8.

Environmental Chemistry of the Atmosphere

8.1. The Atmosphere and Atmospheric

Chemistry
Dry air is air is 78.1% (by volume) nitrogen,
21.0% oxygen, 0.9% argon, and 0.04% carbon
dioxide
Air contains 1-3% water vapor
Minor amounts of other gases including neon,
helium, methane, krypton, nitrous oxide,
hydrogen, xenon, sulfur dioxide, ozone, nitrogen
dioxide, ammonia, carbon monoxide, and even
chlorofluorocarbons (see Table 8.1)
Atmospheric Chemistry and Photochemistry
Molecules in atmospheric air are far apart compared to liquids and
solids
The most significant feature of atmospheric chemistry is the
occurrence of photochemical reactions resulting from the
absorption by molecules of photons of electromagnetic radiation
from the sun, mostly in the ultraviolet region of the spectrum

The meaning of h: The energy, E, of a photon of visible or

ultraviolet light is given by the equation, E = h, where h is Planck’s
constant and n is the frequency of electromagnetic inversely
proportional to its wavelength, 
• Ultraviolet radiation energetic enough to break chemical bonds

• Example: O3 + h( < 420 nm)  O* + O2

Species Formed by Photochemical Reactions
• Excited state, such as O* or NO2*, in which
electrons are in a higher energy state
making a species much more reactive
• Reactive free radicals containing an
unpaired electron denoted with a dot, •
O* + H2O HO • + HO •
Third body, M, to absorb excess reaction
energy
O* + O2 + M O3 + M
8.2. IMPORTANCE OF THE ATMOSPHERE

Atmosphere as a source of
chemicals
• Carbon dioxide for plant
photosynthesis
• Oxygen for respiration
• Chemically bound nitrogen for plants
and chemical production
• Water for rainfall
Protective function of the atmosphere
• Absorbs cosmic radiation
• Absorbs electromagnetic radiation from
the sun
• Allows transmission in the regions of
300-2500 nanometers (near-ultraviolet,
visible, and near-infrared radiation)
• Allows transmission of radio waves,
0.01–40 meters
• Absorbs damaging ultraviolet radiation
below 300 nm protecting from its
destructive effects
• Absorbs some of the infrared radiation
8.3. PHYSICAL CHARACTERISTICS OF THE
ATMOSPHERE
Variation of Pressure and Density with
Temperature, ÞC
Altitude
-100 -80 -60 -40 -20 0
100

80
Altitude, Pressure:
km
60 Temperature:
------
40

20

0
-6 -5 -4 -3 -2 -1 0
log ph
More than 99% of the total
mass of the atmosphere is
found within approximately 30
km of Earth’s surface
• A particle with a mean free path of 1
 10-6 cm at sea level has a mean free
path greater than 1  106 cm at an
altitude of 500 km
• At very high altitudes, reactive
species, such as O, persist for very
long times before colliding with
something with which they can react
8.4. ENERGY TRANSFER IN THE ATMOSPHERE

Energy and mass transfer in the

atomsphere
• Determine physical characteristics of
the atmosphere
• Indirectly determine chemical
characteristics
• The solar constant or flux is 1.34 
103 watts per square meter (Figure
8.3)
Figure 8.2. Major regions
of the atmosphere
Figure 8.3. Illustration of
the solar constant
Energy Transport in the Atmosphere
• Radiation (such as infrared)
• Conduction
• Convection
• Sensible heat (like you feel when you bite into
a tamale caliente)
• Latent heat (water vapor)
Figure 8.4. Earth’s radiation budget expressed as portions of the
solar flux.
Earth’s Radiation Budget

• Average surface temperature of about 15˚C because

of reabsorption of outgoing infrared radiation by
primarily water vapor and carbon dioxide
• Increasing carbon dioxide levels in the atmosphere
may cause a greenhouse effect (global warming)
• Effect of surface albedo (reflection of sunlight)
• Freshly fallen snow 90%
• Freshly plowed (cultivated land) 2.5%
8.5. ATMOSPHERIC MASS TRANSFER, METEOROLOGY,
AND WEATHER

Meteorology is the science of atmospheric

phenomena encompassing the study of the
movement of air masses as well as heat, wind,
and transitions of water vapor between liquid
and vapor
Meteorological phenomena affect, and are
affected by, chemical phenomena
• Stagnant air masses subjected to strong
sunlight can result in formation of
photochemical smog
• Air pollutants can form clouds and increase
rainfall
Weather consists of short-term variations in
meteorological phenomena

