CHM 404

INTRODUCTION TO ENVIRONMENTAL
AND PETROLEUM CHEMISTRY
 OUTLINE
• General introduction to environmental chemistry
• Concepts of elementary cycle.
• Characteristics of the Atmosphere
• Sources, types and effects of environmental
pollution
• Water and waste water treatment
• Composition of domestic water
• Water chemistry and analysis
• Recycling and uses of waste products
 INTRODUCTION
• Environmental chemistry is the aspect of chemistry that deals
with the nature, source, transport, reaction and fate of a
chemical substance in the environment.
• When we talk about the environment, we are talking about air,
water and soil environment.
• Nature of the Environment.
 A lot of damages has been done to the environment in recent
times through:
 Nuclear accidents
 Global wars
 Oil spillage
 Use of pesticides
• Etc.
Challenges of Environmental chemistry
• The major challenges include:
• Dealing with the determination of the nature and quantities
of specific pollutants in the environment. Therefore, chemical
analysis is a major part of environmental chemistry.

• Many species are involved.

• Significant level of some chemical species in the air may just

be few micrograms per cubic meter, for water 1ppm might be
very significant. Hence, chemical analyses used to study some
environmental systems require a very low limit of detection.
Nature of the Problems that environmental chemistry tries to solve

1. Fresh air is rare particularly in urban cities

2. Underground sources of drinking water are
being threatened.
3. Exhaust of fuel combustion.
4. Impacts of CFC, acid rain, green-house gases
etc.
5. Impact of industries and developmental
activities
 Subdivisions of Environmental Chemistry

• The atmosphere: Envelope of gases surrounding the

Earth.
• The hydrosphere: Dealing with water in many
forms.
• The lithosphere: Dealing with outer part of the solid
earth
• Biosphere: Refers to life, including living organisms
and their immediate environment.
 DEFINITIONS
Some terminologies commonly used in environmental chemistry are as
follows:
1. Samples - Substances collected for the purpose of analysis
2. Contaminant - A substance that is present in greater
than normal concentration in the environment.
3. Pollutant - A substance that is present in greater than
normal concentration in the environment and possess
detrimental effect on man or something of value in
the environment.
4. Source - The place of origin of a pollutant. This is a logical
place to eliminate a pollutant.
5. Receptor- Something that is being affected by a pollutant
6. Sink - Final repository of a pollutant. e.g. limestone can be
a sink for H2SO4.
H2SO4 + CaCO3 ----------- CaSO4 + H2O + CO2
 The Atmosphere
Importance of atmosphere

1. The atmosphere is the protective blanket that nurtures life on the earth and protect it from
the hostile environment of the outer space.

2. The atmosphere is the source of carbon dioxide for plant photosynthesis and oxygen for
respiration.

3. It provides nitrogen

4. It serves to transport water from ocean to land thereby acting as a condenser.

5. It has been used as a dumping ground for many pollutant material

6. It serves protective functions as it absorbs most of the cosmic rays from outer space and
protects organisms from their effects.

7. The atmosphere stabilizes earth temperatures

Physical Characteristics of the Atmosphere

Thermosphere 500 km

Mesosphere

Stratosphere O3

Troposphere

Earth
 Composition of Air

• Dry air within several kilometers of ground

level consists of :
• Nitrogen - 78.08% by volume
• Oxygen - 20.95%
• Argon - 0.934%
• Carbon Dioxide -0.035%
• Other noble gases and some trace gases are
also present in dry air in minute quantities.
 Air Pollution
• Air pollution may be defined as any atmospheric
condition in which substances are present at
concentrations high enough above their normal
ambient levels to produce a measurable effect on
man, animals, vegetation, or materials.
• Substances mean any natural or anthropogenic
(man-made) chemical compounds capable of
being airborne. They may exist in the atmosphere
as gases, liquid drops, or solid particles.
 Pollutants
• The following are designated as air pollutants of
national concern in many countries of the world.
• Sulfur Dioxide
• Carbon Monoxide
• Carbon Dioxide
• Hydrocarbons
• Ozone and other photochemical oxidants
• Chlorofluorocarbons (CFC).
 Classifications of Air Pollutants
A. According to chemical composition:
• 1. Sulfur-containing compounds.
• 2. Nitrogen-containing compounds.
• 3. Carbon-containing compounds.
• 4. Halogen-containing compounds.
• 5. Toxic substances (any of about).
• 6. Radioactive compounds.
 Air Pollution classifications cont.
B. According to physical state:
• 1. Gaseous. 2. Liquid (aqueous). 3. Solid.
C. According to the manner in which they reach
the atmosphere:
1. Primary pollutants (those emitted directly from the
sources).
2. Secondary pollutants (those formed in the
atmosphere by chemical interactions among
primary pollutants and normal atmospheric
conditions).
 Air Pollution classifications cont.
D. According to the space /scales of their effects:
• 1. Local (or indoor).
• 2. Regional.
• 3. Global.
 Criteria air pollutants
• There are six major pollutants defined by EPA
(Environmental Protection Agency) for which
ambient air standards have been set to protect
human health and welfare.
• 1. Ozone, O3.
• 2. Carbon monoxide, CO.
• 3. Sulfur dioxide, SO2.
• 4. Nitrogen oxides, NOx.
• 5. Lead, Pb.
• 6. Particulates, PM10.
 Ozone as a pollutant
• Ozone, O3, is a gas.
• At ground level, ozone is a hazard (‘bad’
ozone)
• In the stratosphere, it serves to absorb some
of the potentially harmful UV radiation from
the sun, (‘good’ ozone).
• Sources: Formed from precursors: VOCs, and
nitrogen oxides.
 "Bad" ozone effects:

