EnE 250 Air Pollution

Lecture 2

Sources, Sinks, Health & Environmental Impacts

Analiza P. Rollon
Department of Chemical Engineering
College of Engineering
University of the Philippines
Atmospheric pollution

Introduction

• The major atmospheric

pollutants

• The impacts of
combinations of
atmospheric pollutants

Summary
Introduction

• Primary pollutants: Environmentally damaging

materials that arise as the result of either man-
made or natural processes.

• Secondary pollutants: Products of reactions

involving primary pollutants.
Sources of primary air pollutants
Air pollutants:
Residence time, highly variable
Outline

Major atmospheric
pollutants

• SO2
• Oxides of nitrogen
• Hydrocarbons
• Oxides of carbon
• Halogenated hydrocarbons
• Suspended particulates (aerosols) in
the troposphere
Sulfur dioxide (SO2)

Detectable at > 1 ppm

• Sense of smell is lost at > 3 ppm

Concentrations at the trophosphere

• areas far from industrial activity: < 1 ppb

• highly polluted areas: 2 ppm
• urban and industrial countries: 0.1 - 0.5 ppm
• rural areas of northern hemisphere:  30 ppb
Sulfur dioxide
(SO2)

Detectable at > 1 ppm

• Sense of smell is lost at
> 3 ppm

Concentrations at the
troposphere:
• areas far from
industries: < 1 ppb
• highly polluted areas: 2
ppm
• urban and industrial
countries: 0.1 - 0.5 ppm
• rural areas of northern
hemisphere:  30 ppb
Sulfur dioxide
Source: comes largely from burning of fossil fuels
Sulfur dioxide
Global estimate of sulfur emissions for the year 2020!
Natural Sources of SOx, etc.
• Volcanoes: SO2, H2S, COx, particles,
H2O, CO2, HCl…
The sulfur cycle
Oxides of nitrogen

• Nitrous oxide (dinitrogen oxide), N2O

• Nitric oxide (NO)

• Nitrogen dioxide (NO2)

The nitrogen cycle
What happens to NOx in the
troposphere?
Hydrocarbons: Methane (CH4)

 Natural source: Produced almost entirely by microorganisms

under anaerobic conditions (ex. Wetlands, intestines of
ruminant animals) - (8.6 x1012 - 2.9 x 1013 mol C per year)

 Human activity: 1.5 x1013 - 3.6 x 1013 mol C per year

 from paddy rice production
 low temperature biomass burning
 cattle rearing
 waste disposal
 fossil fuel extraction
Hydrocarbons: Methane (CH4)
Main reactions in the day-time tropospheric oxidation of methane
Hydrocarbons: Methane (CH4)
Historical changes in the tropospheric methane levels
Oxides of carbon

• Carbon monoxide (CO)

• Carbon dioxide (CO2)

The carbon cycle
Oxides of carbon: CO2

CO2 from human activity

• burning fossil fuels and biomass (ex. During forest clearance)
• Anthropogenic flux: 4 x1014 - 1.7 x1014 mol C per year
• Deforestation  decrease in photosynthetic sink of CO2

Effects of higher temperature

• decrease in solubility of gases in water
• decrease in flux of CO2 from oceans.
• At high temperature and high levels of CO2 rate of
photosynthesis may also increase.
Oxides of carbon: CO

• Generated biologically (on land and within oceans)

• Produced as a consequence of atmospheric
oxidation of hydrocarbons

• Natural flux: 1.8 x 1013 mol C per year

• Anthropogenic: 2.7 x 1013 mol C per year, increasing

• Background level of CO: > 0.1 ppm

• 2 - 20 ppm in urban location
• > 100 ppm in tunnels, heavy road traffic,
places with restricted air movement

• Northern hemisphere is more contaminated with CO

than the southern hemisphere.
CO concentrations across latitudes
Health concerns with CO

• CO combines with blood oxygen carrier, haemoglobin

(Hb)
HbO2 + CO <-> O2 + HbCO
HbO2 = oxygenated haemoglobin
HbCO = carboxyhaemoglobin

• This reaction can result in insufficient O2 supply to vital

organs.  decrease in behavioral effectiveness.

