Title: Chapter 3 Stratospheric Ozone Chemistry

1 Chapter 3Stratospheric Ozone Chemistry

y y

CH350/EV350 Spring 2008

2 Profile of Ozone (O3) with altitude

y y y

Good ozone in stratosphere Bad ozone in troposphere Compare mixing ratio and ozone density with altitude

3 UV light from sun

y y y y

Small percentage of total radiation but UV radiation is important UV-A 315-400 nm not harmful in short term UV-B 280-325 nm can be harmful to plants and animals UV-C lt280 nm rapidly damages living organisms

4 Solar flux vs. wavelengthO2 O3 absorption vs. wavelength

y y y

O2 absorbs most light below 175 nm O3 absorbs between 200 and 300 nm O2 O3 protects organisms from all UV-C some UV-B

5 Measuring O3
y y

O3 not stable in containers Very difficult to take air sample like a water sample

y y y y y y

y y y y y

O3 present at low concentrations Take instrument to the air Instruments need to operate at cold temperatures Ground based DIAL-differential absorption lidar 308 nm light directed into air O3 absorbs light particles scatter light back to detector the amount of light absorbed indicates O3 concentration Dobson ozone spectrometer Measures solar UV at several wavelengths some of which are absorbed by O3 and others that are not Gives total O3 in air column 300 Dobson units (DU) contains the equivalent of 3 mm thick layer at 273 K and 1 atm. Satellite and airplane based instruments that work on similar principles

6 Synthesis and noncatalytic decomposition of ozone

y y y y y y

3.1 O2 hn (l lt 240 nm) O O 3.2 O O2 O3 heat O O2 O3 O3 M O3 M 3.3 O3 hn (l lt 320 nm) O2 O 3.4 O3 O O2 O2

7 Ozone layer profile

y y y y y y y y y y

Upper stratosphere high energy light Not much O2 due to rxn 3.1 O2 lifetime 1 hr O3 production limited by the amount of O2 3.1 O2 hn (l lt 240 nm) O O 3.2 O O2 O3 heat O O2 O3 O3 M O3 M 3.3 O3 hn (l lt 320 nm) O2 O 3.4 O3 O O2 O2

8 Ozone layer profile

y y y y y y y y y y

Lower stratosphere little high energy light Not much O generated by rxn 3.1 O2 lifetime 5 yr O3 production limited by the amount of O atoms 3.1 O2 hn (l lt 240 nm) O O 3.2 O O2 O3 heat O O2 O3 O3 M O3 M 3.3 O3 hn (l lt 320 nm) O2 O 3.4 O3 O O2 O2

9 Ozone layer profile

y

Oxygen chemistry only accounts for 20 of O and O3 removal (rxn 3.4) 3.1 O2 hn (l lt 240 nm) O O 3.2 O O2 O3 heat O O2 O3 O3 M O3 M 3.3 O3 hn (l lt 320 nm) O2 O 3.4 O3 O O2 O2

y y y y y y

10 Natural Catalytic Destruction of Ozone

y y y y y y y y y y

X O3 XO O2 XO O X O2 Net O3 O 2O2 X .H .OH .NO .NO2 3.1 O2 hn (l lt 240 nm) O O 3.2 O O2 O3 heat O O2 O3 O3 M O3 M 3.3 O3 hn (l lt 320 nm) O2 O 3.4 O3 O O2 O2

11 HOx Catalytic Destruction of Ozone CH4 Oxygen radicals CO2 H2O H2O O 2.OH H2O hn .H .OH .OH O3 .OOH O2 .OOH O .OH O2 Net O3 O 2O2 .H O3 .OH O2 .OH O .H O2 Net O3 O 2O2
y y y

CH4 is natural but human activities do increase its concentration in the atmosphere CH4 doesnt precipitate in troposphere like water and some migrates to stratosphere These mechanisms are responsible for 70 of O3 destruction at 50 km

