“Stratospheric Ozone Depletion by

Chlorofluorocarbons”
U.C.I.-NASA
July 14, 2009
Prof. F. Sherwood Rowland
University of California, Irvine, CA
Gay-Lussac & Biot
Paris, 1804
N2/O2 = 4
GREENHOUSE GASES
Dobson Götz Chapman

International Ozone Conference, Oxford, U.K., 1936

Stratospheric O3 Formation
The “Chapman Reactions”,
(oxygen-only, 1930)
O2 + hν → O + O (1)
O + O 2 + M → O3 + M (2)
O3 + hν → O + O2 (3)
O + O3 → O2 + O2 (4)
(Sunlight)
One D.U.
~ 10-9

USSR
Global

average

ozone about
Australia
300

Switzerland

Peru

Seasonal & Latitudinal Variations of Atmospheric Ozone (Dobson, 1968)

F. S. Rowland, Lecture
Notes, Fort Lauderdale
Florida Feb. 1972
1973
UCI Laboratory, F. S. R., with Mario Molina,
People Magazine, October 1976
 Free Radicals
Odd number of electrons

Hydrogen H (1), HO (9), HO2

Nitrogen NO (15), NO2
Halogen Cl (17), ClO (25), Br, BrO
ODD PLUS EVEN ALWAYS GIVES ODD
Mario J. Molina & F. S. Rowland
Department of Chemistry, University of California, Irvine, California 92664

Chlorofluoromethanes are being added to the

environment in steadily increasing amounts.
These compounds are chemically inert and may
remain in the atmosphere for 40-150 years, and
concentrations can be expected to reach 10 to 30
times present levels. Photodissociation of the
chlorofluoromethanes in the stratosphere
produces significant amounts of chlorine atoms,
and leads to the destruction of atmospheric ozone.
Nature, June 28, 1974
 CHLORINE ATOM ATMOSPHERES
PRODUCTION RATE
50 CM-3 SEC-1
-.001
ALTITUDE 10 20

40
KM B,C
-.01
30 A

20
0.1
LIFETIMES
TROPOPAUSE
A 41 YEARS A B C
10 B 42 YEARS
1972 C 52 YEARS
1.0
0
0 200 400 600 800

CCl3F PPTV
Calculated vertical profile for CCl3F, 30° N
Rowland & Molina, Rev. Geophys. Space Phys., 1975
NAS Reports

September 1976

(scheduled for
April)
 Formation of Chlorine Nitrate
in the Atmosphere
ClO + NO2 + M → ClONO2 + M

Others = HCl, HOCl, HONO2,

HOONO, H2O2, ClOOCl, etc.,

September 13, 1976, Los Angeles Times
British Antarctic Survey Base, Halley Bay, Antarctica, 75.5° S
New York Times September 19, 1987
White spaces = no data
 HCl + ClONO2 → Cl2 + HNO3
H. SATO & F. S. ROWLAND
05/15/84 17:43:09

05/15/84 17:43:10

Add HCl 05/15/84 17:43:11

05/15/84 17:43:12

HNO3 ClONO2
 (a)
(b)
0 (c)
CONNELL AND (a) 4.2%
WUEBBLES,1984

-10
∆O3 %
(a) STANDARD CASE
(b) H2O
-20 (c) HCl (b) 24.0%

1950 1960 1970 1980 0 100 200 400

DATE FUTURE YEARS (c) 31.7%
FROM (1983)

H2O + ClONO2 → HOCl + HNO3

HCl + ClONO2 → Cl2 + HNO3
 Antarctic ClO in 1986 (deZafra & P. Solomon 1987)
50

40
Altitude (Km)

30

20

10
0.0 0.5 1.0 1.5 2.0
Mixing Ratio (ppb)
O + O3 → 2O2
{ Cl + O3 → ClO + O2
ClO + O → Cl + O2

2O3 → 3O2
{ 2[Cl + O3 → ClO + O2]
2ClO →ClOOCl
ClOOCl + hν → Cl + ClO → 2Cl + O
Mid-winter, 28 July 1999 – 255 DU
29 September 1999 – Total Ozone – 90 DU
-- Temperature

PSCs
PERCENT DIFFERENCE

% TOTAL OZONE CHANGE

WINTER (DJFM)
(1976 – 1986) MINUS (1965 – 1975)

NORTH LATITUDE
% OZONE CHANGES VERSUS LATITUDE
(1970 – 1986) MINUS (1969 & EARLIER)
Harris and Rowland, 1988
June, 1989
 USHUAIA, ARGENTINA (55°S)
AUSTRAL SPRING 1991
100

10.0

TOMS OZONE 189

1.0

0.10
TOMS OZONE 355

0.010 OCT. 20
OCT. 21
OCT. 23
NOV. 6
0.0010
290 295 300 305 310

UV WAVELENGTH, NANOMETERS
Surface UV-B intensities on 4 different days
BIOSPHERIC INSTRUMENTS, INC.
October 4, 2004

Total Ozone (Dobson Units)

110 220 330 440 550

 26.9 27.1 27.4

2007, 200
about lik
N 2004/2005
O

D
A
T
A
 280

CFC-11 (ppt)
270

260

1996 2000 2004

Concentration of CCl3F (CFC-11) vs. time. Units parts per 1012 .

Northern Hemisphere (blue), Global (green), Southern Hemisphere (red).

Dutton et al., NOAA/CMDL

 530

CFC-12 (ppt)
520

510

500

1996 2000 2004

Concentration of CCl2F2 (CFC-12) vs. time. Units parts per 1012 .

Northern Hemisphere (blue), Global (green), Southern Hemisphere (red).
 Ozone Hole October 8, 2005

Punta Arenas 156 D.U.

Halley Bay 113 D.U.
Ushuaia 161 D.U.

Total Ozone (Dobson Units)

110 220 330 440 550

 April 2, 2007 Supreme Court Decision,
Majority Opinion, J. P. Stevens

(1) A well-documented rise in global temperatures

(2) a significant increase in the concentration of carbon

dioxide in the atmosphere.

(3) respected scientists believe the two trends are

related.
_1.0

_0.5

_0.0
Increasing concentrations of atmospheric carbon dioxide
388.5, May 2008

Keeling and Whorf, 2005

Mauna Loa, Hawaii

(Red)
When is Inadvertent Geoengineering
of the Atmosphere no longer
“inadvertent”?
 Watts per square meter
Cooling warming IPCC

albedo
Watts per square meter
cooling warming
IPCC
 HCFC-22 CHClF2 PRODUCTION

FLUORINATION OF CHLOROFORM

CHCl3 → CHCl2F → CHClF2 → CHF3

HCFC-21 HCFC-22 HFC-23

kHO 820 1.7 35 1.7

-16
(In units of 10 cm3

Atmospheric
molecule-1 sec-1 at 7 C) 0.41 1.7 12 270
Lifetime, years
100-year GWP
(WMO-50, 2007) -- 151 1810 14,760
IMOS Report
June 1975
White
House, July
1997