Stratospheric Ozone Depletion

1. Stratospheric Ozone Depletion

2. Ozone and LIfe In the absence of an ozone layer, life could only evolve under water

3. Formation of O3 in the Atmosphere • O2 + UV  O + O • O + O2  O3 • O + O2  O3 • Overall Reaction: 3O2 + UV  2O3

4. Atmospheric gradient Most of the ozone present in the atmosphere (~90%) is located in the stratosphere. Atmospheric concentrations of ozone average 12 parts per million (ppm).

5. How Does Stratospheric Ozone Protect Us? • O3 “absorbs” UV-B radiation and “uses up” its energy, converting it to harmless heat • UV + O3 O + O2 • Some of the free oxygen atoms combine with other ozone to form oxygen: O + O3  O2 + O2 • Or, they recombine with existing oxygen to re-form ozone: O + O2  O3 + heat • The ozone layer does not really “shield” us or “reflect” harmful UV-B radiation, but rather “uses up” its energy before it can reach earth

6. Timeline of CFC Development • 1928: DuPont scientists first develop CFCs as a refrigerant and a propellant. • CFCs believed ideal: non-flammable, non-toxic, good insulator, inexpensive, stable (inert), light. • However, because CFCs are inert and light, they do not react in the lower atmosphere, and can be carried by updrafts to the stratosphere where intense UV radiation can break them apart. • It can take 5-15 years for a CFC molecule to migrate to the stratosphere.

7. Timeline of CFC Development (cont’) • 1951: DuPont begins mass production of CFCs • 1971: Scientist James Lovelock first speculates that CFCs released to the atmosphere could still be there. (Where is Away??) • 1973: Atmospheric scientists Mario Molina and F. Sherry Rowland hypothesize that CFCs could be reaching the stratosphere, where they can be broken apart and a single chlorine atom could contribute to the destruction of 100,000 ozone molecules. • 1974: Molina and Rowland publish their theory in the journal Nature; the story is picked up by a science writer at The New York Times and published on the front page. • 1974: DuPont responds with their own study claiming that CFCs are safe in the troposphere; calls for more research.

8. Timeline of CFC Development (cont’) • 1975: 200% increase in CFC use from 1968-1975, annual growth in consumption of 10-20%/year. • 1979: The FDA and the EPA ban “non-essential” uses of CFCs in aerosol cans. THE FIRST TIME A SUBSTANCE WAS BANNED WITHOUT DEFINITIVE PROOF OF HARM. • 1982: 20 other nations join U.S. ban on non-essential uses.

9. Early Warnings of Ozone Depletion • 1982: British scientific team in Antarctica using ground-based instruments announce 20% decline in O3 levels in the stratosphere (in their spring). • 1982: U.S. team using satellite-based Total Ozone Mapping Spectrometer (TOMS) reports no ozone loss over Antarctica. • 1983: British team reports a 30% decline in ozone levels, U.S. team contradicts. • 1985: British team reports a 50% decline in ozone levels. At first, U.S. team contradicts, re-check their instruments and then confirm the British findings. • Acknowledgement of “ozone hole” in the media creates public and political alarm.

10. Early Warnings (cont’) • 1986: Australian government announces doubling of skin cancer cases in previous 10 years. • 1986: DuPont scientists speculate that tropospheric (“bad”) ozone will migrate to stratosphere to “fill” the hole. • 1987: Preliminary research indicates that loss of ozone over Antarctica due primarily to human emissions of ozone-depleting chemicals. • 1987: UN holds meetings in Montreal, and 45 nations sign the Montreal Protocol to reduce CFC use by 50% by the year 2000. Protocol is ratified in 1989. • 1988: DuPont continues to argue that CFCs are safe to use, and initially oppose the Montreal Protocol. However, by year end they announce an impending phase-out of CFC production.

11. Monthly average ozone levels over Antarctica 1956-1994, for the month of October

12. Newspaper cartoon from 1986

13. OZONE DEPLETING CHEMCIALS • Contain: chlorine or bromine • CFC’s: Chlorofluorocarbons, (“Freon”) has caused most damage • used in air conditioners, refrigerators, aerosols, foams • no longer used for aerosols, still widely used as refrigerants. • CCl4, methyl chloroform: methyl bromide, solvents used in dry cleaning • Halons: used in fire extinguishers, refrigerants and foams • AvgRetetion Time of ozone depleting substances = 75 – 150 years. Ozone depletion will continue until the mid 21st century

14. Major ozone-depleting substances developed in the past centurya type of halogenated organic gases

15. O3 Chemistry UV + CFC  releases “chlorine free radical” (Cl) Cl + O3  ClO (chlorine oxide) + O2 ClO + O  Cl (free radical) + O2 Cl free radical destroys O3, creating ClO, which reacts with free atomic oxygen (O) to create another Cl free radical and start the process all over again. One CFC molecule can destroy an estimated 100,000 molecules of O3

16. Natural balance between ozone creation and ozone destruction Creation O + O2 O3 +heat Ozone Balance O3 creation = O3 destruction Destruction UV + O3 O + O2

17. O3 Destruction Human – made compounds add to natural rates of ozone destruction, resulting in a net loss of stratospheric ozone Creation O + O2 O3 +heat Ozone Destruction O3 creation < O3 destruction Destruction UV + O3 O + O2 Plus human – made compounds

18. uv Protection The ozone layer absorbs and uses up most incoming UV-B radiation before it can strike the surface of the earth. UV-B radiation can cause skin cancer, cataracts, and reduced immune system as well as harming plant life.

