white males, the evidence linking cortical opacities to sunlight exposure was the strongest to date. Based on these results, ozone depletion is predicted to cause hundreds of thousands of additional cataracts by 2050.

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. The risks are particularly high for young children, the elderly, and those with asthma or other respiratory difficulties. At this time, ozone at ground level is produced mainly by the action of UV radiation on combustion gases from vehicle exhausts.

Increased production of vitamin D

Vitamin D is produced in the skin by ultraviolet light. Thus, higher UVB exposure raises human vitamin D in those deficient in it. Recent research (primarily since the Montreal Protocol) shows that many humans have less than optimal vitamin D levels. In particular, in the U.S. population, the lowest quarter of vitamin D (<17.8 ng/ml) were found using information from the National Health and Nutrition Examination Survey to be associated with an increase in all-cause mortality in the general population. While blood level of vitamin D in excess of 100 ng/ml appear to raise blood calcium excessively and to be associated with higher mortality, the body has mechanisms that prevent sunlight from producing vitamin D in excess of the body's requirements.

Effects on animals

A November 2011 report by scientists at the Institute of Zoology in London, England found that whales off the coast of California have shown a sharp rise in sun damage, and these scientists "fear that the thinning ozone layer is to blame". The study photographed and took skin biopsies from over 150 whales in the Gulf of California and found "widespread evidence of epidermal damage commonly associated with acute and severe sunburn", having cells that form when the DNA is damaged by UV radiation. The findings suggest "rising UV levels as a result of ozone depletion are to blame for the observed skin damage, in the same way that human skin cancer rates have been on the increase in recent decades." Apart from whales many other animals such as dogs, cats, sheep and terrestrial ecosystems also suffer the negative effects of increased UV-B radiations.

Effects on crops

An increase of UV radiation would be expected to affect crops. A number of economically important species of plants, such as rice, depend on cyanobacteria residing on their roots for the retention of nitrogen. Cyanobacteria are sensitive to UV radiation and would be affected by its increase. "Despite mechanisms to reduce or repair the effects of increased ultraviolet radiation, plants have a limited ability to adapt to increased levels of UVB, therefore plant growth can be directly affected by UVB radiation."

Effects on plant life

Over the years, the Arctic ozone layer has depleted severely. As a consequence species that live above the snow cover or in areas where snow has melted abundantly, due to hot temperatures, are negatively impacted due to UV radiation that reaches the ground. Depletion of the ozone layer and allowing excess UVB radiation would initially be assumed to increase damage to plant DNA. Reports have found that when plants are exposed to UVB radiation similar to stratospheric ozone depletion, there was no significant change in plant height or leaf mass, but showed a response in shoot biomass and leaf area with a small decrease. However, UVB radiation has been shown to decrease quantum yield of photosystem II. UVB damage only occurs under extreme exposure, and most plants also have UVB absorbing flavonoids which allow them to acclimatize to the radiation present. Plants experience different levels of UV radiation throughout the day. It is known that they are able to shift the levels and types of UV sunscreens (i.e. flavonoids), that they contain, throughout the day. This allows them to increase their protection against UV radiation. Plants that have been affected by radiation throughout development are more affected by the inability to intercept light with a larger leaf area than having photosynthetic systems compromised. Damage from UVB radiation is more likely to be significant on species interactions than on plants themselves.

Another significant impact of ozone depletion on plant life is the stress experienced by plants when exposed to UV radiation. This can cause a decrease in plant growth and an increase in oxidative stress, due to the production of nitric oxide and hydrogen peroxide. In areas where substantial ozone depletion has occurred, increased UV-B radiation reduces terrestrial plant productivity (and likewise carbon sequestration) by about 6%.

Moreover, if plants are exposed to high levels of UV radiation, it can elicit the production of harmful volatile organic compounds, like isoprenes. The emission of isoprenes into the air, by plants, can severely impact the environment by adding to air pollution and increasing the amount of carbon in the atmosphere, ultimately contributing to climate change.

Public policy

NASA projections of stratospheric ozone concentrations if chlorofluorocarbons had not been banned

The full extent of the damage that CFCs have caused to the ozone layer is not known and will not be known for decades; however, marked decreases in column ozone have already been observed. The Montreal and Vienna conventions were installed long before a scientific consensus was established or important uncertainties in the science field were being resolved. The ozone case was understood comparably well by lay persons as e.g. Ozone shield or ozone hole were useful "easy-to-understand bridging metaphors". Americans voluntarily switched away from aerosol sprays, resulting in a 50 percent sales loss even before legislation was enforced.

After a 1976 report by the United States National Academy of Sciences concluded that credible scientific evidence supported the ozone depletion hypothesis a few countries, including the United States, Canada, Sweden, Denmark, and Norway, moved to eliminate the use of CFCs in aerosol spray cans. At the time this was widely regarded as a first step towards a more comprehensive regulation policy, but progress in this direction slowed in subsequent years, due to a combination of political factors (continued resistance from the halocarbon industry and a general change in attitude towards environmental regulation during the first two years of the Reagan administration) and scientific developments (subsequent National Academy assessments that indicated that the first estimates of the magnitude of ozone depletion had been overly large).

A critical DuPont manufacturing patent for Freon was set to expire in 1979. The United States banned the use of CFCs in aerosol cans in 1978. The European Community rejected proposals to ban CFCs in aerosol sprays, and in the U.S., CFCs continued to be used as refrigerants and for cleaning circuit boards. Worldwide CFC production fell sharply after the U.S. aerosol ban, but by 1986 had returned nearly to its 1976 level. In 1993, DuPont Canada closed its CFC facility.

The U.S. government's attitude began to change again in 1983, when William Ruckelshaus replaced Anne M. Burford as Administrator of the United States Environmental Protection Agency (EPA). Under Ruckelshaus and his successor, Lee Thomas, the EPA pushed for an international approach to halocarbon regulations. In 1985 twenty nations, including most of the major CFC producers, signed the Vienna Convention for the Protection of the Ozone Layer, which established a framework for negotiating international regulations on ozone-depleting substances. That same year, the discovery of the Antarctic ozone hole was announced, causing a revival in public attention to the issue.

In 1987, representatives from 43 nations signed the Montreal Protocol. Meanwhile, the halocarbon industry shifted its position and started supporting a protocol to limit CFC production. However, this shift was uneven with DuPont acting more quickly than its European counterparts. DuPont may have feared court action related to increased skin cancer, especially as the EPA had published a study in 1986 claiming that an additional 40 million cases and 800,000 cancer deaths were to be expected in the U.S. in the next 88 years. The EU shifted its position as well after Germany gave up its defence of the CFC industry and started supporting moves towards regulation. Government and industry in France and the UK tried to defend their CFC producing industries even after the Montreal Protocol had been signed.

At Montreal, the participants agreed to freeze production of CFCs at 1986 levels and to reduce production by 50 percent by 1999. After a series of scientific expeditions to the Antarctic produced convincing evidence that the ozone hole was indeed caused by chlorine and bromine from manmade organohalogens, the Montreal Protocol was strengthened at a 1990 meeting in London. The participants agreed to phase out CFCs and halons entirely (aside from a very small amount marked for certain "essential" uses, such as asthma inhalers) by 2000 in non-Article 5 countries and by 2010 in Article 5 (less developed) signatories. At a 1992 meeting in Copenhagen, Denmark, the phase-out date was moved up to 1996. At the same meeting, methyl bromide (MeBr), a fumigant used primarily in agricultural production, was added to the list of controlled substances. For all substances controlled under the protocol, phaseout schedules were delayed for less developed ('Article 5(1)') countries, and phaseout in these countries was supported by transfers of expertise, technology, and money from non-Article 5(1) Parties to the Protocol. Additionally, exemptions from the agreed schedules could be applied for under the Essential Use Exemption (EUE) process for substances other than methyl bromide and under the Critical Use Exemption (CUE) process for methyl bromide.

