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AIR POLLUTION
Mobile Sources

ü Have knowledge of air pollution:

Types, sources, properties, impacts, standards

ü Learn about transport and the environment

ü Be knowledgeable about the fate and dispersion of

air pollutants in the environment

ü Gain familiarity with indoor air quality

ü Be knowledgeable about air pollution control

Methods and equipment

OUTLINE

• Introduction

• Magnitude of the Problem

• Engine Fuel Characteristics

• Vehicle Emission Control

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INTRODUCTION
Generalities
• Mobile sources:
» Cars
» Trucks
» Buses
» Motorcycles
» Airplanes
» Boats
» Trains
» Bulldozers
» Tractors
• Emit similar by-products:
CO, NOx, SOx, HCs VOCs, PM, Pb, CO2, O3

INTRODUCTION
Sources of emissions
Highway vehicles emit the lion’s share

Air condition units ® Freon ® chlorine atoms are released

in the stratosphere ® destruction of the ozone layer

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INTRODUCTION
Generalities (cont’d)
• Major urban areas all around the world have
become congested with motor vehicles and have
become severely polluted

• Urban-area CO emissions attributable to mobile

sources can reach up to 95%

INTRODUCTION
Generalities (cont’d)
• Proliferation of mobile sources has altered the
field of air pollution control:

» Huge number of small, diverse, decentralized sources;

more difficult to regulate and control than stationary
sources

» Sources of emissions (vehicles) are usually very close

to receptors (people)

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INTRODUCTION
Exhaust emissions
• Perfect Combustion:
Fuel + Air è Carbon Dioxide + Water + Nitrogen

• Typical Engine Combustion:

Fuel + Air è Carbon Dioxide + Water + Nitrogen
+ Pollutants-CO, NOx, SOx, HCs/VOCs, PM, Pb

NOx+ VOC + Sunlight è Tropospheric O3

Health and Environmental Impacts

INTRODUCTION
Summary of control measures
• Regulations of in-use vehicle maintenance
practices, of fuel quality composition, and of
individual driving habits have been adopted

• Development of pollution control technology and

regulatory strategies in the past few decades

• Almost as fast as reductions in per vehicle

emissions are achieved, those gains are
offset by the continuing growth in the
number and usage of motor vehicles

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INTRODUCTION
Exhaust emissions (cont’d)

Vehicle miles traveled vs.

average per-vehicle emission of HCs

INTRODUCTION

• Since 1970, fastest growth rates in motorization

in upper-income developing countries

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MAGNITUDE OF THE PROBLEM

MAGNITUDE OF THE PROBLEM (cont’d)

Estimated annual
emissions of air
pollutants in selected
countries

OLD FIGURES

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MAGNITUDE OF THE PROBLEM (cont’d)

Types and numbers of

vehicles in use

OLD FIGURES

MAGNITUDE OF THE PROBLEM (cont’d)

• Although less-developed countries generally

cannot afford sophisticated pollution control
technology, a few multinational companies
account for much of the world vehicle production
Þ global cooperation to reduce emissions

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MAGNITUDE OF THE PROBLEM (cont’d)

• During the past 40 to 50 years, overall growth:

» In the number of motor vehicles in the world: x 10
» In world population: x 2

• Reasons:
» Increasing urbanization
» Increasing real incomes
» Decreasing real costs of vehicles
» Desire for improving social status
» Desire for independence

ENGINE CHARACTERISTICS
Characteristics of non-OECD vehicle fleet

• Most two- and three-wheeled vehicles are

equipped with highly polluting two-stroke engines

• Many fleets in developing countries are old and

poorly maintained with Higher proportions of
trucks and buses

• Poor quality fuels are sold in developing countries

resulting in more pollution emissions

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ENGINE CHARACTERISTICS
Characteristics of engines in mobile sources

• Assumptions:
» Gasoline can be represented by octene
» Complete combustion with the stoichiometric amount of air
» Nitrogen is completely inert
• Overall stoichiometry of the reaction:
C8H16 + 12 O2 + 45.1 N2 ® 8 CO2 + 8 H2O + 45.1 N2
• Stoichiometric AFR (mass air-to-fuel ratio)= 14.7
• Equivalence ratio (ER) = actual AFR / stoichiometric AFR
Stoichiometric ratio (SR) (New version of the book)

