Environmental Chemistry and Toxicology

(Chem 452)

Department of Chemistry
Hawassa University, College of Natural and Computational
Chemistry

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 Unit One: Introduction to Environmental
Chemistry and Toxicology
1.Basic concepts in Environmental Chemistry
• To understand environmental chemistry, it is important to have some appreciation of
environmental science as a whole.

• What is Environmental Science?

• Is the science of
• The complex interactions that occur among the
• Terrestrial, (Geosphere)
• Atmospheric, (Atmosphere)
• Aquatic, (Hydrosphere)
• Living, (Biosphere) and
• Anthropological environments (Anthrosphere)
• It includes all the disciplines, such as chemistry, biology, ecology, sociology, and
government that affect or describe these interactions.
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 • Is the science of (in relation to environmental chemistry)
• The study of the earth, air, water, and living environments, and the
effects of technology thereon.
• Ecology
• The study of environmental factors that affect organisms and
• How organisms interact with these factors and with each other.

• Environmental science
• Has been divided among the study of

• The atmosphere, the hydrosphere, the geosphere, the biosphere,

and their interactions with the anthrosphere.

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03/28/2022 4
Environmental
  Chemistry
 

• Defined as the study of the origins, transport,

reactions, effects and fates of chemical species in
water, air, terrestrial and living environments, and
the effects of human activity thereon.

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• An environmental chemistry encompasses the many diverse topics

• It may involve a study of chlorofluorocarbons (Freon) reactions in the

stratosphere or

• An analysis of polychlorinated biphenyls (PCB) deposits in ocean

sediments

• It also covers the chemistry and biochemistry of volatile and soluble

organo-metallic compounds biosynthesized by anaerobic bacteria.

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• The ultimate  environmental concern is that of life itself

• The discipline that deals specifically with the effects of environmental chemical

species on life is environmental biochemistry

• A related area, toxicological chemistry, is the chemistry of toxic substances with

emphasis upon their interactions with biologic tissue and living organisms.

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  Components of the environment
(Environmental Segments)

air, water, earth, life, and technology

Air – atmosphere
Water – hydrosphere
Earth – geosphere
Life – Biosphere
Technology – anthrosphere

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The hydrosphere
 
 
o Contains Earth’s water
o A collective term given to all different forms of water
o It includes all types of water resources such as oceans, seas, rivers, lakes, streams,
reservoirs, glaciers and ground waters.
• Only 1% of the total water supply is available as fresh water
• in the form of rivers, lakes, streams and ground water for human consumption and
other uses
• The extent of the use of available fresh water for various purposes is
• 50% for thermal power plants,
• 30% for irrigation,
• 13% for industrial uses and
• 7% for domestic uses

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The
  geosphere

o Consists of the solid earth, including soil, which

supports most plant life
Or
o The geosphere, or solid Earth, is that part of the
Earth upon which humans live and from which they
extract most of their food, minerals, and fuels.

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• The earth is  divided into layers, including
 
• the solid, iron-rich inner core,
• molten outer core,
• mantle, and
• Crust
• Environmental science is most concerned with the lithosphere, which consists
of the outer mantle and the crust

• The crust is the earth’s outer skin that is accessible to humans

• It is extremely thin compared to the diameter of the earth, ranging from 5 to
40 km thick.

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The biosphere
 
o All living entities on Earth compose the biosphere

o The biosphere refers to the realm of living organisms and their

interactions with the environment (VIZ: atmosphere, hydrosphere
and lithosphere)

o The biosphere is very large and complex and is divided into

smaller units called ecosystems

o Plants, animals and microorganisms which live in a definite zone

along with physical factors such as soil, water and air constitute an
ecosystem
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The biosphere
o Within each ecosystems there are dynamic inter relationships between living forms and

their physical environment

o These inter relationships manifest as natural cycles (hydrologic cycle, oxygen cycle,

nitrogen cycle, phosphorous cycle and sulfur cycle)

o The natural cycles operate in a balanced manner providing a continuous circulation of

essential constituents necessary for life and this stabilizes and sustains the life

processes
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Cont’d
 

The Anthrosphere, the technology,

oIt is one of the significant spheres of the
environment
oTechnology refers to the ways in which
humans do and make things with materials
and energy
oIn the modern era, technology is to a large
extent the product of engineering based on
scientific principles.
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Cont’d
 

The Anthrosphere, the technology,

o Science deals with
o The discovery, explanation, and development
of theories pertaining to interrelated natural
phenomena of energy, matter, time, and space
o Based on the fundamental knowledge of
science, engineering provides the plans and
means to achieve specific practical objectives.
Technology uses these plans to carry out the
desired objectives.

