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![Page 1: III/1 Atmospheric transport and chemistry lecture I.Introduction II.Fundamental concepts in atmospheric dynamics: Brewer-Dobson circulation and waves III.Radiative.](https://reader035.fdocuments.in/reader035/viewer/2022062907/5a4d1b887f8b9ab0599bd979/html5/thumbnails/1.jpg)
III/1
Atmospheric transport and chemistry lecture
I. IntroductionII. Fundamental concepts in atmospheric dynamics:
Brewer-Dobson circulation and wavesIII. Radiative transfer, heating and vertical transport
IV. Stratospheric ozone chemistry
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III/2
Processes affecting stratospheric O3
3/1997 3/1999
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III/3
IV. Stratospheric ozone chemistry
1. Basic concepts of atmospheric chemistry2. Ozone chemistry and ozone distribution3. Sources and distribution of ozone-related species4. Ozone trends5. The ozone hole6. Ion chemistry and solar variation7. Middle atmosphere processes: sprites, meteors, aurora
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III/4
IV. Stratospheric ozone chemistry
1. Basic concepts of atmospheric chemistry
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III/5
What goes in ? What goes out ? horizontal / vertical transport
What goes on in there ?
gas-phase reactionssurface reactionsion reactions
External forcing ?
solar radiation, (solar / magnetospheric particles in polar regions)
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III/6
What goes in ? What goes out ? horizontal / vertical transport
What goes on in there ?
gas-phase reactionssurface reactionsion reactions
External forcing ?
solar radiation, (solar / magnetospheric particles in polar regions)
Most commonly, reactions in the stratosphere are neutral gas-phase reactions of two reactants, involving at least one radical
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III/7
Second order (bimolecular) reaction
dDcCbBaA
reactants A and B form products C and Da,b,c,d: stoechiometric quantity of A, B, C, D
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III/8
Second order (bimolecular) reaction
dDcCbBaA
Rate R of the reaction:
dtdD
ddtdC
cdtdB
bdtdA
aR 1111
rate of change of A
R: [molecules / cm3s]
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III/9
Second order (bimolecular) reaction
dDcCbBaA
Rate R of the reaction:
dtdD
ddtdC
cdtdB
bdtdA
aR 1111
R: [molecules / cm3s]
BAkR k rate constant of the reaction[A] concentration (number density) of A[B] concentration of B
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III/10
Second order (bimolecular) reaction
dDcCbBaA
Rate R of the reaction:
dtdD
ddtdC
cdtdB
bdtdA
aR 1111
R: [molecules / cm3s]
BAkadtdA
BAkR
rate of change of A
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III/11
dDcCbBaA
BAkadtdA
rate constant k: from laboratory measurements
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III/12
dDcCbBaA
BAkadtdA
rate constant k: from laboratory measurements
An estimate of k from collision theory: molecules A and B are hard spheres of radii rA and rB
2
8
BAcollission
BA
BABoltzmannthermal
thermalcollission
rr
mmmmTk
v
vk
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III/13
dDcCbBaA
BAkadtdA
rate constant k: from laboratory measurements
An estimate of k from collision theory: molecules A and B are hard spheres of radii rA and rB
smoleccmk
Tk
vk thermalcollission
3
11
21
104
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III/14
BACACBCBA *
activated complexreactants products
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III/15
BACACBCBA *
activated complexreactants products
E1: Activation energy
E2 energy gained by reactionH: reaction enthalpy
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III/16
BACACBCBA *
activated complexreactants products
E1: Activation energy
E2 energy gained by reactionH: reaction enthalpy
The reaction takes place if the thermal energy of the reactants is larger than E1:k = A* exp(-E1/(kT))
Boltzmann factor
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III/17
BACACBCBA *
activated complexreactants products
E1: Activation energy
E2 energy gained by reactionH: reaction enthalpy
The reaction takes place if the thermal energy of the reactants is larger than E1:k = A* exp(-E1/(kT))Arrhenius-form
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III/18
Summary of gas-phase reactions
CBA First order (unimolecular) reactionphotolysis or thermal decomposition
EDBA Second order (bimolecular) reaction
DBA Three-body reaction
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III/19
Summary of gas-phase reactions
CBAMA * First order (unimolecular) reactionthermal decompositionpressure and temperature dependent
EDBA Second order (bimolecular) reactiontemperature dependent
DBA Three-body reaction
pressure
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III/20
Summary of gas-phase reactions
CBAMA * First order (unimolecular) reactionthermal decompositionpressure and temperature dependent
EDBA Second order (bimolecular) reactiontemperature dependent
DMD
DBA
*
* Three-body reactionpressure and temperature dependent
pressure
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III/21
Photodissociation
ABJdtABd
BAhAB
AB
JAB: photolysis rate
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III/22