Civil society, including especially non-governmental organizations (NGOs), played critical roles at all stages of policy development leading to the Vienna Conference, the Montreal Protocol, and in assessing compliance afterwards. The major companies claimed that no alternatives to HFC existed. An ozone-safe hydrocarbon refrigerant was developed at a technological institute in Hamburg, Germany, consisting of a mixture of the hydrocarbon gases propane and butane, and in 1992 came to the attention of the NGO Greenpeace. Greenpeace called it "Greenfreeze". The NGO then worked successfully first with a small and struggling company to market an appliance beginning in Europe, then Asia and later Latin America, receiving a 1997 UNEP award. By 1995, Germany had made CFC refrigerators illegal. Since 2004, corporations like Coca-Cola, Carlsberg, and IKEA formed a coalition to promote the ozone-safe Greenfreeze units. Production spread to companies like Electrolux, Bosch, and LG, with sales reaching some 300 million refrigerators by 2008. In Latin America, a domestic Argentinian company began Greenfreeze production in 2003, while the giant Bosch in Brazil began a year later. By 2013 it was being used by some 700 million refrigerators, making up about 40 percent of the market.

In the U.S., however, change has been much slower. To some extent, CFCs were being replaced by the less damaging hydrochlorofluorocarbons (HCFCs), although concerns remain regarding HCFCs also. In some applications, hydrofluorocarbons (HFCs) were being used to replace CFCs. HFCs, which contain no chlorine or bromine, do not contribute to ozone depletion although they are potent greenhouse gases. The best known of these compounds is probably HFC-134a (R-134a), which in the United States has largely replaced CFC-12 (R-12) in automobile air conditioners. In laboratory analytics (a former "essential" use) the ozone depleting substances can be replaced with other solvents. Chemical companies like Du Pont, whose representatives disparaged Greenfreeze as "that German technology," maneuvered the EPA to block the technology in the U.S. until 2011. Ben & Jerry's of Unilever and General Electric, spurred by Greenpeace, had expressed formal interest in 2008 which figured in the EPA's final approval.

The EU recast its Ozone Regulation in 2009. The law bans ozone-depleting substances with the goal of protecting the ozone layer. The list of ODS that are subject to the regulation is the same as those under the Montreal Protocol, with some additions.

More recently, policy experts have advocated for efforts to link ozone protection efforts to climate protection efforts. Many ODS are also greenhouse gases, some thousands of times more powerful agents of radiative forcing than carbon dioxide over the short and medium term. Thus policies protecting the ozone layer have had benefits in mitigating climate change. The reduction of the radiative forcing due to ODS probably masked the true level of climate change effects of other greenhouse gases, and was responsible for the "slow down" of global warming from the mid-90s. Policy decisions in one arena affect the costs and effectiveness of environmental improvements in the other.

ODS requirements in the marine industry

The IMO has amended MARPOL Annex VI Regulation 12 regarding ozone depleting substances. As from July 1, 2010, all vessels where MARPOL Annex VI is applicable should have a list of equipment using ozone depleting substances. The list should include the name of ODS, type and location of equipment, quantity in kg and date. All changes since that date should be recorded in an ODS Record book on board recording all intended or unintended releases to the atmosphere. Furthermore, new ODS supply or landing to shore facilities should be recorded as well.

Prospects of ozone depletion

Ozone levels stabilized in the 1990s following the Montreal Protocol, and have started to recover. They are projected to reach pre-1980 levels before 2075.
Ozone-depleting gas trends

Since the adoption and strengthening of the Montreal Protocol has led to reductions in the emissions of CFCs, atmospheric concentrations of the most-significant compounds have been declining. These substances are being gradually removed from the atmosphere; since peaking in 1994, the Effective Equivalent Chlorine (EECl) level in the atmosphere had dropped about 10 percent by 2008. The decrease in ozone-depleting chemicals has also been significantly affected by a decrease in bromine-containing chemicals. The data suggest that substantial natural sources exist for atmospheric methyl bromide (CH
3
Br
). The phase-out of CFCs means that nitrous oxide (N
2
O
), which is not covered by the Montreal Protocol, has become the most highly emitted ozone-depleting substance and is expected to remain so throughout the 21st century.

According to the IPCC Sixth Assessment Report, global stratospheric ozone levels experienced rapid decline in the 1970s and 1980s and have since been increasing, but have not reached preindustrial levels. Although considerable variability is expected from year to year, including in polar regions where depletion is largest, the ozone layer is expected to continue recovering in coming decades due to declining ozone-depleting substance concentrations, assuming full compliance with the Montreal Protocol.

The Antarctic ozone hole is expected to continue for decades. Ozone concentrations in the lower stratosphere over Antarctica increased by 5–10 percent by 2020 and will return to pre-1980 levels by about 2060–2075. This is 10–25 years later than predicted in earlier assessments, because of revised estimates of atmospheric concentrations of ozone-depleting substances, including a larger predicted future usage in developing countries. Another factor that may prolong ozone depletion is the drawdown of nitrogen oxides from above the stratosphere due to changing wind patterns. A gradual trend toward "healing" was reported in 2016. In 2019, the ozone hole was at its smallest in the previous thirty years, due to the warmer polar stratosphere weakening the polar vortex. In September 2023, the Antarctic ozone hole was one of the largest on record, at 26 million square kilometers. The anomalously large ozone loss may have been a result of the 2022 Tonga volcanic eruption. According to a 2023 United Nations assessment, the ozone layer is on track to recover to 1980 levels by around 2066 over Antarctica, by 2045 over the Arctic, and by 2040 for the rest of the world, assuming current regulations remain in place.

Research history

The basic physical and chemical processes that lead to the formation of an ozone layer in the Earth's stratosphere were discovered by Sydney Chapman in 1930. Short-wavelength UV radiation splits an oxygen (O
2
) molecule into two oxygen (O) atoms, which then combine with other oxygen molecules to form ozone. Ozone is removed when an oxygen atom and an ozone molecule "recombine" to form two oxygen molecules, i.e. O + O
3
→ 2O
2
. In the 1950s, David Bates and Marcel Nicolet presented evidence that various free radicals, in particular hydroxyl (OH) and nitric oxide (NO), could catalyze this recombination reaction, reducing the overall amount of ozone. These free radicals were known to be present in the stratosphere, and so were regarded as part of the natural balance—it was estimated that in their absence, the ozone layer would be about twice as thick as it currently is.

In 1970 Paul Crutzen pointed out that emissions of nitrous oxide (N
2
O
), a stable, long-lived gas produced by soil bacteria, from the Earth's surface could affect the amount of nitric oxide (NO) in the stratosphere. Crutzen showed that nitrous oxide lives long enough to reach the stratosphere, where it is converted into NO. Crutzen then noted that increasing use of fertilizers might have led to an increase in nitrous oxide emissions over the natural background, which would in turn result in an increase in the amount of NO in the stratosphere. Thus human activity could affect the stratospheric ozone layer. In the following year, Crutzen and (independently) Harold Johnston suggested that NO emissions from supersonic passenger aircraft, which would fly in the lower stratosphere, could also deplete the ozone layer. However, more recent analysis in 1995 by David W. Fahey, an atmospheric scientist at the National Oceanic and Atmospheric Administration, found that the drop in ozone would be from 1–2 percent if a fleet of 500 supersonic passenger aircraft were operated. This, Fahey expressed, would not be a showstopper for advanced supersonic passenger aircraft development.

Rowland–Molina hypothesis

In 1974 Frank Sherwood Rowland, Chemistry Professor at the University of California at Irvine, and his postdoctoral associate Mario J. Molina suggested that long-lived organic halogen compounds, such as CFCs, might behave in a similar fashion as Crutzen had proposed for nitrous oxide. James Lovelock had recently discovered, during a cruise in the South Atlantic in 1971, that almost all of the CFC compounds manufactured since their invention in 1930 were still present in the atmosphere. Molina and Rowland concluded that, like N
2
O
, the CFCs would reach the stratosphere where they would be dissociated by UV light, releasing chlorine atoms. A year earlier, Richard Stolarski and Ralph Cicerone at the University of Michigan had shown that Cl is even more efficient than NO at catalyzing the destruction of ozone. Similar conclusions were reached by Michael McElroy and Steven Wofsy at Harvard University. Neither group, however, had realized that CFCs were a potentially large source of stratospheric chlorine—instead, they had been investigating the possible effects of HCl emissions from the Space Shuttle, which are very much smaller.