12 NOx Catalytic Destruction of Ozone Supersonic jets produce 160 kg NOx per hour N2O O 2.NO (lt30 km) N2 hn(llt126 nm) N N (gt30 km) N O2 .NO O .NO O3 .NO2 O2 .NO2 O3 .NO3 O2 .NO2 O .NO O2 .NO3 O .NO2 O2 Net O3 O 2O2 Net O3 O 2O2
y y

NO and NO2 in troposphere have a short residence time and are rained out N2O is naturally produced by soil bacteria but more N2O is released from soils heavily fertilized with nitrate. 120 year residence time in troposphere These mechanisms may be responsible for 70 of O3 destruction at tropopause

13 Catalyst Removal .NO .OH HNO2 .NO2 .OH HNO3 .OOH .NO2 M HO2NO2 M .NO3 .NO2 M N2O5 M
y

HNO2 HNO3 and N2O5 are reservoir species and do not catalytically destroy ozone because they are not radicals. 50 of NOx is stored in nitric acid reservoir

14 Two unlikely players

y y y y y y y y

Sherry Rowland Radiochemist (nuclear chemist) In Jan 1972 Rowland went to a meeting designed to bring chemists and meteorologists together No background in atmospheric chemistry but wanted to apply his radiochemistry knowledge James Lovelock presented work about invention of electron capture gas chromatograph Measured chloroflurocarbons (CFCs) in atmosphere Found concentrations were 230 parts per trillion Rowland figured out that the amount of CFCs in atmosphere were equivalent to the total amount of CFCs produced It didnt appear that these chemicals broke down in the environment.

15 Two unlikely players

y y y

y y

Mario Molina Had just completed Ph.D. in photochemistry at UC Berkely Few Days before Christmas 1973 working as a faculty research position at UC Irvine under Sherry Rowland on the fate of CFCs in the atmosphere Determined CFCs migrate to stratosphere slowly then breakdown under UV light CF2Cl2 UV-C CF2Cl Cl

16
y y

Molina and Rowland thought of publishing work showing fate of CFCs On a hunch Rowland suggested to find out the fate of the resulting Cl atom

17 Disturbing Results

.Cl O3 .ClO O2 .ClO O .Cl O2 Net O3 O 2O2

y

They were unsure of the results because Molina predicted that at 1973 levels of CFCs between 7 and 13 of O3 would be depleted in 100 years. This would seriously affect biological organisms

18 Absorption of light by DNA compared to intensity of light at the earths surface Figure taken from Environmental Chemistry 2nd Ed. By Colin Baird 1999 19 Skin Cancer Rates with UV Exposure Figure taken from Environmental Chemistry 2nd Ed. By Colin Baird 1999 20 Help in the Atmospheric Community
y y y y

Molina and Rowland talked with Harold Johnston (UC Berkeley). Johnston was an atmospheric chemist They hoped he would show them the flaw in their work. He could find none but didnt want to become involved because of the political issues he knew would follow the release of this work.

21 Releasing the work to the scientific community

y y y

Molina and Rowland published work in Nature June 28 1974 Molina and Rowland present their work at ACS meeting September 1974 This work caused quite an uproar. Why

22 CFCs
y y

Chlorofluorocarbons Contain C H Cl F atoms

y y y y y y

CFC-xyz x C atoms 1 (omitted if x 0) y H atoms 1 z F atoms Examples CF2Cl2 CFC-12

23 CFCs
y y y y y y y y y y

Low viscosity Low surface tension Low boiling point CFC-11 boils near room temperature Easily compressed at room temperature Chemical and Biologically inert Not corrosive Not toxic Prior to WWII used ammonia as a refigerant CFCs replaced ammonia as a refigerant DuPont obtained patents for many CFCs

24 CFC Uses
y y y y

Refrigerants Foam blowing agent Aerosol propellants Cleaning agents

25 Economic Impact of banning CFCs

y y y y y

1974 CFC production 500 million 600000 jobs with a payroll of 6.7 billion 1.5 million additional workers were indirectly dependent on CFCs There was a lot of opposition to banning CFCs even though some people thought they might harm the environment!

