1/12/2014

1
Stratospheric
Chemistry
Frances Pauline U. Onting
Ma. Jedil R. Esteba
Why should we care ?


1/12/2014
2
Why should we care ?


Stratospheric ozone levels are declining.
6 - 10% decline in stratospheric ozone levels
during the past three decades
Some degree of stratospheric ozone loss has
affected all latitudes

Every time even a small amount of
the ozone layer is lost, more ultraviolet light
from the sun can reach the Earth.


By 2075 about 60 million will have skin
cancer

1/12/2014
3
Flashback on Stratospheric Chemistry
1923
Gordon Dobson developed the first spectrometer to
measure ozone in the atmosphere and characterized
its latitudinal seasonal variability
1928
Thomas Midgley develops CFC, replacing ammonia
and SO
2
1930
Sydney Chapman published several theoretical papers
on upper-atmospheric ozone now known as the
Chapman Cycle
1950
The atmosphere was viewed as largely a chemical inert
fluid
that moves heat, momentum and moisture
that transports pollutants away from cities
Photochemistry limited to the upper atmosphere
(ionosphere)
Urban Photochemistry (LA smog)
1960
CFCs become popular in industry
air conditioning
spray cans
1/12/2014
4
1970
The atmosphere started to be seen as a chemically
dynamic system
New analytic instrumentation
New measurements of chemical rate constant
Simple atmospheric model

Stratospheric ozone became a major scientific issue
Aircraft NO
x
Industrially manufactured CFCs

Photochemistry of tropospheric ozone started to be
investigated at the global scale.
1980

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
CO
2
in the climate system
1/12/2014
5
1990
Role of the biosphere for the chemistry of the
troposphere (e.g., biogenic hydrocarbons)
Role of chemical compounds in the climate system
Aerosols and cloud microphysics
New research infrastructure and approaches for
tropospheric studies
Spacecraft
Surface networks
Large airborne campaigns
Comprehensive chemical-transport models
International efforts (e.g., IGAC)
OZONE
ozein -to smell
Officially named as a chemical in 1840, after
noted that it had similar smell to phosphorus when
exposed to air Electric discharges in air "
Ozone was realized to be a good disinfectant


1/12/2014
6
UV shield
Greenhouse gas
Precursor of OH,
main atmospheric oxidant
Toxic to humans and
vegetation
10%
Troposphere
Stratosphere:
90% of total
Consequences of less Ozone
CONSEQUENCE CAUSE
Increase in skin cancer
UV light penetrate more deeply and
mutate skin DNA
Increase in cataract Energetic UV light damages eyes
Decline in Plant Productivity UV light easily damages plant tissue
Decline in Animal Productivity
Reduces plankton population
Reduces penguin population
Reduces the percentage of
hatching of frog eggs
UV light easily damages animal tissue

Lowered White Blood Cell sunburn from UV exposure
Global Warming
Green House Effect
lower plant productivity, less CO2
removed
the more CO2. more radiated heat can
be absorbed
1/12/2014
7
UV Absorption of Ozone
UV Absorption of Ozone
AGING
BURNING
DANGER
1/12/2014
8
Dobson Unit
Measurement for total column ozone
Production of Ozone

The Chapman mechanism
O
2
+ h O + O (< 240nm)
O + O
2
+ M O
3
+ M
O
3
+ h O
2
+ O
O + O
3
O
2
O + O + M O
2
+ M
Smogchemistry
(CH
4
, CO, HC) + OH HO
2
HO
2
+ NO OH + NO
2
NO
2
+ h NO + O
O + O
2
+ M O
3
+ M

O O
3
O
2
slow
slow
fast
Odd oxygen family
[O
x
] = [O
3
] + [O]
R2
R3
R4
R1
1/12/2014
9
Steady state ozone
1. Ozone is formed in one step and consumed in two
steps
d[O
3
]/dt= -d[O
3
]/dt]
rate
b
= rate
c
+ rate
d

2. Atomic oxygen is formed in two steps, consumed
in two steps.
d[O]/dt = -d [O]/dt
2 (rate
a
+ rate
c
) = rate
b
+ rate
d