The Rowland–Molina hypothesis was strongly disputed by representatives of the aerosol and halocarbon industries. The Chair of the Board of DuPont was quoted as saying that ozone depletion theory is "a science fiction tale ... a load of rubbish ... utter nonsense". Robert Abplanalp, the President of Precision Valve Corporation (and inventor of the first practical aerosol spray can valve), wrote to the Chancellor of UC Irvine to complain about Rowland's public statements. Nevertheless, within three years most of the basic assumptions made by Rowland and Molina were confirmed by laboratory measurements and by direct observation in the stratosphere. The concentrations of the source gases (CFCs and related compounds) and the chlorine reservoir species (HCl and ClONO
2
) were measured throughout the stratosphere, and demonstrated that CFCs were indeed the major source of stratospheric chlorine, and that nearly all of the CFCs emitted would eventually reach the stratosphere. Even more convincing was the measurement, by James G. Anderson and collaborators, of chlorine monoxide (ClO) in the stratosphere. ClO is produced by the reaction of Cl with ozone—its observation thus demonstrated that Cl radicals not only were present in the stratosphere but also were actually involved in destroying ozone. McElroy and Wofsy extended the work of Rowland and Molina by showing that bromine atoms were even more effective catalysts for ozone loss than chlorine atoms and argued that the brominated organic compounds known as halons, widely used in fire extinguishers, were a potentially large source of stratospheric bromine. In 1976 the United States National Academy of Sciences released a report concluding that the ozone depletion hypothesis was strongly supported by the scientific evidence. In response the United States, Canada and Norway banned the use of CFCs in aerosol spray cans in 1978. Early estimates were that, if CFC production continued at 1977 levels, the total atmospheric ozone would after a century or so reach a steady state, 15 to 18 percent below normal levels. By 1984, when better evidence on the speed of critical reactions was available, this estimate was changed to 5 to 9 percent steady-state depletion.

Crutzen, Molina, and Rowland were awarded the 1995 Nobel Prize in Chemistry for their work on stratospheric ozone.

Antarctic ozone hole

The discovery of the Antarctic "ozone hole" by British Antarctic Survey scientists Farman, Gardiner and Shanklin (first reported in a paper in Nature in May 1985) came as a shock to the scientific community, because the observed decline in polar ozone was far larger than had been anticipated. Satellite measurements (TOMS onboard Nimbus 7) showing massive depletion of ozone around the south pole were becoming available at the same time. However, these were initially rejected as unreasonable by data quality control algorithms (they were filtered out as errors since the values were unexpectedly low); the ozone hole was detected only in satellite data when the raw data was reprocessed following evidence of ozone depletion in in situ observations. When the software was rerun without the flags, the ozone hole was seen as far back as 1976.

Susan Solomon, an atmospheric chemist at the National Oceanic and Atmospheric Administration (NOAA), proposed that chemical reactions on polar stratospheric clouds (PSCs) in the cold Antarctic stratosphere caused a massive, though localized and seasonal, increase in the amount of chlorine present in active, ozone-destroying forms. The polar stratospheric clouds in Antarctica are only formed at very low temperatures, as low as −80 °C, and early spring conditions. In such conditions the ice crystals of the cloud provide a suitable surface for conversion of unreactive chlorine compounds into reactive chlorine compounds, which can easily deplete ozone.

Moreover, the polar vortex formed over Antarctica is very tight and the reaction occurring on the surface of the cloud crystals is far different from when it occurs in atmosphere. These conditions have led to ozone hole formation in Antarctica. This hypothesis was decisively confirmed, first by laboratory measurements and subsequently by direct measurements, from the ground and from high-altitude airplanes, of very high concentrations of chlorine monoxide (ClO) in the Antarctic stratosphere.

Alternative hypotheses, which had attributed the ozone hole to variations in solar UV radiation or to changes in atmospheric circulation patterns, were also tested and shown to be untenable.

Meanwhile, analysis of ozone measurements from the worldwide network of ground-based Dobson spectrophotometers led an international panel to conclude that the ozone layer was in fact being depleted, at all latitudes outside of the tropics. These trends were confirmed by satellite measurements. As a consequence, the major halocarbon-producing nations agreed to phase out production of CFCs, halons, and related compounds, a process that was completed in 1996.

Since 1981 the United Nations Environment Programme, under the auspices of the World Meteorological Organization, has sponsored a series of technical reports on the Scientific Assessment of Ozone Depletion, based on satellite measurements. The 2007 report showed that the hole in the ozone layer was recovering and the smallest it had been for about a decade.

A 2010 report found, "Over the past decade, global ozone and ozone in the Arctic and Antarctic regions is no longer decreasing but is not yet increasing. The ozone layer outside the Polar regions is projected to recover to its pre-1980 levels some time before the middle of this century. In contrast, the springtime ozone hole over the Antarctic is expected to recover much later."

In 2012, NOAA and NASA reported "Warmer air temperatures high above the Antarctic led to the second smallest season ozone hole in 20 years averaging 17.9 million square kilometres. The hole reached its maximum size for the season on Sept 22, stretching to 21.2 million square kilometres." A gradual trend toward "healing" was reported in 2016 and then in 2017. It is reported that the recovery signal is evident even in the ozone loss saturation altitudes.

The hole in the Earth's ozone layer over the South Pole has affected atmospheric circulation in the Southern Hemisphere all the way to the equator. The ozone hole has influenced atmospheric circulation all the way to the tropics and increased rainfall at low, subtropical latitudes in the Southern Hemisphere.

Arctic ozone "mini-hole"

On March 3, 2005, the journal Nature published an article linking 2004's unusually large Arctic ozone hole to solar wind activity.

On March 15, 2011, a record ozone layer loss was observed, with about half of the ozone present over the Arctic having been destroyed. The change was attributed to increasingly cold winters in the Arctic stratosphere at an altitude of approximately 20 km (12 mi), a change associated with global warming in a relationship that is still under investigation. By March 25, the ozone loss had become the largest compared to that observed in all previous winters with the possibility that it would become an ozone hole. This would require that the quantities of ozone to fall below 200 Dobson units, from the 250 recorded over central Siberia. It is predicted that the thinning layer would affect parts of Scandinavia and Eastern Europe on March 30–31.

On October 2, 2011, a study was published in the journal Nature, which said that between December 2010 and March 2011 up to 80 percent of the ozone in the atmosphere at about 20 kilometres (12 mi) above the surface was destroyed. The level of ozone depletion was severe enough that scientists said it could be compared to the ozone hole that forms over Antarctica every winter. According to the study, "for the first time, sufficient loss occurred to reasonably be described as an Arctic ozone hole." The study analyzed data from the Aura and CALIPSO satellites, and determined that the larger-than-normal ozone loss was due to an unusually long period of cold weather in the Arctic, some 30 days more than typical, which allowed for more ozone-destroying chlorine compounds to be created. According to Lamont Poole, a co-author of the study, cloud and aerosol particles on which the chlorine compounds are found "were abundant in the Arctic until mid March 2011—much later than usual—with average amounts at some altitudes similar to those observed in the Antarctic, and dramatically larger than the near-zero values seen in March in most Arctic winters".

In 2013, researchers analyzed the data and found the 2010–2011 Arctic event did not reach the ozone depletion levels to classify as a true hole. A hole in the ozone is generally classified as 220 Dobson units or lower; the Arctic hole did not approach that low level. It has since been classified as a "mini-hole."

Following the ozone depletion in 1997 and 2011, a 90% drop in ozone was measured by weather balloons over the Arctic in March 2020, as they normally recorded 3.5 parts per million of ozone, compared to only around 0.3 parts per million lastly, due to the coldest temperatures ever recorded since 1979, and a strong polar vortex which allowed chemicals, including chlorine and bromine, to reduce ozone.

A rare hole, the result of unusually low temperatures in the atmosphere above the North Pole, was studied in 2020.

