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Chapter 12
ORGANIC AIR POLLUTANTS

Environmental Chemistry, 9th Edition

Stanley E. Manahan
Taylor and Francis/CRC Press
2010

For questions, contact:

Stanley E. Manahan
manahans@missouri.edu

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12.1 Organic Compounds in the Atmosphere
Direct effects
• Example: Cancer from vinyl chloride
Secondary pollutants
• Especially photochemical smog
Loss of Organic Substances from the Atmosphere
• Precipitation (rainwater) • Dry deposition
• Photochemical reactions • Incorporation into particles
• Tend to undergo photochemical reactions leading to
solids that are purged from the atmosphere
• Uptake by plants, especially trees
• Absorbed by lipophilic layer on leaves and needles of
trees
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Global Distillation and Fractionation of Persistent
Organic Pollutants
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12.2 Biogenic Organic Compounds in the Atmosphere (1)
Natural sources most abundant sources of atmospheric
organics
• Methane from bacteria and geosphere is the most
abundant organic in the atmosphere
• Anoxic bacteria: 2{CH2O} CH4 + CO2
• Flatulent emissions from livestock
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12.2 Biogenic Organic Compounds in the Atmosphere (2)
Terpenes from vegetation, primarily pine and citrus trees,
are second to methane as organics in the atmosphere
• Generally very reactive (in photochemical smog formation)
• Form much of the small particulate matter in atmosphere
• See structural formulas, next slide
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Figure 12.1 Common terpenes emitted by trees such as pine
and citrus
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Oxidation Products of Terpenes

Pinonic Acid from

Oxidation of -Pinene

Reaction of Limonene with Ozone

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Esters in the Atmosphere
• Many kinds of esters, largely from plant sources
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Removal of Atmospheric Organic Compounds by Plants
Repositories of persistent organic pollutants
Leaves and needles covered by epicular organophilic wax
that accumulates atmospheric organics
• Especially in evergreen boreal coniferous forests in the
northern temperate zone
• Heavy forestation and large leaf surface per unit forest
area
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12.3 Pollutant Hydrocarbons
Alkanes, such as 2,2,3-
Trimethylbutane

Alkanes are relatively very stable

Alkanes undergo abstraction reactions
• React with HO•

• Subsequent reaction with O2 causes formation

• React with O from NO2 photodissociation
• Additional reactions that produce solid aerosols and
soluble substances that are removed from the atmosphere
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Alkenes
Among top 50 chemicals produced annually

Alkynes are unsaturated hydrocarbons sometimes highly

reactive. They are encountered at very low levels in the
atmosphere
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Alkenes undergo addition reactions
Example: Propene adds HO•, then reacts with O2 and
undergoes further reactions

O2

Further reactions with radicals, NO, and other species to

produce aldehydes, additional reactive products
Ozone adds across alkene double bonds
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NO3 radical reacts with alkenes
Especially at night when NO3 is relatively long-lasting

Alkenes reacting with hydroxyl radical in presence of N

oxides can produce hydroxynitrates
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Aromatic (Aryl) Hydrocarbons
• Single ring • Double ring • Polycyclic

Aromatic Hydrocarbons Among Top 50 Chemicals

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Reactions of Atmospheric Aromatic Hydrocarbons
• Addition reactions, especially with HO•

Benzene + HO•

Electron delocalized on aromatic ring

Aliphatic side chains on substituted aromatics may undergo
abstraction reactions with hydroxyl radical
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12.4 Carbonyl Compounds: Aldehydes and Ketones

Carbonyl compounds generated from organic alkoxyl

radicals by reactions such as the following:
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Atmospheric Aldehydes and Ketones

Most common atmospheric carbonyl is formaldehyde

typically generated from methoxyl radical

H3CO• + O2 HOO• +
The carbonyl group is a chromophore absorbing ultraviolet
photons, h
• Produces formyl radical, HCO, as shown for acetaldehyde:

Because of the C=C bond, alkenyl aldehydes

are especially reactive in the atmosphere
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12.5 Miscellaneous Oxygen-Containing Compounds