• Temperature • Clouds • Winds • Humidity

• Pressure
• Kind and quality of precipitation

Climate consists of longer term variations in

weather
Atmospheric Water in Energy and Mass Transfer
• Large amounts of solar heat are converted to
latent heat in evaporating water and
released when it condenses
Heat from oceans to heat on land
Psychrometric chart Water-Air
Atmospheric water as vapor, liquid droplets, or
ice crystals
• Humidity refers to water content in air,
relative humidity
• Dew point is temperature where water
condenses
• Condensation nuclei to form water droplets
(salt crystals, sulfuric acid droplets,
organic materials, various air pollutants)
• Clouds formed as small water droplets in
rising, adiabatically cooling masses of air
• Cirrus, cumulus, and stratus clouds are
major types (rain) falls from clouds by
Precipitation
relatively complex processes by which cloud
droplets come together to form drops (bodies
of ice, snowflakes) large enough to fall
Air masses are a major feature of the
troposphere
• Horizontally homogeneous (uniform)

• Uniform in temperature and water content

• Various types depending upon where they are

formed
• Polar continental • Polar maritime
• Tropical
continental
• Example of hot, dry, dusty air mass that
moved from the Sahara to North America,
early August, 2005
• The movement of air masses and the
conditions in them may have important
Topographical Effects

• Surface affects winds and air currents

• Differential heating and cooling from land

and water surface
• Effects of mountains

• Blocking air masses by mountains

8.7. GLOBAL CLIMATE AND MICROCLIMATE
Climate may vary during the year
• Example: Monsoons with heavy rainfall
Climate may vary over several years periods
of time
• Back-and-forth shift of the southern
boundary of the Sahara desert
• The El-Niño-Southern Oscillation occurs
with a period of several years when a large,
semi-permanent tropical low-pressure area
shifts into the Central Pacific region from
its more common location in the vicinity of
Indonesia affects rainfall and climate in
Mexico
Very long-term variation in climate

• Ice ages lasting thousands of years (last

one ended only about 10,000 years ago)
• “Mini ice age” during 1300s

• 300-year drought in northern Mexico,

southwestern U.S. several centuries past
Effects of Urbanization on Microclimate
Microclimate may range from the area within a
few cm of soil surface to the envelope of air
over a major and
• Vegetation urban area of water have a
bodies
moderating effect, absorbing modest amounts
of solar energy and releasing it slowly
• Cities strongly absorb solar energy, and re-
radiate heat back to the urban microclimate
• Heat islands capped by a heat dome in which
the temperature is as much as 5˚C warmer
than in the surrounding rural areas
• Rising warmer air may bring in wind from
surrounding areas
• Particulate matter in the city atmosphere
causes it to be warmer, foggier, and
overlain with more cloud cover for longer
8.8. Chemical and Photochemical Reactions in the Atmosphere
One Huge Atmospheric Chemical Cycle with Many
Subcycles: Gaseous Atmospheric Chemical Species
Include
• Inorganic oxides (CO, CO2, NO2, SO2)

• Oxidants (O3, H2O2, HO. radical, HO2. radical,

ROO. radicals, NO3)
• Reductants (CO, SO2, H2S)

• Organics (also reductants, CH4 predominates

but others more active)
• Oxidized organic species (carbonyls, organic
nitrates)
• Photochemically active species (NO2,
formaldehyde)
• Unstable reactive species (electronically
Role of Particles in Atmospheric Chemistry
• Solid particles provide surface reactive
sites and sinks
• Liquid droplets enable solution reactions
and serve as sources and sinks for reactive
Two Important Influences on Atmospheric
species
Chemistry
• Radiant energy from the sun, predominantly
ultraviolet (energy)
• Hydroxyl radical, HO (key intermediate in
chain reactions)
Importance of chemical kinetics (rates of
reactions)
Photochemical Processes
Photochemical reactions that otherwise would
not occur
Formation of an electronically excited
•species
Free radicals and ions may also form from
absorption of photons
NO2 + h NO2*
• Excited states, which may lose energy by
several chemical and physical processes
Each horizontal line denotes
an orbital and each arrow
denotes an electron with one
of two possible spins

Ground Singlet Triplet

state state state
Infrared radiation cannot break chemical
bonds
• Increases vibrational and rotational energy

• Energy dissipated as heat that warms

surroundings
Ions and Radicals in the Atmosphere

• Ionosphere above 50 km altitude (raises at

night)
• Ions generated in the troposphere by
shearing processes
Free radicals with unpaired electrons, •
O O
H3C C H + h H3C• + • C H

