Chemical Aspects

of Air Pollution
Titik Istirokhatun
 Units for NAAQS
National Ambient Air Quality Standards

• ppm, ppb for gases

• μg/m3 for particles (and gases)

(μg/m3 = micrograms per cubic meter)

 Parts Per Million (or Billion)

• For gases, the basis is VOLUME

– i.e., volume of pollutant per volume of air

• For example, 1 ppm of a gaseous pollutant is

1 m3 of pollutant per 1 million (106) m3 of air

• Or, 1 liter of pollutant per million liters of air,

etc.

Similarly, ppb is per billion (109) volumes of air

 Conversion: % to ppm
3
0.036m CO2
0.036% CO2 
100m3 air
Multiply both sides by 10,000:
0.036m 3 CO2 10,000
0.036% CO2  3
*
100m air 10,000
360m3 CO2
6 3
 360 ppm
10 m air
 Moles and Atomic Weight
• A mole of anything is Avogadro’s Number (6.022
x 1023) of those things. A mole of a chemical is
therefore 6.022 x 1023 molecules.
– For reference: the universe is thought to have existed
for about 1018 seconds!
• The atomic weight of an element is the weight of
one mole of those atoms
– We can find this on the periodic table
– E.g. the atomic weight of carbon is about 12 g/mole
 Molecular Weight
• The molecular weight (sometimes called
“formula weight” ) of a chemical substance is the
weight of one mole of its molecules in grams.
– The molecular weight of water is 18 g/mole.
• Why?
 Molecular Weight
• The molecular weight (sometimes called
“formula weight” ) of a chemical substance is the
weight of one mole of its molecules in grams.
– The molecular weight of water is 18 g/mole.
• Why?
– One mole of water (H2O) is therefore 18 grams of
water.
– The molecular weight of table salt (NaCl) is 58.5
g/mole. One mole of table salt weighs 58.5 grams.
 Ideal Gas Law
• The Ideal Gas Law describes quite accurately
how most gases, under typical environmental
conditions, respond to changes in those
conditions.
• PV = nRT
P = total pressure (in atmospheres)
V = volume (in liters)
n = number of moles of the gas
R = gas constant (0.0821 L·atm/mole·K)
T = absolute temperature (in K, which is °C + 273)
 Molar Volume
• The molar volume of an ideal gas at 1 atm and
0°C is 22.4 liters.
• For more typical environmental conditions of 20-
25°C, the molar volume is approximately 24
L/mole.
Unit Conversions: ppm or ppb μg/m3
• For most calculations, we can assume the gaseous
pollutant behaves as an ideal gas
• At typical ambient temperatures (20-25°C) and
atmospheric pressure, one mole of an ideal gas
occupies about 24 L (22.4 L at 0°C) [molar volume
 24 L/mole]
• One mole of any chemical substance weighs its
molecular weight in grams (e.g., MW of benzene = 78; 1
mole = 78g)
 Unit Conversions: ppm or ppb
μg/m3

• Example: convert 10 ppm of benzene  ? μg/m3

– MW of benzene = 78 g/mole (or 78 x 106 μg/mole)
– 10 ppm = (10L benzene/106L air)

 10 Lb  78 x106 ugb  1000 Lair 

10 ppm   6   3

  32,000 ug
m3
 10 Lair  24 Lb  mair 

– Similarly, 10 ppb  32 μg/m3

• For more precise calculations and significantly different
temperatures or pressures, use the Ideal Gas Law
 Basic Pollutants (1 of 3)
Categories of pollutants
● Primary – emitted directly from a source
● Secondary – formed in the atmosphere from a reaction of
primary pollutants
● Precursors – primary pollutants (gases) that participate in the
formation of secondary pollutants
Pollutants originate from
● Combustion of fossil fuels and organic matter
● Evaporation of petroleum products or compounds used in
commercial products, services, and manufacturing
● Natural production of smoke from fires, dust from strong
winds, and emissions from the biosphere and geosphere
 Basic Pollutants (2 of 3)
Pollutant Abbreviation Type

Carbon Monoxide CO Primary

Sulfur Dioxide SO2 Primary

Ozone O3 Secondary

Nitrogen Dioxide NO2 Secondary

Hydrocarbon Compounds
(also called VOCs – volatile HC Primary & Secondary
organic compounds )