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Cont’d
 
• Technology, properly applied,
• Is an enormously positive influence for
environmental protection
• The most obvious such application is in
air and water pollution control. As
necessary as “end-of-pipe” measures are
for the control of air and water pollution,
it is much better to use technology in
manufacturing processes to prevent the
formation of pollutants.

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Cont’d
 
• Technology is being used increasingly
• To develop highly efficient processes of
energy conversion,
• To develop renewable energy resource
utilization, and conversion of raw materials
to finished goods with minimum generation
of hazardous waste by-products
• In the transportation area, properly applied
technology in areas such as high speed train
transport can enormously increase the speed,
energy efficiency, and safety of means for
moving people and goods.
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Cont’d
 
• Until very recently, technological advances were made
largely without heed to environmental impacts
• Now, however, the greatest technological challenge
• Is to reconcile technology with environmental
consequences
• The survival of humankind and of the planet that supports it
now requires that the established two-way interaction
between science and technology become a three-way
relationship including environmental protection.

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  Some common terms related to pollution
Pollutant:
If the concentration of a substance already present in nature is increased to un-
required ratio due to human activity, which ultimately has a detrimental effect
on the environment either by reducing the quality of life or affecting the health
then it is known as a pollutant. For example, sulphur dioxide, carbon
monoxide, lead, mercury, excess heat, sound etc. are all called as pollutants.

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Cont’d
 
Contaminant:
• A contaminant is a substance that
does not occur in nature, but is
introduced by human activity into the
environment. A contaminant is called
a pollutant when it exerts detrimental
effect on human health. It is also a
pollutant.

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Cont’d
 
Receptor:
A receptor may be anything which
is affected by the pollutant. For
example, man is a receptor of
contaminated water because
cholera and gastroenteritis are
caused by it.

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Cont’d
 
Sink:
It is the medium, which interacts and
retains the long lived pollutant. The
oceans are the sinks for atmospheric
carbon dioxide. Ground water and
subsoil water act as sinks for pesticides
employed in agriculture.

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Cont’d
 
Dissolved Oxygen (DO):
• Oxygen dissolved in water is vital for aquatic life. The
optimum value for dissolved oxygen in good quality
water is 4-8 mg/L
• It is consumed by oxidation of organic matter/
reducing agent etc. present in water
• Water which has DO value less than 4 mg/L is termed
as polluted and is unfit for human or aquatic animal
consumptions.

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Cont’d
 
Chemical Oxygen Demand (COD):
• It is an index of the organic content of water, since the
most common substance oxidized by the dissolved
oxygen in water is organic matter, which has a
biological origin, such as dead plants etc. The COD of
a water sample is determined by the chemical
oxidation of the organic matter by K2Cr2O7 in 50%
H2SO4. This method includes other reducible inorganic
species that may be present in water such as NO2-,
S2O32-, S2-, etc., and hence this method does not truly
reflect the organic content in water. However since
this method is rapid, it is widely used.
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Cont’d
 
Biological Oxygen Demand (BOD):
• The capacity of the organic matter in the sample of
natural water to consume oxygen is called its BOD. It
is determined experimentally by determining the
dissolved oxygen (DO) at the beginning and at the end
of a 5-day period in a sealed sample. The BOD gives
the measure of oxygen utilized or consumed in the
period as a result of oxidation of dissolved organic
matter present in the water sample.

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Cont’d
 
Threshold limit value (TLV):
• This value indicates the permissible level
of a toxic pollutant in atmosphere to
which a healthy industrial worker can be
exposed during an eight-hour day without
any adverse effect. TLV of a pollutant is
found by experimentation on animals,
medical knowledge and experience and
environmental studies.

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 1.2
 
Properties of chemicals in the environment
 
• When chemicals, especially organics such as pesticides, are released
in the environment, it becomes distributed among four major
compartments: water, air, soil, and biota (living organisms).

• The fraction of the chemical that will move into each compartment
is governed by the physico-chemical properties of that chemical.

• An example is BCF (bio-concentration factor), which is a measure

of the amount of pesticide that will accumulate in aquatic organisms.
•
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Cont’d
 

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• Chemicals  may be released and dispersed into the environment during manufacture,

distribution or use.

