stratospheric ozone distribution
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STRATOSPHERIC OZONE DISTRIBUTION
Marion Marchand CNRS-UPMC-IPSL
O2 + UV-c -> O + O
O + O2 + M -> O3 + M
d[O3]/dt = 2 JO2 [O2]0 2 4 6 8 10 12 14
0
10
20
30
40
Altitude (km)
O
3
(ppmv)
O
3
(molecules cm
-3
x 10
-12
)
Air (molecules cm
-3
x 5 x 10
-19
)
O2 (molecules.cm-3
x 10-19)
Alt
itu
de
(km
)
Photolysis coefficient (s-1)
O3 (molecules.cm-3 x 10-12)
JO2 (s-1)
Altitude (km)SHAPE OF OZONE PROFILE
UV
VMR (Volume Mixing Ratio)=[O3]/[M] (-> better indicator of chemistry )
O3
[M] total air concentration (molec.cm-3x 10-16)
[O3] [M]
[O3] concentration
(molec.cm-3 x 10-12)
Brewer (1949) quotes from Dobson et al. (1929): 'The only way in which we can reconcile the observed high ozone concentration in the Arctic in spring and the low concentration in the tropics, with the hypothesis that the ozone is formed by the action of the sunlight, would be to suppose a general slow poleward drift in the highest atmosphere with a slow descent of air near the poles. Such a current would carry the ozone formed in low latitudes to the poles and concentrate it there. If this were the case the ozone at the poles would be distributed through a moderate depth of atmosphere while that in low latitudes would all be high up.’ [SPARC]
O3 production from O2 photolysis (molec.cm-3)O3 column (Dobson units)
tropical minimum
tropical maximum
latitude
lati
tude
month
Alt
itu
de (
km)
Why?
(=O3 concentration)
Brewer (1949) said `The observed distributions of water vapour can be explained by the existence of a circulation in which air enters the stratosphere at the equator, where it is dried by condensation, travels in the stratosphere to temperate and polar regions, and sinks into the troposphere.' [SPARC]
Troposphere is humid but stratosphere is very dry. Why?
very dry statosphere
humid troposphere
Temperature (°K)
tropopause
stratopause
GLOBAL DISTRIBUTION OF CHEMICAL TRACERS
hours
days
months
dO3/dt~f(dynamics)
dO3/dt~f(chemistry)
months
dO3/dt = f(chemistry + dynamics)
CHEMISTRY OF OZONE:CONCEPTS
OXYGEN-ONLY CHEMISTRY
° First chemistry scheme proposed by Chapman in 1930, also called the ‘Chapman cycle’.
° The reactions are
O2 + h → O + O jO2 < 242 nm
O + O2 + M → O3 + M kO+O2
O3 + h → O + O2 jO3 < 336 nm
O + O3 → O2 + O2 kO+O3
O2 + h → O + O
O + O2 + M → O3 + M
O3 + h → O + O2
O + O3 → O2 + O2
d[O3]/dt = kO+O2.[O2].[O].[M] -JO3.[O3] -kO+O3.[O3].[O]
d[O]/dt = 2.JO2.[O2] +JO3.[O3] -kO+O2.[O2].[O].[M] -kO+O3.[O3].[O]
° kO+O2 et JO3 interconvert
O3 and O very rapidly, so
introduce new species
Ox[=O + O3] known as “odd-oxygen”
d[Ox]/dt = d[O]/dt + d[O3]/dt
= 2.JO2.O2 - 2.kO+O3.O3.O
Production - Destruction
If Ox steady-state (i.e. d[Ox]/dt = 0),
JO2.[O2]= kO+O3.[O3].[O]
ODD OXYGEN CHEMICAL FAMILY
fast
fast
slowslow
Mass balance for atomic oxygen O:
d[O]/dt = 2.JO2.[O2] +JO3.[O3] -kO+O2.[O2].[O].[M] -kO+O3.[O3].[O]
