ATMOS 348 Atmospheric Chemistry Lecture 7: Stratosphere

Don Wuebbles Department of Atmospheric Sciences University of Illinois, Urbana-Champaign

February 2004

A Historical Perspective on Atmospheric Chemistry 1950s

The atmosphere was viewed as largely a chemical inert fluid
that moves heat, momentum and moisture that transports pollutants away from cities

Importance of photochemistry limited to the upper atmosphere (ionosphere) Urban Photochemistry (LA smog)

1970s
The atmosphere started to be seen as a chemically dynamic system
New analytic instrumentation New measurements of chemical rate constants Simple atmospheric models

1970s
Stratospheric ozone became a major scientific issue
Aircraft NOx Industrially manufactured CFCs

Photochemistry of tropospheric ozone started to be investigated at the global scale.

1980s
Discovery of the stratospheric ozone hole and role of heterogeneous chemistry Recognition that air pollution is becoming a global issue Potential importance of greenhouse gases other than CO2 in the climate system

1990s
Role of the biosphere for the chemistry of the troposphere (e.g., biogenic hydrocarbons) Role of chemical compounds (including aerosols) in the climate system Aerosols and cloud microphysics

1990s
New research infrastructure and approaches for tropospheric studies
Spacecraft Surface networks Large airborne campaigns Comprehensive chemical-transport models International efforts (e.g., IGAC)

Stratospheric Chemistry Questions

What is good ozone? What is bad ozone? What is the Chapman mechanism? What is the ozone hole? How much (percent change) ozone loss has occurred at N.H. midlatitudes since 1970? How much has your potential risk of getting skin cancer increased? What is the Montreal Protocol? When will stratospheric ozone recover?

Total Ozone

Ozone Density

Total Ozone (Dobson units)

Stratospheric Ozone: Physics and Chemistry

Production of Ozone
The Chapman mechanism -- middle/upper stratosphere ( < 240 nm) O2 + h O + O O + O2 + M O3 + M O3 + h O2 + O O + O3 O2 O + O + M O2 + M (often left out) (M=N2, O2, Ar, etc.)

Smog chemistry -- troposphere and lower stratosphere (CH4, CO, HC) + OH HO2 HO2 + NO OH + NO2 NO2 + h NO + O O + O2 + M O3 + M

Transport of Stratospheric Constituents

The Chapman Mechanism

a) O2 + h O + O b) O + O2 + M O3 + M c) O3 + h O2 + O d) O3 + O O2 + O2 dnO/dt = 2janO2 kbnOnO2nM + jcnO3 kdnOnO3 dnO3/dt = kbnOnO2nM - jcnO3 - kdnOnO3 ja kb jc kd

Lifetime of O is very short need very small time steps to integrate equations

The Concept Of Odd Oxygen

a) O2 + h O + O b) O + O2 + M O3 + M c) O3 + h O2 + O

d) O3 + O O2 + O2

Interconversion of O and O3 is rapid compared to formation and loss of O3 + O Define Ox = O3 + O note nO is very small, so nOx nO3 Reactions (b) and (c) have no effect on Ox but have an effect on relative amounts of O and O3 in Ox Reaction (a) generates 2 Ox and reaction (d) destroys 2 Ox

A Steady State for Ozone

a) O2 + h O + O b) O + O2 + M O3 + M c) O3 + h O2 + O d) O3 + O O2 + O2 Control of nO/nO3 by reactions (b) and (c) kbnOnO2nM = jcnO3 nO = (jcnO3)/(kbnO2nM) ja kb jc kd

Rate of formation of odd oxygen dnOx/dt dnO3/dt = 2janO2 - 2kdnOnO3

If O3 is at steady-state nO3 = (2janO2)/(2kdnO) = nO2 [(jakbnM)/(kdjc)]1/2

Observed O and O3 in the Stratosphere

45

altitude (km)

45 40 35 30 25 20 15 10 1.E+00 1.E+02 1.E+04 1.E+06 1.E+08 1.E+10

nO (molecules cm-3)

altitude (km)

40 35 30 25 20 15 10 0 1E+12 2E+12 3E+12 4E+12

nO3 (molecules

cm-3)

nO/nO3 << 1 at all altitudes nO/nO3 increasing with altitude Maximum in nO3 at about 25 km Maximim nO3 3.2 x 1012 molecules cm-3

Lifetime for O(3P) in Stratosphere

a) O2 + h O + O b) O + O2 + M O3 + M c) O3 + h O2 + O

d) O3 + O O2 + O2

For stratospheric conditions O < 1 s

Lifetime = (number concentration)/(loss rate) O = nO/(kbnOnO2nM + kdnOnO3) = 1/(kbnO2nM + kdnO3) 1/(kbnO2nM)

Prod. rate of O and O do not change much on timescales of s Pseudo-state approximation for O is appropriate Rate of prod. of O by reaction (c) >> by reaction (a) nO/nO3 is determined by a balance between rxn. (b) and (c)

Relative Amounts of Stratospheric O and O3

a) O2 + h O + O b) O + O2 + M O3 + M c) O3 + h O2 + O d) O3 + O O2 + O2 Rate of prod. of O by reaction (c) >> by reaction (a) nO/nO3 is determined by a balance between rxn. (b) and (c) For stratospheric conditions nO/nO3 << 1 and increases with altitude agrees with observations nOx = nO + nO3 nO3 Effective lifetime of O3 is defined by lifetime of Ox

Calculated O3 with Chapman Mechanism

a) O2 + h O + O b) O + O2 + M O3 + M c) O3 + h O2 + O d) O3 + O O2 + O2 Assuming steady-state for Ox (i.e. for O3) Steady-state nO3 = (2janO2)/(2kdnO) = nO2 [(jakbnM)/(kdjc)]1/2 For stratospheric conditions Steady-state nO3 has max. at about 25 km agrees with observations nO3 larger than obs. at all alt. does not agree with observations Questions Is assumption of steady-state for Ox correct? Is reaction mechanism sufficient to explain nO3?

LIFETIME OF Ox IN THE STRATOSPHERE a) O2 + h O + O b) O + O2 + M O3 + M c) O3 + h O2 + O d) O3 + O O2 + O2 Lifetime = (number concentration)/(loss rate) Ox = nOx/(2kdnOnO3) 1/(2kdnO) Ox = several years in the lower stratosphere Do not expect steady-state to hold transport plays a role Ox < 1 day in the upper strat. Expect steady-state to hold deficiency in Chapman mech.

Missing Chemistry in Chapman Mechanism

calculated measured

Global Ox production rate = 5 times destruction rate Imbalance suggests overest. of prodn. or underest. of loss Ox production well constrained by good spectroscopic data Implies missing chemical sinks for Ox Reactions of radicals with O and/or O3 But radicals will also be consumed by reaction

Stratospheric O3: Physics and Chemistry

Destruction of stratospheric ozone Occurs primarily through catalytic mechanisms Examples:
For X = OH or NO or Cl or Br X + O3 XO + O2 XO + O X + O2 ----------------------------O + O3 2O2