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 < 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() is the biological
damage function as a
function of wavelength
F() is the light that
penetrates to ground level for
two different column ozone
levels: normal and
depleted.
The product B()F() 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

O3

10-4 - 10 s

60 - 3 min

h
odd-oxygen species (Ox) are rapidly interconverted
Ox = O + O 3

O2

Evaluation of Chapmans Model

How to evaluate Chapmans 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
Chapmans model

Problem with Chapmans 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:
Nitrogen oxides: NOx

1.

2.

NO + NO2

Hydrogen oxides: HOx

3.

OH + HO2

Chlorine: ClOx

4.

Cl + ClO

Bromine: BrOx

Br + BrO

A common type of catalytic

destruction cycle (there are others)

Y+O3 YO+O 2
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: CFC11, 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

CFC-11: CFCl3
CFC-12: CF2Cl2
CFC-113: CF3CCl3
HCFC-22: CHF2Cl

Aside: to convert a
CFC number to a
chemical formula, use
the rule of 90.

Despite the fact that

tropospheric concentration
of HCl is far greater than
of CFCs, it is not a great
contributor of
stratospheric chlorine.

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 ( < 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

Main chlorine
species is HCl

CCly refers to
CFCs and other
tropospheric
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

Circulation-driven

Supported by the timing (ozone hole began appearing in the 1970s),

BUT
Existing chemical models inadequate
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