Steady state ozone
1. kb (O)(O
2
)(M)= kc (O
3
) + kd (O)(O
3
)
2. 2ka (O
2
) + kc (O
3
)+ kb (O)(O
2
)(m) + kd (O)(O
3
)

Through Addition:
2ka (O
2
) + 2kd (O)(O
3
)

Through Subtraction:
kb (O)(O
2
)(M) = ka (O
2
) +kc (O
3
)

1/12/2014
10
Steady state ozone
Since ka (O
2
) << kc (O
3
)

From subtraction:
kb (O)(O
2
)(M) = kc (O
3
) so,
(O) = kc (O
3
)/kb (O
2
)(M)
from that substitute to addition,
2ka (O
2
) = 2kd (O)(O
3
)
2ka (O
2
) = 2kdkc (O
3
2
) / kb (O
2
)(M)
REARRANGE,
(O
3
2
)/(O
2
2
) = kakb[M]/kckd
Factors that change in increasing altitude
[O]/[O
3
] << 1 at all altitudes
[O]/[O
3
] increasing with altitude
(ka, kc)
Temperature profile changes
Maximum in [O
3
] at about 25 km
Maximum [O
3
] 3.2 x 10
12
molecules cm
-3
1/12/2014
11
Chapman mechanism reproduces shape
but is too high by factor 2-3
Chapman got it almost right
CATALYTIC CYCLES FOR OZONE LOSS
General Idea
O
3
+ X XO + O
2
O + XO X + O
2
Net: O
3
+ O 2 O
2
X is a catalyst
The catalyst is neither created nor destroyedbut the rate for the
catalytic cycle [odd-O removal in this case] depends on catalyst
concentrations
1/12/2014
12
Hydroxyl Radical
O
3
+ OH HO
2
+ O
2
O + HO
2
OH + O
2
Net: O
3
+ O 2 O
2

Chlorine and Bromine
O
3
+ Cl ClO + O
2
O + ClO Cl + O
2
Net: O
3
+ O 2 O
2



Nitric Oxide
O
3
+ NO NO
2
+ O
2
O + NO
2
NO + O
2
Net: O
3
+ O 2 O
2


WATER VAPOR IN STRATOSPHERE
Source:
transport from troposphere, oxidation of methane (CH
4
)

1
1L1 Z=<11
1/12/2014
13
HO
x
-CATALYZED OZONE LOSS
HO
x
H + OH + HO
2
family
Initiation:
1
2
HO+O( ) 2OH D
Propagation: 3 2 2
2 3
3
2
2
OH+O HO O
HO+
Net:
O OH+
2O
2O
3O

Termination:
2 2 2
OH+HO HO+O
OH HO
2
H
2
O
slow
slow
fast
Termination Recycling
NO
2
+ OH + M HNO
3
+ M HNO
3
+ h NO
2
+ OH
NO
2
+ O
3
NO
3
+ O
2
HNO
3
+ OH NO
3
+ H
2
O
NO
3
+ NO
2
+ M N
2
O
5
+ M NO
3
+ h NO
2
+ O
N
2
O
5
+ H
2
O 2HNO
3
N
2
O
5
+ h NO
2
+ NO
3
Propagation
NO + O
3
NO
2
+ O

NO + O
3
NO
2
+ O
2

NO
2
+ h NO + O NO
2
+ O NO + O
2
O + O
2
+ M O
3
+ M
Null cycle Net O
3
+ O 2O
2









Initiation N
2
O + O(
1
D) 2NO






NO
x
-CATALYZED OZONE LOSS
(NO
x
NO + NO
2
)
Day
Night
1/12/2014
14
STRATOSPHERIC DISTRIBUTION OF CFC-12
Initiation: Cl radical generation from non-radical precursors
CF
2
Cl
2
+ h CF
2
Cl + Cl
Propagation:
Cl + O
3
ClO + O
2

ClO + O Cl + O
2

Net: O
3
+ O 2O
2

ClO
x
-CATALYZED OZONE LOSS
(ClO
x
Cl + ClO)
Termination: Recycling:
Cl + CH
4
HCl + CH
3
HCl + OH Cl + H
2
O
ClO + NO
2
+ M ClNO
3
+ M ClNO
3
+ hv Cl + NO
3