19. Ozone shields life on land from damaging UV radiation ( of 0.1 m - 0.4 m) UVA = .4-.32 m--least energetic, not affected by stratospheric ozone UVB  = .32-.28 m--can cause damage, mostly absorbed by ozone* UVC  = .28-.1 m --most energetic, absorbed in stratosphere, doesn't reach Earth's surface Ozone depletion allows more UVB – this is the problem

20. Daily Dynamic of Ozone Layer What is a Dobson Unit? The Dobson Unit (DU) is the unit of measure for total ozone. If you were to take all the ozone in a column of air stretching from the surface of the earth to space, and bring all that ozone to standard temperature (0 °Celsius) and pressure (1013.25 millibars, or one atmosphere, or “atm”), the column would be about 0.3 centimeters thick. Thus, the total ozone would be 0.3 atm-cm. To make the units easier to work with, the “Dobson Unit” is defined to be 0.001 atm-cm. Our 0.3 atm-cm would be 300 DU.

21. Yearly Dynamic of Ozone Layer • http://ozonewatch.gsfc.nasa.gov/

22. Consequences of high uvSkin Cancer

23. Consequences of high uvCataracts • Cataracts may be a more widespread health effect of ultraviolet-B radiation than skin cancers, because all populations will be affected. Cataracts occur when the lens inside your eye becomes increasingly opaque resulting in 'misty' or 'foggy' vision.

24. Consequences of high uvWeakened Immune System • UV-B irradiation has suppressive effect on immune system • Skin is an immune organ - certain types of lymphoid cells found predominantly in skin • Skin-associated lymphoid tissue responds to antigens that enter the body by way of the skin. • This cutaneous immune surveillance system is vital to our ability to resist invasions by infectious agents.

25. Consequences of high uv- Ecosystems • Ecosystems • Reduced yield for some crops • (e.g. wheat, oats) • Decreased forest productivity • Reduced surface phytoplankton • affects aquatic productivity

26. Consequences of high uvAntarctic Food Chain uvb Reduces algal growth Krill

27. Increased Smog • Atmospheric Chemistry • Increased smog (more uv to provide energy for atmospheric chemical reactions)

28. Other greenhouse gases - CFCs

29. Northern Latitudes? • Southern “hole” now greater than ever • “hole” migrates toward equator • hole now instead over Arctic • usually less (less land area – need frozen H2O) • but, more CFCs • Europe – O3 decline 8% in last 10 yrs. • winter decline over U.S. – 5% • hole never expected over U.S. – now observed • http://visibleearth.nasa.gov/view_rec.php?id=9556

30. Science and Politics of Ozone Depletion • 1990: Follow-up meeting in London leads to new goal of complete CFC phase-out in developed countries by 2000 and in developing countries by 2010. • 1992: Follow up meeting in Copenhagen calls for complete phase-out by 1996, DuPont promises to halt production by 1997. • 1992: Rush Limbaugh publishes book claiming that the ozone depletion “crisis” is a hoax. (see also http://www.nas.nasa.gov/About/Education/Ozone/controversy.html) • 1995: Congressional hearings also challenge ozone science. • 1995: Ironically, Rowland and Molina receive Nobel Prize in chemistry for their early work on ozone depletion. • 1996: Satellite study provides definitive confirmation of human role in stratospheric ozone depletion. Junk science continues. • 1996: CFC ban begins, but black market appears.

31. TOMS Total Ozone Monthly Averages

32. What’s Happening to the Ozone Layer Today? • Stratospheric ozone concentrations have stabilized, and concentrations of Cl in the stratosphere are nearing their peak. However, atmospheric concentrations of bromine compounds (another ozone depleter) are still increasing. • Stratospheric ozone levels over the mid-latitudes of the northern hemisphere are 3-6% below pre-1980 levels, with higher losses in the winter/spring and losses of 1-3% in summer/fall. • Levels of UV-B radiation reaching the earth’s surface continue to increase, although this trend is expected to reverse itself as the ozone layer is replenished. • Phase-out of CFC use is almost complete. CFC substitutes like HCFCs and HFCs also deplete the ozone layer, but at only a fraction (1-15%) of the rate of CFCs because they react in the lower atmosphere. • Recent years have seen record levels of ozone depletion over Antarctica due to atmospheric conditions (polar stratospheric clouds).

33. Good News Bad News The Bad News We continue to use other ozone-depleting chemicals besides CFCs. Recently, the Bush administration sought to exempt U.S. farmers from a Montreal Protocol requirement to phase-out use of the pesticide methyl bromide. The Good News To the extent that CFCs and other ozone-depleting chemicals are phased out, the ozone layer should be able to replenish itself by the middle of this century.

34. Cl and Br Sources

35. Good Ozone v. Bad Ozone • Remember! • Difference between good ozone and bad ozone. • Stratospheric ozone depletion is not the same as global warming. These are two different, albeit related, environmental problems.

36. Lessons Learned from the Ozone Depletion Story • There is no away (TINA). • Scientific uncertainty is no excuse for inaction. Uncertainty will almost always be present. • Not all science is created equal. • Standard media ethics that call for “both sides of the story” can complicate coverage of some environmental issues. • The “burden of proof” typically rests with environmentalists. • Global problems require global solutions.