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Section 7
Chemical Aspects
of Air Pollution
Overview of Basic Pollutants
Ozone
Particulate Matter
Carbon Monoxide
Sulfur Dioxide
Nitrogen Oxides
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Photochemical Smog

Air pollution formed by sunlight catalyzing chemical reactions

of emitted compounds
Los Angeles, California
• Early pollution due to London-type smog.
1905-1912, L.A. City Council adopts regulation controlling smoke
• Early 1900’s, automobile use increases.
1939-1943 visibility decreases significantly.
• Plume of pollution engulfs downtown (26 July 1943).
1943: L.A. County Board of Supervisors bans emission of dense
smoke and creates office called Director of Air Pollution Control
• 1945. L.A. Health Officer suggests pollution due to locomotives,
diesel trucks, backyard incinerators, lumber mills, dumps, cars.
• 1946. L.A. Times hires air pollution expert to find methods to
ameliorate pollution.
Section 7 – Chemical Aspects of Air Pollution
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(December 3, 1909)

Library of Congress Prints and Photographs Division, Washington, D. C.

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Discovery of Ozone in Smog
• 1948: Arie Haagen-Smit (1900-1977), biochemistry professor at
Caltech, begins to study plants damaged by smog.
• 1950: Finds that plants sealed in a chamber and exposed to
ozone exhibit similar damage as did plants in smog
• Also finds that ozone caused eye irritation, damage to materials,
respiratory problems.
• Other researchers find that rubber cracks within minutes when
exposed to high ozone.
• 1952: Haagen-Smit finds that ozone forms when oxides of
nitrogen and reactive organic gases are exposed to sunlight.
Postulates that ozone and precursors are main constituents of
L.A. smog.
• Oil companies and business leaders argue that ozone in L.A.
originates from stratosphere.
• Measurements of low ozone over Catalina Island disprove this.

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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

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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

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Basic Pollutants (3 of 3)

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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)
25% 20%

Mobile
National air toxics emissions sources in 1996 Point
(onroad)
24%
U.S. Environmental Protection Agency, 1998 31%

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Basic Pollutants – Toxics (2 of 2)

• Differences between toxics and criteria

pollutants
– Health criteria are different
• No AQI-like standards for toxics
• Cancer/non-cancer benchmarks (long-term exposures)
• Short-term exposure limits for some
– 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
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Basic Pollutants – Sources (1 of 4)

• Combustion
• Evaporation
• Natural Production

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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

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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)

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Basic Pollutants – Sources (4 of 4)

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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

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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

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Solar radiation and chemistry
• The reaction that produces ozone in the
atmosphere:
O + O2 + M  O3 + M
• Difference between stratospheric and
tropospheric ozone generation is in the source
of atomic O
• For solar radiation with a wavelength of less
than 242 nm:
O2 + hv  O + O

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Solar radiation and chemistry
• Photochemical production of O3 in troposphere tied to NOx (NO +
NO2)
• For wavelengths less than 424 nm:
NO2 + hv  NO + O
• But NO will react with O3
NO + O3  NO2

• Cycling has no net effect on ozone

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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

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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)

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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

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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
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THE OH RADICAL: MAIN
TROPOSPHERIC OXIDANT
• Primary source:
• O3 + hn  O2 + O(1D) (1)
• O(1D) + M  O + M (2)
• O(1D) + H2O  2OH (3)

• Sink: oxidation of reduced species –leads

to HO2(RO2) production
• CO + OH  CO2 + H Major
• CH4 + OH  CH3 + H2O OH sinks
• HCFC + OH

• Global Mean [OH] = 1.0x106 molecules

cm-3

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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  O 3
CO + 2 O2 + hv  CO2 + O3

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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

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What breaks the cycle?
• 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
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Ozone Chemistry
Summary of ozone chemistry
Meteorology

• NO2 + Sunlight  NO + O Production

• O+ O2  O3 Production
Emissions Chemistry

• NO + O3  NO2 + O2 Destruction
• VOC + OH  RO2 + H2O Production of NO2 without the
• RO2 + NO  NO2 + RO Destruction of O3
RO=Reactive Organic compound such as VOC
Key processes
• Ample sunlight (ultraviolet)
• High concentrations of precursors (VOC, NO, NO2)
– Weak horizontal dispersion
– Weak vertical mixing
• Warm air
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Day and Night Chemistry

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Ozone Precursor Emissions (1 of 2)

● Man-made sources Meteorology

– Oxides of nitrogen (NOx) through

combustion
– VOCs through combustion and Emissions Chemistry

numerous other sources

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

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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