• In some instances, the chemical is highly reactive and degrades very rapidly; often the

main mechanism is breakdown by bacteria or other organisms and there are standard tests

to evaluate the biodegradability of synthetic chemicals.

• On the other hand, many such chemicals, in order to be useful in products, are relatively

long-lived and hence may be persistent within the environment.

• 03/28/2022 29
• In general, chemicals undergo degradation and their
degradation may proceed by a wide number of
processes and the reactivity of a chemical is governed
by its stereochemistry (3- dimensional structure),
bond strengths and the presence of functional
groups.

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1.3.  Environmental transformation and degradation

• Abiotic and biotic transformation and degradation

• Both abiotic and biotic processes will transform a chemical pollutant.

• Abiotic processes

• oxidation,

• reduction,

• hydrolysis and photolysis.

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• Indeed these generic reactions are not mutually exclusive, as the
generation of oxidants present in the atmosphere for example,
requires the action of sunlight on precursor molecules (e.g. the
formation of the OH radical from ozone).

• Processes of distribution and fate of chemicals in the

environment
• There are generally three processes that determine the distribution
and degradation of chemicals in the environment
• physical,
• chemical and
• biological processes.
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Cont’d
 
• Physical processes
• Sedimentation,
• Adsorption and,
• Volatilization
• Chemical processes
• Oxidation & Reduction,
• Hydrolysis and photolysis
• Biological mechanisms
• Oxidation & Reduction,
• Hydrolysis and conjugation to degrade chemicals

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The process of degradation will largely be governed by the

o Compartment (water, soil, atmosphere, biota) in which the pesticide is

distributed, and
o This distribution is governed by the physical processes
• For instance,

• Reduction reactions may occur on pesticides possessing nitro (−NO2),

aliphatic Chloro (−Cl) and Carbonyl (−C=O) groups.
• Hydrolysis reactions may occur on Epoxide (−O−), Carboxylic
(−COOR) and Phosphate (P−OR) esters and Amide (−NH2) groups
• Oxidation reactions may occur on Sulfo (−S=O) and Alkyl (CnH2n+1)
groups and on Benzene ring and C=C bond.
• 03/28/2022
Conjugation may occur in the process of methylation (by fungi) and34
 Factors
 
affecting the distribution and fate of chemicals in the
  environment

• Solubility,

• Octanol/water partition coefficient,

• Hydrolysis,

• Soil adsorption coefficient,

• Bio-concentration factor,

• Vapour pressure,

• Henry´s law constant,

• Volatilization,

• Photolysis,

•03/28/2022
Microbial metabolism (biodegradation). 35
 Solubility
• If a chemical’s water solubility is known the distribution of that chemical
in the environment and possible degradation pathways can be determined.
For example, chemicals that have high solubility will remain in water
and tend to not be adsorbed on soil and living organisms

• This solubility is in turn affected by molecular polarity, hydrogen

bonding, molecular size, temperature, pH and symmetry.

• A chemical that is very soluble in water will tend to not accumulate in soil
or biota because of its strong polar nature. This suggests that it will
degrade via hydrolysis which is the reaction that is favored in water.

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 Octanol/Water partition coefficient – Kow

• Partition coefficient is an indicator of the environmental fate of a chemical

since it gives a general idea of how a chemical will be distributed in the
environment.

• Kow (octanol/water partition coefficient) is defined as the ratio of a chemical’s

concentration in octanol divided by its concentration in water. (Kow is unitless).
• Values of Kow are presented in books in log (Kow) values and range from -3 to 7.

• Chemicals with large log Kow values are of great concern since they can be
adsorbed in soils and living organisms.

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03/28/2022 38
• The factors that affect Kow include molecular polarity and physical factors such
as molecular surface area, boiling point, molar volume, molecular weight and
density.
 
• Generally, highly polar molecules have low Kow. Moreover, the Kow will increase
when the values of the above physical factors increase.

• In general, a large Kow, value means that a chemical tends to be in an organic

(non-polar) environment and not in water (polar environment). This means that it
will have low water solubility. Most pesticides are less polar than water, thus they
tend to accumulate in soil or living organisms which contain organic matter.

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 Hydrolysis
• Hydrolysis is an important reaction that takes place in water for pesticide
degradation. A pesticide reacts with water to form degradation products that can be
distributed in the environment.