ER(SR)= (A/F)actual A = air intake rate, g/s

(A/F)stoich F = fuel usage rate, g/s

ENGINE CHARACTERISTICS
Characteristics of engines in mobile sources (cont’d)

• Stoichiometric balance
b b b b
C aHb + (a + )O 2 + (a + )N2 ® aCO 2 + ( )H2 O + (a + )N2
4 4 2 4
b b
( a + )32 + 3.75( a + )28
A 4 4
=
F 12a + b

With an oxygen deficit of c moles (incomplete combustion):

b b
C aHb + (a + - c )O 2 ® (a - 2c )CO 2 + ( )H2 O + (2c )CO
4 2

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ENGINE CHARACTERISTICS
Characteristics of engines in mobile sources (cont’d)

» ER (SR) <1 ® fuel rich mixture, insufficient O2

® high CO and VOC emissions

» ER (SR) ~1 ® emissions decrease rapidly

» ER (SR) >1 ® fuel lean mixture, engine

operates “rougher”. At greater values of ER
(SR), the combustion becomes unstable and
CO and VOC emissions increase again

EXAMPLE 1

a. Calculate the stoichiometric air-to-fuel ratio for the combustion of

benzene, one of the aromatic compounds found in gasoline
b. For an equivalence ratio of 1.1, calculate the volume of exhaust
gases produced at STP per kg of benzene burned
» First, write the reaction identifying reactants and products only
C6H6 + O2 + N2 ® CO2 + H2O + N2
» Next, balance it stoichiometrically, starting with the carbon atoms,
followed by the hydrogen, oxygen, and nitrogen, in that order. Keep in
mind that 3.76 moles of nitrogen are present in air for every mole of
oxygen. The stoichiometric equation is:
C6H6 + 7.5O2 + 28.2N2 ® 6CO2 + 3H2O + 28.2N2
» The stoichiometric AFR is
(7.5molesO2x32g / mole) + (28.2molesN2x28g / mole)
AFR =
1mole - benzenex78g / mole
AFR = 13.2 g air per g benzene

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EXAMPLE 1 (cont’d)

» For an ER of 1.1, the re-balanced equation is

C 6H6 + 8.25O2 + 31N2 ® 6CO2 + 3H2 O + 31N2 + 0.75O2
78g 264g 868g 264g 54g 868g 24g

» In this case, for every 78 g of benzene, there are 1132

g of air, and 1210 g of exhaust gases. Because 40.75
moles of gases are produced in this reaction, the
volume of gases produced is
40.75moles - gas 24.45L 1m3 12.77m3
V= x x =
0.078kg - fuel mole 1000L kg - fuel

» Where the constant 24.45 liters/mole is the molar

volume of gas at STP (25 C and 1 atm)

VEHICLE EMISSIONS AND CONTROLS

Factors affecting emissions

• Factors affecting emissions from motor vehicles

» Engine design and operating features

» Driver Operating and maintenance practices
» Fuel composition
» Add-on emission control technology
» Environmental conditions
» Other Measures (I&M, TCMs and TMTs)

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ENGINE DESIGN & OPERATING FEATURES

Catalytic converters

• Air-to-fuel ratio is the engine design feature that affects

emissions most strongly

• Modern vehicles equipped with catalytic converters burn

at precisely controlled, slightly rich mixture (ER = 0.98-
0.99) ® prevents excessive NOx formation, without
producing excessive amounts of CO and VOCs

• Important factors to control:

» Flow rate of fuel to provide adequate macromixture
» Methods of mixing air and fuel into a homogenous micromixture in
every part of the cylinder

VEHICLE EMISSIONS AND CONTROLS

Factors affecting emissions

• Factors affecting emissions from motor vehicles

» Engine design and operating features

» Driver Operating and maintenance practices
» Fuel composition
» Add-on emission control technology
» Environmental conditions
» Other Measures (I&M, TCMs and TMTs)

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DRIVER OPERATING AND

MAINTENANCE PRACTICES
• Good operation:
» Driving sensibly
» Not overloading the vehicle
» Proper fuel usage

• Maintenance:
» Keeping the engine in tune
» Changing oil regularly
» Keeping spark plugs clean
» Keeping proper air pressure in the tires

