SCIENCE OF

THE
ATMOSPHERE
CHAPTER 3
M A R I N A M O K H TA R
 CO & PO FOR CEV420

Explain basic knowledge in environmental sciences to solve the

CO1 environmental problems (C6).

Propose solutions for environmental issues using basic knowledge in

CO2 environmental sciences (C6).

Ability to apply knowledge of mathematics, science, engineering

fundamentals to solve complex engineering problems in
PO1 chemical and environmental engineering.

Ability to engage in independent learning and life-long learning.

PO11
COURSE LEARNING
OUTCOMES:
The student should be able to:

• Identify the structure and characteristics of atmosphere

• Explain the initiation of atmospheric photo-reaction by
light energy.
• Describe the chemical transformation and sinks of
substance that occur in atmosphere
• Discuss on the ozone hole, greenhouse effect and global
warming scenarios.
CONTENT
1. Physical structure of the atmosphere
- layer
- pressure
- heat
2. The Earth’s weather
3. Trace gases and pollutants in the atmosphere
4. Solar energy
- Initiation of photochemistry by light
- Tropospheric oxidation chemistry
- Radiation
5. Ozone and global warming
• The atmosphere is the thin veil of gas molecules that separates the Earth
from the cold void of space. Its heat trapping ability helps to keep the
Earth warm enough for life, and it also protects the Earth from
harmful shortwave solar radiation and cosmic rays. This protective layer
was initially formed by gases vented during the geologic tumult of the
young Earth but was later altered by the work of photosynthesizing
organisms of the early biosphere, providing the oxygen we depend
upon. The atmosphere is a dynamic body that interacts with all the
“spheres” of Earth. The dynamism of the atmosphere can be witnessed
every day as it transfers solar heat from the equator toward the poles,
creating regular wind patterns such as the trade winds. Locally, we
experience this mass movement of air molecules as a gentle breeze or in
more rare and extreme instances, as hurricanes or tornados. The
atmosphere in motion also transfers water evaporated from the oceans
to the continents, providing precipitation critical to sustain terrestrial
ecosystems. Without the atmosphere, the Earth would be like a bigger
version of the moon – cold and lifeless.
PHYSICAL STRUCTURE OF 1

ATMOSPHERE
Atmosphere: The thin envelope of gases surrounding the
earth

 Highly compressible
 Density decreases rapidly with height

 Atmosphere can be divided into layers based on their

temperature. Each layer is called sphere & the boundary is
called pause
Study of the lower 1
atmosphere is known as
meteorology; study of the
upper atmosphere is
called aeronomy.

The Earth's atmosphere

is characterized by
variations of
temperature and
pressure with height.
 Troposphere* (10 km above the earth surface) 1
- Temperature decrease with altitude
- Most of atmosphere’s mass; all of its water

 Stratosphere* (10-15 km up to about 50 km)

- Ozone (O3) Layer (UV absorbing property)-plays a
major part in heating the air at this altitude.
- Vertical transport of material is slow, radiative transfer of
energy dominates.
- Temperature inversion
 1
 Mesosphere (surface to about 90 km)
- Region of large temperature extremes & strong turbulent
motion
- Air thin, pressure low
- Need oxygen to live in this region

 Ionosphere (above 100km altitude)

- Subdivided into 3 regimes (D, E and F)
- Characterized by the types of dominant photo ionization.
- Ionized layers reflect radio signals and very importance in
communication (satellite communication)
- Also the region for Aurorae
 1
 Thermosphere
- N2 & O2 gasses absorb high energy UV and dissociated
into atoms to O and N, the pressure is low
- “Hot Layer”-oxygen molecules absorb energy from solar
rays, warming the air.
- The temp. increases very rapidly with altitude about 200 –
2000 C
- Very few atoms and molecules in this region
1
AT WHAT ALTITUDE, THE 1

PLANE FLEW?
• The Ukrainian government had restricted airspace access over
the conflict zone to an altitude of 32,000 feet, but MH17 flew at
33,000 feet.
• It was a rainy day over eastern Ukraine, with occasional flashes
of lightning; some 27 minutes before the crash, the air traffic
controller in Dnipropetrovsk asked the pilots if they could go
higher — to 35,000 feet — to avert a conflict with another
plane. The pilots replied they would rather maintain altitude;
the dispatcher got the other aircraft to ascend, and the chance
that could have saved the MH17 was missed.
 VERTICAL PRESSURE 1

PROFILE
The atoms and
molecules that make
up the various layers
in the atmosphere
are always moving
in random
directions. Despite
their tiny size, when
they strike a surface
they exert pressure.