Tibet ozone hole

As winters that are colder are more affected, at times there is an ozone hole over Tibet. In 2006, a 2.5 million square kilometer ozone hole was detected over Tibet. Again in 2011, an ozone hole appeared over mountainous regions of Tibet, Xinjiang, Qinghai and the Hindu Kush, along with an unprecedented hole over the Arctic, though the Tibet one was far less intense than the ones over the Arctic or Antarctic.

Potential depletion by storm clouds

Research in 2012 showed that the same process that produces the ozone hole over Antarctica, occurs over summer storm clouds in the United States, and thus may be destroying ozone there as well.

Ozone hole over tropics

Physicist Qing-Bin Lu, of the University of Waterloo, claimed to have discovered a large, all-season ozone hole in the lower stratosphere over the tropics in July 2022. However, other researchers in the field refuted this claim, stating that the research was riddled with "serious errors and unsubstantiated assertions." According to Dr Paul Young, a lead author of the 2022 WMO/UNEP Scientific Assessment of Ozone Depletion, "The author's identification of a 'tropical ozone hole' is down to him looking at percentage changes in ozone, rather than absolute changes, with the latter being much more relevant for damaging UV reaching the surface." Specifically, Lu's work defines "ozone hole" as "an area with O3 loss in percent larger than 25%, with respect to the undisturbed O3 value when there were no significant CFCs in the stratosphere (~ in the 1960s)" instead of the general definition of 220 Dobson units or lower. Dr Marta Abalos Alvarez has added "Ozone depletion in the tropics is nothing new and is mainly due to the acceleration of the Brewer-Dobson circulation."

Depletion caused by wildfire smoke

Analyzing the atmospheric impacts of the 2019–2020 Australian bushfire season, scientists led by MIT researcher Susan Solomon found the smoke destroyed 3–5% of ozone in affected areas of the Southern Hemisphere. Smoke particles absorb hydrogen chloride and act as a catalyst to create chlorine radicals that destroy ozone.

Ozone depletion and global warming

Among others, Robert Watson had a role in the science assessment and in the regulation efforts of ozone depletion and global warming. Prior to the 1980s, the EU, NASA, NAS, UNEP, WMO and the British government had dissenting scientific reports and Watson played a role in the process of unified assessments. Based on the experience with the ozone case, the IPCC started to work on a unified reporting and science assessment to reach a consensus to provide the IPCC Summary for Policymakers.

There are various areas of linkage between ozone depletion and global warming science:

Radiative forcing from various greenhouse gases and other sources
  • The same CO
    2
    radiative forcing that produces global warming is expected to cool the stratosphere. This cooling, in turn, is expected to produce a relative increase in ozone (O
    3
    ) depletion in polar areas and the frequency of ozone holes.
  • Conversely, ozone depletion represents a radiative forcing of the climate system. There are two opposing effects: Reduced ozone causes the stratosphere to absorb less solar radiation, thus cooling the stratosphere while warming the troposphere; the resulting colder stratosphere emits less long-wave radiation downward, thus cooling the troposphere. Overall, the cooling dominates; the IPCC concludes "observed stratospheric O
    3
    losses over the past two decades have caused a negative forcing of the surface-troposphere system
    " of about −0.15 ± 0.10 watts per square meter (W/m2).
  • One of the strongest predictions of the greenhouse effect is that the stratosphere will cool. Although this cooling has been observed, it is not trivial to separate the effects of changes in the concentration of greenhouse gases and ozone depletion since both will lead to cooling. However, this can be done by numerical stratospheric modeling. Results from the National Oceanic and Atmospheric Administration's Geophysical Fluid Dynamics Laboratory show that above 20 km (12 mi), the greenhouse gases dominate the cooling.
  • Ozone depleting chemicals are also often greenhouse gases. The increases in concentrations of these chemicals have produced 0.34 ± 0.03 W/m2 of radiative forcing, corresponding to about 14 percent of the total radiative forcing from increases in the concentrations of well-mixed greenhouse gases.
  • The long term modeling of the process, its measurement, study, design of theories and testing take decades to document, gain wide acceptance, and ultimately become the dominant paradigm. Several theories about the destruction of ozone were hypothesized in the 1980s, published in the late 1990s, and are now being investigated. Dr Drew Schindell, and Dr Paul Newman, NASA Goddard, proposed a theory in the late 1990s, using computational modeling methods to model ozone destruction, that accounted for 78 percent of the ozone destroyed. Further refinement of that model accounted for 89 percent of the ozone destroyed, but pushed back the estimated recovery of the ozone hole from 75 years to 150 years. (An important part of that model is the lack of stratospheric flight due to depletion of fossil fuels.)

In 2019, NASA reported that there was no significant relation between size of the ozone hole and climate change.

Misconceptions

CFC weight

Since CFC molecules are heavier than air (nitrogen or oxygen), it is commonly believed that the CFC molecules cannot reach the stratosphere in significant amounts. However, atmospheric gases are not sorted by weight at these altitudes; the forces of wind can fully mix the gases in the atmosphere. Some of the heavier CFCs are not evenly distributed.

Percentage of human-made chlorine

Sources of stratospheric chlorine

Another misconception is that natural sources of chlorine are several times larger than human-made ones. While this statement is true for tropospheric chlorine, that is irrelevant to ozone depletion, which is only affected by stratospheric chlorine. Chlorine from ocean spray is soluble and thus is washed by rainfall before it reaches the stratosphere. CFCs, in contrast, are insoluble and long-lived, allowing them to reach the stratosphere. In the lower atmosphere, there is much more chlorine from CFCs and related haloalkanes than there is in HCl from salt spray, and in the stratosphere halocarbons are dominant. Only methyl chloride, which is one of these halocarbons, has a mainly natural source, and it is responsible for about 20 percent of the chlorine in the stratosphere; the remaining 80 percent comes from human-made sources.

Very violent volcanic eruptions can inject HCl into the stratosphere, but researchers have shown that the contribution is not significant compared to that from CFCs. A similar erroneous assertion is that soluble halogen compounds from the volcanic plume of Mount Erebus on Ross Island, Antarctica are a major contributor to the Antarctic ozone hole.

Nevertheless, a 2015 study showed that the role of Mount Erebus volcano in the Antarctic ozone depletion was probably underestimated. Based on the NCEP/NCAR reanalysis data over the last 35 years and by using the NOAA HYSPLIT trajectory model, researchers showed that gas emissions from the volcano (including hydrogen chloride (HCl)) can reach the Antarctic stratosphere via high-latitude cyclones and then the polar vortex. Depending on the level of its volcanic activity, the additional annual HCl mass entering the stratosphere from Erebus varies from 1.0 to 14.3 kt.

First observation

G.M.B. Dobson mentioned that when springtime ozone levels in the Antarctic over Halley Bay were first measured in 1956, he was surprised to find that they were only about 320 DU, about 150 DU below typical spring Arctic levels of around 450 DU. What Dobson observed was not an ozone hole but in fact a typical annual maximum Antarctic ozone concentration: actual ozone hole values are in the 150–100 DU range. While Arctic ozone concentrations vary on a smooth annual cycle from around 300 to 450 DU, peaking in the northern hemisphere spring, Antarctic concentrations drop sharply in the southern hemisphere spring from highs of around 300 DU to much lower values. Peak values are not reached again until December.

Location of hole

Some people thought that the ozone hole should be above the sources of CFCs. However, CFCs are well mixed globally in the troposphere and stratosphere. The reason for occurrence of the ozone hole above Antarctica is not because there are more CFCs concentrated but because the low temperatures help form polar stratospheric clouds. In fact, there are findings of significant and localized "ozone holes" above other parts of the Earth, such as above Central Asia.

Awareness campaigns

Public misconceptions and misunderstandings of complex issues like ozone depletion are common. The limited scientific knowledge of the public led to confusion about global warming or the perception of global warming as a subset of the "ozone hole". In the beginning, classical green NGOs refrained from using CFC depletion for campaigning, as they assumed the topic was too complicated. They became active much later, e.g. in Greenpeace's support for a CFC-free refrigerator produced by the former East German company VEB dkk Scharfenstein.