VEHICLE EMISSIONS AND CONTROLS

Factors affecting emissions

• Factors affecting emissions from motor vehicles

» Engine design and operating features

» Driver Operating and maintenance practices
» Fuel composition
» Add-on emission control technology
» Environmental conditions
» Other Measures (I&M, TCMs and TMTs)

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FUEL COMPOSITION

• Level of impurities in fuel:

» Sulfur:
–Leads directly to the formation of SO2
(criteria pollutant)
–S temporarily poisons the catalyst
in catalytic converters ® increased
emissions of CO and VOCs

• Fuel refining or Hydrodesulfurization:

organic S is removed from hydrocarbons by
reaction with hydrogen

FUEL COMPOSITION (cont’d)

• Lead:
» Added during final blending of gasoline in order to
boost octane
» Phase-out ® dramatic reduction in lead emissions into
urban air
» However, oil companies are forced to add more
aromatics and olefins (higher octane stocks) to the
blend ® higher soot formation, higher motor vehicle
emissions of “air toxics”, and higher degree of
photochemical activity of the exhausted VOCs

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VEHICLE EMISSIONS AND CONTROLS

Factors affecting emissions

• Factors affecting emissions from motor vehicles

» Engine design and operating features

» Driver Operating and maintenance practices
» Fuel composition
» Add-on emission control technology
» Environmental conditions
» Other Measures (I&M, TCMs and TMTs)

ADD-ON EMISSION CONTROL

TECHNOLOGY
• Most obvious: catalytic converter, used to treat engine
exhaust emissions:
» Oxidation of CO and VOC to CO2 and H2O
» Chemical reduction of NOx to N2 and O2
• Requires precise computer control of the engine AFR and
real-time oxygen sensors in the exhaust

Platinum-rhodium catalyst N + CO + H O
NO + CO + HC
2 2 2

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ADD-ON POLLUTION CONTROL

TECHNOLOGY (cont’d)
• Carbon canister: small carbon
bed adsorber (activated
charcoal) that collects
evaporative emissions of VOCs
from the hot engine after the
vehicle has been shut down

• Next time the car is operated,

carbon bed is desorbed by
passing some of the intake air
through the carbon canister, and
VOCs are routed back into the
cylinders

ADD-ON POLLUTION CONTROL

TECHNOLOGY (cont’d)

Trap-oxidizer:
Device that is used on diesel vehicles
• Combination of a catalytic converter and
particulate filter
• Soot and other diesel emissions are caught
on the trap and later oxidized

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ADD-ON POLLUTION CONTROL

TECHNOLOGY (cont’d)
• Operator tampering with pollution control equipment can
increase emissions as much as 700% relative to a similar
untampered vehicle Þ introduction of auto emission
testing
• Tampering includes:
» Disconnecting the carbon canister
» Disconnecting the oxygen sensor
» Removing the catalytic converter
» Removing the fuel inlet restrictor
• Misfueling (putting leaded gasoline into cars designed for
unleaded) is a form of tampering that has been
particularly troubling in the past: deactivates the catalytic
converter

VEHICLE EMISSIONS AND CONTROLS

Factors affecting emissions

• Factors affecting emissions from motor vehicles

» Engine design and operating features

» Driver Operating and maintenance practices
» Fuel composition
» Add-on emission control technology
» Environmental conditions
» Other Measures (I&M, TCMs and TMTs)

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ENVIRONMENTAL CONDITIONS

• Ambient temperature and pressure can affect vehicle

emission rates significantly
• The engine consumes liquid fuel and ambient air, on a
volumetric basis
• Their densities (esp. air) change with ambient
temperature ® mass of air relative to mass of fuel
changes even with constant volumetric flow rate ®
change in AFR
• Cold temperatures also extend engine warm-up time,
during which the cold cylinder surfaces more quickly
quench combustion reactions ® increase in emissions

ENVIRONMENTAL CONDITIONS
(cont’d)
• New vehicles are tested in a 75 F chamber to see if they
meet EPA emission limits Þ manufacturers tend to
optimize the engine and pollution control system to
minimize emissions at 75 F
• Actual emissions tend to increase at temperatures above
and below 75 F
• Emission rates are significantly higher during the first 3-8
minutes after start-up (before the catalytic converter
reaches its operating temperature)
• Ambient pressure affects air density directly (esp. with
large change in altitude, i.e., less O2) but has almost no
effect on fuel density