• Hydrolysis means that a chemical has reacted with water to form a new product.

• Pesticide hydrolysis rates are generally described in half lives which is the amount
of time it takes for half of an amount of a chemical to be hydrolyzed.

• Hydrolysis reactions are not always just one step, there can be several steps and
different pathways that hydrolysis can follow.

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Factors Influencing Hydrolysis
• Substituents, temperature and pH. Hydrolysis is very temperature sensitive because an
increase of 1oC can increase the rate by 10% and a difference of 10oC can affect the rate
by as much as a factor of 2.5.

Chemical Hydrolysis half-life (Days)

Atrazine ……………………. 42-180

Carbaryl…………………….. <14

DDT…………………………. >180

• Hydrolysis half life values will help one to estimate how long a chemical will persist in an
aqueous environment. If the chemical resists hydrolysis then it may degrade via some other
pathway such as microbial metabolism.

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 Soil adsorption coefficient: Koc/Kd
• Adsorption of pesticides on soils or sediments is a major factor in the
transportation and eventual degradation of chemicals.

• Most pesticides are non-polar and hydrophobic, which means that they are not
very soluble in water.

• Water solubilizes polar chemicals because it can bond with them more easily.

• Chemicals that are non-polar tend to be pushed out of water and onto soils
which contain non-polar carbon material.

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• Soils vary in the amount of organic carbon content, which is mainly what
determines the amount of pesticide adsorbed. Kd is called the sorption
coefficient and it measures the amount of chemical adsorbed onto soil per
amount of water

• Values for Kd vary greatly because the organic content of soil is not
considered in the equation. The preferred value for determining a soil’s ability
to adsorb is Koc, since it considers the organic content of the soil.

• Kd=
• Koc=

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Factors influencing soil adsorption coefficient
• Organic carbon content
• The amount of carbon present in soil is probably the greatest factor influencing the
amount of chemical adsorbed.
• This is because organic matter is non-polar and has a relatively light negative charge.
Most pesticides are non-polar and will be attracted to the lightly charged surface. As the
organic content of soil increases so does the amount adsorbed.

• Polarity
• Polarity greatly determines whether the chemical will partition into the soil. A polar
pesticide will be highly water soluble and tend not to be adsorbed onto soil.
• If the pesticide is non-polar, it will tend to leave water and be adsorbed onto soil. Once
adsorbed, non-polar molecules will more strongly bind to soils than polar ones, so polar
molecules will be more mobile in soil.
• This process occurs when water is present because the chemical is able to dissolve in
water and move through soil. The chemical move by dissolution and deposit on another
portion
03/28/2022 of soil and the process continues. 44
 Cont’d
• pH
• Weak acids and bases are generally the only ones affected by pH. Soil has a slight
negative charge (acidic) and tends to adsorb positively charged chemicals. Pesticides
that are not ionizable are generally not affected by pH.

• Salinity
• An increase in the amount of salts present in water will generally decrease the amount
of chemicals adsorbed that are in the cationic (positive) form. This is due to the
competition for bonding sites on the soil.

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Organic matter in solution

• Organic matter can be dissolved or suspended in water. Non-polar

chemicals can be adsorbed by this organic matter in water which can

then settle to the floor or be transported away.

• E.g. Koc (Soil adsorption values) values of pesticides: Carbaryl=230;

DDT=23800; Dicamba=0.4

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• There are two major ways that pesticides can reach surface and ground
waters: runoff and leaching. Runoff will occur if the chemical does not
adsorb onto soil.

• Leaching occurs when the chemical is weakly adsorbed by soil and can
easily move through the soil. Weak acid pesticides are bound weakly to soil
so they can easily move downward to ground waters.

• If a pesticide’s Koc is small and half-life long it will be lost through leaching

into the groundwater. However, if its Koc is large and have a short half-life it
will be lost through run off.
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 Bioconcentration factor – BCF

• Bioconcentration factor (BCF) is an indicator of how much a chemical will accumulate

in living organisms such as fish.

• Chemicals that have high BCF values are generally no longer used because of possible
hazards to living organisms.

• Once absorbed into an organism, chemicals can move through the food chain (e.g. DDT).

03/28/2022 48
• DDT moves from one organism to another as it is ingested by the
next animal in the food chain.

• The increase in concentration of a chemical as it moves through a

food chain is called biomagnification.

