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
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 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
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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