The Ozone Layer:

Formation and Depletion

 Outline of Lectures
• Introduction
– Structure and function of the ozone layer
– Briefly: health effects of ozone depletion
• Formation of the Ozone Layer
– The Chapman cycle
– Problems with the Chapman cycle
• Catalytic Destruction of the Ozone Layer
– General mechanism
– Sources of catalysts, including CFCs
– CFC-induced ozone destruction
– Relative contributions of different catalysts
– The ozone hole
• Phasing Out CFCs and other ODSs
– Global trends in stratospheric ozone and ground-level UV light
– The Montreal Protocol
 Ozone Layer: Function

• Question
– What does the ozone layer do for us?
– Ozone is the only major atmospheric
constituent that absorbs significantly
between 210 and 290 nm.
– Without it life would have remained
underwater
– The ozone layer is a consequence of
oxygen-only chemistry. It formed once
photosynthetic marine organisms
(cyanobacteria) began “polluting” the
atmosphere with oxygen.
Attenuation of Solar Flux in the Stratosphere

• Ground-level sunlight is
limited to l < 290nm
• Stratosphere filters out
light between 180 and
290 nm
• There is a “spectral
window” centered at
205nm where uv light
penetrates more deeply
into the stratosphere.
UV Absorption by Dioxygen and Ozone

O3
Health Effects of Ozone Depletion

• B(l) is the biological

“damage” function as a
function of wavelength

• F(l) is the light that

penetrates to ground level for
two different column ozone
levels: “normal” and
“depleted.”

•The product B(l)F(l) gives an

indication of the additional
biological damage potentially
caused by ozone depletion
 The Ozone Layer
• Lecture Questions
– At what altitudes is the ozone layer located?

• 16 – 35 km (above bkgd level)

• Stratosphere contains about 90%
of all atmospheric ozone
• Total column ozone: ~300 DU (1
DU = 0.3 cm thick layer at 1 atm)

– What is the maximum concentration of ozone in the ozone layer?

• Maximum of absolute conc about 23 km (up to 1013 molecules/mL)
• Maximum of relative conc about 35 km (up to 10 ppm)
 Structure of the Ozone Layer

Observations: (i) O3 is NOT the most concentrated gas in the ozone layer
(not even close!) (ii) maximum concentration is in the middle stratosphere.
Big question: why does the ozone layer exist in the stratosphere? What
processes are responsible for its formation and maintenance?
 The Chapman Cycle
• 1930
– Sydney Chapman proposed a series of reactions to account for the
ozone layer: the Chapman Cycle
• Lecture Question
– The Chapman Cycle explains how the ozone layer is formed and
maintained. Describe this process in some detail.
– Four chemical reactions
• Initiation O2 + light  2O (120 – 210 nm)

• Propagation (cycling)
O + O2 + M  O3 + M* (generates heat)
O3 + light  O2 + O (220 – 320 nm)

• Termination O3 + O  2O2
 The Chapman Cycle
Oxygen-only Chemistry

O2

O2 h O O3 O O2
10-4 - 10 s 60 - 3 min

h

“odd-oxygen” species (Ox) are rapidly interconverted

Ox = O + O 3
 Evaluation of Chapman’s Model
• How to evaluate Chapman’s Theory?
• Qualitative agreement:
– Predicts stratosphere as a source of ozone
– Predicts thermal inversion in the stratosphere
• Quantitative agreement?
– Check by comparing measured ozone levels with those predicted by
Chapman’s model
Problem with Chapman’s Model

• Qualitative agreement: presence of an

ozone layer at the right height; predicts
thermal inversion. But…
• Predicts too much ozone
• What is wrong?
– Either there is an extra source of Ox OR
– There are other sinks: pathways that
destroy ozone
 Missing Element –
Catalytic Destruction of Ozone

• Four main “families” of chemicals responsible for catalyzing ozone

destruction:
1. Nitrogen oxides: NOx
• NO + NO2
2. Hydrogen oxides: HOx
• OH + HO2 A common type of catalytic
3. Chlorine: ClOx destruction cycle (there are others)
• Cl + ClO
4. Bromine: BrOx Y+O3  YO+O 2
• Br + BrO
YO+O  Y+O 2
where Y = NO, OH, Cl or Br
 Sources of Catalysts
• Stratospheric NOx
– Source: tropospheric N2O
– Natural sources (mostly)
– 10% increase since 1850 (ie, due to anthropogenic activities...mostly
fertilizer application)
• Stratospheric HOx
– Source: tropospheric CH4, H2, H2O
– Much is natural, however...
– 150% increase in tropospheric CH4 since 1850 (agricultural activities;
landfills; other sources)
• Stratospheric Cl and Br
– Almost entirely due to human activity
– Sources: tropospheric CFCs, HCFCs, halons
 CFCs
• Lecture Question
– What are CFCs? What are they used for?

– CFCs are chlorofluorocarbons; they are small molecules that contain

chlorine, fluorine and carbon atoms. Usually there are only 1-2 carbon
atoms.
– CFCs are sometimes called Freons (that was their trade name for
DuPont)
– CFCs are referred to by a number. The most common CFCs are: CFC-
11, CFC-12, CFC-113 (formulas on the next page)
– HCFCs are CFCs that contain hydrogen. This makes them more
reactive to the OH radical, decreasing their tropospheric lifetime. That
means that, on a pound-per-pound basis, HCFCs (“soft CFCs”) destroy
less stratospheric ozone than CFCs (“hard CFCs”) because a smaller
fraction of HCFCs “survive” to reach the stratosphere
 Most Stratospheric Chlorine is Anthropogenic

Despite the fact that

CFC-11: CFCl3 tropospheric concentration
CFC-12: CF2Cl2 of HCl is far greater than
CFC-113: CF3CCl3 of CFCs, it is not a great
HCFC-22: CHF2Cl contributor of
stratospheric chlorine.