Atmospheric
pressure
decreases rapidly
with height.
 1

Each molecule is too small to feel and only exerts a tiny bit of
pressure. However, when we add up the all the pressures from the
large number of molecules that strike a surface each moment, then
the total pressure is considerable. This is air pressure. As the
density of the air increases, then the number of strikes per unit of
time and area also increases.
An aside: flying in commercial airliners. 1

Usually when you fly on a commercial airline, the pilot comes on

the loudspeaker and announces thank you for flying their airline,
the estimated time of arrival (ETA) and the height you'll be
flying, e.g., 39,000'.

Well, they are not exactly telling you the truth. Since pressure
changes from place to place, owing to weather systems,
temperature, and elevation, airliners will fly at a constant air
pressure rather than constant altitude.

So, for example, if the pilot sets the airline to fly at 265 mb, that
should be approximately 10 km (32,800'), but the actual
elevation above sea level is variable.
THE TRANSFER OF HEAT 1

ENERGY
• The heat source for our planet is the sun. Energy from the
sun is transferred through space and through the earth's
atmosphere to the earth's surface. Since this energy
warms the earth's surface and atmosphere, some of it is
or becomes heat energy.

• There are three ways heat is transferred into and through

the atmosphere:
- Radiation - Conduction - Convection
 1
• Radiation
Radiation is the transfer of heat energy through space by
electromagnetic radiation. A mixture of electromagnetic
waves ranging from infrared (IR) to ultraviolet rays (UV).

• Conduction
Conduction is the transfer of heat energy from one
substance to another or within a substance.

• Convection
Convection is the transfer of heat energy in a fluid.
1
THE EARTH’S WEATHER 2

• Earth is able to support a wide variety of living beings

because of its diverse regional climates, which range from
extreme cold at the poles to tropical heat at the Equator.
Regional climate is often described as the average weather
in a place over more than 30 years.

What is the difference between weather & climate?

• Weather  it means the instantaneous conditions within

the atmosphere
• Climate  it means monitors the mean conditions of
atmosphere over a period of time
 2
The key parameters in observing the weather especially in
the Earth’s troposphere:
– Air temperature
– Atmospheric pressure
– Wind speed and direction
– Rainfall
– Humidity
– The amount of cloud cover & the type of cloud
– Visibility

Collection of data from a network of weather stations

across the country and neighbouring countries and across
the seas not only will allow today’s weather to be
monitored, but also allow the weather forecasters to
predict what the weather may be tomorrow & several days
ahead.
TRACE GASSES AND 3

POLLUTION

About 90% of total

atmospheric mass exists in the
troposphere (chart) with
varying amounts of water
vapor depending on
temperature and altitude
TRACE GASES FROM THE 3

SURFACE
TRACE GASES FROM THE 3

SURFACE
 3

 Source of pollutant gases can be break-down into

its specific contributor
 See example of “Sources of emission in the UK”
 Sources of emission in other countries is expected
to be similar (using more or less similar technology
and performing similar activities)
3
OUTDOOR AIR POLLUTION 3

• Pollution is any addition of matter or energy that

degrades the environment for humans and other
organisms.
• Most air pollutants are gaseous but some are aerosols,
which consist of tiny particles of solid or droplets of
liquids suspended in the air.
CATEGORIES OF AIR 3

POLLUTANTS
1. can be categorized according to their source, whether
natural (unregulated) or anthropogenic or man-
made (regulated).

2. can also be categorized according to the way in which

they are formed in the atmosphere, primary or
secondary pollutants.
PRIMARY POLLUTANTS 3

• Pollutants that are emitted directly into the atmosphere

by natural events or human activities.
• These include CO, VOC, PM, SO2 and NOx.
SECONDARY POLLUTANTS 3

• Primary pollutants may react with one another in the

presence of sunlight to form new compounds that are
known as secondary air pollutants.
• Secondary air pollutants can also form from reactions with
substances that occur naturally in the atmosphere.
• Examples include O3, most NO3- and SO42- salts, H2O2,
aldehydes and PAN.
CRITERIA AIR POLLUTANTS 3

• The U.S Environmental Protection Agency (EPA)

and other countries has a category of air
pollutants known as criteria air pollutants.
• The U.S EPA has established air quality
standards for six principal air pollutants (thus
they are called criteria air pollutants)
• These include NO2, O3, SO2, particulate matter
(PM), CO and Pb.
• In addition, certain compounds with high toxicity
are known as hazardous air pollutants or air
toxics.
U.S. CRITERIA AIR 3