• Bioaccumulation, however, is the progressive increase in the

concentration of a chemical in an organism because of the rate of
intake via the body surface or food and is greater than the
organism’s ability to remove the chemical from its body.

• Bioconcentration factor (BCF) is a measure of the absorption of a

chemical from an aqueous environment by a single organism.
03/28/2022 49
• BCF is the accumulation of a chemical in living organisms (biota)
compared to the concentration in water.

BCF=

03/28/2022 50
 Factors that influence BCF:

• Polarity:

Polar molecules are soluble in water and not very soluble in tissues (non-polar).

Polar chemicals tend not to bioconcentrate in biota because of this low solubility,
whereas non-polar chemicals will accumulate in fatty tissues.

• Solubility

If a chemical is very soluble in water, it will tend to stay in water and not accumulate in
biota, whereas non-water soluble chemicals are more non-polar and tend to be more
likely to accumulate.
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• Lipid content
• Every living organism has different lipid content so each will absorb different
amounts of a chemical accordingly.
• If the lipid content is high, the organism will tend to absorb more of the chemical.

• Metabolism
• When an animal absorbs a chemical, the biological system of that animal has
mechanisms for getting the chemical out of the system.
• This is done by changing part of the chemical in order to make it water soluble so
that it can be expelled through the urine.

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 Vapor pressure (Pv) Cont’d
•Henry’s law constant, vapor pressure, and volatilization are
all interrelated in that they deal with how chemicals are
transported from a surface into the atmosphere.

•Vapor pressure is often used as an indicator of the rate at

which a chemical will evaporate. Another feature of vapor
pressure is that it will indicate whether a chemical will stay in
one area or volatilize and disperse over a large area.
• Vapor pressure values of some chemicals: 2,4-D=27.78; DDT= 0.00015;
Atrazine= 0.0014
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03/28/2022 54
 Cont’d
• Pesticides with high vapor pressures may become environmental
problems because they can volatilize and disperse over a large area.

• Chemicals with a high vapor pressure need to be handled in such a way

so that the vapors do not escape into the atmosphere.

• A chemical with a low vapor pressure does not move into air so there is
a potential for accumulation in water if it is water soluble. If it is not
water soluble the chemical may accumulate in soil or biota.

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 Henry’s law constant - H’ Cont’d
• Henry’s law constant is the air/water partition coefficient, describing
the relative concentrations of a chemical in air (the vapor phase) and
the chemical dissolved in water, in a closed system at equilibrium.

• H’ can be measured directly or estimated as the ratio of Pv to Solubility,

and gives an indication of a chemical's tendency to volatilize from water
to air or dissolve into water from air.

03/28/2022 56
 Cont’d
• A pesticide with a high H’ will volatilize from water into
air and be distributed over a large area.

• Chemicals with a low H’ tend to persist in water and may

be adsorbed onto soil.

H’ =

03/28/2022 57
 Cont’d
Volatilization
• It is the transport process by which a chemical substance enters the
atmosphere by evaporation from soil or water.

• Volatilization can be described by flux which is the amount of

chemical that flows from a unit surface area into the air, or half life
(how long it takes for half of the chemical to volatilize).

• Chemicals do not have constant volatilization rates since they greatly

depend on climatic conditions (wind, temperature, etc).

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Photolysis Cont’d
• is the transformation of a chemical by light energy.
• Large quantities of pesticides are lost by volatilization into the atmosphere.

• In the atmosphere, there are two major degradation pathways that occur.

• photochemical reactions caused by sunlight and

• free radical reactions.

The products formed may or may not be more toxic than the parent
chemical.
Photochemical reactions can take place in air or water when sunlight is
present.
03/28/2022 59
 Cont’d
Factors influencing photolysis

• Time of the day, weather, chemical radicals

present, particulate matter present, water depth

• These rates can be determined by combining the

reaction rates of direct photodegradation, free
radical reactions, and environmental conditions.
03/28/2022 60
 Cont’d
• Photochemical and free radical reactions are major
degradation pathways in the atmosphere, so an
understanding of the products that are formed is
important.
• The products formed by photolysis may or may not be
more toxic than the parent compound. Once a
pesticide has been degraded, a major removal process
for chemicals is to precipitate out of air and return to
the earth’s surface. Another removal process is for the
products to be dissolved in rain and fall back to earth.
The most important factor in determining the rate of
photolysis is the amount of light (photons) present.