quantum yield = 0: AB is not dissociatedquantum yield = 1: AB is totally dissociated
Photodissociation
number of photons absorbed
ABJdtABd
BAhAB
AB
JAB: photolysis rate
hFT
ddJ AB ,
quantum yield absorption cross section
actinic flux
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III/23
First-order reaction
CBA
AkdtdA
A
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III/24
First-order reaction
CBA
tkAtA
AkdtdA
A
A
exp0
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III/25
First-order reaction
CBA
dtdAtkAtA
AkdtdA
A
A
exp0
Lifetime of A:
Ak1
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III/26
Second-order reaction
DCBA
Lifetime of A:
BkAB
1
Valid if [B] is constant, i.e., if the lifetime of B is larger than the lifetime of A
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III/27
Calculating the behaviour of gas [A]
d[A] / dt = (sum of formation reactions) – (sum of loss reactions)
d[A] / dt = kij[Ci][Cj] - kj[A][Cj] + Jj[Ci] – JA [A]
gas-phase productionand loss reactions of A
photolysis reactions forming and dissociationg A
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III/28
IV. Stratospheric ozone chemistry
2. Ozone chemistry and ozone distribution- Oxygen atmosphere- Ozone distribution- Catalytic cycles
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III/29
Purely oxygen atmosphere (Chapmann cycle)
)(
2
12
323
323
232
22
rethermosphekMOMOOJOOhOkOOOkMOMOO
JOOhO
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III/30
Ozone altitude distribution at 8°N, January 28, 2004Model result from the modified Leeds-Bremen model
Mixing ratio
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III/31
Ozone altitude distribution at 8°N, January 28, 2004Model result from the modified Leeds-Bremen model
Mixing ratio
Ozone maximum
Second ozone maximum
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III/32
Ozone altitude distribution at 8°N, January 28, 2004Model result from the modified Leeds-Bremen model
Mixing ratio Number density
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III/33
Ozone altitude distribution at 8°N, January 28, 2004Model result from the modified Leeds-Bremen model
Mixing ratio Number density
Maximum 30-40 km Maximum 20-30 km
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III/34
Ozone altitude distribution at 8°N, January 28, 2004Model result from the modified Leeds-Bremen model
Mixing ratio Number density
Maximum 30-40 km Maximum 20-30 km The ozone colume (= total ozone) is dominated by the lower stratosphere
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III/35
Purely oxygen atmosphere (Chapmann cycle)
)(2
)(2
2
)(
5231
421
4221
4221
*2
12
*3
123
323
323
232
12
22
slowkOODO
rethermosphekOODO
kOOODO
kNONDO
JODOhO
JDOOhO
JOOhOkOOOkMOMOO
rethermosphekMOMOOJOOhO
c
b
a
![Page 36: III/1 Atmospheric transport and chemistry lecture I.Introduction II.Fundamental concepts in atmospheric dynamics: Brewer-Dobson circulation and waves III.Radiative.](https://reader035.fdocuments.in/reader035/viewer/2022062907/5a4d1b887f8b9ab0599bd979/html5/thumbnails/36.jpg)
III/36
The Ox-family
Ox: reactive oxygenOx = O + O(1D) + O3
lifetime of family is long, family members transfer into each other in fast reactions
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III/37
The Ox-family
Ox: reactive oxygenOx = O + O(1D) + O3
lifetime of family is long, family members transfer into each other in fast reactions
2131
5332*22 2222 OkODOkOOkOJJ
dtOd x
formation of Ox loss of Ox
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III/38
Photochemical lifetimes of O3, O and Ox
compared to horizontal transport u
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III/39
Photochemical lifetimes of O3, O and Ox
compared to horizontal transport u
>40 km: Ox is dominated by transport40-80 km: Ox is dominated by chemistry>80 km: Ox is dominated by transport
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III/40
Photochemical lifetimes of O3, O and Ox
compared to horizontal transport u
>40 km: Ox is dominated by transport of ozone40-80 km: Ox is dominated by chemistry>80 km: Ox is dominated by transport of O
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III/41
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III/42
Dynamical control of Ox (ozone) in polar night
Dynamical control throughout the upper mesosphere / lower thermosphere
Dynamical control in the lower stratosphere
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III/43
Dynamical control of Ox (ozone) in polar night
Dynamical control throughout the upper mesosphere / lower thermosphere
Dynamical control in the lower stratosphere
Chemical control from mid-stratosphere to mid-mesosphere
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III/44
Dynamical control of Ox (ozone) in polar night
Dynamical control throughout the upper mesosphere / lower thermosphere
Dynamical control in the lower stratosphere
Chemical control from mid-stratosphere to mid-mesosphere
Transition zone of transport/chemistry control
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III/45
The Ox-family: partitioning of family members
31
5
21
421
42*23
*3
1
33222
1
21
421
4332*222
31
53*333322
3
2
2
ODOk
ODOkNDOkOJOJdt
DOd
OOkOOkOk
ODOkNDOkOJOJOJdtOd
ODOkOJJOOkOOkdtOd
ba
ba
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III/46
The Ox-family: partitioning of family members