1/12/2014
15
1/12/2014
16
1/12/2014
17
By the simulated year 2020, 17 %of ozone is depleted
globally

By 2040, global ozone concentrations is the same level
the "hole" over Antarctica. The UV index in mid-latitude
cities reaches 15, giving a sunburn in about 10 minutes

In 2050, Ozone levels in the stratosphere over the tropics
collapse to near zero

By 2065, global ozone drops to 110 DU, a 67% drop. Year-
round polar values hover between 50 and 100 DU. The
intensity of UV radiation doubles; at certain shorter
wavelengths, intensity rises by 10,000 times.
WORLD WITHOUT CONTROL
The polar winter leads to the formation of the polar
vortex which isolates the air within it.
Cold temperatures form inside the vortex; cold enough
for the formation of Polar Stratospheric Clouds (PSCs).
As the vortex air is isolated, the cold temperatures and
the PSCs persist.

Polar Stratospheric Clouds
1/12/2014
18
UV Light breaks CFC
apart.
Resulting Cl exists
either as ClO or as free
Cl.
Gases in atmosphere
react with ClO and Cl
to trap in inert
reservoirs of ClONO
2
and HCl

How PSC Help Chlorine Destroy Ozone
Without
With
PSC free Cl
2
from reservoirs.
ClO-ClO cycle begins once
sunlight breaks Cl
2
apart.
Cl atoms react with O
3
,
forming ClO and O
2
.
ClO forms dimer and breaks
down to Cl and O
2
. Cl attacks
ozone again
PSC prevent reservoirs from
forming by removing nitrogen
from atmosphere through
precipitation of HNO3.

1/12/2014
19
No ozone loss occurs until sunlight returns to the air
inside the polar vortex and allows the production of
active chlorine and initiates the catalytic ozone
destruction cycles.

Ozone loss is rapid. The ozone hole currently covers a
geographic region a little bigger than Antarctica and
extends nearly 10km in altitude in the lower
stratosphere.
MT. PINATUB0 ERUPTION
1/12/2014
20
Ozone reduction of 6-30%.
Pinatubo aerosols may be
responsible for the a loss
of 10% of Antarctic ozone
"before" the Antarctic
ozone hole formed in
1992.
Over the Antarctic ozone
was 50% lower than
normal between 13-16 km
altitude and was totally
absent between 16-18 km.
Ozone hole appeared
over Europe for the 1st
time.
Eruption caused low ozone record
1/12/2014
21
Measurements of Stratospheric Ozone
What has been done?
Montreal protocol
Ban of production of CFCs
Substitutes for CFCs

x
1/12/2014
22
About the Montreal Protocol

TOO LATE
NO COUNTRY TOOK IMMEDIATE ACTION
No practical action done by those signed!
CHEMICALS ALREADY IN ATMOSPHERE AND ATTACK OZONE
Chemicals were already produced!
MANY REFUSED TO SIGN
(China / India) unless they get some financial help in
their demand!
DEVELOPING COUNTRIES EXEMPTED
- do not have technology to switch alternatives


There are TWO SUBSTITUTES FOR CFCs
reactive in Earths lower atmosphere
lesser chance of their Cl and F components ever
reaching the stratosphere
Not ENTIRELY SAFER
react to form another type of acid rain detrimental to
wetlands


1/12/2014
23
UPDATES ON
STRATOSPHERIC OZONE
1/12/2014
24
Important points from article:
WARM Antarctic temperature = HELP UV-protecting
layer
Seasonal hole is at smallest maximum extent,
SECOND smallest average in 20 years
The average size of 2012 ozone hole at 17.7 million
square kilometers
COLD TEMPERATURES = DESTROY OZONE LAYER
Natural weather fluctuations led to warmer Antartic
temperature LIMITED damage
Stratospheric ozone
levels increases during
the next 30-50 years



The Montreal Protocol
provisions lower ozone-
depleting chemicals in
the upper atmosphere