Aside: to convert a
CFC number to a
chemical formula, use
the “rule of 90.”
 Destruction of Ozone Layer by CFCs
• Lecture Question
– How do CFCs destroy ozone? Answer in some detail.

– “Hard” CFCs are unreactive to OH and other reactive radicals in the

troposphere. They are also pretty insoluble in water. That means their
tropospheric lifetimes are easily long enough that the majority of
tropospheric CFCs pass through the tropopause into the stratosphere.
– Once there, they are subject to light of shorter wavelengths (ie, more
energetic photons). In particular, many CFCs absorb in the “uv window”
(centered at 205 nm) between strong O2 and O3 absorption. That
means most can photodissociate in the bottom half of the stratosphere.
– Photodissociation releases chlorine atoms:
• For example: CFCl3 + light  CFCl2 + Cl (l < 225 nm)
– Chlorine atoms deplete odd oxygen (Ox) largely by the following cycle
• Cl + O3  ClO + O2
• ClO + O  Cl + O2
 Atmospheric Fate of CFCs

Vertical concentration profiles of “hard CFCs” consistent

with long tropospheric lifetimes followed by destruction in
the stratosphere.
 Chlorine in the Stratosphere
• Question
– Once released from CFCs, what happens to chlorine in the
stratosphere? How does it leave the stratosphere?

– Chlorine undergoes a series of reactions to form a variety of compounds

– Some of these are active in depleting ozone:
• Cl, ClO
– Some of these do not directly deplete ozone; these are chlorine
reservoirs
• HCl, ClONO2, HOCl
– The most important (long-lived) stratospheric chlorine reservoir is HCl
– The reservoirs can become activated by various processes such as
photodissociation or reaction with OH
– Loss of stratospheric chlorine occurs when they cross-back into the
troposphere and are removed from the atmosphere
• Most common route: HCl crosses back, dissolves in water, and is washed
out
Chlorine in the Stratosphere
•“CCly” refers to
CFCs and other
Main chlorine tropospheric
species is HCl sources of Cl
•Cly refers to the
statospheric
chlorine “family” of
active and
reservoir species
Relative Contributions to Ozone Loss
Relative contributions to ozone
loss by family
•Predictions from computer models
•Note that plots show relative
contributions, not absolute rate of
Ox destruction
•Remember that max Ox
concentration is at about 25km,
and max production/loss peaks at
about 40km
•NOx is the most important family,
particularly in the middle
stratosphere.
•HOx is most important at top and
bottom of stratosphere
•ClOx contributes up to 30% of
loss under typical circumstances
(exception: polar ozone holes)
 The “Ozone Hole”
• Lecture Questions
– What is the “ozone hole?” When did it first appear? How does it form?

The ozone hole is the region

over Antarctica with total
ozone 220 Dobson Units or
lower. (The avg total column
ozone in the atmosphere is
about 300 DU.)

Ozone hole in Sept 2005. Source: NASA

 Detection of the Antarctic Ozone Hole
global tropospheric
CFC-11

Crosses are BAS measurements;

triangles and circles are NASA satellite
measurements. Measurements are
October averages.

BAS reported their findings in

1985. NASA later verified their
results.
 Concentration Profile during Ozone Hole

The “ozone hole” is a sudden, marked depletion of ozone – a loss of 50% or more of
total column ozone – in the lower stratosphere of the Antarctic in the weeks after the
Spring sunrise. In 1985 the area of the hole was 10 million sq. km (and growing yearly).
What causes it???
Unique Feature of Antarctic Meteorology: Winter Vortex

•Polar vortex develops

during the winter
•Atmosphere is effectively
isolated from the rest of the
southern hemisphere
•Interior temperatures
plummet during long winter
night – large area is below
200K, and it can get as
cold as 180K
 Three Competing Theories
• Chlorine-induced
– Supported by the timing (ozone hole began appearing in the 1970’s),
BUT
– Existing chemical models inadequate
• Circulation-driven
– After sun rises, tropospheric upwelling “pushes” ozone out of the
vortex (ozone displacement, not destruction)
• Solar storms
– NOx created in upper stratosphere during winter
Concentration Gradients Develop Across Vortex

During ozone hole episode, polar region is very dry and denitrified
(low NOy). Concentrations of active chlorine (ClOx) increases
dramatically.
The “Smoking Gun” Points to Chlorine!
The Ozone Hole – Explained!
 Global Ozone Depletion (and Effects)
• Lecture Question
– How severe is ozone depletion now on a global scale?
– What was the name of the treaty signed to halt ozone depletion?

– Roughly 3% global stratospheric ozone has been depleted (averaged

globally – excepting the ozone hole – and annually)
– The Montreal Protocol was signed in 1987 by 46 countries, including the
US. It entered into force in 1989.
– By 1996, developed countries phased out use of CFCs, halons and
CCl4; developing countries have until 2010.
– Developed countries are scheduled to phase out production of HCFCs
by 2030; developing countries have until 2040.
Global Ozone Depletion Trends
Ozone and UV Trends
Effect of the Montreal Protocol on Stratospheric Cl