03/28/2022 61
 Microbial Metabolism (Biodegradation) Cont’d
• Microbial metabolism of pesticides is an important degradation
process in water and soil.

• The process can take several steps and the end goal is to mineralize
the chemical.

• Mineralization is the process of changing a chemical into the basic

components of CO2, H2O, and mineral salts.

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• Higher organisms, such as fish, are able to metabolize chemicals but

they are not able to mineralize them.

• There are four types of microbes: bacteria, fungi, protozoa, and algae

which may mineralize pesticides.

• Bacteria and fungi are the most abundant in nature so they are the

most important in biological transformation processes.

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 1.4. Matter and Cycles Of Matter
• Cycles of matter, often based on elemental cycles, are of utmost
importance in the environment.

• Global geochemical cycles can be regarded from the viewpoint of various

reservoirs, such as oceans, sediments, and the atmosphere, connected by
conduits through which matter moves continuously.

• The movement of a specific kind of matter between two particular

reservoirs may be reversible or irreversible. The fluxes of movement for
specific kinds of matter vary greatly as do the contents of such matter in a
specified reservoir.

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 Endogenic and Exogenic Cycles
• Endogenic cycles, which predominantly involve subsurface rocks of
various kinds(Figure 1.3)

• Exogenic cycles (Figure 1.3), which occur largely on Earth’s surface and
usually have an atmospheric component.

• Most biogeochemical cycles can be described as :

 elemental cycles involving nutrient elements such as: carbon,
nitrogen, oxygen, phosphorus, and sulfur.

03/28/2022 65
 Cont’d

Figure 1.3. General outline of exogenic and endogenic cycles.

03/28/2022 66
 Hydrologic cycle:

• The hydrologic cycle involves a continuous exchange of water between sea,

atmosphere, land and living animals through massive evaporation of water

from the ocean, cloud formation and precipitation

03/28/2022 67
 The main processes in the hydrologic cycle include:

 Lose of water from the land surface and water surfaces on earth by evaporation by solar

energy (normal evaporation of water from ocean exceeds precipitation by rain into seas by

10%, this 10% excess which precipitates on land balances the hydrological cycle.

 Some of the precipitated rain seeps into the soil as ground water.

 Ground water moves up by capillary action and there by maintains a continuous supply of

water to the surface layer of soil.

•  03/28/2022 68
• The water from the surface layer of the soil is absorbed by plants, which in turn is

returned to atmosphere through transpiration.

•  Surface water or runoff flows into streams, rivers, lakes and catchment areas or

reservoirs.

• Animals also take water which is also returned to the atmosphere through evaporation

•  Thus there is always a balanced continuous cycling of water between earth’s

surfaces and atmosphere

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 The carbon cycle Cont’d
• Carbon is circulated through the carbon cycle shown in Figure 1.4.
• This cycle shows that carbon may be present as gaseous
atmospheric CO2, constituting a relatively small but highly
significant portion of global carbon.
• Some of the carbon is dissolved in surface water and groundwater
as HCO3− or molecular CO2 (aq).
• A very large amount of carbon is present in minerals, particularly
calcium and magnesium carbonates such as CaCO3.
• Photosynthesis fixes inorganic C as biological carbon, represented
as (CH2O), which is a constituent of all life molecules.
03/28/2022 70
 Cont’d

Figure 1.4. The carbon cycle. Mineral carbon is held in a reservoir of limestone,
CaCO3, from which it may be leached into a mineral solution as dissolved hydrogen
carbonate ion, HCO3-, formed when dissolved CO2(aq) reacts with CaCO3. In the
03/28/2022 atmosphere carbon is present as carbon dioxide, CO2. 71
• Another fraction of carbon is fixed as petroleum and natural gas, with a
much larger amount as hydrocarbonaceous kerogen (the organic matter in oil
shale), coal, and lignite, represented as CxH2x.

• Manufacturing processes are used to convert hydrocarbons to xenobiotic

compounds with functional groups containing halogens, oxygen, nitrogen,
phosphorus, or sulfur.

• Though a very small amount of total environmental carbon, these compounds

are particularly significant because of their toxicological chemical effects.

03/28/2022 72
 The Nitrogen Cycle
• As shown in Figure 1.5, nitrogen occurs prominently in all the spheres of the environment.

• The atmosphere is 78% elemental nitrogen, N2, by volume and comprises an inexhaustible
reservoir of this essential element.

