Ozone Depletion

What is the “ozone layer?”

How does it protect us?
How did it come about?
 Evolution of the Ozone Layer
Early planet history:
– no ozone present

– UV light directly
hit planet’s surface

– Oceans provided
only refuge from
UV radiation
Oxygen in the Atmosphere
O
UV
O2 + radiation +

O +
O2 O3 (ozone)
 O +
UV + O3
(ozone) O2

O + O3 O2 + O2
(ozone)

+
O + O2 O3
(ozone)
heat
 Dynamic Equilibrium
creation of ozone

breakdown of
ozone
 Anthropogenic Ozone Depletion
creation of ozone

breakdown of
ozone
 Modern Impacts to Ozone

Chlorofluorocarbons (CFCs)

• What are they?

• How do they impact the ozone layer?
 Development of CFCs
1928: DuPont scientists develop CFCs
“ideal compounds” for
refrigerants and propellants

WHY??
 CFCs as Refrigerants
Traditional Refrigerants vs. CFCs
(ammonia, sulfur dioxide, methyl chloride)

- Highly volatile - Non-flammable

- Caustic and toxic - Non-toxic

- Remove heat through - Trap heat

vaporization of liquefied gas (good insulators!)
(only adequate as refrigerants) - Inexpensive
- Expensive - Light
- Heavy (transport, storage) -Extremely stable,
inert
 CFCs as Propellants
• Light weight
• Extremely stable or “inert”

What are the consequences of these two

physical characteristics?

• CFCs likely to migrate upwards

• Too light to precipitate out with rainfall
• 5-15 years to migrate to stratosphere
 Marketing of CFCs
1958: DuPont releases CFCs on the market
commercially
1971: James Lovelock speculates that CFCs
put into the atmosphere may still be
present
1973: Mario Molina and F. Sherry Roland
start to investigate
 Original Research
1974: Rowland and Molina
Cl
C
F
Cl
UV F
C
+ radiation
F Cl +
F Cl-
“free
radical”
 Cl- “Free Radicals”…

+ +
Cl- O3
ClO O2
“free radical” (ozone)

+ +
O
ClO Cl- O2
“free radical”
 In the news…
1974: Molina and Rowland publish their
hypothesis in Nature.
New York Times runs front page
DuPont responds with study
showing that CFCs in troposphere
are benign
 High Risk and Political Savvy
1975: 200% increase in CFC use from
1968, only eight years
1979: The FDA, EPA ban non-essential
uses of CFCs !
First time substance EVER banned
without direct proof of harm
1982: 20 other countries join US in ban of CFCs
 Scientific Controversies

1982: British science teams in Antarctica

observe 20% decline in O3 layer
US scientists relying on TOMS
(Total Ozone Mapping
Spectrometer) measurements from
space claim to observe nothing
 Scientific Evidence
1983: British scientists observe 30%
reduction in ozone layer.
US scientists claims no reduction.
1985: British observe 50% reduction.
US claims no reduction.
US re-tests and confirms.
WHY THE SCIENTIFIC SNAFUS??
 Total ozone

Total ozone measured above Antarctica,

in Dobson Units. From Horel and Geisler, 1996
TOMS Data (corrected)
October Average for
Total Ozone over
Antarctica, 1955-1995

Based on British
measurements from
weather balloons
 Understanding the Science
1986: DuPont scientists continue to argue
that tropospheric ozone (smog)
will migrate up and “fill the ozone
hole” in the stratosphere

Why doesn’t this theory fly?

 Location of Stratosphere

Exosphere 400 km

Thermosphere 300 km

Mesosphere 50 km
Stratosphere 40 km
10 km
Troposphere
 Montreal Protocol Landmark
1987: 2 yrs of intensive research reveal
that ozone hole is anthropogenic
1988: UN hold meeting in Montreal
45 Nations sign to reduce CFC use
by 50% by year 2000.
Developing countries’ efforts
would be ‘subsidized’
 Two steps forward…
1990- Follow up meetings result in:
1992: Industrialized nations: total ban by 2000
Developing nations: ban by 2010, with
assistance from developed nations

US agrees to complete phaseout by 1996;