POLLUTANTS STANDARD
Air Pollutant Concentration
CO 9 ppm (8-hr average)
SO2 0.03 ppm (annual mean)
NO2 0.053 ppm (annual mean)
O3 0.08 ppm (8- hr average)
Pb 1.5 ug/m3 (3 mth average)
PM10 150 ug/m3(24-hr average)
PM2.5 65 ug/m3 (24-hr average)

Other Common Pollutants

Benzene No standards set (current levels below 2.5 ug/m3
VOCs No standards set but reductions needed
to reduce ground-level ozone.
EUROPEAN UNION AIR 3

QUALITY OBJECTIVES
Air Pollutant Concentration
CO 10 mg/m3 (8-hr average)
SO2 125 ug/m3( (24-hr average)
NO2 40 ug/m3(annual mean)
O3 120 ug/m3 (8- hr average)
Pb 0.5 ug/m3 (3- mth average)
PM10 50 ug/m3(24-hr average)
PM2.5

_______Other Common Pollutants_________________

Benzene 5.0 ug/m3
RECOMMENDED MALAYSIAN AIR 3
QUALITY
GUIDELINES (RMAQG)
There are no ambient air quality standards in
Malaysia. The Malaysian government, however,
established ambient air quality guidelines in 1988.

Pollutants addressed in the guidelines

 include O3, CO, NO2, SO2, total suspended
particles, PM10, Pb and dust fall.
 3

Pollutants Averaging ppm ug/m3

Time

Photochemical/Tropospheric 1 hr 0.10 200

ozone 8 hr 0.06 120

Carbon Monoxide 1 hr 30 35
8 hr 9 10

Nitrogen Dioxide 1 hr 0.17 320

24 hr 0.04

Sulfur Dioxide 1 hr 0.13 350

24 hr 0.04 105
 3
Pollutants Averaging Time ppm ug/m3

Particulate Matter 24 hr 150

(PM10) 1 Year 50

Total Suspended 24 hr 260

Particulate (TSP) 1 Year 90

Lead 3 month 1.5

Dust fall 1 Year 133

mg/m2/day
CARBON MONOXIDE (CO) 3

• Produced when organic materials such as

gasoline, coal, wood and trash are burnt with
insufficient oxygen.
• Any process that involves the burning of fossil
fuels has the potential to produce carbon
monoxide.
• The single largest source of CO is the
automobile.
• The remainder comes from other processes that
involve burning (power plants, industry, burning
leaves etc)
 3
• Although increased fuel efficiency and the use of catalytic
converters have reduced carbon dioxide emissions per
kilometer driven, CO remains a problem because the
number of automobiles on the road and the number of
kilometers driven have risen.
• In urban areas, as much as 90% of CO is from motor
vehicles.
• In many parts of the world, automobiles are poorly
maintained and may have inoperable pollution control
equipment, resulting in even greater amounts of carbon
monoxide.
• Fortunately, CO is not a persistent pollutant. It readily
combines with oxygen to form CO2.
HEALTH EFFECTS OF CO 3

• CO is dangerous because it binds to the hemoglobin in

the blood and makes the hemoglobin less able to carry
oxygen.
• CO is most dangerous in enclosed spaces where it is not
diluted by fresh air entering the space.
– Several hours of exposure to air containing only 0.001% of CO
can cause death.
• Since CO remains attached to hemoglobin for a long time,
even small amounts tend to accumulate and reduce the
blood’s oxygen carrying capacity.
• The amount of CO produced in heavy traffic can cause
headaches, drowsiness and blurred vision.
• Cigarette smoke is also an important source of carbon
monoxide.
PARTICULATE MATTER (PM) 3

 PM consists of minute (10 microns and smaller) solid

particles and liquid droplets dispersed into the
atmosphere.
 The EPA has set standards for particles smaller than
10 microns (PM10) and 2.5 microns (PM2.5).
 Most of the coarse particles (greater than 2.5
microns) are primary pollutants such as dust and
carbon particles that are released into the air.
 Roads, agricultural activities, construction sites,
industrial processes and smoke particles from fires
are primary sources of coarse particles.
 3

• Fine particles (less than 2.5 microns) are mostly

secondary pollutants that form in the atmosphere from
interactions of primary air pollutants.
• Sulfates and nitrates formed from sulfur dioxide and
nitrogen oxides are examples of fine particulates.
HEALTH AND OTHER EFFECTS 3

OF PARTICULATE MATTER
• Reduced visibility
• PM of asbestos is carcinogenic and can cause cancer.
• Particles can accumulate in the lung and interfere with
their ability to exchange gases.
• Sulfuric, nitric and carbonic acids, which irritate the lining
of our respiratory system, frequently are associated with
particulates.
SULFUR DIOXIDE 3