• Free radicals are involved with most

significant atmospheric processes
• Because of their unpaired electrons and the
strong pairing tendencies of electrons under
most circumstances, free radicals are highly
reactive
• Can last long times at high altitudes
because of rarefied conditions (thin air)
• Chain terminating reactions involving free
radicals
H3C• + H3C• C2H6
Hydroxyl and Hydroperoxyl Radicals in the
Atmosphere
The hydroxyl radical, HO•, is the single most
important reactive intermediate species in
atmospheric chemical processes formed by
• Stratosphere: H2O + h  HO• + H•
several processes
• In the laboratory and troposphere: HONO +
h  HO• + NO•
• By H2O2 + h  HO• + HO•
• From: O3 + h( < 315 nm)  O* + O2, O* +
H2O  2HO•
HO• involved in chemical transformations of
trace species in the atmosphere including
hydroxyl radical are carbon monoxide, sulfur
dioxide, hydrogen sulfide, methane, and
nitric oxide
Hydroxyl radical is most frequently removed
from the troposphere by reaction with methane
or carbon monoxide:
CH4 + HO•  H3C• + H2O
CO + HO•  CO2 + H•
The hydrogen atom produced in the above
reaction reacts with O2 to produce
hydroperoxyl radical, an intermediate in some
important chemical reactions:
The hydroperoxyl radical can undergo chain
termination reactions, such as
HOO• + HO•  H2O + O2
HOO• + HOO•  H2O2 + O2
or reactions that regenerate hydroxyl
radical:
HOO• + NO  NO2 + HO•
HOO• + O3  2O2 + HO•
Chemical and Biochemical Processes in
Evolution of the Atmosphere
• Original atmosphere reducing

• Photosynthesis by cyanobacteria produced

atmospheric O2
CO2 + H2O + h {CH2O} +
O2(g)
• Led to other changes, such as formation iron
ore deposits
4Fe2+ + O2 + 4H2O  2Fe2O3 +
8H+
• Eventually organisms developed that could
utilize O2
8.9. ACID-BASE REACTIONS IN THE ATMOSPHERE
Atmosphere normally slightly acidic because
of the following reactions that occurs in
atmospheric water
CO2(g) CO2(aq) (8.9.1)
CO2(aq) + H2O H+ + HCO3-
(8.9.2)
Stronger acids from pollutant sources
SO2(g) + H2O H+ + HSO3-
(8.9.3)
Strongest acids as secondary pollutants in
acid rain
• HNO3 • H2SO4
Ammonia is the significant base species in the
atmosphere
• From bacterial reduction of nitrate:

NO3-(aq) + 2{CH2O} (biomass) + H+ 

NH3(g) + 2CO2 + H2O
• Neutralizes atmospheric acids

NH3(aq) + HNO3(aq) NH4NO3(aq)

(8.9.6)
NH3(aq) + H2SO4(aq) NH4HSO4(aq)
(1) Result in the presence of NH4+ ion in
(8.9.7)
the atmosphere as dissolved or solid
• These reactions
salts
(2) Serve in part to neutralize acidic
constituents of the atmosphere
8.10. REACTIONS OF ATMOSPHERIC OXYGEN
The oxygen cycle is critically important in
atmospheric chemistry, geochemical
transformations, and life processes
Oxygen in the troposphere plays a strong role
in processes that occur on the earth’s
surface.
• Energy-producing reactions, such as burning
of fossil fuels:
CH4(in natural gas) + 2O2  CO2 +
2H2O (8.10.1)
• Utilized by oxic organisms in the
degradation of organic material
• Oxidative weathering of minerals

4FeO + O2  2Fe2O3 (8.10.2)

Oxygen is returned to the atmosphere by plant
photosynthesis:
CO2 + H2O + h {CH2O} + O2
 h

O3 + h  O + O2
ozone shield: absorption
O + O2 + M  O 3 + M of ultraviolet radiation
from 220 nm to 330 nm
O2 + h  O + O