Particulate Matter PM Primary & Secondary

17
Basic Pollutants (3 of 3)

18
 Basic Pollutants – Toxics (1 of 2)
● Air toxics (hazardous air pollutants) are known or
suspected to cause cancer or other serious health
effects.
● EPA’s 188 hazardous air pollutants include
– Benzene (motor fuel, oil refineries, chemical processes)
– Perchlorethylene (dry cleaning, degreasing)
– Chloroform (solvent in adhesive and pesticides, by-product of
chlorination processes)
– BTEX, Dioxins, PAHs, Metals (Hg, Cr)
Area/ Mobile
Other (nonroad)
National air toxics emissions sources in 25% 20%

1996
U.S. Environmental Protection Agency, Point Mobile
(onroad)
24%
1998 31%

19
 Basic Pollutants – Toxics (2 of 2)
• Differences between toxics and criteria pollutants
– Health criteria are different
• No Air Quality Index-like standards for toxics
• Cancer/non-cancer benchmarks (long-term exposures)
• Short-term exposure limits for some objects
– A challenge to monitor
• Usually not available in real-time
• Example: Dioxin requires 28 days of sampling to
acquire measurable amounts in ambient air
– Often localized near source

20
 Basic Pollutants – Sources (1 of 4)
• Combustion
• Evaporation
• Natural Production

21
 Basic Pollutants – Sources (2 of 4)
Combustion
• Complete combustion
Fuel  water and carbon dioxide (CO2)

• Incomplete combustion
Fuel  water, CO2, and other pollutants
Pollutants are both gases and particles

22
 Basic Pollutants – Sources (3 of 4)
Evaporation
• Thousands of chemical compounds
• Liquids evaporating or gases being released
• Some harmful by themselves, some react to produce other
pollutants
• Many items you can smell are evaporative pollutants
– Gasoline – benzene (sweet odor, toxic, carcinogenic)
– Bleach – chlorine (toxic, greenhouse gas)
– Trees – pinenes, limonene (ozone- and particulate matter forming)
– Paint – volatile organic compounds (ozone- and particulate matter
forming)
– Baking bread, fermenting wine and beer – VOCs and ethanol
(ozone-forming)

23
 Basic Pollutants – Sources (4 of 4)
Natural Production
• Fires (combustion) produce
gases and particles
• Winds “pick up” dust, dirt,
sand and create particles
of various sizes
• Biosphere emits gases from
trees, plants, soil, ocean,
animals, microbes
• Volcanoes and oil seeps
produce particles and gases

24
 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

25
 Solar radiation and chemistry
• The reaction that produces ozone in the atmosphere:
O + O2 + M O3 + M
O3 is produced in the troposphere from the oxidation of
CO and hydrocarbons by OH in the presence of NOx
• 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

26
 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

27
 Tropospheric Ozone Photolysis
Troposphere ozone photolysis takes place in a narrow UV window
(300-320 nm), NO2 broadly below 428

30o equinox
midday
Solar spectrum

28
 Nitrogen Oxides
● Nitrogen oxides, or NOx, is the generic term for a group of
highly reactive gases, all of which contain nitrogen and
oxygen in varying amounts.
● Nitrogen dioxide is most visually prominent (it is the yellow-
brown color in smog)
● The primary man-made sources of NOx are motor vehicles;
electric utilities; and other industrial, commercial, and
residential sources that burn fuels
● Affects the respiratory system
● Involved in other pollutant chemistry
– One of the main ingredients in the formation of ground-level ozone
– Reacts to form nitrate particles, acid aerosols, and NO2, which also
cause respiratory problems
– Contributes to the formation of acid rain (deposition)

29
 Must make NO2
• To make significant amounts of ozone must
have a way to make NO2 without consuming
ozone
• Presence of peroxy radicals, from the
oxidation of hydrocarbons, disturbs O3-NO-
NO2 cycle
NO + HO2· NO2 + OH·
NO + RO2· NO2 + RO·
– leads to net production of ozone
 The Hydroxyl Radical
• produced from ozone photolysis
– for radiation with wavelengths less than 320 nm:
O3 + hv O(1D) + O2
followed by
O(1D) + M O(3P) + M (+O2 O3) (~90%)
O(1D) + H2O 2 OH· (~10%)

• OH initiates the atmospheric oxidation of a wide range of compounds in

the atmosphere
– referred to as ‘detergent of the atmosphere’
– typical concentrations near the surface ~106 - 107cm-3
– very reactive, effectively recycled

31
Oxidation of CO - 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 + 2 O2 + hv CO2 + O3

32
 Carbon Monoxide
• Odorless, colorless gas
• Caused by incomplete combustion of fuel
• Most of it comes from motor vehicles
• Reduces the transport of oxygen through the
bloodstream
• Affects mental functions and visual acuity, even
at low levels