• Nitrogen, though constituting much less of biomass than carbon or oxygen, is an essential
constituent of proteins.

• The N2 molecule is very stable so that breaking it down into atoms that can be
incorporated with inorganic and organic chemical forms of nitrogen is the limiting step in
the nitrogen cycle. This does occur by highly energetic processes in lightning discharges
that produce nitrogen oxides.
03/28/2022 73
 Cont’d

Figure 1.5. The nitrogen cycle.

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• Elemental nitrogen is also incorporated into chemically bound forms, or fixed by
biochemical processes mediated by microorganisms.

• The biological nitrogen is mineralized to the inorganic form during the decay of
biomass.

• Large quantities of nitrogen are fixed synthetically under high temperature and high
pressure conditions according to the following overall reaction:
• N2 + 3H2 → 2NH3

• The production of gaseous N2 and N2O by microorganisms and the evolution of these
gases to the atmosphere completes the nitrogen cycle through a process called
denitrification.
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 Nitrogen fixation
• In this step the atmospheric nitrogen is chemically bound to form ammonia by

bacteria and algae.

• 3(CH2O) + 2N2 + 3H2O + 4H+ → 3CO2 + 4NH4+

• Biological nitrogen fixation is mediated by organisms like Rhizobium that live a

symbiotic relation with nodules on the roots of particular species of plants.

• These organisms are capable of catalysing the conversion of atmospheric nitrogen into

forms usable by plants.

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 Nitrification
• It is the conversion of N (-III) to N (V) catalysed by Nitrosomonas and Nitrobacter

2O2 + NH4+ → NO3- + 2H+ + H2O

• Ammonium ion present in water or soil is subjected to oxidation in an aerobic environment.

• The optimum pH for nitrification is between 6.5 and 8, and the reaction rate decreases
significantly when the pH falls below 6.

• Nitrification is important in nature, since nitrogen is absorbed by plants primarily as nitrate.

• Even when nitrogen is applied in the form of ammonium salts as fertilisers, the ammonia is
microbially oxidized to nitrate so that it can be assimilated by plants

•
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 Nitrate Reduction
• This refers to the reduction of nitrogen in chemical compound by microbial action to

lower oxidation states in the absence of free oxygen.

• 2NO3- + {CH2O} → 2NO2- + H2O + CO2

• 2NO2- + 3{CH2O} + 4H+ → 2NH4+ + 3CO2 + H2O

• In the absence of dissolved oxygen (e.g.: in water logged soils) Bacterium denitrificans

mediates the reaction to produce ammonium ion.

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Denitrification
•There are several types of denitrification reactions.

• One of these is the reduction of nitrate to form nitrogen gas.

•The process involves several steps. A number of heterotrophic bacteria including species of Pseudomonas and

Anchromobacter mediate these processes.

•In this process N2 gas is produced from chemically fixed nitrogen

4NO3- + 5{CH2O} + 4H+ → 2N2 + 5CO2 + 7H2O

•By this natural microbial mediated process N2 gas is returned to the atmosphere. By all these processes the

nitrogen cycle is balanced and thus the N2 concentration in the atmosphere is relatively kept constant.

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 The Oxygen Cycle
• The oxygen cycle (Figure 1.6) involves the interchange of oxygen between:

The elemental form of gaseous O2, contained in a huge reservoir in the atmosphere

 Chemically bound O in CO2, H2O, and organic matter.

• The oxygen cycle is strongly tied with other elemental cycles, particularly the
carbon cycle.

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• Elemental oxygen becomes chemically bound by various energy yielding processes,

particularly :

 Combustion in organisms.

 Metabolic processes in organisms

• It is released in photosynthesis.

• This element readily combines with and oxidizes other species such as carbon in aerobic

respiration, or carbon and hydrogen in the combustion of fossil fuels such as methane:

CH4 + 2O2 → CO2 + 2H2O

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 Cont’d

Figure 1.6. Oxygen exchange among the atmosphere, geosphere, hydrosphere, and biosphere.

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• Elemental oxygen also oxidizes inorganic substances such as iron (II) in minerals:

4FeO + O2 → 2Fe2O3

• A particularly important aspect of the oxygen cycle is stratospheric ozone, O3.

• The oxygen cycle is completed by the return of elemental O2 to the atmosphere.

• The only significant way in which this is done is through photosynthesis mediated
by plants.