CO is implicated in increased incidence of road traffic

accidents in highly polluted areas.
Environmental concerns with CO

• High emissions of CO

 Reduce tropospheric concentrations of OH

radicals

(Reaction with OH is a major sink for other

contaminants)

 Reduce rate of removal of many other pollutants

• CO is a greenhouse gas  global warming

Halogenated Hydrocarbons
Halogenated hydrocarbon:  1 H is replaced by F, Cl, Br, I

Example: CFCs (chlorofluorocarbons)

 No natural source, introduced in the 1930’s by Du
Pont & Gen. Motors
 CFC-11 (CCl3F), 0.280 ppb ( 4% /a)
 CFC-12 (CCl2F2), 0.484 ppb ( 4% /a)

 Inert, non-toxic, non-flammable, odorless

 Used as refrigerant, solvents, blowing agents in the

manufacture of framed plastics, propellants in aerosol
sprays.
Halogenated Hydrocarbons
CFCs (chlorofluorocarbons)

 CFCs are not chemically altered during use; eventually

released into the atmosphere (reaches the stratosphere)

 Atmospheric lifetime: 10-100 years

 At the stratosphere, CFCs are degraded via photolysis:

CF2Cl2 + h (  250 nm)  CF2Cl + Cl
Cl in the stratosphere enters the catalytic cycles that
destroy ozone.
Halogenated Hydrocarbons
Chlorinated hydrocarbons:
 CCl4, 1,1,1-trichloroethane (CCl3CH3, methyl chloroform)
 undergoes photolysis in the stratosphere liberating Cl atoms

Halons (brominated CFC analogs):

 CF2ClBr (also H1211: 1C, 2F, 1Cl, 1Br), used in fire
extinguishers, no natural sources

 CH3Br (bromomethane): mostly of natural origin, used as

fumigant, undergoes photolysis in the stratosphere liberating
Br atoms (Br atoms synergistically enhance the rate of O3
depletion by Cl atoms)
Halogenated hydrocarbons
Halogenated
hydrocarbons

Predicted levels
Residence times and spatial variability
 Primary source of tropospheric OH [Levy, 1971]

O3 + h  O2 + O* 290 nm <<330 nm
O* + M  O + M M (“third body”) = O2 or N2
O+ O2 + M  O3 + M
O* + H2O  OH + OH
~1%

(~99%)

2 OH
(~1%)
Solar radiation
(290<<330 nm)
 Sinks of OH

Dominant sinks of OH in the

global troposphere:
 CO + OH CO2 + H
 CH4 + OH  CH3 + H2O NMHCs
…CO
CH4
Over continents, reactions with
non-methane hydrocarbons CO
(NMHCs) dominates:
 NMHC + OH  products

Lifetime of OH ~ 1 second!
Suspended Particulates

Particulate pollutants - finely divided solids or liquids (dust smoke,

fumes, fly ash, mist)

Size:
Aggregates of 0.002 µm in diam. (larger than a single
molecule) to 500 µm; of interest is the size range 0.01 - 100

Optical qualities: Can scatter light (0.38 - 0.76 µm)

Settling properties:
suspended: < 1 µm - 20 µm
settleable or dustfall: > 10 µm
Mode of formation:
Dust, smoke, fumes, fly ash, mist, spray
Suspended Particulates
Mode of formation:

dust - solid particles created by break up of large masses; do

not diffuse; settle by gravity
smoke - result from incomplete combustion of organics; consist
mainly of carbon
fumes - formed by condensation of vapors of solid materials;
flocculate then coalesce, then settle out
fly ash - non-combustible particles rising with flue gas
mist - liquid formed by condensation of vapors, dispersion of
liquid, or chemical reaction; causes fog
spray - atomization of liquids
Suspended Particulates
Natural Sources
 Aerial entrapment of soil
 sea spray
 pollen and spores brought by wind
 volcanic activity
 burning of biomass

These sources generate coarse particles ( 2.5 µm).