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An example of gridded NOx emissions

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

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GOME Can Provide Info on Daily Info

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Lightning Flashes Seen from Space

DJF

JJA

2000 data
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Global Budget of CO

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GAW Satellite Observations of Biomass
Fires (1997)

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Daily Los Angeles Emission (1987)
Gas Emission (tons/day) Percent of total
Carbon monoxide 9796 69.3
Nitric oxide 754
Nitrogen dioxide 129
Nitrous acid 6.5
Total NOx+HONO 889.5 6.3
Sulfur dioxide 109
Sulfur trioxide 4.5
Total SOx 113.5 0.8
Alkanes 1399
Alkenes 313
Aldehydes 108
Ketones 29
Alcohols 33
Aromatics 500
Hemiterpenes 47
Total ROGs 2429 27.2
Methane 904 6.4

Total emission 14,132 100

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Percent Emission by Source-LA

Source Category CO(g) NOx(g) SOx(g) ROG

Stationary 2 24 38 50
Mobile 98 76 62 50
Total 100 100 100 100

Section 7 – Chemical Aspects of Air Pollution

Table 4.2
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Most Important Gases in Smog in Terms of
Ozone Reactivity and Abundance

1. m- and p-Xylene
2. Ethene
3. Acetaldehyde
4. Toluene
5. Formaldehyde
6. i-Pentane
7. Propene
8. o-Xylene
9. Butane
10. Methylcyclopentane

Section 7 – Chemical Aspects of Air Pollution

Table 4.4
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Lifetimes of ROGs Against Chemical
Loss in Urban Air
ROG Species Phot. OH HO2 O NO3 O3
n-Butane --- 22 h 1000 y 18 y 29 d 650 y
trans-2-butene --- 52 m 4y 6.3 d 4m 17 m
Acetylene --- 3d --- 2.5 y --- 200 d
Formaldehyde 7h 6h 1.8 h 2.5 y 2d 3200 y
Acetone 23 d 9.6 d --- --- --- ---
Ethanol --- 19 h --- --- --- ---
Toluene --- 9h --- 6y 33 d 200 d
Isoprene --- 34 m --- 4d 5m 4.6 h

Table 4.3
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Summary

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Ozone Meteorology – Key Processes

• Dispersion (horizontal mixing)

• Vertical mixing
• Sunlight Meteorology

• Transport
• Weather pattern
•
Emissions Chemistry
Geography
• Diurnal
• Season

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Ozone Precursor Emissions (2 of 2)

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

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Daily Variation

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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

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Figure 4.10
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Ozone Isopleth Plot
0.25
0.08 = O (g), ppmv 0.4

0.32
0.32
0.2
(g) (ppmv)

0.08
x x (ppmv)

0.24
0.24
0.15
3
NO

0.16

0.1
0.16
NO

0.05

0
0 0.5 1 1.5 2
ROG (ppmC)
Contours are ozone (ppmv)
Section 7 – Chemical Aspects of Air Pollution Figure 4.9
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THIS OZONE BACKGROUND IS A SIZABLE INCREMENT
TOWARDS VIOLATION OF U.S. AIR QUALITY STANDARDS
(even more so in Europe!)

Europe
(8-h avg.)
Europe U.S. U.S.
(seasonal) (8-h avg.) (1-h avg.)

0 20 40 60 80 100 120 ppbv

preindustrial present
background

Section 7 – Chemical Aspects of Air Pollution

Slide courtesy of D. Jacob 46
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EU/USA
SURFACE OZONE ENHANCEMENTS CAUSED BY
ANTHROPOGENIC EMISSIONS FROM DIFFERENT CONTINENTS
GEOS-CHEM
model, July 1997

North America

Europe

Asia

Li et al. [2002]
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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

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

Particle sizes
• Ultra-fine particles (<0.1 μm)
• Fine particles (0.1 to 2.5 μm)
PM10

• Coarse particles (2.5 to 10 μm)

Crustal material Carbon chain agglomerates

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Particulate Matter (3 of 3)

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

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Particulate Matter Composition (1 of 3)

PM is composed of a mixture of primary and secondary

compounds.