• SO2 is a compound of sulfur and oxygen that is produced when sulfur-

containing fossil fuels are burned.
S + O2  SO2
• There is sulfur in coal and oil and this sulfur combines with oxygen
when fossil fuels are burned.
• More than 50% of SO2 comes from industries and power plants.
HEALTH AND OTHER EFFECTS 3

OF SO 2
• SO2 has sharp odor
• Causes headaches, sore throats and nausea.
• Irritates respiratory tissue
• Aggravates asthmatic conditions
• Reacts with water, oxygen and other materials to
form sulfur containing acids.
– These acids can become attached to particles that
when inhaled, are very corrosive to lung tissue.
– These acid containing particles are also involved in
acid deposition.
OXIDES OF NITROGEN 3

• Burning of fossil fuels produces a mixture of nitrogen-

containing compounds commonly known as oxides of
nitrogen.
• The two most common molecules are nitrogen monoxide
(NO) and nitrogen dioxide (NO2).
• The primary molecule produced is nitrogen monoxide
(NO)
N2 + O2  2NO
• But nitrogen monoxide can be converted to nitrogen
dioxide in the air.
2NO + O2  2NO2
 3
• Primary source of nitrogen oxides is the
automobile engine which accounts for more than
50% of oxides of nitrogen released.
• Catalytic converters (act to convert approx 75%
of NO back to N2 and O2) significantly reduce
the amount of NO released from internal
combustion engines.
• However, the increase in the number of cars and
the kilometers driven, still has an impact in the
amount of nitrogen oxides produced.
HEALTH AND OTHER EFFECTS 3

OF NO 2
• NO2 is a highly reactive, reddish brown gas which is a
secondary pollutant.
• Causes respiratory problems
• Component of acid precipitation
• Important in the production of mixture of secondary air
pollutants called smog (especially ozone).
POLLUTANT STANDARDS 3

INDEX (PSI)
The United States Environment Protection Agency (USEPA) developed
the Pollutant Standards Index (PSI) to provide accurate, timely and
easily understandable information about daily levels of air pollution.

The index provides a uniform standard of measuring pollution levels for

the major air pollutants:

• PM10 (particulate matter less than 10 microns in size; 1 micron =

1/1,000th of 1 mm or 1 x 10-6 m);
• sulphur dioxide;
• ozone;
• carbon monoxide;
• nitrogen dioxide.
 3
The PSI value gives an indication of the air quality as shown:

PSI Value PSI Descriptor

0 to 50 Good
51 - 100 Moderate
101 - 200 Unhealthy
201- 300 Very Unhealthy
Above 300 Hazardous
AIR QUALITY INDEX (AQI) 3

• In the US, PSI is no longer in use, having been replaced by

the AQI, which is more sensitive. For example, particulate
matter with an aerodynamic diameter less than 2.5
micrometres (PM2.5) is a sub index, replacing the less
sensitive PM10 component of the PSI.
AIR POLLUTANT INDEX (API) 3

IN MALAYSIA
• In 1989, the Department of Environment (DOE)
formulated a set of air quality guidelines, termed
Recommended Malaysian Air Quality Guidelines
(RMAQG) for air pollutants, defining the concentration
limits of selected air pollutants which might adversely
affect the health and welfare of the general public.
• Based on the (RMAQG) , the Department subsequently
developed its first air quality index system, known as the
Malaysian Air Quality Index (MAQI) in 1993.
• An index system plays an important role in conveying to 3
both decision-makers and the general public the status of
ambient air quality, ranging from good to hazardous.
 Application of the index system, particularly in
industrialized countries, has demonstrated the useful role
in providing a sound basis for both the effective
management of air quality , as well as the effective
protection of public health.
 In line with the need for regional harmonization and easy
comparison with countries in the region, the
Department revised its index system in 1996, and the Air
Pollutant Index (API) was adopted. The API system of
Malaysia closely follows the Pollutant Standard Index (PSI)
system of the United States.
 3
• An air pollution index system normally includes the major
air pollutants which could cause potential harm to human
health should they reach unsafe levels.
• The pollutants included in Malaysia's API are
– photochemical/troposheric ozone (O3),
– carbon monoxide (CO),
– dinitrogenoxide (N02),
– sulphur dioxide (S02)
– and suspended particulate matter less than 10
microns in size (PM10).
 3
 Generally, an air pollution index system is
developed in easily understood ranges of values,
instead of using the actual concentrations of air
pollutants, as a means for reporting the quality of
air or level of air pollution.
 To reflect the status of the air quality and its
effects on human health, the range of index
values could then be categorized as follows :
good, moderate, unhealthy, very unhealthy
and hazardous.
Malaysian API Status Indicator 3
 SOLAR ENERGY 4

 located at center of the Solar System

 1,392,000 km in diameter
 A mass of 1000 times that of the rest of the Solar
System combined
 Composed of 70% H2 & the rest Helium
 Max. temp. can reach 15 million OC
 Total solar output into space ~ 2.33 x 1025 kJ/min
 SUNLIGHT 4

 All chemical reaction is initiated with an energy.