These particulates are returned to the Earth’s surface via
sedimentation and washout (rain, snow)

Human activity increases the flux from natural sources.

 Poor agricultural practices (large scale loss of soil by wind
erosion)
 Burning of fossil fuels and biomass
Suspended Particulates:
Chemical and Physical Impacts
 Large surface area of particulates increases the rate of
chemical reactions (example: SO2  SO3).

 Fine particulates scatter light,  solar radiation reaching

surface

 Dust can entrap solar radiation  surface warming

 Soiling of clothing and textiles; discoloring and destroying

painted surfaces
Suspended Particulates: Health Impacts

 Respiratory diseases (especially caused by

anthropogenic particulates)

 Fuel smoke particulates  health effect of other

pollutants

 Some particulates carry toxicants (soot, lead

compounds)

 Aeroallergens: airborne substances causing allergies

Suspended Particulates: Soot
Soot - black particulate material, generated from incomplete
burning of fossil fuels or biomass; impure form of carbon

 Contains many organic compounds

Example: PAHs (polycyclic aromatic hydrocarbons:
pyrene, benzo(a)pyrene);
 Some PAHs are carcinogens!

Yield of soot depends on fuel and mode of combustion.

In spark ignition: Otto engines - 0.1 g C/kg fuel
Diesel engine - 3 g C/kg fuel
Soot

Typical examples of PAHs: pyrene and benzo(a)-pyrene

Suspended Particulates: Lead
compounds
> 90% of lead in the atmosphere: anthropogenic sources

 Tetraalkyl lead compounds, especially Pb(C2H5)4: additive

to increase octane rating of Otto engine fuels

 To prevent Pb build-up within engines, dibromoethane and

dichloroethane are added to leaded fuels.

  allow the relatively volatile compounds, PbBr2, PbBrCl

and PbCl2 to be eliminated with the exhaust gases. These
form into particles, which are 50% coarse (diam. > 5 µm)
and 33% small (diam. < 0.5 µm).

Fine particles remain in the atmosphere for long periods of

time and are transported to great distances.
Suspended Particulates: Lead
compounds
Impacts of leaded fuels:

 Lead rapidly incapacitates (‘poisons’) the catalytic systems

fitted to vehicles in order to decrease the emission of CO,
HCs, NOx

 Lead in humans acts as a cumulative poison (even at low

levels, may induce hyperactivity and mental retardation)

 Toxicant via absorption after ingestion or inhalation

Suspended particulates: lead
Impacts of Combination of
Atmospheric Pollutants

• Smog
• Acid rain
• Greenhouse effect and climate changes
• Stratospheric ozone depletion
Formation of smog (smoke + fog: London type of smog)
Smoke remains due to lack of air movement initiated by night-time radiative cooling of the
air near the Earth’s surface. (Temperature inversion, cold dense air lay below warm air).
Night-time cooling decreases the moisture carrying capacity of the air allowing fog to form
around suspended smoke particles.

/Temperature
Death rates and atmospheric pollution
(London smog of 1952)

Death rate  as SO2

and smoke .
Smog

Synergistic effects of SO2 and smoke particulates:

1. SO2 slows down the rate at which hairs within the lungs beat.
This beating action removes the contaminant from the upper
lungs. When impaired, irritants (ex. particulates) have greater
access to the respiratory tract.

2. The soot particles within the smoke offer surfaces upon which
SO2 may be oxidized to H2SO4 (a powerful irritant)

Smog causes the bronchial passages within the lungs to become

inflamed and to make large amount of mucus  prompts
coughing  makes breathing difficult  heart attack among
elderly as they fight for breath.
Smog

Smog - a combination of smoke and fog (“London

type of smog”)

Formation of smog:
Smoke remains due to lack of air movement initiated by night-time
radiative cooling of the air near the Earth’s surface.
(Temperature inversion, cold dense air lay below warm air).
Night-time cooling decreases the moisture carrying capacity of the
air allowing fog to form around suspended smoke particles.
Photochemical Smog

Photochemical smog - a complex mixture of O3, nitrogen oxides

and hydrocarbons (“Los Angeles type of smog”).