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EXAMPLE 2
• The design AFR for a particular vehicle burning a certain grade of gasoline is
14.7, based on an air density of 1.2 kg/m3. If this same car is driven in
Mexico City with no adjustments (that is, it draws in the same volume of air
per unit of liquid fuel), calculate its actual AFR and the equivalence ratio.
Mexico City has an elevation of 2240 m above sea level, and its air has a
density of 1 kg/m3.
» Choose a basis of 1kg of fuel burned. At sea level, with an AFR of 14.7, the volume
of air taken in is
14.7kg - air 1m3 - air
1kg - fuelx x = 12.24m3
1kg - fuel 1.2kg - air
In Mexico City, the mass of air in this volume of air is
1kg - air
12.24m3 x = 12.24kg - air
1m3 - air
The actual AFR and ER (SR) are
AFR = 12.24 kg air / kg fuel; and ER = 12.24 / 14.7 = 0.83 (approximately 17%
below stoichiometric)
The jets in the carburetor (or the fuel injectors) of this vehicle should be replaced.

VEHICLE EMISSIONS AND CONTROLS

Factors affecting emissions

• Factors affecting emissions from motor vehicles

» Engine design and operating features

» Driver Operating and maintenance practices
» Fuel composition
» Add-on emission control technology
» Environmental conditions
» Other Measures (I&M, TCMs and TMTs)

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OTHER MEASURES TO CONTROL

EMISSIONS FROM VEHICLES

• Regulatory control of mobile sources as a

group is the responsibility of
governmental agencies

• 3 broad categories:
» Inspection and maintenance (I/M) programs
» Transportation control measures
» Changes in automotive fuels

OTHER MEASURES
Inspection and maintenance programs (cont’d)

• Regular vehicle inspections to ensure that vehicles meet

minimum in-use emission standards
• Minimum emission standards are purposely set high:
Only high polluting vehicles do not pass
• Inspection stations are usually operated by private
contractors under state supervision
• Drivers are required to get annual inspection stickers
• Inspection covers key emission control equipment and
checks tailpipe emissions

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OTHER MEASURES
Inspection and maintenance programs (cont’d)

• Cars that do not meet the limits must correct the

problems and be re-inspected in order to receive their
“operating permit” (sticker)

• I/M programs are very effective at reducing in-use fleet

emissions by identifying and removing from the road
“super-emitters” (vehicles that emit up to 100 times the
average), and by reducing tampering rates

OTHER MEASURES
Inspection and maintenance programs (cont’d)

• The vehicle fleet on the road is a mixture of:

» Many car types (cars/trucks/buses…)
» Different fuels (gasoline/diesel…)
» A wide age distribution

• Each year, some of the oldest vehicles are removed from

the fleet and replaced by the newest models

• Newest models: built to meet the most stringent

emission standards ® least polluting if maintained and
operated properly

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OTHER MEASURES
Inspection and maintenance programs (cont’d)

• A suitable standardized tailpipe test procedure

• Effective enforcement for full compliance
• Qualified mechanics and continuing training
programs for diagnostics and repairs
• Different but effective in-use standards for
vehicles of different model years
• Minimization of waivers and exemptions
• Periodic evaluation and review by regulatory
agency

OTHER MEASURES
Transportation control measures (TCMs)
Traffic management techniques (TMTs)

• TCMs and TMTs can be very effective at reducing

air pollution within urban areas

• TCMs and TMTs result in fewer vehicles on the

roads and/or smoother traffic operations ®
emissions are reduced

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OTHER MEASURES
Transportation control measures (cont’d)

1. Vehicle-use limitations/restrictions
2. Employer-based transportation management
3. Improved public transit
4. Parking management
5. Park and ride/fringe parking
6. Flexible work schedules
7. Traffic flow improvements
8. Area-wide rideshare incentives
9. High-occupancy vehicle facilities
10. Bicycling and pedestrian programs
11. Voluntary removal of old vehicles

OTHER MEASURES
Transportation control measures (cont’d)

• Categories of TCMs:
» Transit options (more buses, exclusive bus
lanes, park-and-ride lots)
» Economic incentives/penalties (high-priced
parking, car pool subsidies, higher gasoline
taxes, road use taxes)
» Regulatory steps (parking bans, auto-free
zones, gasoline rationing, restricted driving
days – rationed by odd or even numbers on
the license plates)