33
 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
34
Day and Night Chemistry

35
Ozone Precursor Emissions (1 of 2)
● Man-made sources Meteorology
– Oxides of nitrogen (NOx) through
combustion
– VOCs through combustion and
numerous other sources Emissions Chemistry

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

36
NOx EMISSIONS (Tg N yr-1) TO TROPOSPHERE

Stratosphere
0.2

Lightning
5.8
Soils
5.1 Fossil Fuel
23.1

Biomass
Burning
5.2 Biofuel
2.2

Aircraft
0.5

37
 Mapping of Tropospheric NO2
From the GOME satellite instrument (July 1996)

Section 7 – Chemical Aspects

38
of Air Pollution
 Global Budget of CO

Section 7 – Chemical Aspects

39
of Air Pollution
Ozone Meteorology – Key Processes

• Dispersion (horizontal mixing)

• Vertical mixing Meteorology

• Sunlight
• Transport Emissions Chemistry

• Weather pattern
• Geography
• Diurnal
• Season
40
 Ozone Precursor Emissions
Wind speed (WS)

S Concentration  S/WS

S Vertical mixing (VM)

Concentration  S/VM
● Key processes Courtesy of New Jersey
Department of Environmental Protection
– Source location, density, and strength
– Dispersion (horizontal mixing) - wind speed
– Vertical mixing - inversion

Section 7 – Chemical Aspects

41
of Air Pollution
Daily Variation

42
 Source/Receptor Regions in Los Angeles

Volume mixing ratio (ppmv)

Volume mixing ratio (ppmv)

Volume mixing ratio (ppmv)

Urban center Sub-urban
0.3 0.3
Central Los Angeles San Bernardino
August 28, 1987 August 28, 1987 O3
0.2 0.2
NO NO2 NO2
0.1 O3 0.1

NO
0 0
0 6 12 18 24 0 6 12 18 24
72
Hour of day Hour of day

43
 Particulate Matter (1 of 3)
● Complex mixture of solid and liquid particles
● Composed of many different compounds
● Both a primary and secondary pollutant
● Sizes vary tremendously
● Forms in many ways
● Clean-air levels are < 5 µg/m3 *
● Background concentrations can be higher
due to dust and smoke
Ultra-fine fly-ash or
● Concentrations range from 0 to 500+ µg/m3 * carbon soot
● Health concerns
– Can aggravate heart diseases
– Associated with cardiac arrhythmias and heart attacks
– Can aggravate lung diseases such as asthma and bronchitis
– Can increase susceptibility to respiratory infection *
24-hour average

44
 Particulate Matter (2 of 3)
Particles come in different shapes and sizes

Particle sizes
• Ultra-fine particles (<0.1 μm)
PM10

• Fine particles (0.1 to 2.5 μm)

• Coarse particles (2.5 to 10 μm)

Crustal material Carbon chain agglomerates

45
 Particulate Matter (3 of 3)

A clear (left) and dirty (right) PM filter

46
 Particulate Matter Composition
PM is composed of a mixture of primary and secondary compounds.

● Primary PM (directly ● Secondary PM (precursor gases

emitted)
– Suspended dust
– Sea salt
– Organic carbon
– Elemental carbon
– Metals from combustion
– Small amounts of sulfate
and nitrate
that form PM in the atmosphere)
– Sulfur dioxide (SO2): forms sulfates
– Nitrogen oxides (NOx): forms
nitrates
– Ammonia (NH3): forms ammonium
compounds
– Volatile organic compounds
(VOCs): form organic carbon
compounds

47
 Particulate Matter Composition
Most PM mass in urban and nonurban areas is composed of a
combination of the following chemical components
• Geological Material – suspended • NaCl – salt is found in PM near sea
dust consists mainly of oxides of Al, coasts and after de-icing materials
Si, Ca, Ti, Fe, and other metal are applied
oxides • Organic Carbon (OC) – consists of
hundreds of separate compounds
• Ammonium – ammonium bisulfate, containing mainly carbon, hydrogen,
sulfate, and nitrate are most and oxygen
common • Elemental Carbon (EC) –
• Sulfate – results from conversion of composed of carbon without much
SO2 gas to sulfate-containing hydrocarbon or oxygen. EC is
particles black, often called soot.
• Nitrate – results from a reversible • Liquid Water – soluble nitrates,
gas/particle equilibrium between sulfates, ammonium, sodium, other
ammonia (NH3), nitric acid (HNO3), inorganic ions, and some organic
material absorb water vapor from
and particulate ammonium nitrate the atmosphere

Chow and Watson (1997)

48
 PM Emissions Sources (1 of 4)
Point – generally a major facility emitting pollutants from identifiable
sources (pipe or smoke stack). Facilities are typically permitted.