31
5
21
421
42*23
*3
1
33222
1
21
421
4332*222
31
53*333322
3
2
2
ODOk
ODOkNDOkOJOJdt
DOd
OOkOOkOk
ODOkNDOkOJOJOJdtOd
ODOkOJJOOkOOkdtOd
ba
ba
from these equation the partitioning of family members can be calculated if photochemical equilibrium is assumed for O and O(1D), i.e,
0,01
dt
DOddtOd
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III/47
The Ox-family: partitioning of family members from photochemical equilibrium
3322
3*3
3
2424
*3
3
1
OkOkJJ
OO
OkNkJ
ODO
ba
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III/48
The Ox-family: partitioning of family members from photochemical equilibrium
3322
3*3
3
2424
*3
3
1
OkOkJJ
OO
OkNkJ
ODO
ba
both O and O(1D) are zero during night-time
in the stratosphere:[O3] >> [O] (Ox O3)
in the upper mesosphere:[O3] < [O] (Ox O)
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III/49
Altitude distribution of Ox species, 8°N, January 28, 2004Model result from the modified Leeds-Bremen model
(non-equilibrium model)
Noon
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III/50
Altitude distribution of Ox species, 8°N, January 28, 2004Model result from the modified Leeds-Bremen model
Noon< 50 km: Ox O3
> 70 km: Ox O50-70 km: transition zone, O and O3
O(1D) more than five orders of magnitude smaller
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III/51
Altitude distribution of Ox species, 8°N, January 28, 2004Model result from the modified Leeds-Bremen model
Noon Night
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Altitude distribution of Ox species, 8°N, January 28, 2004Model result from the modified Leeds-Bremen model
Noon Night
Ox O3 up to ~ 75 km
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Diurnal variation of Ox species, 8°N, January 28, 2004Model result from the modified Leeds-Bremen model
40 km: no diurnal variation of ozone and Ox
OzoneOOx
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Diurnal variation of Ox species, 8°N, January 28, 2004Model result from the modified Leeds-Bremen model
50 km: small diurnal variation of O3, Ox constant
OzoneOOx
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Diurnal variation of Ox species, 8°N, January 28, 2004Model result from the modified Leeds-Bremen model
60 km: night: Ox = O3
day: Ox OOzoneOOx
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Diurnal variation of Ox species, 8°N, January 28, 2004Model result from the modified Leeds-Bremen model
70 km: night: Ox = O3
day: Ox = OOzoneOOx
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Diurnal variation of Ox species, 8°N, January 28, 2004Model result from the modified Leeds-Bremen model
80 km: Ox OOzoneOOx
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III/58Brasseur and Solomon
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Latitudinal distribution of O3, Northern winter (January), ppm Model result from the modified Leeds-Bremen model Unrealistic high values
in polar night (equilibrium model!)
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Latitudinal distribution of O3, Southern winter (July), ppm Model result from the modified Leeds-Bremen
modelUnrealistic high values in polar night (equilibrium model!)
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Annual variation of O3, Southern winter (July), ppm Model result from the modified Leeds-Bremen model
tropics (0°N)
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Annual variation of O3, ppm Model result from the modified Leeds-Bremen model
tropics (0°N)
mid-lats (47°N)
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Annual variation of O3, ppm Model result from the modified Leeds-Bremen model
tropics (0°N)
mid-lats (47°N)
polar (75°N)
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Variation of ozone in latitude and season, measured by the TOMS satellite instrument for 1990
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Variation of ozone in latitude and season, measured by the TOMS satellite instrument for 1990
Downward transport during polar winter
Ozone hole (Antarctic winter)
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Variation of total ozone related to the altitude of the tropopause and the 200 hPa level
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Catalytic destruction of ozone
23
2
23
2: OOOnet
OXOOXOOXOX
First proposed by Bates and Nicolet, 1950, reactants: HOx
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Catalytic destruction of ozone
23
2
23
2: OOOnet
OXOOXOOXOX
First proposed by Bates and Nicolet, 1950, reactants: HOx Molina and Rowland, 1974: Stratospheric sink for chlorofluoromethanes: Chlorine atom catalysed destruction of ozoneCrutzen, 1970th: Numerous studies about catalytic cycles of HOx and NOx
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Catalytic destruction of ozone: usefull terms
23
2
23
2: OOOnet
OXOOXOOXOX
chain center
Chain lengths N: number of times the cycle is executed before the chain center is destroyed
N
: rate of propagation (i.e., the rate of the slowest reaction involved, the rate-limiting step): rate of termination (rate of destruction of the chain center)
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Catalytic destruction of ozone: usefull terms
23
2
23
2: OOOnet
OXOOXOOXOX
chain center
Chain lengths N: number of times the cycle is executed before the chain center is destroyed
N
Chain effectiveness : N