The metaphors used in the CFC discussion (ozone shield, ozone hole) are not "exact" in the scientific sense. The "ozone hole" is more of a depression, less "a hole in the windshield". The ozone does not disappear through the layer, nor is there a uniform "thinning" of the ozone layer. However, they resonated better with non-scientists and their concerns. The ozone hole was seen as a "hot issue" and imminent risk as laypeople feared severe personal consequences such as skin cancer, cataracts, damage to plants, and reduction of plankton populations in the ocean's photic zone. Not only on the policy level, ozone regulation compared to climate change fared much better in public opinion. Americans voluntarily switched away from aerosol sprays before legislation was enforced, while climate change failed to achieve comparable concern and public action. The sudden identification 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. Scientific consensus was established after regulation.

While the Antarctic ozone hole has a relatively small effect on global ozone, the hole has generated a great deal of public interest because:

  • Many have worried that ozone holes might start appearing over other areas of the globe, though to date the only other large-scale depletion is a smaller ozone "dimple" observed during the Arctic spring around the North Pole. Ozone at middle latitudes has declined, but by a much smaller extent (a decrease of about 4–5 percent).
  • If stratospheric conditions become more severe (cooler temperatures, more clouds, more active chlorine), global ozone may decrease at a greater pace. Standard global warming theory predicts that the stratosphere will cool.
  • When the Antarctic ozone hole breaks up each year, the ozone-depleted air drifts into nearby regions. Decreases in the ozone level of up to 10 percent have been reported in New Zealand in the month following the breakup of the Antarctic ozone hole, with ultraviolet-B radiation intensities increasing by more than 15 percent since the 1970s.

World Ozone Day

In 1994, the United Nations General Assembly voted to designate September 16 as the International Day for the Preservation of the Ozone Layer, or "World Ozone Day". The designation commemorates the signing of the Montreal Protocol on that date in 1987.

Ozone–oxygen cycle

From Wikipedia, the free encyclopedia
Ozone–oxygen cycle in the ozone layer: 1. Oxygen photolyzed to atomic oxygen 2. Oxygen and ozone continuously interconverted. Solar UV breaks down oxygen; molecular and atomic oxygen combine to form Ozone. 3. Ozone is lost by reaction with atomic oxygen (plus other trace atoms).

The ozone–oxygen cycle is the process by which ozone is continually regenerated in Earth's stratosphere, converting ultraviolet radiation (UV) into heat. In 1930 Sydney Chapman resolved the chemistry involved. The process is commonly called the Chapman cycle by atmospheric scientists.

Most of the ozone production occurs in the tropical upper stratosphere and mesosphere. The total mass of ozone produced per day over the globe is about 400 million metric tons. The global mass of ozone is relatively constant at about 3 billion metric tons, meaning the Sun produces about 12% of the ozone layer each day.

Photochemistry

The Chapman cycle describes the main reactions that naturally determine, to first approximation, the concentration of ozone in the stratosphere. It includes four processes - and a fifth, less important one - all involving oxygen atoms and molecules, and UV radiation:

Creation

An oxygen molecule is split (photolyzed) by higher frequency UV light (top end of UV-B, UV-C and above) into two oxygen atoms (see figure):

1. oxygen photodissociation: O2 + ℎν(<242 nm) → 2 O

Each oxygen atom may then combine with an oxygen molecule to form an ozone molecule:

2. ozone creation: O + O2 + A → O3 + A
where A denotes an additional molecule or atom, such as N2 or O2, required to maintain the conservation of energy and momentum in the reaction. Any excess energy is produced as kinetic energy.

The ozone–oxygen cycle

The ozone molecules formed by the reaction (above) absorb radiation with an appropriate wavelength between UV-C and UV-B. The triatomic ozone molecule becomes diatomic molecular oxygen, plus a free oxygen atom (see figure):

3. ozone photodissociation: O3 + ℎν(240–310 nm) → O2 + O

The atomic oxygen produced may react with another oxygen molecule to reform ozone via the ozone creation reaction (reaction 2 above).

These two reactions thus form the ozone–oxygen cycle, wherein the chemical energy released by ozone creation becomes molecular kinetic energy. The net result of the cycle is the conversion of penetrating UV-B light into heat, without any net loss of ozone. While keeping the ozone layer in stable balance, and protecting the lower atmosphere from harmful UV radiation, the cycle also provides one of two major heat sources in the stratosphere (the other being kinetic energy, released when O2 is photolyzed into individual O atoms).

Removal

If an oxygen atom and an ozone molecule meet, they recombine to form two oxygen molecules:

4. ozone conversion: O3 + O → 2 O2

Two oxygen atoms may react to form one oxygen molecule:

5. oxygen recombination: 2O + A → O2 + A
as in reaction 2 (above), A denotes another molecule or atom, like N2 or O2 required for the conservation of energy and momentum.

Note that reaction 5 is of the least importance in the stratosphere, since, under normal conditions, the concentration of oxygen atoms is much lower than that of diatomic oxygen molecules. This reaction is therefore less common than ozone creation (reaction 2).

The overall amount of ozone in the stratosphere is determined by the balance between production from solar radiation and its removal. The removal rate is slow, since the concentration of free O atoms is very low.

Additional reactions

In addition to these five reactions, certain free radicals - the most important being hydroxyl (OH), nitric oxide (NO), and atomic chlorine (Cl) and bromine (Br) - catalyze the recombination reaction, leading to an ozone layer that is thinner than it would be if the catalysts were not present.

Most OH and NO are naturally present in the stratosphere, but human activity - especially emissions of chlorofluorocarbons (CFCs) and halons - has greatly increased the concentration of Cl and Br, leading to ozone depletion. Each Cl or Br atom can catalyze tens of thousands of decomposition reactions before it is removed from the stratosphere.

Main reactions in different atmospheric layers

Thermosphere

For given relative reactants concentrations, The rates of ozone creation and oxygen recombination (reactions 2 and 5) are proportional to the air density cubed, while the rate of ozone conversion (reaction 4) is proportional to the air density squared, and the photodissociation reactions (reactions 1 and 3) have a linear dependence on air density. Thus, at the upper thermosphere, where air density is very low and photon flux is high, oxygen photodissociation is fast while ozone creation is low, thus its concentration is low. Thus the most important reactions are oxygen photodissociation and oxygen recombination, with most of the oxygen molecules dissociated to oxygen atoms.

As we go to the lower thermosphere (e.g. 100 km height and below), the photon flux in the <170 nm wavelengths drops sharply due to absorption by oxygen in the oxygen photodissociation reaction (reaction 1). This wavelength regime has the highest cross section for this reaction (10−17 cm2 per oxygen molecule), and thus the rate of oxygen photodissociation per oxygen molecule decreases significantly at these altitudes, from more than 10−7 per second (about once a month) at 100 km to 10−8 per second (about once every few years) at 80 km . As a result, the atomic oxygen concentration (both relative and absolute) decreases sharply, and ozone creation (reaction 2) is ongoing, leading to a small but non-negligible ozone presence.

Note that temperatures also drop as altitude decreases, because lower photon photodissociation rates mean lower heat production per air molecule.

Below thermosphere: Reaction rates at steady state

Odd oxygen species (atomic oxygen and ozone) have net creation rate only by oxygen dissociation (reaction 1), and net destruction by either ozone conversion or oxygen recombination (reactions 4 and 5). At steady state these processes are balanced, so the rates of these reactions obey:

(rate of reaction 1) = (rate of reaction 4) + (rate of reaction 5).

At steady state, ozone creation is also balanced with its removal. so:

(rate of reaction 2) = (rate of reaction 3) + (rate of reaction 4).

It thus follows that:

(rate of reaction 2) + (rate of reaction 5) = (rate of reaction 3) + (rate of reaction 1).

The right-hand side is the total photodissociation rate, of either oxygen or ozone.