2CO + O2  2CO2
oxygen consumed
by reducing gases O2 CO2
of volcanic origin CO2

O2 O2 O2
{CH2O} + O2  CO2 + H2O
CO 2 CO2
respiration by animals

C + O2  CO2
oxygen consumed CO2 + H2O + h  {CH2 O} + O2
by burning fossil O2 + 4FeO  2Fe2 O3
fuels Oxidative weathering (photosynthesis)
of reduced minerals
Ca2+ + CO32+  CaCO2
Figure 8.7. Major aspects of the combined oxygen
held in sediments
exchange of oxygen among the
environmental spheres.
Oxygen in the upper atmosphere
• Less O2 and more O, O*, O2*, and O3
• O2 + h(wavelengths 135-176 nm and 240-260
nm)  O + O
• Oxygen atoms in the ground state (O) and in
excited states (O*)
• O3 + h(< 308 nm) O* + O2 (8.10.5)
• O + O + O O2 + O* (8.10.6)
• O* emits airglow at wavelengths of 636 nm,
630 nm, and 558 nm
Protective ozone in the Stratosphere
• O2 + h(wavelength less than 242.4 nm), 
O + O
• O + O2 + M O3 + M
• Ozone reaches maximum fraction of air at an
altitude of 25-30 km high in the
stratosphere where it may reach 10 ppm
• The absolute concentration of ozone in the
atmosphere peaks at a value of almost 1013
molecules/cm3 at an altitude of 20–25 km
where the atmospheric pressure is less than
1/10 atmospheric pressure
• Ozone absorbs ultraviolet radiation very
strongly in the region 220-330 nm
Ozone is thermodynamically unstable: 2O3 
3O
• This
2 reaction is catalyzed by many species including
NO, NO2, H, HO, HOO, ClO, Cl, Br, and BrO

• Example of NO catalysis of ozone

destruction
NO + O3  NO2 + O2
O3 + h  O2 + O
O + NO2  NO + O2
2O3  3O2 (Net reaction)
Ozone in the Troposphere
• Species most characteristic of photochemical
smog
• Toxic to animals and plants
• Damages materials, particularly rubber
8.11. REACTIONS OF ATMOSPHERIC NITROGEN
N2 is extremely stable
At altitudes exceeding approximately 100 km
N2 + h  N + N (8.11.1)
The N2+ ion is generated by photoionization in
the atmosphere:
N2 + h  N2+ + e- (8.11.2)
The NO+ ion, is one of the predominant ionic
species in the E region of the ionosphere
Pollutant oxides of nitrogen, particularly
NO2, are key species involved in air
pollution and the formation of photochemical
smog
8.12. ATMOSPHERIC WATER
Water vapor in the atmosphere
• Water vapor content of the troposphere is
normally within a range of 1–3% by volume
with a global average of about 1%
• As little as 0.1% or as much as 5% water

• Percentage of water in the atmosphere

decreases rapidly with increasing altitude
• Water circulates through the atmosphere in
the hydrologic cycle as shown in Figure 2.2
• Absorbs infrared radiation more strongly
than carbon dioxide
Evaporation and condensation of water vapor
strongly involved in energy transfer
Atmospheric water droplets are involved with
pollutant reactions, corrosion, visibility
Very cold tropopause prevents movement of
water into the stratosphere
Main source of water in the stratosphere is
the following:
(several steps)
CH4 + 2O2 + h CO2
+ 2H2O (8.12.1)
This is a source of stratospheric hydroxyl
radical:
H2O + h  HO• + H•
8.13. PARTICLES IN THE ATMOSPHERE
• Range in size from about one-half millimeter
(the size of sand or drizzle) down to
molecular dimensions
• Great variety of materials and discrete
objects that may consist of either solids or
liquid droplets
• Particulates is a term that has come to
stand for particles in the atmosphere
• Makes up the most visible and obvious form
of air pollution
• Atmospheric aerosols are solid or liquid
particles smaller than 100 µ m in diameter
• Pollutant particles in the 0.001 to 10 µ m
range are commonly suspended in the air near
Some Terms Describing Atmospheric Particles