1. Diverse effects on human health

2. Ecological effects: damage vegetable and
trees
3. Formation of photochemical smog
 Major sulfur-containing compounds:

• Sulfur dioxide, SO2,

• It is a colorless gas with a sharp odor,
• It is a primary pollutant,
• It has anthropogenic (man-made) and natural
sources.
 Sources of SO2
• Anthropogenic: industries burning sulfur-
containing fossil fuels, ore smelters, oil
refineries.
Sulfur is present in many fuels (e.g., coal, crude
oils) over a wide range of concentrations.
Combustion causes its oxidation to sulfur
dioxide.
• Natural: marine plankton, sea water, bacteria,
plants, volcanic eruption.
• H2S can also be converted to SO2 by the
following process:
• H2S + 3/2 O2 ---- SO2 + H2O
• H2S + HO* ---- HS* + H2O
• HS* + O2 ----- HO* + SO*
• SO* + O2 ----- SO2 + O*
 Effects of SO2
• At relatively high concentrations SO 2 causes severe
respiratory problems.
• Sulfur dioxide is an acid precursor, which is a source of acid
rain produced when SO2 combines with water droplets to
form sulfuric acid, H2SO4
• Sulfur dioxide is a precursor of sulfate particulates (sulfates)
which affect the radiation balance of the atmosphere and
can cause global cooling
• Low pH affect fish directly
• It contributes to the increase in the solubility of metals
(from sediment to water).
 Major Nitrogen-containing Compounds

• Nitrogen, N2, is a dominant gas of the atmosphere

about 78% by volume
• NOx stands for a mixture of NO, and NO2
• Nitrogen oxides, NOx, are formed mainly from N2
and O2 during high-temperature combustion of
fuel.
• Anthropogenic sources: motor vehicles, biomass
burning
• Natural sources: bacteria, lightning, biomass
burning
 Effects of Atmospheric Nitrogen
• At high altitude > 100km, atomic N is
produced by photochemical reaction
• N2 + hv --- N + N
• N2+ + O --- NO* + N
• NO react with ozone to form NO2
• NO + O3 -- NO2 + O2
• This step is important in ozone layer
distruction.
 Effects of NOX
• Causes the reddish-brown haze in city air which
contributes to heart and lung problems and may be
carcinogenic.
• NOx is an acid precursor, which is a source of acid rain
• NO2 + H2O ---- HNO3
• Nitrogen oxides are the precursors of nitrate particulates
(nitrates) which affect the radiation balance of the
atmosphere and can contribute to global cooling .
• Nitrogen oxides are major contributors to the formation
of ground level ‘bad’ ozone
 Major carbon-containing compounds
• The 2 major carbon containing gases in the
atmosphere are:
– Carbon monoxide
– Carbon dioxide
 Carbon monoxide, CO
• CO is a colorless odorless flammable gas.
• It is a major pollutant of an urban air,
produced from incomplete combustion.
• Anthropogenic sources: petrol engine motor
cars, cigarette smoke, biomass burning
• Natural sources: biomass burning
 Effects of CO
• CO is highly poisonous to humans and most
animals when inhaled, CO reduces the ability
of blood hemoglobin to attach oxygen.
• NOTE: Don’t confuse carbon monoxide, CO,
and carbon dioxide, CO2. Carbon dioxide is a
complete oxidation product of fuel
combustion.
• In the atmosphere, CO is oxidized to CO2.
 Carbon Dioxide CO2
• Carbon dioxide, CO2, is a key greenhouse gas