 Reactants must achieve its activation energy before its
convert into products (and by-products).
 Form of energy:

ENERGY

Heat Electricity Electromagnetic

irradiation (light)
 Light: electromagnetic field vibration 4

spreading in quanta
(photons)

Photon: the smallest amount of light

carrying energy
 The light source for photochemistry in the
atmosphere is the sun (over a wide spectral range)
 4
Chemical bond energies:
from 100 – 1000 kJ/mol

Light spectral range:

604 kJ/mol-1 302 151

ULTRAVIOLET VISIBLE INFRARED

200 nm 400 nm 800 nm

So UV – and VIS region is expected to induce chemical

reactions.
https://science.nasa.gov/science-news/science-at-nasa/2010/15jul_thermosphere
 4
The Earth's troposphere is an efficient oxidizing and "cleansing"
medium. Its capacity to remove carbon-based trace species and
pollutants, biogenic and anthropogenic, is determined by a
number of chemical and photochemical processes, initiated
mainly by hydroxyl radicals (•OH ) and depending on the levels of
nitrogen oxides (NOx ). An overview is presented on the major
tropospheric (photo)chemical reactions, involving mainly hydroxyl
(•OH ) and peroxy (HO2•) radicals, nitrogen oxides (NO and
NO2), ozone (O3), nitrate (NO3•) radicals and halogen atoms, and
organic peroxy and oxy radicals. The •OH radical is the most
important reactive species in the troposphere, since it is formed
in large amounts and because it reacts with the majority of the
chemical compounds emitted into the atmosphere from the
biosphere.
4
PHOTOCHEMISTRY BY LIGHT 4

a) Photodissociation / photolysis
h
X2 X + X (photodissociation)
(energy of the photon supplies the “dissociation heat”)
b) Photosynthesis
h; chlorophyll
6CO2 + 6H2O C6H12O6+6O2
several steps
carbohydrate

c) Photosensitized reactions

AgBr h AgBr*
4
TROPOSPHERIC/ 4

PHOTOCHEMICAL OZONE
• Highly reactive, irritating gas with an unpleasant odor that
forms in the troposphere as a major component of
photochemical smog.
• Ground-level or troposheric ozone is produced in the
presence of sunlight when nitrogen dioxide breaks down
to nitrogen monoxide and atomic oxygen:
NO2  NO + O*
O* + O2  O3 (tropospheric ozone)

Atomic oxygen is extremely reactive and will react with

molecular oxygen in the air to form ozone.
HEALTH EFFECTS OF 4

GROUND-LEVEL OZONE
• Breathing problems
• Coughing
• Eye, nose and throat irritation
• Aggravates chronic diseases such as asthma, bronchitis,
emphysema, and heart disease.
• Reduces resistance to colds and pneumonia
• May speed up lung tissue aging.
 4
Other effects
• Can damage plants (destroys chlorophyll), and trees.
• Damages rubber, fabrics and paints.

• During late afternoons or early evenings, the

concentration of ozone increases and dominates the API
readings in some places.
• In sunlight, oxides of nitrogen and volatile organic
compounds (VOCs) from motor vehicle exhaust and
industries react to form tropospheric ozone.
TROPOSPHERIC OXIDATION 4

CHEMISTRY
N2 and O2 are by far the most abundant gases in the
atmosphere.
Crucial importance of the stratospheric layer of ozone, O3.
Oxygen reacts with atmospheric chemical species.