° if Ox steady-state (i.e. d[Ox]/dt = 0), JO2.[O2]= kO+O3.[O3].[O]
-> d[O]/dt = JO2.[O2] +JO3.[O3] -kO+O2.[O2].[O].[M]
° interconversion terms >> net chemical terms (chemical family approach): JO3.[O3] >> JO2.[O2]
-> d[O]/dt ~ JO3.[O3] -kO+O2.[O2].[O].[M]
° lifetime of O = [O]/loss = 1/(kO+O2.[O2].[M]) < 1 sec
-> O steady-state (i.e. d[O]/dt = 0),
[O]/[O3] = JO3 / (kO+O2.[O2].[M])
° as expected, interconversion terms determine partitioning within chemical family
Volume mixing ratio
Altitude (km)
° Chapman’s model of [O]/[O3] validated against observations
° [O]/[O3] << 1 -> Ox[=O + O3] ~ O3 and d[Ox]/d= d[O3]/dt
O3
O
° if Ox steady-state (i.e. d[Ox]/dt = 0),
JO2.[O2]= kO+O3.[O3].[O]
° if O steady-state (i.e. d[O]/dt = 0),
[O]/[O3] = JO3 / (kO+O2.[O2].[M])
° using [O]=f([O3]) expression in JO2.[O2]= kO+O3.[O3].[O],
[O3] = [O2] . (kO+O2.[M] / kO+O3)1/2 . (JO2 / JO3 )1/2
with [O2] =0.21 [M]
Calculated [O3] from Chapman’s model is much too high compared to observations. Why?
d[O3]/dt = JO2.[O2] - kO+O3.[O3].[O]
calculated
observed
OZONE DESTROYING CATALYTIC CYCLES
° Bates and Nicolet introduced in 1950 the idea of ozone being destroyed via the following catalytic cycle:
OH + O3 → HO2 + O2
HO2 + O → OH + O2
net: O + O3 → O2 + O2
° NO2 cycle in 1970 by Crutzen and also Johnston
NO + O3 → NO2 + O2
NO2 + O → NO + O2
net: O + O3 → O2 + O2
° ClO cycle in 1974 by Stolarski and Cicerone.
Cl + O3 → ClO + O2
ClO + O → Cl + O2
net: O + O3 → O2 + O2
° A general form:
X + O3 → XO + O2 fast
XO + O → X + O2 slow
net: O + O3 → O2 + O2
with X, the catalyst, being radical H, OH, NO, Cl or Br
° slow reaction is the limiting step in the cycle,
d[O3]/dt ~ - 2.kXO+O.[XO].[O]
d[O3]/dt ~ +2.JO2.[O2] -2.kO+O3.[O3]. [O] -2.kHO2+O3. [HO2]. [O3]
-2.kNO2+O. [NO2]. [O] -2.kHO2+O3. [ClO]. [O]
Catalyst: H, OH, NO, Cl, Br,..
STRATOSPHERIC SOURCE GASES The key stratospheric source gases are long-lived in the troposphere, and hence, once emitted at the surface, they can reach the stratosphere
° Stratospheric hydrogen radicals (OH, HO2) originate mostly from H2O injected from the troposphere and from the in-situ oxidation of (natural and anthropogenic) CH4 by,
O(1D) + H2O → OH + OH
O(1D) + CH4 → OH + CH3 --> more oxidation, more OH
° Most of the stratospheric nitrogen oxide radicals (NO2, NO) originates from N2O oxidised in the stratosphere via the following reaction,
O(1D) + N2O → NO + NO
STRATOSPHERIC SOURCE GASES ° Stratospheric chlorine radicals (Cl, ClO) originate mostly from CFCs that are photolysed by UV radiation following,
CFxCly + h → Cl + CFxCl(y-1) --> more oxidation, more Cl
° Sources of stratospheric chlorine radicals (Cl, ClO)
natural
anthropogenic
RESERVOIR SPECIES ° Up to now, we considered the different catalytic cycles independently. But radicals from one chemical family can interact with radicals from another family.
° Reactions between radicals lead to formation of species with longer lifetimes, much less reactive, called reservoirs, e.g.