49
 PM Emissions Sources (2 of 4)
Area – any low-level source of air pollution released over
a diffuse area (not a point) such as consumer products, architectural
coatings, waste treatment facilities, animal feeding operations, construction,
open burning, residential wood burning, swimming pools, and charbroilers

50
 PM Emissions Sources (3 of 4)
Mobile
• On-road is any moving source of air pollution such as cars, trucks,
motorcycles, and buses
• Non-road sources include pollutants emitted by combustion engines on
farm and construction equipment, locomotives, commercial marine
vessels, recreational watercraft, airplanes, snow mobiles, agricultural
equipment, and lawn and garden equipment

51
 PM Emissions Sources (4 of 4)
Natural – biogenic and geogenic emissions from wildfires, wind blown
dust, plants, trees, grasses, volcanoes, geysers, seeps, soil, and
lightning

52
 Particulate Matter Chemistry (1 of 4)
Coagulation: Particles collide and stick together.

Condensation: Gases condense onto a small solid particle

to form a liquid droplet.

Cloud/Fog Processes: Gases dissolve in a water droplet and chemically react. A

particle exists when the water evaporates.

Sulfate

Chemical Reaction: Gases react to form particles.

Section 7 – Chemical Aspects

53
of Air Pollution
 Particulate Matter Composition (2 of 3)
PM contains many compounds
Primary Particles Secondary Particles
(directly emitted) (from precursor gases)

VOCs
Carbon Organic
(Soot) Carbon
SO2

Metals

Ammonium Composition of PM tells

Sulfate us about
Crustal
(soil,dust)
the sources and
Ammonium formation processes
Other
Nitrate
(sea salt)
Ammonia
Gas

NOx
Particle

54
 Sulfur Dioxide
• Sulfur dioxide (SO2) belongs to the family of sulfur oxide (SOx)
gases.
• Gases are formed when fuel containing sulfur (mainly coal and oil) is
burned and during metal smelting and other industrial processes.
• Affects the respiratory system
• Reacts in the atmosphere to form acids, sulfates, and sulfites
• Contributes to acid rain

Impact of low soil

pH on agriculture
in Victoria
German sandstone
statue, 1908, 1969

Low crown density

55 of spruce trees
 Particulate Matter Chemistry
Sulfate Chemistry Heterogeneous Oxidation

● Virtually all ambient sulfate (99%)

is secondary, formed within the
atmosphere from SO2 during the
summer.
● About half of SO2 oxidation to sulfate
occurs in the gas phase through
photochemical oxidation in the daytime.
NOx and hydrocarbon emissions tend to
enhance the photochemical oxidation rate.
Husar (1999)
● At least half of SO2 oxidation takes place
in cloud droplets as air molecules react in clouds.
● Within clouds, soluble pollutant gases, such as SO2, are scavenged
by water droplets and rapidly oxidize to sulfate.
● Only a small fraction of cloud droplets deposit out as rain; most
droplets evaporate and leave a sulfate residue or “convective
debris”.
● Typical conversion rate 1-10% per hour

56
 Mechanisms of Converting S(IV) to
S(VI)
Why is converting to S(VI) important?
It allows sulfuric acid to enter or form within cloud drops
and aerosol particles, increasing their acidity

Mechanisms
1. Gas-phase oxidation of SO2(g) to H2SO4(g) followed by
condensation of H2SO4(g)

2. Dissolution of SO2(g) into liquid water to form

H2SO3(aq) followed by aqueous chemical conversion of
H2SO3(aq) and its dissociation products to H2SO4(aq) and
its dissociation products.
57
58
 Particulate Matter Chemistry
Nitrate Chemistry
● NO2 can be converted to nitric acid (HNO3) by reaction with
hydroxyl radicals (OH) during the day.
– The reaction of OH with NO2 is about 10 times faster than the OH
reaction with SO2.
– The peak daytime conversion rate of NO2 to HNO3 in the gas phase
is about 10% to 50% per hour.
● During the nighttime, NO2 is converted into HNO3 by a series of
reactions involving ozone and the nitrate radical.
● HNO3 reacts with ammonia to form particulate ammonium nitrate
(NH4NO3).
● Thus, PM nitrate can be formed at night and during the day;
daytime photochemistry also forms ozone.