 Forms on warm sunny days, when traffic is busy.

 Main primary pollutants: NOx (mainly NO), unburnt HCs from

motor vehicles

 Maximum levels: during morning and evening rush hours.

Smog is at its peak during early afternoon due to secondary
pollutants.
Photochemical Smog

Photochemical smog formation: Oxidation of unburnt HCs.

This process is initiated by OH radicals and maintained
by photochemical reactions.

During this process, NO is converted to NO2.

NO + RCH2O2  RCH2O + NO2
where R = H; CH3; CH2CH3, etc.

The produced NO2 undergoes photolysis, yielding atomic O,

which combines with molecular O2:
NO2 + h (  430 nm)  NO + O
O + O 2 + M  O3 + M
where M = 3rd body (ex. Solid surface, molecule)

These process  tropospheric O3 (in smoggy days).

Photochemical Smog

O3 will rise after all NO has been consumed because:

NO + O3  O2 + NO2 (rapid reaction).

When O3 level rises, O3 with light reacts with NO2  HNO3.

Some of the HNO3 formed are lost via dry or wet deposition.

In the conversion of NO to NO2, organic pollutants are formed.

NO + RCH2O2  RCH2O + NO2
RCH2O + O2  RCHO (aldehydes)+ HO2

Note: Aldehydes may also be produced as primary pollutant due to

incomplete combustion of petroleum fuels.
Photochemical Smog

Aldehydes contribute to further development of

photochemical smog.

 Aldehydes are precursor in the production of peroxyacyl

nitrates (PANs: RCO.O2.NO2)

 Low molecular weight aldehydes may undergo photolysis

and oxidation forming CO and hydroperoxyl radicals
(HO2), which can initiate the attack on further HC
molecules.
Typical daily
variations in the
concentrations of the
major primary and
secondary pollutants
in Los Angeles-type
smog
Smog formation
Temperature inversion
Smog over Los Angeles
Development of a
photochemical smog
over Poland
Photochemical Smog
Photochemical
Smog
Photochemical Smog
Photochemical Smog
Tropospheric ozone, Mar-Dec 1987, North Carolina
Photochemical Smog

Photochemical smog: characterized by the presence of clearly

visible aerosol colored brown-yellow by the presence of NO2.

 Inorganic components: NH4+, NO3-, SO42- ions

 Organic components: partially oxidized species of alcohols,

aldehydes, ketones, esters, peroxides, carboxylic acids (have
lower vapor pressures than the primary pollutants from which
they are derived)  microscopic liquid droplets in air.

 Main undesirable components: O3, PANs, NO2, aerosol

There is synergism! , which  the potency of each pollutants.
Photochemical Smog: Effects

 Respiratory tract irritation (due to O3 and PANs)

 O3 and PAN decreases rate of photosynthesis.

At about 100 ppb O3: 50% decrease in photosynthesis.

 Eye irritation (caused by O3 and PANs)

 Levels:
O3: 100-500 ppb in smog (< 50 ppb in remote areas,
ground)
PANs: 20-70 ppb in smog (< 0.015 ppb in remote areas)
Acid Rain

“Clean” (unpolluted) rain, snow, hail, mist, fog:

- not pure water
- contains small levels of dust, dissolved solids & gases
- dissolved CO2maintains pH of about 5.6

“Acid rain” - precipitation that has pH << pH of unpolluted rain

(pH < 5 mainly due to the presence of SO2 and NOx)

Efficient sink of SOx and NOx: wet deposition

Short atmospheric residence time  Acid rain is a regional
problem!
Global distribution of mean rainwater pH
Acid Rain: Impacts

On vegetation:
- acidic pH decreases productivity
- acidic deposition on leaves of plants can cause damage