ClO + HO2 → HOCl + O2
HO2 + NO2 + M → HO2NO2 + M
ClO + NO2 + M → ClONO2 + M
OH + NO2 + M → HNO3 + M
NO3 + NO2 + M → N2O5 + M
° Reservoir species can be dissociated back rather quickly to release ozone destroying radicals
CHEMICAL MODEL O3 BUDGET : Production - Destruction
d[O3]/dt = 2 JO2 [O2] -2 k[XO][O] with X=O2, OH, NO, Cl
NOx (N2O)
HOx (CH4,H2O)
ClOx (CFCs)
production/destruction rate (molec.cm-3.s-1)
O/O3 cycle
O3=f(X, altitude)
ozone abundance (mPa)
° complete destruction between 14 and 22 km
° - d[O3]/dt ~ 2 %/day
PSC clouds formed at T < ~193 K by co-condensation of HNO3 and H2O
Heterogeneous chemistry: ° chlorine activation (reservoirs species -> into chlorine radicals) ° O3 destruction
-> speed up reactions that are are very slow or non-existent in the gas-phase
Ice or HNO3/H2O PSCs
CATALYTIC CYCLES OF POLAR OZONE DESTRUCTION
° BUT observed loss rates (- d[O3]/dt) ~ 2 %/day -> [O] is much too low (not enough sunlight during early spring) for ClO+O cycle to account for observed loss rates.
° Cl2O2 cycle in 1987 by Molina and Molina.
ClO + ClO + M Cl2O2 + M equilibrium
Cl2O2 + h → Cl + ClOO
ClOO + M → Cl + O2 + M
2 x ( Cl + O3 → ClO + O2 )
-> little sunlight is required (fast JCl2O2) and more efficient at low temperatures because it slows down thermal decomposition of Cl2O2 (Cl2O2 → ClO + ClO)
° ClO-BrO cycle
ClO + BrO → Cl + Br + O2 slow
Cl + O3 → ClO + O2 fast
Br + O3 → BrO + O2 fast
net: O + O3 → O2 + O2
-> little sunlight is required because the cycle does not involve atomic oxygen O
° Polar ozone loss rate:d[O3]/dt ~ -2.JCl2O2. [Cl2O2] -2.kClO+BrO.ClO.BrO
high chlorine loading andvery cold/ isolated polar vortex
INTERACTIONS OZONE-CLIMAT
Effet de Serre
=
Bilan au niveau de la Terre + effet de Serre:
Bilan au niveau de la couche (loi Kirchhoff):
a = 2
Bilan au niveau de la Terre sans effet de Serre (loi de stefan):
= Ts = 255 K seulement !
+ = _2
Stratospheric cooling / heating rate (K/day)
Heating: O3 + UV → O + O2
O + O2 + M → O3 + M (Q) -> dT/dz > 0
Cooling: mainly CO2 +/- IR H2O and O3 significant
Temperature
tropopause
stratopause
O3 and T strongly coupled: d(O3)/dt > 0 -> d(T)/dt > 0 -> attenue le d(O3)/dt > 0 d(T)/dt > 0 -> d(O3)/dt < 0 -> attenue le d(T)/dt > 0
~ 45 kmRelation-2 O3-T:
O + O3 → O2 + O2
k = 2.e-11 *exp( -2350 / T)
Quand T diminue => ralentissement destruction O3
=>d(T)/dt > 0 -> d(O3)/dt < 0
Relation-1 O3 - T :O3 + UV → O + O2
O + O2 + M → O3 + M (Q) => d(O3)/dt > 0 -> d(T)/dt > 0
total
Ozone changes
Greenhouse gas changes
Diminution O3-strato modifie l’équilibre radiatif à la tropopause effet sur la T au sol :-Augmentation de la pénétration des UV dans le système surface-troposphère(Forçage positif)-Sans ajustement de T: réduction des émissions IR de corp noir vers la surface(Forçage négatif)-Avec ajustement de T: diminution de l’absorption du rayonnement UV par l’O3 => refroidissement de la stratosphère => réduction de l’émission des corps noirs vers le sol (Forçage négatif)
-0.15 Wm-2
COMPLEXITY OF INTERACTIONS
CTM + GCM = CCM (Chemistry-Climate Model) -> predict the future evolution of ozone layer
DYNAMICS(T, winds)
RADIATION
CHEMISTRY
CO2
O3, CH4
CCM
Future O3 = f(CFCs, greenhouse gases)
Montreal process: chlorine loading -> ozone layer
Kyoto process greenhouse gases -> climate
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