Below the thermosphere, the atomic oxygen concentration is very low compared to molecular oxygen. Therefore, oxygen atoms are much more likely to hit oxygen (diatomic) molecules than to hit other oxygen atoms, making oxygen recombination (reaction 5) far rarer than ozone creation (reaction 2). Following the steady-state relation between the reaction rates, we may therefore approximate:

(rate of reaction 2) = (rate of reaction 3) + (rate of reaction 1)

In the mesosphere, oxygen photodissociation dominates over ozone photodissociation, so we have approximately:

(rate of reaction 2) = (rate of reaction 1) = (rate of reaction 4)

Thus, ozone is mainly removed by ozone conversion. Both ozone creation and conversion depend linearly on oxygen atom concentration, but in ozone creation an oxygen atom must encounter an oxygen molecule and another air molecule (typically nitrogen) simultaneously, while in ozone conversion an oxygen atom must only encounter an ozone molecule. Thus, when both reactions are balanced, the ratio between ozone and molecular oxygen concentrations is approximately proportional to air density.

Therefore, the relative ozone concentration is higher at lower altitudes, where air density is higher. This trend continues to some extent lower into the stratosphere, and thus as we go from 60 km to 30 km altitude, both air density and ozone relative concentration increase by ~40-50-fold.

Absorption by oxygen in the mesosphere and thermosphere (in the oxygen photodissociation reaction) reduces photon flux at wavelengths below 200 nanometer, where oxygen photodissociation is dominated by Schumann–Runge bands and continuum, with cross-section of up to 10−17 cm2. Due to this absorption, photon flux in these wavelengths is so low in the stratosphere, that oxygen photodissociation becomes dominated by the Hertzberg band of the 200-240 nm photon wavelength, even though the cross-section of this process is as low as 10−24 - 10−23 cm2. The ozone photodissociation rate per ozone molecule has a cross-section 6 orders of magnitude higher in the 220-300 nm wavelength range. With ozone concentrations in the order of 10−6-10−5 relative to molecular oxygen, ozone photodissociation becomes the dominant photodissociation reaction, and most of the stratosphere heat is generated through this procsees, with highest heat generation rate per molecule at the upper limit of the stratosphere (stratopause), where ozone concentration is already relatively high while UV flux is still high as well in those wavelengths, before being depleted by this same photodissociation process.

In addition to ozone photodissociation becoming a more dominant removal reaction, catalytic ozone destruction due to free radicals (mainly atomic hydrogen, hydroxyl, nitric oxide, chlorine and bromide) increases the effective ozone conversion reaction rate. Both processes act to increase ozone removal, leading to a more moderate increase of ozone relative concentration as altitude decreases, even though air density continues to increase.

Due to both ozone and oxygen growing density as we go to lower altitudes, UV photon flux at wavelengths below 300 nm decreases substantially, and oxygen photodissociation rates fall below 10−9 per second per molecule at 30 km. With decreasing oxygen photodissociation rates, odd-oxygen species (atomic oxygen and ozone molecules) are hardly formed de novo (rather than being transmuted to each other by the other reactions), and most atomic oxygen needed for ozone creation is derived almost exclusively from ozone removal by ozone photodissociation. Thus, ozone becomes depleted as we go below 30 km altitude and reaches very low concentrations at the tropopause.

In the troposphere, ozone formation and destruction are no longer controlled by the ozone-oxygen cycle. Rather, tropospheric ozone chemistry is dominated today by industrial pollutants other gases of volcanic source.

Atmospheric chemistry

Atmospheric chemistry is a branch of atmospheric science that studies the chemistry of the Earth's atmosphere and that of other planets. This multidisciplinary approach of research draws on environmental chemistry, physics, meteorology, computer modeling, oceanography, geology and volcanology, climatology and other disciplines to understand both natural and human-induced changes in atmospheric composition. Key areas of research include the behavior of trace gasses, the formation of pollutants, and the role of aerosols and greenhouse gasses. Through a combination of observations, laboratory experiments, and computer modeling, atmospheric chemists investigate the causes and consequences of atmospheric changes.

Atmospheric composition

Visualisation of composition by volume of Earth's atmosphere. Water vapour is not included as it is highly variable. Each tiny cube (such as the one representing krypton) has one millionth of the volume of the entire block. Data is from NASA Langley.
The composition of common nitrogen oxides in dry air vs. temperature
Chemical composition of atmosphere according to altitude. Axis: Altitude (km), Content of volume (%).

The composition and chemistry of the Earth's atmosphere is important for several reasons, but primarily because of the interactions between the atmosphere and living organisms. Natural processes such as volcano emissions, lightning and bombardment by solar particles from corona changes the composition of the Earth's atmosphere. It has also been changed by human activity and some of these changes are harmful to human health, crops and ecosystems.

Average Composition of Dry Atmosphere (mole fractions)
Gas Dry air per NASA
Nitrogen, N2 78.084%
Oxygen, O2 20.946%
Minor Constituents (mole fractions in ppm)
Argon, Ar 9340
Carbon dioxide, CO2 425
Neon, Ne 18.18
Helium, He 5.24
Methane, CH4 1.9
Krypton, Kr 1.14
Hydrogen, H2 0.53
Nitrous oxide, N2O 0.34
Xenon, Xe 0.087
Nitrogen dioxide, NO2 up to 0.02
Ozone, O3, in summer up to 0.07
Ozone, O3, in winter up to 0.02
Sulphur dioxide, SO2 up to 1
Iodine, I2 0.01
Water
Water vapour* Highly variable (about 0–3%);
typically makes up about 1%
Notes
The mean molecular mass of dry air is 28.97 g/mol. The content of the gas may undergo significant variations from time to time or from place to place. The concentration of CO2 and CH4 vary by season and location.

Trace gas composition

Besides the major components listed above, the Earth's atmosphere contains many trace gas species that vary significantly depending on nearby sources and sinks. These trace gasses include compounds such as CFCs/HCFCs which are particularly damaging to the ozone layer, and H2S which has a characteristic foul odor of rotten eggs and can be smelt in concentrations as low as 0.47 ppb. Some approximate amounts near the surface of some additional gasses are listed below. In addition to gasses, the atmosphere contains particles such as aerosol, which includes examples such as droplets, ice crystals, bacteria, and dust.

Gas Composition (ppt by volume unless otherwise stated)
Carbon monoxide, CO (120) 40-200 ppb
Ethene, C2H4 11.2 ppb
Formaldehyde, H2CO 9.1 ppb
Acetylene, C2H2 8.6 ppb
Methanol, CH3OH 1.967 ppb
Ethane, C2H6 781
Dichlorodifluoromethane, CCl2F2 530
Carbonyl sulfide, OCS 510
Chloromethane, CH3Cl 503
Isoprene, C5H8 311
Trichlorofluoromethane, CCl3F 237
Propane, C3H8 200
Hydrogen sulfide, H2S (177.5)
Sulfur dioxide, SO2 (135)
Carbon tetrafluoride, CF4 79
Ethanol, C2H5OH 75
Carbon disulfide, CS2 (30) 15–45
Nitric oxide, NO 16
Benzene, C6H6 11
Bromomethane, CH3Br (9.5) 9–10
Sulfur hexafluoride, SF6 7.3
Iodomethane, CH3I 0.36
Total gaseous mercury, Hg 0.209

History

Schematic of chemical and transport processes related to atmospheric composition

The first scientific studies of atmospheric composition began in the 18th century when chemists such as Joseph Priestley, Antoine Lavoisier and Henry Cavendish made the first measurements of the composition of the atmosphere.

In the late 19th and early 20th centuries, researchers shifted their interest towards trace constituents with very low concentrations. An important finding from this era was the discovery of ozone by Christian Friedrich Schönbein in 1840.

In the 20th century atmospheric science moved from studying the composition of air to consider how the concentrations of trace gasses in the atmosphere have changed over time and the chemical processes which create and destroy compounds in the air. Two important outcomes were the explanation by Sydney Chapman and Gordon Dobson of how the ozone layer is created and maintained, and Arie Jan Haagen-Smit’s explanation of photochemical smog. Further studies on ozone issues led to the 1995 Nobel Prize in Chemistry award shared between Paul Crutzen, Mario Molina and Frank Sherwood Rowland.