Alcohols: Methanol, ethanol, isopropanol, ethylene glycol

among top 50 chemicals worldwide
• Potential air pollutants, especially volatile methanol
Alcohols are removed from atmosphere quickly
• Lower alcohols water-soluble
• Higher alcohols not very volatile
Alcohols react by HO• abstraction of H atoms
Alkenyl alcohols
• Cis-3-hexen-1-ol, “leaf alcohol”: CH3CH2CH=CHCH2CH2OH
Alkenyl alcohols add HO• or O3
across double bond
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Phenols

Phenol among top 50 chemicals produced

• Can cause localized air pollution problems from
industrial use and coal coking
Ethers
• Not very reactive
• Attacked by
hydroxyl radical
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Oxides

Among top 50 chemicals

Ethylene oxide
• Colorless, flammable, explosive
• Uses as chemical intermediate, sterilant, fumigant
• Hazardous due to flammability, toxicity
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Carboxylic Acids, Figure 12.2
Higher carboxylic acid common in particulate matter
• From photochemical oxidation of hydrocarbons
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12.6 Organonitrogen Compounds

More oxidized organonitrogens produced by reaction of

photochemical oxidants, NOx, NO3
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Amines
Hydrocarbon-substituted NH3
Lower amines are volatile and noxious
Some aromatic amines are carcinogens

Most common amide in the atmosphere is

dimethylformamide
Volatile acetonitrile (H3CCN) containing the -C N group
reported as air pollutants from synthetic rubber manufacture
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Nitro Compounds
Nitromethane H3CNO2, nitroethane, nitrobenzene have been
reportrd as air pollutants
Highly oxygenated compounds containing the nitro group
• Secondary pollutants from photochemical smog formation
• Intense irritants to eyes and respiratory tract
• Mutagens • Phytotoxins (harm plants)
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Heterocyclic nitrogen compounds largely in particles

Special case of carcinogenic nitrosamines (N-nitroso

compounds)
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12.7 Organohalide Compounds
Most commonly organochlorine compounds
More volatile ones reported as air pollutants:

Vinyl chloride (right) is widely used

in polyvinylchloride manufacture
and is a known human carcinogen
Aromatic halide compounds
Chlorofluorocarbons such as dichlorodifluoromethane 27
cause stratospheric ozone depletion (see more detail in
Chapter 14)
• Extremely stable
• In stratosphere
• CF2Cl2 + h Cl• + CF2Cl2•
• Cl• + O3 + h ClO• + O2
• Additional reactions generate more Cl and destroy more
fluorocarbon
Chlorofluorocarbons such as dichlorodifluoromethane 28
cause stratospheric ozone depletion (see more detail in
Chapter 14)

• Substitutes for chlorofluorocarbons have been

developed
Halons such CBrClF2C3l3 that contain Br strongly deplete
stratospheric ozone
• No good substitutes for fire extinguisher fluids
Perfluorocarbons
• CF4 and C2F6 released in aluminum manufacture
• Greenhouse gases that are virtually indestructible in the
atmosphere
Marine sources of organohalogens: Many generated by
marine microorganisms
Atmospheric Reactions of Hydrofluorocarbons and
Hydrochlorofluorocarbons

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Polychlorinated Biphenyls (PCBs) and Polychlorinated
Dibenzo-p-Dioxins (TCDD) in the Atmosphere
PCBs and TCDD discussed as water pollutants in Chapter 7
• Not manufactured
• Extremely stable
• Would be associated with particles in the atmosphere
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12.8 Organosulfur Compounds
Predominantly thiols (R-SH) and thioethers (R-S-R)

Lighter thiols are notable for odors

• Skunk odor due to thiols
Dimethylsulfide generated in large quantities by marine
micoorganisms is the largest source of atmospheric SO2 in
marine areas
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12.9 Organic Particulate Matter
End product of photochemical smog formation
Organic matter often associated with
• Condensed PAH solid particles
• Elemental C particles
•And N often added to organic particulate matter by the
action of reactive species
• HO• O3 • NOx • NO3 radical
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12.10 Hazardous Air Pollutants Organic
Compounds
See organic compounds in EPA list of hazardous organic air
pollutants in Table 12.1