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OTHER MEASURES
Traffic management techniques

• Control of the flow of vehicles on the streets, as

well as management of travel demand:
» Timing and sequencing traffic signals
» Improving intersections
» Widening streets
» Adding protected left-turn lanes and free-flowing right-
turn curves
» Creating one-way street pairs
» Designating high-occupancy-vehicle (HOV) lanes
» Planning truck routes
» Excluding trucks from certain streets

OTHER MEASURES
Traffic management techniques (cont’d)

• TMTs tend to reduce congestion and allow for smoother,

more free-flowing traffic
® As the average traffic speed increases, vehicle emission
factors go down
• Travel demand can be altered by encouraging staggered
work hours ® reduces peak hour demand and improves
level of roadway service
• Encourage businesses to adopt four-day work weeks (with
different days for different sets of workers)
• Develop sectors in an urban area with housing and
working areas located in close proximity ® reduction of
total miles traveled

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OTHER MEASURES
Changes in motor vehicle fuels

• Options:
» Modifications to gasolines
» Replacements for gasolines
» Nonhydrocarbon fuel options
• Most successful gasoline modification in modern times:
dramatic reduction in lead content of all gasoline (97%
reduction in the US within 20 years)

OTHER MEASURES
Changes in motor vehicle fuels (cont’d)

• Oxygenated fuels: of high interest (1 or more

oxygen atoms embedded in the fuel molecules)
®Significant reduction in CO when compared with
straight gasoline (30% reduction in CO emissions
as a result of a gasoline blend with 3%
oxygenated fuels)
• But NOx emissions tend to increase slightly Þ
ozone problems
• Methanol, ethanol, tertiary butyl alcohol, and
methyl tertiary butyl ether have been tested and
used during winter months

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OTHER MEASURES
Changes in motor vehicle fuels (cont’d)

• Alternative fuels:
» Compressed natural gas
» Liquefied petroleum gas
» Pure methanol or ethanol

• Alcohols have significantly less energy per unit

mass than the pure hydrocarbon fuels

• Methane and propane have high energy content

per unit mass, but require compression and/or
refrigeration to maintain them as liquids (for ease
of storage)

OTHER MEASURES
Changes in motor vehicle fuels (cont’d)

• Compressed natural gas and liquefied petroleum gas:

» 50% less CO and VOC emissions
» Little or no photochemically active VOCs and no air toxics (such as
benzene)
» But: disadvantage related to on-board fuel storage and handling,
and refueling
– Much higher formaldehyde emissions
– Methanol dissolves several types of rubber and other gasket
materials, and can be absorbed through the skin
– Reduced range of the vehicle: lower energy content per volume of
fuel

• All alternative fuels share the disadvantage of lack of

infrastructure for refueling stations

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OTHER MEASURES
Changes in motor vehicle fuels (cont’d)

• Non-hydrocarbon fuel options:

» Hydrogen
» Electric vehicles (EVs)
» Solar-powered cars
» Fuel cells
• Hydrogen produces no CO, no CO2, no HCs, and
has the highest energy content per mass of any
combustible fuel
• But: technological and safety obstacles to
overcome before hydrogen becomes a practical
commercial alternative for highway vehicles
• Solar-powered cars: still in the experimental stage

OTHER MEASURES
Changes in motor vehicle fuels (cont’d)

• Electric-powered vehicles: of current practical

interest
• EVs requiring tracks or overhead electric lines
have been used for decades (e.g., trolleys)
• Greater interest in electric vehicles that do not
require such devices
» Battery operated cars and light duty vans
• Prototype vehicles have been manufactured that
give acceptable driving performance
• Operate essentially pollutant-free on the street,
with very low noise levels

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OTHER MEASURES
Changes in motor vehicle fuels (cont’d)

• Air pollution emissions at fossil-fuel power plant,

associated with generation of electricity required
to recharge the batteries ® well controlled, and
far removed from urban streets
• Current limitations of a battery powered vehicle:
» Limited range (80-150 miles)
» Extra weight of batteries
» Long time required to recharge the battery (6-8 hours)
» High cost

End of Lecture

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