Through action of intermediate species, particularly

hydroxyl radical, HO,
 SO2 is converted to H2SO4
 CO is converted to CO2
 4
Atmospheric oxygen comes from photosynthesis
CO2 + H2O + h {CH2O} + O2
where {CH2O} is a generic formula representing biomass

Nitrogen in the atmosphere:

 Atmospheric N2 is very unreactive
 Most important reaction of N-containing species in the
atmosphere
NO2 + h  NO + O
 Reactive O atom initiates many tropospheric
photochemical reactions.
 4
• Degradation of atmospheric pollutants starts with the OH
radical (•OH )
• •OH is often called ‘the detergent of the atmosphere’
• •OH is very reactive because it has an unpaired electron:
•O-H
• Measuring •OH is hard! There’s not much of it, and it doesn’t
live for long
• Tropospheric oxidation results in ground level O3, which is a
greenhouse gas harmful to health

O3 + h  O* + O2
O* + H2O  2 •OH
 SOLAR RADIATION AND 4

ENERGY
• If the solar photon energy is > ionization energy of
molecule then the molecule may be photo-ionized by
the incident solar photons (E = hv)  positive ions & free
electrons
• This is the process the Earth’s ionsphere is formed &
absorbs much of the Sun’s far UV radiation below 150 nm
SOLAR RADIATION AND 4

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
• photochemical production of O3 in troposphere 4
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

O3-NO-NO2 photochemical steady state 4

• consider the two reactions just seen

NO2 + hv (+O2)  NO + O3 J1
NO + O3  NO2 K1

• ignoring other reactions, during daylight this

forms a fast cycle in steady-state
d[NO2]/dt = Prod - Loss = 0
K1[NO][O3] = J1[NO2]
[NO]/[NO2] = J1/K1[O3]
• partioning of NOx between NO and NO2 has
important implications for removal of NOx
from the atmosphere
• presence of peroxy radicals, from the oxidation of 4
hydrocarbons, disturbs O3-NO-NO2 cycle
NO + HO2 •  NO2 + • OH
NO + RO2 •  NO2 + RO •
– leads to net production of ozone
OXIDATION OF CO - 4

PRODUCTION OF OZONE
CO + •OH  CO2 + H•
H• + O2 + M  HO2• + M
NO + HO2•  NO2 + OH•
NO2 + hv  NO + O
O + O2 + M  O3

CO + 2O2 + hv  CO2 + O3
WHAT BREAKS THE CYCLE? 4

• cycle terminated by
OH• + NO2  HNO3
HO2• + HO2•  H2O2
• both HNO3 and H2O2 will photolyze or react with OH to,
in effect, reverse these pathways
– but reactions are slow (lifetime of several days)
– both are very soluble - though H2O2 less-so
• washout by precipitation
• dry deposition
– in PBL they are effectively a loss
– situation is more complicated in the upper
troposphere
• no dry deposition, limited wet removal
METHANE OXIDATION CYCLE 4

• CH4 is simplest alkane species

– features of oxidation cycle common to other organic
compounds
• long photochemical lifetime
– fairly evenly distributed throughout troposphere
– concentrations ~1.8ppmv
• reactions form ‘bedrock’ of the chemistry in the
background troposphere
 CH4 + •OH  CH3• + H2O 4
CH3• + O2 + M  CH3O2• + M
CH3O2• + NO  CH3O• + NO2
CH3O• +O2  HCHO + HO2•
HO2• + NO  •OH+ NO2
2{NO2 + hv (+O2)  NO + O3}

CH4 + 4 O2 + 2 hv  HCHO + 2O3 + H2O

HCHO will also undergo further reaction

HCHO + hv  H2 + CO  H• + HCO
HCHO + OH  HCO + H2O
HCO + O2  HO2• + CO
H• + O2  HO2•
CYCLE LIMITING REACTIONS 4

OH• + NO2  HNO3

HO2• + HO2•  H2O2
but also
HO2• + CH3O2•  CH3OOH + O2

• methyl hydroperoxide (CH3OOH)

– can photolyze or react with OH with a lifetime of ~ 2 days
• return radicals to system
• important source of radicals in upper tropical troposphere
– moderately soluble and can be removed from atmosphere by wet
or dry deposition
• loss of radicals
CONCEPTUALLY 4

• photolysis of ozone most significant source of OH

• atmospheric oxidation of hydrocarbons initiated by OH
radical
– production of peroxy radicals (HO2, RO2) which interact with
O3-NO-NO2 cycle to photo-chemically produce ozone
– produce carbonyl compounds (aldehydes and ketones) which
undergo further oxidation
– recycling of OH
• termination by formation of nitric acid (OH + NO2 
HNO3) or peroxides (H2O2, ROOH)
NITROGEN SPECIES 4

• NOx (NO + NO2) plays a critical role in the atmospheric

oxidation of hydrocarbons
• short chemical lifetime
– from ~ 6 hours in PBL to several days to a week in the
upper troposphere
• large variations in concentration
– from 10s ppbv in urban areas to 10s pptv in remote
regions (UT and remote MBL)
• gives rise to different chemical regimes
REGIONAL OZONE PERSPECTIVE - 4