On waterbodies: pollution, negative effect on aquatic ecosystem

On soil:
- leaching of essential elements (Ex. Mg)
- increasing solubility and level of phytotoxic elements (Ex. Al)

On buildings: acid rain dissolves the structurally important

carbonates in building materials
Fate of fish populations, as pH was reduced by acid
deposition
Greenhouse Effect & Climate Change

Global warming caused by anthropogenic emissions of

greenhouse gases:

Main greenhouse gases:

- natural: H2O, CO2, CH4, N2O
- man-made: CFCs

Possible consequences:
- significant rise in sea level
- increased evaporation  further atmospheric warming
Observed recent trends in global mean surface
temperatures
Trends in the atmospheric
concentrations of the main
greenhouse gases
Radiative forcing:
observed and predicted

Trends in global
temperature
Temperature change in relation to the concentration of
atmospheric carbon
Sea level rise
Changing distributions of trees with global warming
 Stratospheric Ozone Depletion
Ozone is found at trace levels
(8 - 10 ppm) in the stratosphere.

Ozone production:
O2 + h (  240 nm)  2O
O + O2 + M  O3 + M
where M = 3rd body (ex. Solid
surface, molecule)

Ozone destruction:
O3 + h (  325 nm)  O2 + O
O + O3  2O2
or via catalytic reaction:
XO + O3  XO + O2
XO + O  X + O2
Stratospheric Ozone Depletion

Man-made threats to stratospheric ozone:

NOx: act as X or XO in the O3 destroying catalytic reactions

Halogenated HCs: their photolysis in the stratosphere yield Br and

Cl atoms, which act as X in the O3 destroying catalytic reactions.

Polar stratospheric clouds (containing HNO3.3H2O): provide surface

for the reaction: HCl + ClONO2  HNO3 + Cl2
Cl2 is photolysed: Cl2 + h  2 Cl
Cl + O3  ClO + O2 (ozone destruction)
Consequences of Stratospheric O3 Loss

Ozone absorbs UV light, mainly in 230 -

320 nm (UV-B). This UV can damage
several biological systems, including
DNA.

Plants: Phytoplankton (mainly responsible

for the primary productivity of oceans)
are more severely affected.
 Affects organisms up the food chain.

Human health: sunburn, snow-blindness,

enhanced aging of skin; cataracts, eye
and skin cancers

UV-B adversely affects skin immune

system. Diseases that involve the skin
(measles, chicken pox, malaria,
leprosy) will be more problematic.
Ozone Destruction

http://www.theozonehole.com/ozonedestruction.htm
Ozone Destruction:
Effect of Clouds

http://www.theozonehole.com/ozonedestruction.htm
Ozone Destruction:
Effect of Temperature

http://www.theozonehole.com/ozonedestruction.htm
Ozone Destruction:
Effect of Temperature
 Stratospheric air temperatures in both polar regions reach
minimum values in the lower stratosphere in the winter
season.
 Average minimum values over Antarctica are as low as –
90°C in July and August in a typical year.
 Over the Arctic, average minimum values are near –80°C in
January and February.
 Polar stratospheric clouds (PSCs) are formed when winter
minimum temperatures fall below the formation temperature
(about –78°C).
 This occurs on average for 1 to 2 months over the Arctic and
5 to 6 months over Antarctica (see heavy red and blue lines -
- previous slide).
http://www.theozonehole.com/ozonedestruction.htm
Ozone Depletion: Effect of
Temperature
 Reactions on PSCs cause the highly reactive chlorine gas
ClO to be formed, which increases the destruction of ozone.
 The range of winter minimum temperatures found in the
Arctic is much greater than in the Antarctic.
 In some years, PSC formation temperatures are not reached
in the Arctic, and significant ozone depletion does not occur.
 In the Antarctic, PSCs are present for many months, and
severe ozone depletion now occurs in each winter season.