In the 21st century the focus is now shifting again. Instead of concentrating on atmospheric chemistry in isolation, it is now seen as one part of the Earth system with the rest of the atmosphere, biosphere and geosphere. A driving force for this link is the relationship between chemistry and climate. The changing climate and the recovery of the ozone hole and the interaction of the composition of the atmosphere with the oceans and terrestrial ecosystems are examples of the interdependent relationships between Earth's systems. A new field of extraterrestrial atmospheric chemistry has also recently emerged. Astrochemists analyze the atmospheric compositions of the Solar System and exoplanets to determine the formation of astronomical objects and find habitual conditions for Earth-like life.

Carbon dioxide in Earth's atmosphere if half of anthropogenic CO2 emissions are not absorbed
(NASA simulation; 9 November 2015)
 
Nitrogen dioxide 2014 - global air quality levels

Methodology

Observations, lab measurements, and modeling are the three central elements in atmospheric chemistry. Progress in atmospheric chemistry is often driven by the interactions between these components and they form an integrated whole. For example, observations may tell us that more of a chemical compound exists than previously thought possible. This will stimulate new modeling and laboratory studies which will increase our scientific understanding to a level where we can explain the observations.

Observation

Field observations of chemical systems are essential to understanding atmospheric processes and determining the accuracy of models. Atmospheric chemistry measurements are long term to observe continuous trends or short term to observe smaller variations. In situ and remote measurements can be made using observatories, satellites, field stations, and laboratories.

Routine observations of chemical composition show changes in atmospheric composition over time. Observatories such as the Mauna Loa and mobile platforms such as aircraft ships and balloons (e.g. the UK's Facility for Airborne Atmospheric Measurements) study chemical compositions and weather dynamics. An application of long term observations is the Keeling Curve - a series of measurements from 1958 to today which show a steady rise in the concentration of carbon dioxide (see also ongoing measurements of atmospheric CO2). Observations of atmospheric composition are increasingly made by satellites by passive and active remote sensing with important instruments such as GOME and MOPITT giving a global picture of air pollution and chemistry.

Surface observations have the advantage that they provide long term records at high time resolution but are limited in the vertical and horizontal space they provide observations from. Some surface based instruments e.g. LIDAR can provide concentration profiles of chemical compounds and aerosols but are still restricted in the horizontal region they can cover. Many observations are available online in Atmospheric Chemistry Observational Databases

Laboratory studies

Laboratory studies help understand the complex interactions from Earth’s systems that can be difficult to measure on a large scale. Experiments are performed in controlled environments, such as aerosol chambers, that allow for the individual evaluation of specific chemical reactions or the assessment of properties of a particular atmospheric constituent. A closely related subdiscipline is atmospheric photochemistry, which quantifies the rate that molecules are split apart by sunlight, determines the resulting products, and obtains thermodynamic data such as Henry's law coefficients.

Laboratory measurements are essential to understanding the sources and sinks of pollutants and naturally occurring compounds. Types of analysis that are of interest include both those on gas-phase reactions, as well as heterogeneous reactions that are relevant to the formation and growth of aerosols. Commonly used instruments to measure aerosols include ambient and particulate air samplers, scanning mobility particle sizers, and mass spectrometers.

Three boxes stacked on top of one another with vertical arrows to show elevation and horizontal arrows to show transportation. Aerosols enter the box via human, plant, and wind transport and exit via dry or wet deposition.
Schematic of a one-dimensional column model depicting the movement and transformation of aerosols

Modeling

Models are essential tools for interpreting observational data, testing hypotheses about chemical reactions, and predicting future concentrations of atmospheric chemicals. To synthesize and test theoretical understanding of atmospheric chemistry, researchers commonly use computer models, such as chemical transport models (CTMs). CTMs provide realistic descriptions of the three-dimensional transport and evolution of the atmosphere. Atmospheric models can be seen as mathematical representations that replicate the behavior of the atmosphere. These numerical models solve the differential equations governing the concentrations of chemicals in the atmosphere.

Depending on the complexity, these models can range from simple to highly detailed. Models can be zero-, one-, two-, or three-dimensional, each with various uses and advantages. Three-dimensional chemical transport models offer the most realistic simulations but require substantial computational resources. These models can be global e.g. GCM, simulating the atmospheric conditions across the Earth, or regional, e.g. RAMS focusing on specific areas with greater resolution. Global models typically have lower horizontal resolution and represent less complex chemical mechanisms but they cover a larger area, while regional models can represent a limited area with higher resolution and more detail.

A major challenge in atmospheric modeling is balancing the number of chemical compounds and reactions included in the model with the accuracy of physical processes such as transport and mixing in the atmosphere. The two simplest types of models include box models and puff models. For example, box modeling is relatively simple and may include hundreds or even thousands of chemical reactions, but they typically use a very crude representation of atmospheric mixed layer. This makes them useful for studying specific chemical reactions, but limited in stimulating real-world dynamics. In contrast, 3D models are more complex, representing a variety of physical processes such as wind, convection, and atmospheric mixing. They also provide more realistic representations of transportation and mixing. However, computational limits often simply chemical reactions and typically include fewer chemical reactions than box models. The trade-off between the two approaches lies in resolution and complexity.

To simplify the creation of these complex models, some researchers use automatic code generators like Autochem or Kinetic PreProcessor. These tools help automate the model-building process by selecting relevant chemical reactions from databases based on a user-defined function of chemical constituents. Once the reactions are chosen, the code generator automatically constructs the ordinary differential equations that describe their time evolution, greatly reducing the time and effort required for model construction.

Differences between model prediction and real-world observations can arise from errors in model input parameters or flaws representations of processes in the model. Some input parameters like surface emissions are often less accurately quantified from observations compared to model results. The model can be improved by adjusting poorly known parameters to better match observed data. A formal method for applying these adjustments is through Bayesian Optimization through an inverse modeling framework, where the results from the CTMs are inverted to optimize selected parameters. This approach has gained attention over the past decade as an effective method to interpret large amounts of data generate by models and observations from satellites.

One important current trend is using atmospheric chemistry as part of Earth system models. These models integrate atmospheric chemistry with other Earth system components, enabling the study of complex interactions between climate, atmospheric composition, and ecosystems.

Applications

Atmospheric chemistry is a multidisciplinary field with wide-ranging applications that influence environmental policy, human health, technology development, and climate science. Examples of problems addressed in atmospheric chemistry include acid rain, ozone depletion, photochemical smog, greenhouse gasses and global warming. By developing a theoretical understanding, atmospheric chemists can test potential solutions and evaluate the effects of changes in government policy. Key applications include greenhouse gas monitoring, air quality and pollution control, weather prediction and meteorology, energy and emissions, sustainable energy development, and public health and toxicology. Green atmospheric chemistry research prioritizes the sustainable, safe, and efficient use of chemicals, which led to government regulations minimizing the use of harmful chemicals like CFCs and DDT.

Advances in remote sensing technology allow scientists to monitor atmospheric chemical composition from satellites and ground-based stations. Instruments such as the Ozone Monitoring Instrument (OMI) and Atmospheric Infrared Sounder (AIRS) provide data on pollutants, greenhouse gasses, and aerosols, enabling real-time monitoring of air quality.

Atmospheric chemistry is vital for evaluating the environmental impacts of energy production, including fossil fuels and renewable energy sources. By studying emissions, researchers can develop cleaner energy technologies and assess their effects on air quality and climate. Atmospheric chemistry also helps quantify the concentration and persistence of toxic substances in the air, including particulate matter and volatile organic compounds (VOCs), guiding public health measures and exposures assessments.

Damocles

From Wikipedia, the free encyclopedia
Damocles
Δαμοκλῆς
Damocles sits on a throne, looking apprehensively at a sword suspended above him. Dionysius is standing next to him and gestures at the sword. Servants, courtiers, and guards surround the two men.
In Richard Westall's Sword of Damocles, 1812, the boys of Cicero's anecdote have been changed to maidens for a neoclassical patron, Thomas Hope.

Damocles is a character who appears in an ancient Greek anecdote commonly referred to as "the sword of Damocles", an allusion to the imminent and ever-present peril faced by those in positions of power. Damocles was a courtier in the court of Dionysius I of Syracuse, a ruler of Syracuse, Sicily, Magna Graecia, during the classical Greek era.