O 3 PRODUCTION
• More accurate to talk of NOx/VOC ratio
• VOC - volatile organic carbon
• High NOx/VOC environments
– OH reaction with NO2 dominates
– NO-NO2 cycling inefficient compared with NOx loss
– only found in urban areas
• Low NOx/VOC environments
– high peroxy radical concentrations
– peroxy radical self-reactions become important sink for radicals
• production of H2O2 and ROOH
GLOBAL PERSPECTIVE 4

• NOx concentrations almost always low enough that ozone production

is NOx limited
• globally NOx concentrations control whether local chemistry creates
or destroys ozone
• for [NOx] less than ~20 pptv, chemistry results in net ozone
destruction
– no NOx to turn-over the NO-NO2 cycle
O3+ hv  O(1D) + O2
O(1D) + H2O  2 OH·
– also
HO2· + O3  OH· + 2 O2
– particularly important in tropical marine boundary layer
OTHER NITROGEN SPECIES 4

• Peroxyacyl nitrates (PANs)

– most important being peroxyacetyl nitrate
• CH3C(O)OONO2
– formed from oxidation of acetaldehyde
CH3CHO + OH· (+ O2)  CH3C(O)O2 + H2O
CH3C(O)O2 + NO2 + M  CH3C(O)O2NO2 + M
– decomposition is strongly temperature dependent
• from 30 minutes at 298K near the surface to several months
under upper tropospheric conditions
• NOx exported from boundary layer to remote troposphere
in the form of PAN
– observations show PAN is dominant NOy compound in northern
hemisphere spring troposphere
• insoluble
HALOGENS (Cl AND Br) 4

• Also known as a compound that destroy ozone

• Source: Chlorofluorocarbons (CFCs)
- Used as commercial refrigerants (Freon-) and
propellants.
- Trichlorofluoromethane (CCl3F), CCl2F2
OZONE AND GLOBAL 5

WARMING
• Ozone was required for the evolution of life on land
• Possibly as a result of photosynthesis
• Originally studied in mid-1800s
• Comes from Greek word ozein meaning smell
– Creation and destruction of ozone, not ozone itself, has a strong
odor
• O3 absorbs radiation in the 200-400 nm range
– UVA: 320-400 nm. Responsible for tanning process
– UVB: 290-320 nm. Causes sunburn, cancer, eye damage, inhibits
photosynthesis, harms plankton, etc.
– UVC: 200-290 nm. Used to be called “death rays”. Can completely
ruin DNA.
5
5
CHAPMAN CYCLE (NATURAL 5

OZONE)
• O2 + UV light  2O

• O + O2  O3 (exothermic)

• O + O3  2 O2 (exothermic)

• O3 + UV light  O + O2
THE OZONE HOLE 5

• In 1985 Dr Joe Farman (British Antarctic Survey)

discovered that the concentration of ozone in the
stratosphere over the Antarctic had been
decreasing since the early 1970s by up to 50%.
The ‘hole’ appears in spring ie September –
October, each year.
• An ozone hole has also been observed over the
Arctic since the mid 90s.
TOMS ozone: shows strong spatial variability. Low 5
around equator, high in mid-latitude, very low at
Antarctic (especially around this time of year).
WHAT CAUSES THE OZONE 5

HOLE?
• Synthetic chlorinated fluorocarbons (CFCs or Freons) are
man-made molecules and were used as propellants in
spray cans, as gases in the production of foams and in
refrigeration systems.
• CFSs are extremely stable and eventually find their way up
to the stratosphere.
 DEPLETION OF OZONE IN THE 5

STRATOSPHERE
Anthropogenic O3 destruction

UV
CFCl3 CFCl2 + Cl
UV
CF2Cl2 CF2Cl + Cl

+ Cl + O3 ClO + O2
ClO + O Cl + O2
O3 + O 2O2

Cl catalyzes the reaction

 5
• One Cl radical can destroy up to 100,000
ozone molecules.
• Chlorine radicals are eventually removed by
reactions:
– Cl + CH4  HCl + CH3
– ClO + NO2  ClONO2
IS THE CLIMATE BECOMING 5

WARMER AND WARMER?