http://www.theozonehole.com/ozonedestruction.htm
 Stratospheric Halogen Gases

 Ozone is destroyed by reactions with chlorine, bromine, nitrogen, hydrogen, and oxygen gases.
Reactions with these gases typically occurs through catalytic processes. A catalytic reaction cycle is a
set of chemical reactions which result in the destruction of many ozone molecules while the molecule
that started the reaction is reformed to continue the process. Because of catalytic reactions, an
individual chlorine atom can on average destroy nearly a thousand ozone molecules before it is
converted into a form harmless to ozone.
http://www.theozonehole.com/ozonedestruction.htm
Ozone Destruction Process

http://www.theozonehole.com/ozonedestruction.htm
Ozone Destruction Process

http://www.theozonehole.com/ozonedestruction.htm
“Ozone Hole”

Washingtonpost.com (for confirmation)

“Ozone hole” North Pole

Ozone hole in North America during 1984 (abnormally warm

reducing ozone depletion) and 1997 (abnormally cold resulting
in increased seasonal depletion). Source: NASA
Antarctic Ozone

http://collidecolumn.files.wordpress.com/2012/09/antarctic-ozone-hole-over-the-years.jpg
 Ozone Depletion

 British Antarctic Survey (BAS) , High Cross, Madingley Road

CAMBRIDGE, CB3 0ET , United Kingdom
Contact Person for Ozone Concentrations Over Antarctica:
Jon Shanklin ; email: j.shanklin@bas.ac.uk http://www.epa.gov/ozone/science/indicat/techsupp.html
Size of the Antarctic ozone hole
‘Ozone hole’ & CFCs

 March 2011: Strongly reduced ozone values (left, dark blue) and
significantly increased concentration of chlorine monoxide (right, red) that is
directly involved in ozone degradation. Geophysical Research Letters,
volume 38, doi:10.1029/2011GL049784 (to be confirmed)
Ozone hole, Temperature,
CFCs
 “According to IMK studies, occurrence of the Arctic ozone
hole was mainly due to the extraordinarily cold temperatures
in the ozone layer that is located at about 18 km height in the
stratosphere, i.e. the second layer of the earth’s atmosphere.
There, chlorine compounds originating from
chlorofluorocarbons (CFC, e.g. greenhouse gases and
refrigerants) and other pollutants are converted chemically at
temperatures below -78°C. These chemical conversion
products attack the ozone layer and destroy it partly. ”
 “If the trend to colder temperatures in the stratosphere
observed in the past decades will continue, repeated
occurrence of an Arctic ozone hole has to be expected.”
 IMK = Institute of Meteorology and Climate Research
Summary
• the atmospheric pollutants causing most concern: sulfur dioxide,
oxides of nitrogen and carbon, halogenated hydrocarbons
(particularly CFCs), suspended particulates and the secondary
pollutants

• recently, human activity caused massive increase in the amounts

of these trace elements; some are solely anthropogenic (e.g.
many of the hydrocarbons and their halogenated analogues)

• burning of fossil fuels and biomass: single most significant source

of atmospheric pollution

• release of CFCs is probably the most important industrial

contamination that is not related to fuel combustion

• agriculture: major significance in methane and nitrous oxide

production
Summary, … cont’d
• some the pollutant species, … low tropospheric residence
times; rapidly removed from the atmosphere by efficient sink
mechanisms; thus, … local or regional problems, including
smogs and acid rain, … severity, dependent on the presence of
secondary pollutants

• Greenhouse gases: carbon dioxide, methane, CFCs and

nitrous oxide, … longer-lived atmospheric species; … causing
longer-term problems of global significance

• Greenhouse gases contribute to global warming

• CFCs and nitrous oxide enter the stratosphere, where they

contribute to the processes that control the levels of
stratospheric ozone
Main Reference:
Andrew R.W. Jackson & Julie M. Jackson (1996)
Environmental Science. Longman Group Limited,
Edinburgh Gate, Harlow, Essex CM20 2JE, England

Please do not give copies to anybody outside the EnE

250 class. This lecture is yet to be revised to incorporate
references of photos.