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 Cont’d

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 The Phosphorus Cycle
• The phosphorus cycle, Figure 1.7, is crucial because phosphorus is usually the limiting nutrien
in ecosystems.

• There are no common stable gaseous forms of phosphorus, so the phosphorus cycle is
endogenic.

• In the geosphere, phosphorus is held largely in poorly soluble minerals,

• such as hydroxyapatite a calcium salt, deposits of which constitute the major reservoir o
environmental phosphate.

• Soluble phosphorus from phosphate minerals and other sources such as fertilizers

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 Cont’d

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Figure 1.7. The phosphorus cycle. 86
• Phosphorus is taken up by plants and incorporated into nucleic acids which
make up the genetic material of organisms.

• Mineralization of biomass by microbial decay returns phosphorus to the salt

solution from which it may precipitate as mineral matter.

• Large quantities of phosphates are extracted from phosphate minerals for

fertilizer, industrial chemicals, and food additives.

• Phosphorus is a constituent of some extremely toxic compounds, especially

organophosphate insecticides and military poison nerve gases.

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 Use of Phosphorus
• For the growth and maintenance of animal bones and teeth phosphates are necessary.

• Organophosphates are essential for cell division involving the production of nuclear DNA and RNA.

• Terrestrial plants absorb inorganic phosphate salts from the soil and convert these into organic

phosphate. Animals obtain their phosphate by eating plants. Plants and animals after their death

return the phosphate to the soil

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• The microorganisms present in the soil convert them into soluble inorganic phosphate, a process

known as mineralisation or biodegradation.

• Biodegradation also deactivates highly toxic organophosphate compounds, such as phosphate ester

insecticides.

• In water phosphorous solubility is controlled by the availability of iron and aluminium under acid

conditions and calcium under alkaline conditions; each of these metals forms insoluble phosphates.

•When the pH is slightly acidic, phosphorous has its maximum solubility and under these conditions

H2PO4- the predominant species.

89
 The Sulfur Cycle
• The sulfur cycle, Figure 1.8, is relatively complex in that it involves

several gaseous species, poorly soluble minerals, and several species in

solution.

• It is tied with the oxygen cycle in that

• sulfur combines with oxygen to form

• gaseous sulfur dioxide, SO2, an atmospheric pollutant, and

• soluble sulfate ion, SO42−.

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 Cont’d

03/28/2022 Figure 1.8. The sulfur cycle. 91

Among the significant species involved in the sulfur cycle are :

• gaseous hydrogen sulfide, H2S;

• mineral sulfides, such as PbS, sulfuric acid, H2SO4, the main constituent of acid
rain; and

• biologically bound sulfur in sulfur-containing proteins.

• Insofar as pollution is concerned, the most significant part of the sulfur cycle is the
presence of pollutant SO2 gas and H2SO4 in the atmosphere.

• SO2 gas is a somewhat toxic gaseous air pollutant evolved in the combustion of
sulfur-containing fossil fuels.
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• The sulphur cycle involves inter-conversion among a number of sulphur species.

The major microbially mediated processes in this cycle are the following.

a) Sulphate reduction to sulphide by bacteria such as desulfovibrio

• In an organic rich reducing aqueous environment, sulphate is readily reduced to

species in the -2 or less commonly, oxidation states:

SO42- + 2{CH2O} + 2H+ → H2S + 2CO2 + 2H2O

• The toxic H2S may cause serious problem with water quality.

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b) Sulphide oxidation by bacteria such as thiobacillus

• Sulphide is unstable under aerobic conditions and is easily oxidised via a variety of
pathways.

• The sulphide might have been formed during the decomposition of organic matter or
might have been present as sulphide mineral in the sediment or soil.

2H2S + 4O2 → 4H+ + 2SO42

• The acid tolerant sulphur-oxidising bacteria thiobacillus produce and thrive in,
environmentally damaging acidic waters, such as acid mine water.

• The reaction simultaneously produces hydronium ions and is thus an acidifying

process.
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c) Degradation of organic sulphur compounds:

 The degradation of sulphur-containing organic compounds by bacterially mediated

processes can result in the production of strong-smelling noxious H2S and other volatile

organic sulphur compounds such as methyl thiol CH3SH and dimethyl sulphide CH3SSCH3.

 Thus the above reactions give a brief outline of the major microbially mediated processes in

the sulphur cycle.

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 Thank you

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