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Ozone depletion

Ozone depletion consists of two related events observed since the late 1970s: a steady lowering of about four percent in the total amount of ozone in Earth's atmosphere, and a much larger springtime decrease in stratospheric ozone (the ozone layer) around Earth's polar regions.[1] 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).[2] These compounds are transported into the stratosphere by turbulent mixing after being emitted from the surface, mixing much faster than the molecules can settle.[3] Once in the stratosphere, they release atoms from the halogen group through photodissociation, which catalyze the breakdown of ozone (O3) into oxygen (O2).[4] 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,[5] 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.[6] Currently, scientists plan to develop new refrigerants to replace older ones.[7]


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.[8] Recovery is projected to continue over the next century, and the ozone hole was expected to reach pre-1980 levels by around 2075.[9] In 2019, NASA reported that the ozone hole was the smallest ever since it was first discovered in 1982.[10][11]


The Montreal Protocol is considered the most successful international environmental agreement to date.[12][13] Following the bans on ozone-depleting chemicals, the UN projects that under the current regulations the ozone layer will completely regenerate by 2045, thirty years earlier than previously predicted.[14][15]

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

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).[16] 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.


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. All of these have both natural and man-made sources; at present, most of the OH· and NO· in the stratosphere is naturally occurring, but human activity has drastically increased the levels of chlorine and bromine.[17] 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.


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,[18] 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:


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,[19] while organic molecules containing iodine react so rapidly in the lower atmosphere that they do not reach the stratosphere in significant quantities.[20]


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.[21][22]

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.[167]

[166]

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 losses over the past two decades have caused a negative forcing of the surface-troposphere system"[33] of about −0.15 ± 0.10 watts per square meter (W/m2).[119]

O
3

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.[168]

[166]

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.

[119]

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

Among others, Robert Watson had a role in the science assessment and in the regulation efforts of ozone depletion and global warming.[85] 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[85] to reach a consensus to provide the IPCC Summary for Policymakers.


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


In 2019, NASA reported that there was no significant relation between size of the ozone hole and climate change.[10]

Misconceptions[edit]

CFC weight[edit]

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.[169] 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.[170]

World Ozone Day[edit]

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".[187] The designation commemorates the signing of the Montreal Protocol[188] on that date in 1987.[189]

Climate change in the Arctic

Section 608

Andersen, S. O. and K. M. Sarma. (2002). Protecting the Ozone Layer: The United Nations History, Earthscan Press. London, England.

Benedick, Richard Elliot; World Wildlife Fund (U.S.); Institute for the Study of Diplomacy. Georgetown University. (1998). (2nd ed.). Harvard University Press. ISBN 978-0-674-65003-9. Retrieved May 28, 2016. (Ambassador Benedick was the Chief U.S. Negotiator at the meetings that resulted in the Montreal Protocol.)

Ozone Diplomacy: New Directions in Safeguarding the Planet

Chasek, Pamela S., , and Janet Welsh Brown (2013). Global Environmental Politics, 6th ed., Boulder, Colorado: Westview Press.

David L. Downie

Gareau, Brian (2013). . Yale University Press. ISBN 978-0-300-17526-4. Archived from the original on 2013-03-30.

From Precaution to Profit: Contemporary Challenges to Environmental Protection in the Montreal Protocol

Grundmann, Reiner (2001). . Psychology Press. ISBN 978-0-415-22423-9. Retrieved May 28, 2016.

Transnational Environmental Policy: Reconstructing Ozone

Haas, P. (1992). . International Organization, 46(1), 187–224.

Banning chlorofluorocarbons: Epistemic community efforts to protect stratospheric ozone

Parson, Edward (2004). Protecting the Ozone Layer: Science and Strategy. Oxford, England: Oxford University Press.

at Curlie

Ozone layer

. Chemical Sciences Laboratory, National Oceanic and Atmospheric Administration (NOAA). NOAA/ESRL Ozone Depletion

"WMO/UNEP Scientific Assessments of Ozone Depletion (Latest Report 2022)"

NOAA/ESRL Ozone Depleting Gas Index

Archived 2014-03-08 at the Wayback Machine delivers maps, datasets and validation reports about the past and current state of the ozone layer.

MACC stratospheric ozone service

Green Cooling Initiative on alternative natural refrigerants cooling technologies

premiered April 10, 2019 PBS

"Ozone Hole: How We Saved the Planet"

Distillations Podcast Episode 230, April 17, 2018, Science History Institute

“Whatever happened to the Ozone Hole?”