26 Actual Data
y y y y y y y

Molina and Rowland had no proof that O3 was actually declining All experiments were done in the lab All ground and satellite measurements indicated that O3 levels were fine O3 concentrations fluctuate with hour and season Temperature affects reaction rates Flux of UV affects formation and destruction of O3 Hard to measure a small change above a large cyclical change (figure 35-60oN)

27 Actual Data
y y y y y y y y

Joe Farman professor at Cambridge Farman had been measuring O3 over Antarctica since 1957 He almost lost funding because he hadnt really seen anything change in 25 years Noticed dip in O3 over South pole in Spring 1982 Farman was skeptical His instruments were hard to keep calibrated O3 was lower in Spring of 1983 and 1984 Farman was more confident because they had made extra sure that instruments were working correctly. Published work in Nature May 1985

28 Oops
y y

NASA had been measuring O3 over the earth with satellite imaging The satellites had a lot of problems so NASA scientist programmed the computers to ignore data that was erroneously low Thus they didnt notice the dip in O3 in Antarctic spring until Farman pointed it out.

29 More Study Needed

y y

DuPont and others wouldnt give up easily on CFCs High profile expeditions to Antarctica to study Ozone hole in October (Antarctica Spring) occurred in 1986 and 1987

Figure taken from Environmental Chemistry 2nd Ed. By Colin Baird 1999 30 Antarctic Ozone Hole ChemistryCl reservoir species (removal of Cl from catalytic cycle) .Cl CH4 HCl .CH3 .ClO .OOH HOCl O2 .ClO .NO2 M ClONO2 M
y

70 of stratospheric Cl is present as HCl

31 Antarctic Ozone Hole Chemistry

y

y y

Cold temperatures and polar vortex around Antarctica cause polar stratospheric clouds (PSCs) PSC are made of ice crystals that have an aqueous layer ClONO2 and HCl react with water on the surface of the ice crystal

HCl ClONO2 PSC surface Cl2 HNO3 H2O ClONO2 PSC surface HOCl HNO3 32 In spring (late October) after months of darkness Cl2 hn 2.Cl HOCl hn .Cl .OH .Cl O3 .ClO O2 .ClO O .Cl O2 Net O3 O 2O2 Or 2.Cl 2O3 2.ClO 2O2 .ClO .ClO ClOOCl ClOOCl hn .ClOO .Cl .ClOO .Cl O2 Net 2O3 hn 3O2 33 Figure taken from Environmental Chemistry 2nd Ed. By Colin Baird 1999

34 Montreal Protocol
y y y y y

September 1987 Protocol signed to reduce CFCs by 50 worldwide November 1987 US lawmakers call for new negotiations to strengthen the Montreal Protocol February 1988 Three US Senators ask Du Pont to stop making CFCs (DuPont denied request) March 1988 US ratifies Montreal Protocol with a unanimous vote March 1989 US and European countries develop faster reductions of CFC

35 CFC production 36 (No Transcript) 37 Arctic O3

y y y

Arctic is not as cold but some ice crystals do form O3 hole is not as severe Figure taken in Norway

Figure taken from Environmental Chemistry 2nd Ed. By Colin Baird 1999 38 CFC replacements
y y y

Replacements contain one H atom Easily degraded in troposphere by OH. R-134a is commonly used

Figure taken from Environmental Chemistry 2nd Ed. By Colin Baird 1999 39 (No Transcript) 40 Cool Comfort
y

CE News Jan 7 2008 page 14

y y

The race to find a replacement auto refrigerant heats up in Europe as a Ban on HFC-134A looms Heat Challenged The search is on for car air conditioner fluids that wont harm the environment. CO2 may become the replacement refrigerant.