• According to the National Academy of Sciences, the Earth's surface
temperature has risen by about 1 degree Fahrenheit in the past
century, with accelerated warming during the past two decades. There
is new and stronger evidence that most of the warming over the last
50 years is attributable to human activities. Human activities have
altered the chemical composition of the atmosphere through the
buildup of greenhouse gases – primarily carbon dioxide, methane, and
nitrous oxide. The heat-trapping property of these gases is undisputed
although uncertainties exist about exactly how earth's climate
responds to them. (source:US-EPA)
GLOBAL TEMPERATURE TREND 5
NOTE THAT THESE ARE SURFACE TEMPERATURES AND MOSTLY OVERL AND.
THE TEMPERATURE IN UPPER LEVELS MAY BE DIFFERENT, EVEN REVERSED.
GLOBAL WARMING

Global warming refers to the upward temperature trend

across the entire Earth since the early 20th century, and
most notably since the late 1970s, due to the increase in
fossil fuel emissions since the industrial revolution.
Worldwide since 1880, the average surface temperature has
gone up by about 0.8 °C (1.4 °F), relative to the mid-20th-
century baseline (of 1951-1980).
WHAT CAUSE GLOBAL 5

WARMING?
• There are many possible mechanisms that can cause the warming of
the atmosphere, for example:
– Natural variation – the climate becomes warmer by internal
chaotic dynamics of the earth-atmosphere system (that is, no
external influence).
– Solar activity – either direct increase of solar energy output or
indirect “trigger” mechanisms due to solar activity (though
nobody knows how) may cause the surface temperature to go up.
– Greenhouse effect – increasing “greenhouse” gases such as
CO2, CH4, NO, CFC,…etc. (actually H2O is very efficient, too, but
at present it is assumed to be in steady state).
• The last one is presently thought to be the most likely cause of the
global warming and hence we will examine it here in this chapter..
GREENHOUSE EFFECT 5

• The greenhouse effect is a natural process that warms the

Earth’s surface. When the Sun’s energy reaches the Earth’s
atmosphere, some of it is reflected back to space and the
rest is absorbed and re-radiated by greenhouse gases.

• Greenhouse gases include water vapour, carbon dioxide,

methane, nitrous oxide, ozone and some artificial
chemicals such as chlorofluorocarbons (CFCs).
 5
• The absorbed energy warms the atmosphere and the
surface of the Earth. This process maintains the Earth’s
temperature at around 33 degrees Celsius warmer than it
would otherwise be, allowing life on Earth to exist.

Enhanced greenhouse effect

• The problem we now face is that human activities –
particularly burning fossil fuels (coal, oil and natural gas),
agriculture and land clearing – are increasing the
concentrations of greenhouse gases. This is the enhanced
greenhouse effect, which is contributing to warming of the
Earth.
 5

Step 1: Solar radiation reaches the Earth's atmosphere - some of this is reflected back into space.
Step 2: The rest of the sun's energy is absorbed by the land and the oceans, heating the Earth.
Step 3: Heat radiates from Earth towards space.
Step 4: Some of this heat is trapped by greenhouse gases in the atmosphere, keeping the Earth warm enough to
sustain life.
Step 5: Human activities such as burning fossil fuels, agriculture and land clearing are increasing the amount of
greenhouse gases released into the atmosphere.
Step 6: This is trapping extra heat, and causing the Earth's temperature to rise .
ATMOSPHERIC CARBON 5

DIOXIDE
• This chart shows a steady increase of CO2 concentration in the last
five decades. Although this chart is based on Mauna Loa’s data, the
same trend has been found in many other places.
SOUTH POLE AND BARROW, 5

ALASKA, SHOW THE SAME

TREND AS HAWAII
HOW IS THE CO 2 INCREASE 5

CONNECTED TO THE GLOBAL

WARMING?
• Physically, via the greenhouse effect.
• The connection is usually made via the use of a
climate model.
• Control run versus scenarios.
• If the scenario run results show warmer surface
condition than the control, then it is plausible to
suspect that the increasing CO2 concentration in the
atmosphere may cause warming.
THE DEGREE OF WARMING WILL 5

NOT BE UNIFORM EVERYWHERE

HIGHER L ATITUDES ARE MORE SENSITIVE

Source: IPCC
5
5
IF TEMPERATURE CAN CHANGE, SO DO OTHER
METEOROLOGICAL AND ENVIRONMENTAL VARIABLES. 5

• The change in
temperature may cause a
change in precipitation.
• Vegetation may also
change in response to
temperature and
precipitation changes.
• And there will be changes
in the animal and human
world in response to
these environmental
changes.

Source: NOAA
CLIMATE CHANGE 5

Climate change refers to a broad range of global

phenomena created predominantly by burning fossil fuels,
which add heat-trapping gases to Earth’s atmosphere. These
phenomena include the increased temperature trends
described by global warming, but also encompass changes
such as sea level rise; ice mass loss in Greenland, Antarctica,
the Arctic and mountain glaciers worldwide; shifts in
flower/plant blooming; and extreme weather events.