● Primary PM (directly ● Secondary PM (precursor gases

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

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Particulate Matter Composition (3 of 3)
Most PM mass in urban and nonurban areas is composed of a
combination of the following chemical components
• Geological Material – suspended
dust consists mainly of oxides of Al,
Si, Ca, Ti, Fe, and other metal
oxides
• Ammonium – ammonium bisulfate,
sulfate, and nitrate are most
common
• Sulfate – results from conversion of
SO2 gas to sulfate-containing
particles
• Nitrate – results from a reversible
gas/particle equilibrium between
ammonia (NH3), nitric acid (HNO3),
and particulate ammonium nitrate
Section 7 – Chemical Aspects of Air Pollution
• NaCl – salt is found in PM near sea
coasts and after de-icing materials
are applied
• Organic Carbon (OC) – consists of
hundreds of separate compounds
containing mainly carbon, hydrogen,
and oxygen
• Elemental Carbon (EC) –
composed of carbon without much
hydrocarbon or oxygen. EC is
black, often called soot.
• Liquid Water – soluble nitrates,
sulfates, ammonium, sodium, other
inorganic ions, and some organic
material absorb water vapor from
the atmosphere
Chow and Watson (1997)
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PM Emissions Sources (1 of 4)
Point – generally a major facility emitting pollutants from identifiable
sources (pipe or smoke stack). Facilities are typically permitted.

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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

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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

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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

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AREP COMPOSITION OF PM2.5 IS HIGHLY VARIABLE (NARSTO PM
GAW ASSESSMENT)

Sulfate

Esther (1995-99) Nitrate

4.6 ug m -3 Egbert (1994-99) Toronto (1997-99) Ammonium
8.9 ug m -3 12.3 ug m -3
Black carbon
Abbotsford (1994-95)
7.8 ug m -3 Organic carbon
Soil
Other

St. A ndrews (1994-97)

5.3 ug m -3

Fresno (1988-89)
39.2 ug m -3
Quaker City OH (1999)
12.4 ug m -3

Kern Wildlife Refuge (1988-89)

23.3 ug m -3 Arendstville PA (1999)
10.4 ug m -3

Mexico City -
Netzahualcoyotl (1997) Washington DC (1996-99)
Los Angeles (1995-96) 55.4 ug m -3 14.5 ug m -3
30.3 ug m -3

Colorado Plateau (1996-99) Mexico City - Pedregal (1997) Yorkville (1999) Atlanta (1999)
3.0 ug m -3 24.6 ug m -3 14.7 ug m -3 19.2 ug m -3
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ORIGIN OF THE ATMOSPHERIC AEROSOL

Aerosol: dispersed condensed matter suspended in a gas

Size range: 0.001 mm (molecular cluster) to 100 mm (small raindrop)

Soil dust
Sea salt

Environmental importance: health (respiration), visibility, radiative balance,

cloud formation, heterogeneous reactions, delivery of nutrients…
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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.

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

NOx
Particle

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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

Section 7 – Chemical Aspects of Air Pollution Low crown density

of spruce trees
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Particulate Matter Chemistry (2 of 4)
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
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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.
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Particulate Matter Chemistry (3 of 4)

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.

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Particulate Matter Chemistry (4 of 4)
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

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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 Forest fires, wood burning,

agriculture burning, field tilling,
windblown dust, road dust, and
construction vary by season.
Section 7 – Chemical Aspects
The sun angle changes with season,
which changes the amount of solar
No direct impact.
of Air Pollution
radiation available for
photochemistry.
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GAW 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
Section 7 – Chemical Aspects of Air Pollution
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AEROSOL OPTICAL DEPTH (GLOBAL MODEL)

Annual mean

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AEROSOL OBSERVATIONS FROM SPACE

Biomass fire haze in central America yesterday (4/30/03)

Fire locations
in red

Modis.gsfc.nasa.gov
Section 7 – Chemical Aspects of Air Pollution
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BLACK CARBON EMISSIONS
DIESEL

DOMESTIC
COAL BURNING

BIOMASS
BURNING

Section 7 – Chemical Aspects of Air Pollution

Chin et al. [2000]
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GAW 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
Section 7 – Chemical Aspects of Air Pollution
Garden speech) 73
 Particles Impact Human Health and MORE
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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
Section 7 – Chemical Aspects of Air Pollution
http://www.hazecam.net/
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GAW ASIAN DUST INFLUENCE IN UNITED STATES
Dust observations from U.S. IMPROVE network
April 16, 2001 April 22, 2001
Asian dust in western U.S. Asian dust in southeastern U.S.

0 2 4 6 8
mg m-3

Glen
Canyon,
AZ

Section 7 – Chemical Aspects of Air April

Pollution16, 2001: Asian dust!
Clear day
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Aerosols Link Air Quality, Health and
Climate:
Dirtier Air and a Dimmer Sun

Anderson et al., Science 2003 Smith et al., 2003 He et al., 2002

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77