59
 Particulate Matter Chemistry
PM Sample
Sources Emissions Formation PM Transport/Loss Collection
Chemical Processes
Mechanical Particles
• Sea salt • NaCl
• Dust • Crustal gases condense onto particles
cloud/fog processes Measurement
Issues
Combustion Particles • Inlet cut points
• Motor vehicles • Soot transport • Vaporization of
• Industrial • Metals nitrate, H2O, VOCs
• Fires • OC sedimentation • Adsorption of VOCs
(dry deposition) • Absorption of H2O
Gases condensation and
• NOx coagulation
• SO2 wet deposition
• VOCs photochemical production
• NH3 cloud/fog processes
Other gaseous Gases
• Biogenic • VOCs
• Anthropogenic • NH3
• NOx
Meteorological Processes
Winds Clouds, fog Winds Temperature
Temperature Temperature Precipitation Relative humidity
Solar radiation Relative humidity Winds
Vertical mixing Solar radiation

60
 Particulate Matter Meteorology
How weather affects PM emissions, formation, and transport
Phenomena Emissions PM Formation PM Transport/Loss

Aloft Pressure No direct impact. No direct impact. Ridges tend to produce conditions conducive for accumulation of PM2.5.
Pattern Troughs tend to produce conditions conducive for dispersion and removal of PM and
ozone.
In mountain-valley regions, strong wintertime inversions and high PM2.5 levels may not be
altered by weak troughs.
High PM2.5 concentrations often occur during the approach of a trough from the west.

Winds and No direct impact. In general, stronger winds disperse Strong surface winds tend to disperse PM2.5 regardless of season.
Transport pollutants, resulting in a less ideal Strong winds can create dust which can increase PM2.5 concentrations.
mixture of pollutants for chemical
reactions that produce PM2.5.

Temperature No direct impact. Inversions reduce vertical mixing and A strong inversion acts to limit vertical mixing allowing for the accumulation of PM2.5.
Inversions therefore increase chemical
concentrations of precursors. Higher
concentrations of precursors can
produce faster, more efficient
chemical reactions that produce
PM2.5.

Rain Reduces soil and fire emissions Rain can remove precursors of Rain can remove PM2.5.
PM2.5.

Moisture No direct impact. Moisture acts to increase the No direct impact.

production of secondary PM2.5
including sulfates and nitrates.

Temperature Warm temperatures are associated
with increased evaporative,
biogenic, and power plant
emissions, which act to increase
PM2.5. Cold temperatures can also
indirectly influence PM2.5
concentrations (i.e., home heating
on winter nights).
Photochemical reaction rates
increase with temperature.
Although warm surface temperatures are generally associated with poor air quality
conditions, very warm temperatures can increase vertical mixing and dispersion of
pollutants.
Warm temperatures may volatize Nitrates from a solid to a gas.
Very cold surface temperatures during the winter may produce strong surface-based
inversions that confine pollutants to a shallow layer.

Clouds/Fog No direct impact. Water droplets can enhance the Convective clouds are an indication of strong vertical mixing, which disperses pollutants.
formation of secondary PM2.5. Clouds
can limit photochemistry, which limits
photochemical production.

Season
Section 7Forest fires, wood burning,
– Chemical Aspects
agriculture burning, field tilling,
The sun angle changes with season,
which changes the amount of solar61
No direct impact.

of Air Pollution
windblown dust, road dust, and radiation available for
construction vary by season. photochemistry.
ANNUAL MEAN PARTICULATE MATTER (PM) CONCENTRATIONS AT U.S. SITES, 1995-2000
NARSTO PM Assessment, 2003

PM10 (particles > 10 mm) PM2.5 (particles > 2.5 mm)

Red circles indicate violations of national air quality standard:

50 mg m-3 for PM10 15 mg m-3 for PM2.5

62
BLACK CARBON EMISSIONS
DIESEL

DOMESTIC
COAL BURNING

BIOMASS
BURNING

63 Chin et al. [2000]

 RADIATIVE FORCING OF CLIMATE, 1750-PRESENT

IPCC [2001]

“Kyoto also failed to address two major pollutants that have an impact on warming: black soot and
tropospheric ozone. Both are proven health hazards. Reducing both would not only address
climate change, but also dramatically improve people's health.” (George W. Bush, June 11 2001 Rose
Garden speech)

64
Particles Impact Human Health and MORE
 EPA REGIONAL HAZE RULE: FEDERAL CLASS I AREAS TO RETURN TO “NATURAL”
VISIBILITY LEVELS BY 2064

…will require essentially total elimination of anthropogenic aerosols!

clean day moderately polluted day

Acadia National Park
http://www.hazecam.net/
66