• Aerosol: Colloidal-sized atmospheric particle

• Condensation aerosol: Formed by
condensation of vapors or reactions of gases
• Dispersion aerosol: Formed by grinding of
solids, atomization of liquids, or dispersion of
dusts
• Smoke: Particles formed by incomplete
combustion of fuel
• Mists: Liquid particles
Formation and Origin of Particles
Very small, solid particles include carbon black, silver iodide,
combustion nuclei, and sea-salt nuclei formed by the loss of water
from droplets of seawater
Larger particles include cement dust, wind-blown soil dust, foundry
dust, and pulverized coal
Liquid particulate matter, mist, includes raindrops, fog, and sulfuric
acid droplets
Some particles are of biological origin, such as viruses, bacteria,
bacterial spores, fungal spores, and pollen
Chemical Processes for Inorganic Particle
Formation
Metal oxides
From pyrite in coal: 3FeS2 + 8O2 
Fe3O4 + 6SO2
Organic vanadium in residual fuel oil is
converted to particulate vanadium oxide
Calcining of calcium carbonate: CaCO3 +
Aerosol  CaO acid
heat sulfuric + COmist:
2 2SO2 + O2 +
2H2O  2H2SO4
Formation of salts from aerosol sulfuric acid:
H2SO4(droplet) + 2NH3(g)  (NH4)2SO4
(droplet)
H2SO4(droplet) + CaO(s) 
Fig. 8.8. Origins of
atmospheric particulate
matter
Fly Ash
Fly ash consists of oxides and silicates that
get put out the stack in the combustion of
fossil fuels
• Coal is the most common source

• Some fuel oils produce significant ash

• Smaller particles of fly ash are the most

likely to be released and the most damaging
and hard to control
Composition of fly ash depends upon the
source of fuel
• Predominant constituents are oxides of
aluminum, calcium, iron, and silicon
• Smaller amounts of magnesium, sulfur,
titanium, phosphorus, potassium, and sodium
• Elemental carbon (soot, carbon black) is a
significant fly ash constituent
Organic Particles
Organic particulate matter is produced by
internal combustion engines
• Complicated processes that involve
pyrosynthesis and nitrogenous compounds
• Nitrogen-containing compounds and oxidized
hydrocarbon polymers
• Lubricating oil and its additives may also
contribute to organic particulate matter
quantitatively
• Organic particles include n-alkanes, n-
alkanoic acids, benzaldehydes, benzoic
acids, azanaphthalenes, polycyclic aromatic
hydrocarbons, oxygenated PAHs
Organic particles of greatest concern are PAH
(polycyclic aromatic hydrocarbons) consisting
of condensed ring aromatic molecules
• The most often cited PAH compound is
benzo(a)pyrene, a compound that the body can
metabolize to a carcinogenic form:

Benzo(a)pyrene
PAHs may be synthesized from saturated
hydrocarbons under oxygen-deficient
conditions (see reaction below) or by
pyrolysis of higher alkanes at high
temperatures H
H H H
-H C H -H
H C C H H C C
heat H C heat
H H C H
H
H C
H H
Polycyclic aromatic
hydrocarbons
Effects of Particles
• Reduction of visibility
• Other Effects and processes summarized in
Figure 8.9, below:
Hydrocarbon

h

R* Photochemical processes on
Evolution of particle surface
volatile species

XY
Solution reactions in liquid
droplets, such as,
HCl + NH 3  NH4Cl Catalytic surface on
which
X + Y
Gas/solid reactions, such as
CaO(s) + SO 2(g)  CaSO 3(s)

Condensation of vapor

H2O
8.14. INFLUENCE OF THE ANTHROSPHERE
• Agricultural, industrial, and transportation
activities have substantially altered the
composition of trace gases in the
atmosphere, particularly greenhouse gases
• NO from industrial, transportation, biomass
burning have increased tropospheric ozone
• Chlorofluorocarbons have reduced
stratospheric ozone
8.15. Chemical Fate and Transport in the Atmosphere
Consider sources, transport, dispersal, and fluxes of airborne
contaminants
Pollutants in the atmosphere may be viewed on local, long-
range, and global scales
Example of smoke stack dispersal, below

Wind Vertical and

horizontal spreading

Lift

Stack
Long-range transport of species in the
atmosphere
Example: Contamination of Scandinavia by
Chernobyl nuclear reactor
Some important atmospheric pollutants must be
considered on a global scale for materials
produced from a variety of widely dispersed
sources with very long lifetimes so that they
persist long enough to mix with and spread
throughout the global atmosphere
Example: Greenhouse gas carbon dioxide
emitted to the atmosphere by billions of
heating and cooking stoves, millions of
automobiles, and thousands of power plants
throughout the globe.
Earth’s atmosphere cannot be considered as a
single large mixing bowl for contaminants on
a global scale
• Prevailing winds cause relatively rapid
mixing within the northern and southern
hemisphere, whereas transport of atmospheric
constitutents across the equator is
relatively slow
• Photosynthetic pulse of carbon dioxide in
the northern hemisphere
Distillation effect of semivolatile
persistent organic pollutants into arctic
regions and cold mountainous regions leading
to high levels of PCBs in polar bear fat