Principal sources:
• fossil fuel combustion
• deforestation
• cements production.
 Hydrocarbons and volatile organic carbons
(VOCs):
• Organic gases are those that contain both
hydrogen and carbon, but may also contain
other atoms; hydrocarbons (HCs) are organic
gases that contain only hydrogen and carbon.
Volatile organic compounds (VOCs) are non-
methane hydrocarbons (NMHC) and
oxygenated hydrocarbons (which are
hydrocarbons plus oxygenated functional
groups),
• Methane, CH4, is the most abundant
hydrocarbon in the atmosphere, found in
exhaust gas from automobiles, biomass burning,
agriculture activities (e.g., rice paddies).
• Anthropogenic sources: indoor sources (e.g.,
formaldehyde emission), fossil fuel combustion,
evaporation of gasoline (e.g., petroleum
refineries; during fueling of cars),
• Natural sources: HCs produced from
decomposition of organic matter; emitted by
certain types of plains (e.g., pine trees, creosote
bushes)
 Major halogen- containing compounds
• Chlorofluorocarbons, CFCs, are artificial gases, used as the
coolants in refrigerators and air conditioners,; they are
neither toxic nor flammable. The most abundant CFCs are
CFC-11 (or CFCl3), and CFC-12 (or CF2Cl2).
• CFCs are artificial halocarbons, therefor they are not
biodegradable. CFCs are not water-soluble, therefore they
are not washed from the atmosphere by rain. In the
stratosphere, UV radiation destroys CFCs breaking them
down to a few chemicals (including atomic chlorine and
atomic bromine which efficiently destroy ozone).
• CFCs effects:
• They are the key greenhouse compounds.
• They lead to reduction of stratospheric "good" ozone
 Metals as the pollutants.

• Metals (such as lead, mercury, cadmium,

chromium, nickel) found as impurities in fuels.
• Anthropogenic sources: emitted by metal
mining and processing facilities; motor
vehicle.
• Example: lead is a very useful metal, has been
mined for thousands of years
• Main effect: They are highly toxic.
 Particulate matters
• Particulate matters (aerosols) are solid or aqueous
particles composed of one or several chemicals and small
enough to remain suspended in the air
• Examples: dust, soot, smoke, sulfates, nitrates, asbestos,
pesticides, bio-aerosols (e.g., pollen, spores, bacterial
cells, fragments of insects, etc.)
• PM(10) are particles with diameter < 10 micrometers
(µm).
• Anthropogenic sources: various (biomass burning, gas to
particle conversion; industrial processes; agriculture’s
activities)
• Natural sources: various (sea-salt, dust storm, biomass
burning, volcanic debris, gas to particle conversion)
Forms of Airborne Non-gaseous Pollutants

• Dust: - solid particles that are entrained by

process gas directly from a source. Dust
particles are between 0.1 and 10µm in
diameter
• Fume: Solid particles formed by the
condensation of vapours by sublimation,
distillation, calcination or other chemical
reactions. Fume particles are from 0.03-0.3µm
in diameter
• Mist: Liquid particles formed by the
condensation of a vapour and sometimes by
chemical reaction.
• Smoke: consist of solid particles formed by
incomplete combustion of carbonaceous
materials. Smoke particle diameters are
between 0.05-1µm
• Spray – Liquid particle formed by the
atomization of a parent liquid
• Aerosol: Colloidal sized atmospheric particles.
 Effects of Particulate Matter

• Contribute to urban haze, cause visibility reduction

• Provide active surfaces upon which heterogeneous
atmospheric chemical reactions can occur.
• Diverse health effects (e.g., harmful to human
respiratory system).
• Respiratory system may be damaged directly or
indirectly by particulate matter that enters the blood
system.
• Particles smaller than 0.1µm in diameter can scatter
light like molecules.
• Play a key role in the Earth’s radioactive budget and
global change.
 Control of Particulate Emissions
• The removal of particulate matter from gas
streams is widely practices as air pollution
control.
• 1. Particle removal by sedimentation and
inertia
• Particle filtration – use of bag house
The air pollution problem can be schematically presented as a system consisting of
three basic components:

Emission
Source Atmosphere Receptor
Trace
metal
Source Health effect
Ni Fuel oil, coal, tobacco smoke Lung cancer
Be Coal, industry Acute and chronic system poison, cancer
Se Coal, sulfur May cause dental caries
Hg Coal, electrical batteries & Nerve damage and death
industries

V Petroleum, steel, etc Probably no hazard

Cd Coal, Zinc, water mains & pipes Cardiovascular disease & hypertension
Pb Auto exhaust, paint Brain damage, convulsion, behavioral
disorder and death

Zn Metal plating, mining, tyre wear Possible lung effect, low toxicity
Cr Cr-plating, pigment & alloy Chronic catarrh and carcinogenesis
Mn Iron and steel industry, fuel oil Chronic Mn-poisoning, Mn-pneumonia