1. O 3 zone Story Terry Deshler, Atmospheric Science Formation importance Loss –pre 1974pre 1974 –pre 1985pre 1985 –pre 2010pre 2010 recovery What’s new Relationship to global warming The end

2. Relationship to Global Warming Peripheral Ozone has a slight greenhouse effect, but Loss of ozone over Antarctica may have intensified the polar vortex and reduced the warming expected in Antarctica CFCs are a significant green house gas Reduction of CFCs largest single human action mitigating the current warming

3. The End? No, we have to limit the release of CFCs into the atmosphere from now on. The good news - the atmosphere will cleanse itself of present atmospheric chlorine. The bad news - it will take another 50 years to see the ozone hole above Antarctica disappear.

5. Ozone Formation O 2 + h  O + O Then, O + O + M  O 2 + M orO + O 2 + M  O 3 + M (Ozone created) – Where will this primarily occur? Also, O 3 + h ( > 310 nm )  O 2 + O and O 3 + h ( < 310 nm)  O 2 * + O* (UV absorption) O 2 * + O 2  2O 2 + thermal energy (Excess energy dumped O 2 *  O 2 + h ( = 1.3  m) in ozone layer)

12. Importance of ozone Absorbs DNA damaging UV radiation –This UV affects both animals and plants SH/NH differences - In summer UV radiation is 50% more intense in SH than NH. Australia - world leader in skin cancer –Reasons –10% - Earth is closer to sun in SH summer than NH summer –20% - Antarctic ozone loss/clearer atmosphere –20% - Unknown

13. Food Preservation 100 BC - 1700s, Early methods: Drying, Salting, Cool cellars/Spring houses, Pickling, Fermenting, Canning. Cooking -> could eat spoiled food - spices to hide the flavor. 1803 Ice Boxes - Thomas Moore invented the insulated box, with ice was in a separate container above the food storage area. Relied on stores of natural ice from frozen lakes and rivers. 1850s - Methods to artificially produce ice were developed. 1890 - Warm weather/rain lead to a shortage of natural ice. Spurred the development of mechanical refrigeration.

14. Refrigeration 1918 - Kelvinator, First refrigerator introduced to American market. 1920s - Refrigerators used ammonia (NH 4 ), sulfur dioxide (SO 2 ), (toxic, odorous), and methyl chloride (CH 3 Cl), (toxic, no odor) - silent killer. 1928 - Thomas Midgley, Fridgidaire, dichlorodifluoromethane (CCl 2 F 2 ) 1929 - Fridgidaire and DuPont joined to produce CCl 2 F 2, and CFCl 3 as Freon.

15. CFCs 1928 - First totally safe molecule for mechanical refridgerators - Thomas Midgley, dichlorodifluoromethane (CCl 2 F 2 ), Fridgidaire and DuPont joined to produce CCl 2 F 2, and CCl 3 F as Freon (F12, F11). 1941 - Automobile air conditioning - Packard 1943 - Bug bomb used in WWII  CFCs became propellants for aerosol spray cans. 1940 - 1960 - Uses of Freon boomed. 1970s - CFC production 600,000 tons annually growing 10% per year. Uses with immediate releases to the atmosphere - 66%, refrigeration - 20%

16. 1971 - Lovelock - Electron Capture Device coupled with Gas Chromatography -> First capability to detect molecule concentrations on the order of ppt (parts per trillion = 10 -12 ).

17. 1974 - Molina and Rowland - simple question - What happens to CFCs released into the atmosphere? (awarded Nobel prize Chemistry 1995) CCl 3 F (F-11) + h ( O 3 layer)  CCl 2 F + Cl CCl 2 F 2 (F-12) + h ( O 3 layer)  CClF 2 + Cl Then Cl + O 3  ClO + O 2 ClO + O  Cl + O 2 Net: O 3 + O  O 2 + O 2 This would occur above ozone layer altitudes above 30 km

18. Reservoir molecules 1975 - 1980 – Predicted ozone losses above 30 km were not observed. Reservoir molecules discovered. – Cl + CH 4  HCl + CH 3 –ClO + NO 2  ClONO 2 –HCl and ClONO 2 are reservoir species. 1984 – Models predict 10% ozone loss in 100 years for current CFC production rates.

21. Ozone Profiles McMurdo Station, Antarctica 1986 - 1994 1994 1986 1987 1988 19891990 1991 1992 1993

22. Ozone Profiles McMurdo Station, Antarctica 1995 - 2000 1996 1997 1998 19992000 1995 19961997 19981999 2000

30. Late winter spring During Winter

31. Catalytic Cycle Polar Stratosphere – PSC particle + HCl + ClONO 2  Cl 2 – Cl 2 + h  Cl + Cl – 2 [ Cl + O 3  ClO + O] – ClO + ClO + M  ClOOCl + M ( M=N 2 or O 2 ) – ClOOCl + h  Cl + ClOO – ClOO + M  Cl + O 2 + M –h = Sun’s return Net2O 3 + h  3O 2 A single Cl atom can destroy more than100,000 ozone molecules. This cycle will continue until the NO 2 and OH lost in the form of HNO 3 in polar stratospheric clouds is replenished by mid latitude air, thus converting Cl back to its reservoir species.

37. Nitric acid/water Ice Nitric acid/water Ice

38. Molina & Rowland, 1974 Reservoir Molecules Discovered Montreal Protocol, and amendments Antarctic ozone hole discovered

39. Refrigerants Foam Expansion Solvents Propellants Fire Extinguishants 1974 Ozone Depletion Hypothesis 1986 Base Year for Montreal Protocol 1996 CFC Phaseout Complete in Developed Countries CFCs HCFCs HFCs Refrigerants Other Thousands of tonnes An Industry in Transition

41. Return

43. What do 22 years of ozone measurements at McMurdo indicate?

44. Ozone history compared to PSC volume (alias temperature) 1986 – 2008. Stephanie Luberda

45. 4 K 5 K ICE not shown Nitric acid hydrate Nitric acid Solution drop Stratospheric aerosol volumes

46. Ozone Instruments (Laboratoire Meteorologique Dynamic & U. Colorado) Particle Instruments (U. Wyoming) Flight control (CNES)

53. Measurements continue at McMurdo: To maintain good records in anticipation of ozone recovery. To test quantitative models of ozone loss. –This last aspect is focus of current measurements.

54. McMurdo Antarctica 78  S - 1989

55. Postscript The ozone loss story is a positive one A global problem created by local human activities was identified, and reasonable solutions adopted by the worlds leading countries to reduce and eventually eliminate the problem. Is there a relation to global warming? Physically - minimal. Politically - the actions on ozone loss may serve as a model to direct future decisions by world leaders

57. Tropospheric Chlorine