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This document discusses ozone depletion and the formation of stratospheric ozone. It summarizes the key processes in the Chapman cycle that explain how ozone is formed and maintained in the stratosphere through a series of chemical reactions driven by solar radiation. It also describes how chlorofluorocarbons (CFCs) act as catalysts to deplete ozone levels by destroying ozone molecules. CFCs are identified as the primary cause of ozone layer depletion and the document outlines the global effort to phase out CFCs and other ozone depleting substances through agreements like the Montreal Protocol.

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31 views

2.course Material

This document discusses ozone depletion and the formation of stratospheric ozone. It summarizes the key processes in the Chapman cycle that explain how ozone is formed and maintained in the stratosphere through a series of chemical reactions driven by solar radiation. It also describes how chlorofluorocarbons (CFCs) act as catalysts to deplete ozone levels by destroying ozone molecules. CFCs are identified as the primary cause of ozone layer depletion and the document outlines the global effort to phase out CFCs and other ozone depleting substances through agreements like the Montreal Protocol.

Uploaded by

Neo
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
You are on page 1/ 25

ASL751

Dispersion of Air Pollutants

Ravi Kumar Kunchala


Centre for Atmospheric Sciences
Indian Institute of Technology, Delhi

Cont……
• 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 in the atmosphere

Timeseries of ozone profiles over Edmonton for 2002. From World Ozone
Data Centre (www.woudc.org)

• 90% of total column O3 is found in the


stratosphere
Good Ozone v. Bad Ozone
Good ozone Bad ozone
• located in the • produced in the
stratosphere. troposphere
• It traps ultraviolet rays • Called surface ozone or
• Protects human life ground level (O3)
• main component of
smog
• pollutant
Ozone production from NOx
Photochemical smog reactions
• N2 + O2  2NO
• 2NO + O2  2NO2
• NO2 + h  NO + O
• O + O2 + M  O3 + M
• O3 + NO  NO2 + O2

These reactions are cyclical with little net O3


Hydrocarbons and water can remove NO
Diurnal variations in NOx and O3
Ozone Concentration (ppm) Air Quality Air Quality
(8-hour average, unless noted) Index Values Descriptor

0.0 to 0.064 0 to 50 Good

0.065 to 0.084 51 to 100 Moderate

0.085 to 0.104 101 to 150 Unhealthy


(sensitive groups)
0.105 to 0.124 151 to 200 Unhealthy

0.125 (8-hr.) to 0.404 (1-hr.) 201 to 300 Very


Unhealthy
Nitrogen oxides (NOx)
 Very reactive.
 Formed by the oxidation of nitrogen gas (N2).
 Sources of nitrogen oxides include:
1. Urban traffic
2. Combustion processes (ex: vegetation fires)
3. Lightening storms (Australia and South Africa.)
NOx Sources

Estimates of annual global NOx emissions for the early 1990s. Units of
Tg-N/year.
• Biomass burning includes savannah burning, tropical
deforestation, temperate wildfires and agricultural waste
burning
• Soil emission
– enhanced by application of fertilizers
– largest uncertainty is in estimates of canopy transmission
• Lightning
– models use ~5.0 Tg-N/yr
– scaling up from observations suggest 20 Tg-N/yr
Weather Conditions
– During summers ozone is at highest levels
• Increased sunlight
• higher temperatures (> than 85o F).
• stagnating high-pressure systems
– During winter and wet and cool summers,
ozone levels are greatly reduced.
Influence of Weather and Episodic
Events on Ozone Formation
• The production of surface ozone air pollution:
– peaks in the later afternoon at low elevations
– remain high all day at higher elevations, such as in
the mountains.
– increase seasonally from April through September
• increased amounts of sunlight
• higher temperatures
• commonly occurring stagnating high-pressure systems
Effects of recurrent or long-term
exposure to ozone
• Some early evidence that long-term ozone exposure
may result in new asthma
– young children may be especially susceptible
• Prudent to avoid repeated short-term exposures,
particularly in young children, until more is known
• Each increase of 10 ppb ozone leads to a 4% increase
in deaths associated with respiratory disease
• 250,000 people die each year from respiratory disease
Stratospheric O3: Overview
Most O3 (90%) in
stratosphere.

Remaining 10% in
troposphere.

―Ozone layer‖ (15-30


km) is 3000 – 5000 ppb
of O3.

Surface O3 ~ 40 – 100
ppb.
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
Chapman Mechanism
Net O3 formation O2
hv slow
slow
Net O3 loss

Odd Oxygen Chemical


O
Familly
hv O2
Ox = O3 + O
Fast Fast

O3
Ozone
• Colorless gas
• Composed of three oxygen atoms
– Oxygen molecule (O2)—needed to sustain life
– Ozone (O3) —the extra oxygen atom makes ozone
very reactive
• Secondary pollutant that forms from precursor gases
– Nitric oxide – combustion product
– Volatile organic compounds (VOCs) – evaporative
and combustion products
Solar radiation and chemistry
• The reaction that produces ozone in the
atmosphere:
O + O2 + M  O3 + M
• Difference between stratospheric and
tropospheric ozone generation is in the source
of atomic O
• For solar radiation with a wavelength of less
than 242 nm:
O2 + hv  O + O
20
Solar radiation and chemistry
• Photochemical production of O3 in troposphere tied to NOx (NO + NO2)
• For wavelengths less than 424 nm:
NO2 + hv  NO + O
• But NO will react with O3
NO + O3  NO2

• Cycling has no net effect on ozone

AREP GAW, WMO Report


Ozone Chemistry
Summary of ozone chemistry Meteorology

• NO2 + Sunlight  NO + O Production


• O+ O2  O3 Production Emissions Chemistry

• NO + O3  NO2 + O2 Destruction
• VOC + OH  RO2 + H2O Production of NO2 without the
• RO2 + NO  NO2 + RO Destruction of O3
RO=Reactive Organic compound such as VOC
Key processes
• Ample sunlight (ultraviolet)
• High concentrations of precursors (VOC, NO, NO2)
– Weak horizontal dispersion
– Weak vertical mixing
• Warm air
22
AREP GAW, WMO Report
Ozone Precursor Emissions
● Man-made sources Meteorology

– Oxides of nitrogen (NOx) through


combustion
– VOCs through combustion and
Emissions Chemistry

numerous other sources


● Natural sources (biogenic)
– VOCs from trees/vegetation
– NOx from soils (Midwest fertilizer)
● Concentration depends on
– Source location, density, and strength
– Meteorology

AREP GAW, WMO Report


Relative Contributions to Ozone Loss

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