DuPont to halt production by 1997

1995: Rowland and Molina receive Nobel Prize

 One step back…
1995: Congress challenges ozone science:
Junk science gains credibility
despite scientific consensus of
anthropogenic causes of O3 depletion
1996: Ban begins but black market for CFCs appear
WHY?
CFC substitutes (HFC) break down faster, but still
pose problems for ozone depletion
 Modern Impacts to Ozone (2)

Methyl Bromide

• What is it?
• Challenges to Montreal Protocol
Methyl Bromide
 Uses of Methyl Bromide
60 million lbs /yr in US

• Agricultural (75%)
– Strawberries
• Stored products (11%)
• Flame retardants (6%)
• Pest management (6%)
– Termite removal
• Chemical production (2%)
 Schedule for Elimination
1991: Designated Class I ozone depleter
in Montreal Protocol
1997: Agreed to following schedule
Developed Countries—elimination by 2005
Developing Countries—elimination by 2015
Requests for “Critical Use Exemptions”
 US Strawberry Industry
• US supplies 80% of
plants from nurseries
or strawberries to
world market

• Average consumption:
4 lb/person/yr
 Benefits of Methyl Bromide
• Worker safety
– Non-toxic
– Reduces need for toxic
pesticides
• Economical
• Easy-to-Use
• Effective
 Alternatives
• Fumigants applied
through drip irrigation
• Harnessing “good
microbes”
• Composting for weed
suppression
• Soil solarization
• Crop rotation
Effectiveness
• Other fumigants do
not work
• Worker health issue
• Lower yields
• Loss of nurseries
– Even organic farms get
plant stocks from
nurseries that rely on
methyl bromide
 CFCs vs MEBr
Why did one industry eventually support
ban while another is struggling and begging
for exemptions?

Methyl Bromide CFCs

-no viable alternatives -DuPont developed HFCs
 Another potential threat?
Hydrogen Fuel Cells
 Production of Hydrogen
• Anticipate that 10% of all hydrogen
manufactured will leak into the atmosphere
during production, storage and transport.
• Current loss is higher
• Estimate: 60 million tons / year
• Roughly doubles current input (all sources)
 Hydrogen chemistry
• Hydrogen is light—rises rapidly to
stratosphere
• Reacts with oxygen to form water
• A “wetter” atmosphere would cool the
lower stratosphere, especially around Poles
• Increase in water vapor is catalyst for ozone
depletion by freeing Cl free radicals
 Spatial and Temporal Patterns
• Poles have greater ozone loss than other
regions:
– Colder
– More vapor formation
– Also: polar vortex
• Particularly severe in polar spring (October)
• Increased hydrogen would enhance this
phenomenon
Ozone Layer Impacts
• 7-8% depletion around
Poles anticipated
• Depends upon if and
how quickly hydrogen
economy introduced
• If >50 years, may not
be critical issue
• Possible work to
lessen H leakage
Current Status of Ozone Hole

Extent of ozone depletion:

1981— 900,000 sq mi
2001—17,100,000 sq mi
 Location of Ozone Losses

Ozone loss extends beyond Antarctica and

Arctic Polar regions
Ozone loss over US currently 5% below
normal rates
Current Rate of Ozone Depletion

• Decrease in rate of ozone depletion (since 1997)

• Slowing of buildup of harmful Cl- from CFCs
• Ozone hole is still growing, but…
Models anticipate restoration of “normal”
balance of ozone in stratosphere by 2050
 Impacts of Ozone Depletion
Human Health
• Skin cancer
• Melanoma
• Cataracts
• Immune system function
• Increased incidence,
severity and duration of
infectious diseases
• Reduced efficacy of
vaccinations
Ecological Health
• Pathogen locally up &
down
• Biodiversity locally up &
down
• Aquatic organisms
adversely impacted
• Decreased biomass
productivity
• Polar systems especially
vulnerable
 Impacts of Ozone Depletion
Economic
• Plastics
– designed with stabilizers to withstand UV radiation of
certain intensity
– replacement of key medical equipment and supplies,
decreased lifespan of plastics
• Manufacturing practices
• Agriculture
• Consumer costs and burdens
Breakdown of Sources
A ero so ls
5% Other P ro ducts
12%

So lvent Cleaning
P ro ducts
Fo am P ro ducts 36%
14%

Refrigeratio n
and A ir
Co nditio ning
30%

Sterilizatio n
3%
 Success Story

What characteristics define ozone depletion

“an environmental success story ?”