The anecdote apparently figured in the lost history of Sicily by Timaeus of Tauromenium (c. 356 – c. 260 BC). The Roman orator Cicero (c. 106 – c. 43 BC), who may have read it in the texts of Greek historian Diodorus Siculus, used it in his Tusculanae Disputationes, 5. 61, by which means it passed into the European cultural mainstream.

Sword of Damocles

According to the story, Damocles was flattering his king, Dionysius, exclaiming that Dionysius was truly fortunate as a great man of power and authority without peer, surrounded by magnificence. In response, Dionysius offered to switch places with Damocles for one day so that Damocles could taste that fortune firsthand. Damocles eagerly accepted the king's proposal. Damocles sat on the king's throne amid embroidered rugs, fragrant perfumes, and the service of beautiful attendants. But Dionysius, who had made many enemies during his reign, arranged that a sword should hang above the throne, held at the pommel only by a single hair of a horse's tail to evoke the sense of what it is like to be king: though having much fortune, always having to watch in anxiety against dangers that might try to overtake him, whether it is a jealous advisor or servant, a slanderous rumor, an enemy kingdom, a poor royal decision, or anything else. Damocles finally begged the king for permission to depart because he no longer wanted to be so fortunate, realizing that while he had everything he could ever want at his feet, it could not affect what was above his crown.

Cicero used this story as the last in a series of contrasting examples for concluding his fifth Disputation, in which the theme is that having virtue is sufficient for living a happy life.

Painting of the story of Damocles by British artist Herbert Gandy, featuring a Damocles surrounded by beautiful servants, lavish foods, gold, and riches, yet worriedly gazing up at an unsheathed sword above his head
Painting of the story of Damocles by British artist Herbert Gandy, featuring a Damocles surrounded by beautiful servants, lavish foods, gold, and riches, worriedly gazing up at an unsheathed sword above his head

Differing interpretations

Cicero's meaning in the story of the Sword of Damocles has alternative interpretations. Cicero states, "Doesn't Dionysius seem to have made it plenty clear that nothing is happy for him over whom terror always looms?" arguing that those in positions of power can never rest and truly enjoy that power. Some take this and argue further, stating that the point was that death looms over all, but that it is vital to strive to be happy and enjoy life in spite of that terror. Others take the meaning to be something akin to "don't judge someone until you've walked a mile in their shoes," as it is impossible to know what someone is struggling with, even if their life seems to be perfect to the outside observer. Just as King Dionysius's life looked luxurious and flawless on the outside to Damocles, so too might the lives of others that one covets for oneself. One other interpretation sees the story of the sword of Damocles as explicitly meant for Julius Caesar, implicitly suggesting that he should take care not to act the same way that King Dionysius did, making enemies and denying spiritual life, falling prey to the pitfalls of the tyrant, and mind the sword hanging ever-present over his neck.

Use in culture, art, and literature

The sword of Damocles is frequently used in allusion to this tale, epitomizing the imminent and ever-present peril faced by those in positions of power. More generally, it is used to denote the sense of foreboding engendered by a precarious situation, especially one in which the onset of tragedy is restrained only by a delicate trigger or chance. William Shakespeare's Henry IV expands on this theme: "Uneasy lies the head that wears a crown"; compare the Hellenistic and Roman imagery connected with the insecurity offered by Tyche and Fortuna.

In The Canterbury Tales, Geoffrey Chaucer refers to the sword of Damocles, which the Knight describes as hanging over Conquest. When the Knight describes the three temples, he also pays special attention to the paintings, noticing one on the walls of the temple of Mars:

And al above, depeinted in a tour,
Saugh I Conquest, sitting in greet honour,
With the sharpe swerd over his heed,
Hanginge by a subtil twines threed.

Above, where seated in his tower,
I saw Conquest depicted in his power
There was a sharpened sword above his head
That hung there by the thinnest simple thread.

— Chaucer, Canterbury Tales, l. 2027–2030

A political cartoon from Clifford Berryman following World War I, depicting a German delegate shakily signing a peace treaty as directed by the large hand of the Allied Powers, while a large sword bearing the inscription "Peace of Justice" hangs by a thread above him
A political cartoon from Clifford Berryman following World War I, depicting a German delegate shakily signing a peace treaty as directed by the large hand of the Allied Powers, while a large sword bearing the inscription "Peace of Justice" hangs by a thread above him (1919)

The Roman 1st-century BC poet Horace also alluded to the sword of Damocles in Ode 1 of the Third Book of Odes, in which he extolled the virtues of living a simple, rustic life, favoring such an existence over the myriad threats and anxieties that accompany holding a position of power. In this appeal to his friend and patron, the aristocratic Gaius Maecenas, Horace describes the Siculae dapes or "Sicilian feasts" as providing no savory pleasure to the man, "above whose impious head hangs a drawn sword (destrictus ensis)."

The phrase has also come to be used in describing any situation infused with a sense of impending doom, especially when the peril is visible and proximal—regardless of whether the victim is in a position of power. United States President John F. Kennedy compared the omnipresent threat of nuclear annihilation to a sword of Damocles hanging over the people of the world. Soviet First Secretary Nikita Khrushchev wanted the Tsar Bomba to "hang like the sword of Damocles over the imperialists' heads".

Woodcut images of the sword of Damocles as an emblem appear in 16th- and 17th-century European books of devices, with moralizing couplets or quatrains, with the import METUS EST PLENUS TYRANNIS. A small vignette shows Damocles under a canopy of state, at the festive table, with Dionysius seated nearby; the etching, with its clear political moral, was later used to illustrate the idea.

References to the sword of Damocles can also be found in cartoonist illustrations, such as in Joseph Keppler's magazine Puck, a satiric periodical started in the late 1800s in the United States, and the sword can be used as a device to call attention to the peril that current events or contentious issues of the time place the world in.

The sword of Damocles frequently appears in popular culture, including novels, feature films, television series, video games, and music. Some notable examples include Damocles, a 16-bit videogame from 1990 in which the player races to prevent the titular comet Damocles from destroying a planet, the song "The Sword of Damocles" from The Rocky Horror Picture Show, and a virtual reality headset also called The Sword of Damocles, developed by Ivan Sutherland in 1968, named for its suspension from the ceiling of the lab in which it was developed and its foreboding appearance.

A scene from Keppler's Puck shows Damocles in a crown labeled "industry" standing beneath a sword labeled "coal strikes"
A scene from Joseph Keppler's Puck showing Damocles, wearing a crown labeled "Industry", standing beneath a large sword, labeled "Coal Strikes", which hangs above him by a thread, suggesting that the coal strikes at the beginning of the 20th century were the modern-day sword of Damocles (1903)

In Made in Canada, a Canadian television series that ran from 1998 to 2003, Sword of Damacles was the name of an in-series television show produced by Pyramid, the production company the show centres around.

The Damocles is the name of the ship that is used in a multi-episode plot-line that spanned multiple seasons of the television show NCIS.

The Japanese anime series, K (also referred to as K-Project) utilizes the theme of the sword of Damocles as an integral part of the plot for its main characters.

The CW show The 100 presents its two-part finale of season 5, titled "Damocles." In this finale, General Diyoza confronts Octavia with the words, "Do you know what your mistake was? Your mistake was enjoying it... Power... it’s the kiss of death."

The Finnish band HIM released a song called Shatter Me With Hope on their 2010 album Screamworks:Love In Theory and Practice that features a reference to the sword of Damocles in the lyrics.

The American band Trivium released a song called "Like a Sword Over Damocles" on their 2021 album In the Court of the Dragon.

The British band Sleep Token released a song called "Damocles" on their 2025 album Even in Arcadia.

The sword of Damocles is an oft-used symbol in modern hip hop, an allusion used to impart the threat "kingly" rappers face of being deposed as the best of the best. It is referenced in the lyrics of the song "Zealots" by The Fugees in 1996. It also appears in the music of Kanye West, both in the music video for his single "Power" in 2010, where a sword is positioned above West's head as he stands amidst rows of Ionic columns, and in later cover art for the song, which features the impaled head of a black man wearing a crown.

Illiberal democracy

From Wikipedia, the free encyclopedia https://en.wikipedia.org/wiki/Illiberal_democracy   An illiberal democracy is a governi...